Methods of forming fluorite from fluorine ion-containing fluids using bioactive glass and filter media containing bioactive glass

Abstract

The invention relates to a method for forming fluorite from a fluid containing fluoride ions by using bioactive glass and a filter medium containing bioactive glass. A method of forming fluorite from an F-containing aqueous fluid, the method comprising: contacting a bioactive glass comprising calcium with an F-containing aqueous fluid; and forming fluorite. A filter medium for forming fluorite from an F-containing aqueous fluid and a filter comprising the filter medium, the filter medium comprising: a bioactive glass comprising calcium; and at least one of sand, gravel, charcoal, polymer particles, and ceramic particles.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 544,048, filed on October 13, 2023, which is incorporated herein by reference in its entirety for all purposes. Technical Field

[0003] The present disclosure relates generally to methods of forming fluorspar, and more particularly to methods of forming fluorspar from bioactive glasses and F-containing - Methods of forming fluorspar from aqueous fluids, and filter media for such purposes. Background Art

[0004] Elevated levels of fluoride ions in aqueous environments (e.g., drinking water and the environment) present significant health risks. Therefore, there is a need in the art for methods, filter media, and filters that can be used to capture fluoride ions in aqueous environments and / or reduce the fluoride ion content in aqueous environments. There is also a need in the art for methods of producing pure fluorite forms. The present disclosure is directed to these and other important goals. Summary of the invention

[0005] In various aspects, the present disclosure relates to - A method for forming fluorite from an aqueous fluid, the method comprising: mixing a bioactive glass containing calcium with a bioactive glass containing F - contacting an aqueous fluid; and forming fluorspar.

[0006] In various aspects, the present disclosure relates to methods for obtaining a - The aqueous fluid forms a fluorspar filter media comprising: a bioactive glass comprising calcium; and at least one of: sand, gravel, charcoal, polymer particles, and ceramic particles.

[0007] In various aspects, the present disclosure is directed to methods of making filter media comprising combining bioactive glass with at least one of sand, gravel, charcoal, polymer particles, and ceramic particles.

[0008] In various aspects, the present disclosure is directed to filters comprising filter media.

[0009] In various aspects, the present disclosure is directed to a method of making a filter that includes inserting a filter media into a filter body.

[0010]

[0013] Additional features and advantages of the present disclosure are set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from that description or may be learned by practicing the aspects described herein, including the following detailed description, claims, and accompanying drawings.

[0011] It is to be understood that both the foregoing general description and the following detailed description are exemplary only and are intended to provide an overall review or framework for understanding the nature and character of the present disclosure and claims. The included drawings provide a further understanding of the present disclosure and are incorporated in and constitute a part of this specification. The drawings illustrate various aspects of the present disclosure and together with the description serve to explain the principles and operation of the various aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The following detailed description may be further understood when read in conjunction with the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to represent the same or similar parts. It is to be understood that the drawings are not drawn to scale and are not intended to limit the size of each illustrated component or the relative size of one component relative to another.

[0013] Figure 1 Powder X-ray diffraction (XRD) spectra showing fluorite formation of various glasses.

[0014] Figure 2 is an XRD spectrum showing the fluorite formation of the glass at different time periods.

[0015] Figure 3 is a scanning electron microscope (SEM) image of fluorite formation on the outer surface of glass particles. SEM parameters are 5.0 kV; 8.4 mm; x 10.0 k. Scale bar is 5 μm.

[0016] Figure 4 is a scanning electron microscope (SEM) image of fluorite formation on the outer surface of glass particles. SEM parameters are 5.0 kV; 8.4 mm; x 25.0 k. Scale bar is 2 μm. DETAILED DESCRIPTION

[0017] In the following description, whenever a group is described as comprising at least one element of a group of elements and combinations thereof, it should be understood that the group can contain any number of these listed elements, either in the form of a single element or in combination with each other, or mainly consist of them, or consist of them. Similarly, whenever a group is described as consisting of at least one element of a group of elements or combinations thereof, it should be understood that the group can consist of any number of these listed elements, either in the form of a single element or in combination with each other.

[0018] Unless otherwise indicated in specific cases, the numerical ranges stated herein include upper and lower limits, and the ranges are intended to include their endpoints and all integers and fractions within the range. In addition, when expressing an amount, concentration or other value or parameter in the form of a range, one or more ranges, or listing an upper numerical limit and a lower numerical limit, it is understood that this is equivalent to specifically disclosing all ranges formed by combining any pair of upper range limits or values ​​with any lower range limit or value, regardless of whether such pairs are disclosed separately.

[0019] If the term "about" is used to describe a value or an endpoint of a range, it is understood that the disclosure includes the specific value or endpoint referenced. As used herein, the term "about" indicates that amounts, dimensions, formulations, parameters and other variables and characteristics are not and need not be exact, but may be approximate and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding and measurement errors, etc., as well as other factors known to those skilled in the art. It is noted that the term "substantially" may be used herein to indicate the degree of inherent uncertainty that may be caused by any quantitative comparison, value, measurement or other representation method. These terms are also used herein to indicate that the expressed value of a quantity may deviate from the reference value to a certain extent, but will not result in a change in the basic function of the subject matter under consideration. Thus, for example, a glass that is "free of" or "substantially free of" or "substantially free of" Al2O3 (or any other component) is a case in which Al2O3 (or any other component) is not actively added or dosed into the glass, but may be present in very small amounts as a contaminant (e.g., 500, 400, 300, 200 or 100 ppm or less or other cases).

[0020] Herein, unless otherwise stated, glass compositions are expressed as weight percent of the amount of a particular component contained therein, calculated as an oxide. Any component having more than one oxidation state may be present in the glass composition in any oxidation state. However, unless otherwise stated, the concentration of such component is expressed as the oxide in which such component is in its lowest oxidation state.

[0021] As used herein, a "bioactive" glass means that it is biocompatible with bone, teeth, and / or tissue. For example, in some aspects, "bioactivity" in the present disclosure refers to: (1) the ability to form apatite, brushite, leucoclase, or other bioactive crystalline phases (e.g., hydroxyapatite, fluoroapatite, carbonate apatite, or any combination thereof) in simulated body fluids (e.g., artificial saliva) according to ASTM F1538-03 (2017); (2) the ability to bond to a desired biological material (e.g., bone, teeth, and / or tissue); and / or (3) the ability to remineralize teeth or bones. Generally speaking, there is no toxicity or other significant negative effects in a biological environment (e.g., bone, teeth, and / or tissue).

[0022] As used herein, "non-glass CaO" means CaO that is not present as a component of glass.

[0023] As used herein, the term "substantially" may be used herein to denote the inherent degree of uncertainty that may result from any quantitative comparison, value, measurement, or other method of representation. The term is also used herein to denote that a value expressed in a quantity may deviate from a stated reference value to a certain degree, but without resulting in a change in the basic function of the subject matter under consideration. Thus, for example, a glass or composition that is "substantially free" of a designated substance is one in which the substance is not actively added, but may be present in small amounts, such as as a contaminant, such as less than 0.5 wt%, less than 0.1 wt%, less than 0.01 wt%, and the like (e.g., 500, 400, 300, 200, or 100 ppm or less). Furthermore, if, for example, a substance is purposefully added to a given composition, such a composition may still be considered to be "substantially free" if the substance is present in an amount less than any of the aforementioned amounts (which may be dictated by the context).

[0024] As used herein, a "F-containing fluid" is a fluid that contains at least some fluoride ions in dissolved form.

[0025] As used herein, "weight" and "mass" are used interchangeably with no difference in meaning or purpose.

[0026] Fluoride ion levels in aqueous environments cause significant oral health problems worldwide, especially when persistently above 1 ppm in drinking water. Specifically, elevated fluoride ion levels can lead to dental fluorosis, a condition in which streaks or stains appear on the teeth due to long-term exposure to large amounts of fluoride ions. Fluoride ions in drinking water come from a combination of pollution sources, such as steel production and fossil fuel combustion, as well as from fluoride ions present in minerals in the natural environment. For example, fluorite (CaF2) is a fluoride ion-enriched mineral with 48 wt% F that is abundant in the natural environment, making it a significant source of natural fluoride ions. Generally speaking, fluorite is formed in the environment by hydrothermal processes, and its formation in solution is the following equation:

[0027] Ca 2+ (Water-based)+2F - (Aqueous) → CaF2(s)(1)

[0028] Previously, the removal of fluoride ions from aqueous systems has been achieved using Ca-containing materials (e.g., Ca(OH)2, CaCO3, or non-glass CaO) via precipitation of fluorspar (e.g., as in Equation 1) and / or adsorption of fluorspar on glass surfaces.

[0029] However, the bioactive glasses disclosed herein provide a different approach to supply calcium ions to form fluorite from fluoride ion-containing solutions. 2+ ion sources, which rapidly precipitate fluorite on their surfaces (e.g. within 1 day). In general, the bioactive glasses herein not only contain a significant calcium proportion, but also have a strong tendency to release ionic species when in contact with an aqueous environment. In fact, they tend to decompose significantly faster than Ca-based minerals, highlighting their ability to catalyze fluorite precipitation, for example in charged surface layers.

[0030] Disclosed herein is a method for forming fluorite crystals and / or precipitates on the surface of a bioactive glass by reacting the glass with an aqueous fluoride ion source. The bioactive glass readily dissolves in aqueous solutions, thereby releasing ions (e.g., Ca 2+ ) and rapidly form fluorite precipitates and / or crystals on their surfaces. Ca 2+ The fluoride ions may be released at the surface of the glass and / or enter the surrounding environment. Thus, the bioactive glass herein can be used as a method for removing fluoride ions from water, and in some aspects, the fluorspar formed can be collected and reused as a pure (>90 wt%) raw material. The bioactive glass herein can also be provided in a filter medium to facilitate the capture of fluoride ions from a solution.

[0031] At present, other Ca 2+Sources such as calcite are similarly used to precipitate fluorspar in water; however, due to their higher solubility in water, bioactive glasses can provide the advantage of at least 10 times faster calcium release. Faster precipitation of fluorspar is thus expected with the bioactive glasses disclosed herein, which has been observed in the Examples herein. For example, fluorspar formation via dissolution of the bioactive glass was shown to occur within 1 day of immersion in a fluoride ion-containing solution, with the fluorspar phase being the only crystalline phase formed within 7 days of immersion of the glass ( Figure 1-2 In one aspect, after 7 days of solution exposure, fluorite nanocrystals ( Figure 3-4 ).

[0032] The bioactive glasses disclosed herein are bioactive and / or biodegradable, which makes them less of a human health concern than traditional approaches (eg, those based on calcite).

[0033] Disclosed from the - A method for forming fluorite from an aqueous fluid, the method comprising: mixing a bioactive glass containing calcium with a bioactive glass containing F - contacting an aqueous fluid; and forming fluorspar.

[0034] In some aspects, the F-containing - The fluid contains F in any suitable amount. - Generally speaking, F - In dissolved form in the amounts specified herein (e.g., unless otherwise specified, F - The amount generally does not include any F in solid form (e.g. solid CaF2) - ); however, if so desired, the amounts herein may be expressed as including F in solid form - In some aspects, the F - Fluid contains F - The amount is at least 1 ppm (by mass) based on the F-containing - The total mass of the fluid. There is no particular upper limit, as it is expected that in any F - The methods and disclosures herein can be performed in any manner; however, in some aspects, the - Fluid contains F - The amount is 20,000 ppm or less based on the F-containing - In some aspects, the F-containing - Fluid contains F - The amount is (ppm, mass basis, based on the F-containing -or at least 1000, at least 1500, at least 2000, at least 2500, at least 3000, at least 3500, at least 4000, at least 4500, at least 5000, at least 6000, at least 7000, at least 8000, at least 9000, at least 10000, at least 15000, or at least 20000, at least 25000, at least 30000, at least 35000, at least 40000, at least 45000, at least 50000, at least 60000, at least 70000, at least 80000, at least 90000, at least 100000, at least 150000, or at least 200000. In some aspects, the F-containing - Fluid contains F - The amount is (ppm, mass basis, based on the F-containing - or less, 10 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less. Any of the aforementioned open ranges can be combined in any manner to form closed ranges, for example: 1-100, 50-8000, 10000-20000, etc.

[0035] In some aspects, the method comprises - F in aqueous fluids - The concentration of the aqueous fluid is reduced to below a specific amount. For example, in some aspects, the specific amount is an amount that makes the aqueous fluid suitable for its intended use. In some aspects, the intended use is human and / or animal consumption of the aqueous fluid (e.g., as drinking water). In some aspects, the intended use is discharge of the aqueous fluid from an industrial site into the environment (e.g., land and / or water). In some aspects, the purpose of the method is to form pure fluorspar, in which case the fluorspar containing F is - F in aqueous fluid - The reduction of F is not a goal but only a result. In any event, in some aspects, the method makes the - F in fluid- Concentration (ppm, mass, based on F-containing - In some aspects, the method reduces the total mass of the fluid to: 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1000 or less, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 300 or less, 200 or less, 100 or less, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less. In some aspects, the method reduces the total mass of the fluid to: 10000 or less, 9000 or less, 8000 or less, 700 or less, 600 or less, 500 or less, 400 or less, 300 or less, 200 or less, 100 or less, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less. - F in aqueous fluids - Concentration (ppm, mass, based on F-containing - The total mass of the fluid) is reduced to: 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, 1000 or more, 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 7000 or more, 8000 or more, 9000 or more, or 10000 or more. Any of the foregoing open-ended ranges can be combined in any manner to form closed ranges, for example: 1-100, 500-3000, 50-500, etc.

[0036] In some aspects, the F-containing - The fluid is not or substantially does not contain at least one of: a buffer, saliva, and a simulated body fluid (e.g., artificial saliva). In this regard, many bioactive glasses known in the art are used in medical applications, which necessitate the use of a buffer or simulated body fluid (e.g., artificial saliva or artificial plasma) or testing thereof. However, in some aspects, a unique aspect of the present disclosure is to be used in a fluid containing F - The bioactive glass forming fluorite in the fluid is not or substantially free of at least one of the following: buffer, saliva, and simulated body fluid. Such fluorite-containing bioactive glass that can be used in the present disclosure - Examples of fluids include: water for residential use (e.g., human and / or animal consumption), where a high F -Content (e.g., unsafe or at least not recommended for human and / or animal consumption, at least according to government safety standards such as those set forth by the U.S. Environmental Protection Agency (EPA) and / or the U.S. Food and Drug Administration (FDA)). High F - Other F - fluid, thereby being beneficial to fluorspar production for the purpose of collecting fluorspar.

[0037] In some aspects, the method disclosed herein is performed in a water treatment plant or a resident's home. For example, in some aspects, when performed in a water treatment plant, the water source processed by the method is intended for residential, municipal and / or agricultural purposes (e.g., human consumption, animal consumption, watering crops, etc.). Similarly, in some aspects, when performed in a resident's home (including an apartment, a residential unit, etc.), the method can be performed by filtering tap water consumed by humans for consumption or gardening / landscape purposes.

[0038] In some aspects, the fluorspar formed is as a F-containing - The bioactive glass may at least partially dissolve, release calcium ions into the fluid and / or onto the surface of the bioactive glass, allowing the calcium ions to react with the F-containing liquid. - Fluid F - Contacting thereby precipitates and / or crystallizes fluorspar (in the fluid and / or on the surface of the bioactive glass).

[0039] In some aspects, the bioactive glass and the F-containing -Fluorspar is formed within a suitable time period after the fluid contacts. In some aspects, the time period can be determined by powder X-ray diffraction (XRD) analysis. For example, in some aspects, fluorspar is formed within a time period of 0.25, 0.5, 0.75, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (days). In some aspects, fluorspar is formed over the following time periods (days): 0.25-10, 0.25-9, 0.25-8, 0.25-7, 0.25-6, 0.25-5, 0.25-4, 0.25-3, 0.25-2, 0.25-1, 0.25-0.75, 0.25-0.5, 0.5-10, 0.5-9, 0.5-8, 0.5-7, 0.5-6, 0.5-5, 0.5-4, 0.5-3, 0.5-2, 0.5-1, 0.5-0.75, 0.75-10, 0.75-9, 0.75-8, 0.75-7, 0.75-6, 0.7 5-5, 0.75-4, 0.75-3, 0.75-2, 0.75-1, 1-10, 1-9, 1-8, 1-7, 1-6, 1-5, 1-4, 1-3, 1-2, 2-10, 2-9, 2-8, 2-7, 2-6, 2-5, 2-4, 2-3, 3-10, 3-9, 3-8, 3-7, 3-6, 3-5, 3-4, 4-10, 4-9, 4-8, 4-7, 4-6, 4-5, 5-10, 5-9, 5-8, 5-7, 5-6, 6-10, 6-9, 6-8, 6-7, 7-10, 7-9, 7-8, 8-10, 8-9, or 9-10.

[0040] In some aspects, the contacting step comprises exposing the F-containing - The fluid flows through or in one or more containers containing bioactive glass (e.g., optionally, the bioactive glass is a component of the filter media, as described elsewhere herein). For example, the one or more containers can be one or more circulation tanks (e.g., stirred circulation tanks).

[0041] In some aspects, the contacting step comprises exposing the F-containing - Fluid passes through a filter medium containing bioactive glass. In some aspects, the filter medium is contained in one or more containers (e.g., a circulation tank). In some aspects, the filter medium is arranged in a filter body comprising an inlet and an outlet, wherein the position of the filter medium is between the inlet and the outlet. The filter medium is described in more detail elsewhere herein.

[0042] Some aspects disclosed herein are substantially free of or do not include CaCO3 (e.g., calcite), Ca(OH)2, non-glass CaO, or any combination thereof. For example, in some aspects, the methods are substantially free of or do not include CaCO3 (e.g., calcite, amorphous, or mixtures thereof), Ca(OH)2, non-glass CaO, or any combination thereof. In some aspects, the filter media is substantially free of or does not include CaCO3 (e.g., calcite, amorphous, or mixtures thereof), Ca(OH)2, non-glass CaO, or any combination thereof.

[0043] In some aspects, the bioactive glass disclosed herein comprises calcium. In some aspects, the bioactive glass disclosed herein is at least partially soluble in an aqueous fluid (e.g., water), thereby releasing calcium ions from the bioactive glass after contact with the aqueous fluid. In some aspects, the bioactive glass comprises SiO2 and CaO. In some aspects, the bioactive glass comprises SiO2, CaO, and P2O5. In some aspects, the bioactive glass comprises at least one of: 25-55 wt% SiO2, 20-55 wt% CaO, and 5-20 wt% P2O5.

[0044] Silicon dioxide (SiO2) can be used as the main glass-forming oxide component in the bioactive glass disclosed herein. SiO2 can be included to provide high temperature stability and chemical durability. However, if too much SiO2 is included (e.g., a glass containing pure SiO2), the melting temperature is too high to be easily processable (e.g., greater than 200 poise). In addition, bioactive glasses containing too much SiO2 may suffer from reduced bioactivity. In some aspects, the amount of SiO2 included in the bioactive glass is at least 25% by weight. As an alternative or supplement, in some aspects, the amount of SiO2 included in the bioactive glass is 55% by weight or less. In some aspects, the bioactive glass comprises SiO2 in an amount (wt %) of 25-55, 25-50, 25-45, 25-40, 25-35, 25-30, 30-55, 30-50, 30-45, 30-40, 30-35, 35-55, 35-50, 35-45, 35-40, 40-55, 40-50, 40-45, 45-55, 45-50, or 50-55.

[0045] Phosphorus pentoxide (P2O5) can act as a network former in bioactive glass. In addition, for the bioactivity of the bioactive glass herein, the release of phosphate ions to the surface of the bioactive glass contributes to the formation of apatite. Apatite is an inorganic mineral in bones and teeth, and the formation of apatite in simulated body fluids (such as artificial saliva) is a criterion for the bioactivity of the material (according to ASTM F1538-03 (2017), which is incorporated herein by reference in its entirety for all purposes). Including phosphate ions in bioactive glass can increase the apatite formation rate and the binding capacity of hard tissues (such as bones, teeth, etc.). In addition, P2O5 can increase the viscosity of the glass, which in turn expands the operating temperature range, and is therefore advantageous for the manufacture and formation of glass. In some aspects, the amount of P2O5 included in the bioactive glass herein is at least 5% by weight. In some aspects, the amount of P2O5 included in the bioactive glass herein is 20% by weight or less. In some aspects, the bioactive glass herein comprises P2O5 in an amount (wt%) of 5-20, 5-15, 5-10, 10-20, 10-15, or 15-20. In some aspects, the bioactive glass herein is substantially free of or contains no P2O5.

[0046] In some aspects, the bioactive glasses disclosed herein comprise calcium (e.g., CaO) such that calcium ions (Ca 2+ ions) are released when the bioactive glass is in contact with an aqueous fluid. 2+ In some aspects, calcium ions and fluoride ions (F - ) in the presence of F - In some aspects, the bioactive glass herein comprises CaO in an amount of at least 20 wt %. In some aspects, the bioactive glass herein comprises CaO in an amount of 55 wt % or less. In some aspects, the bioactive glass herein comprises CaO in an amount (wt %) of 20-55, 20-50, 20-45, 20-40, 20-35, 20-30, 20-25, 25-55, 25-50, 25-45, 25-40, 25-35, 25-30, 30-55, 30-50, 30-45, 30-40, 30-35, 35-55, 35-50, 35-45, 35-40, 40-55, 40-50, 40-45, 45-55, 45-50, or 50-55.

[0047] In some aspects, the bioactive glass herein comprises zirconium dioxide (ZrO2), which may function as a network former or an intermediate in the precursor glass and is a key oxide for improving glass thermal stability by significantly reducing glass devitrification during the forming process and lowering the liquidus temperature. In some aspects, ZrO2 may play a role similar to that of aluminum oxide (Al2O3) in other bioactive glass compositions. In some aspects, the bioactive glass herein comprises ZrO2 in an amount of 0 wt% or greater than 0 wt%. In some aspects, the bioactive glass herein comprises ZrO2 in an amount of 10 wt% or less. In some aspects, the bioactive glass comprises ZrO2 in an amount (wt %) of: 0-10, 0-9, 0-8, 0-7, 0-6, 0-5, 0-4, 0-3, 0-2, 0-1, >0-10, >0-9, >0-8, >0-7, >0-6, >0-5, >0-4, >0-3, >0-2, >0-1, 1-10, 1-9, 1-8, 1-7, 1-6, 1-5, 1-4, 1-3, 1- In some aspects, the bioactive glass contains substantially no or no ZrO2.

[0048] In some aspects, the use of alkaline oxides (Na2O, K2O, Li2O, Rb2O, or Cs2O) in the bioactive glass can act as an aid to achieve a low melting temperature and a low liquidus temperature, which can be helpful for the glass melting process. In addition, in some aspects, the addition of alkaline oxides can improve the bioactivity. However, in some aspects, if the amount of alkaline oxide is too high, the bioactive glass has reduced chemical durability; in other words, in some aspects, keeping the amount of alkaline oxide in a certain lower range achieves high chemical durability of the bioactive glass. If any alkaline oxide is used, a balance should be achieved to provide a bioactive glass with suitable dissolution properties so that when calcium ions are combined with F-containing - F in aqueous fluids -In some aspects, the bioactive glass contains no alkaline oxides (e.g., does not contain any added alkaline oxides). In some aspects, the bioactive glass contains substantially no alkaline oxides. In some aspects, the bioactive glass contains a sum of Li2O+Na2O+KO in an amount of 0 wt% or greater than 0 wt%. In some aspects, the bioactive glass contains a sum of Li2O+Na2O+KO in an amount of 30 wt% or less, 25 wt% or less, 15 wt% or less, or 5 wt% or less. In some aspects, the bioactive glass comprises the sum of Li2O + Na2O + K2O in an amount (wt %) of 0-30 wt %, such as the following amounts (wt %): 0-30, 0-25, 0-20, 0-15, 0-10, 0-5, 0-1, 1-30, 1-25, 1-20, 1-15, 1-10, 1-5, 5-30, 5-25, 5-20, 5-15, 5-10, 10-30, 10-25, 10-20, 10-15, 15-30, 15-25, 15-20, 20-30, 20-25, or 25-30. In some aspects, the bioactive glass comprises the sum of R2O (wherein R2O is Na2O, KO, Li2O, Rb2O, and Cs2O) in an amount of 0-30 wt%, such as the following amounts (wt%): 0-30, 0-25, 0-20, 0-15, 0-10, 0-5, 0-1, 1-30, 1-25, 1-20, 1-15, 1-10, 1-5, 5-30, 5-25, 5-20, 5-15, 5-10, 10-30, 10-25, 10-20, 10-15, 15-30, 15-25, 15-20, 20-30, 20-25, or 25-30. In some aspects, the bioactive glass is substantially free of or free of Li2O, Na2O, and KO. In some aspects, the bioactive glass is substantially free of or free of R2O, wherein R2O is Na2O, K2O, Li2O, Rb2O, and Cs2O.

[0049] In some aspects, the amount of Na2O included in the bioactive glass is 0 wt% or greater than 0 wt%. In some aspects, the amount of Na2O included in the bioactive glass is 25 wt% or less. In some aspects, the amount of Na2O included in the bioactive glass (wt%) is: 0-25, 0-20, 0-15, 0-10, 0-9, 0-8, 0-7, 0-6, 0-5, 0-4, 0-3, 0-2, 0-1, 0-0.5, 0-0.1, >0-25, >0-20, >0-15, >0-10, >0-9, >0-8, >0-7, >0-6, >0-5, >0-4, >0-3, >0-2, >0-1, >0-0.5, >0-0.1, 0.1-25, 0.1-20, 0. 1-15,0.1-10,0.1-9,0.1-8,0.1-7,0.1-6,0.1-5,0.1-4,0.1-3,0.1-2,0.1-1,0.1-0.5,0.5-25,0.5-20,0.5-15,0.5-10,0.5-9,0.5-8,0.5-7,0.5-6,0.5-5,0.5-4,0.5-3,0.5-2,0.5-1,1-25,1-20,1-15,1-10,1-9,1-8,1-7,1-6,1-5, 1-4, 1-3, 1-2, 2-25, 2-20, 2-15, 2-10, 2-9, 2-8, 2-7, 2-6, 2-5, 2-4, 2-3, 2.5-25, 2.5-20, 2.5-15, 2.5-10, 2.5-9, 2.5-8, 2.5-7, 2.5-6, 2.5-5, 2.5-4, 2.5-3, 3-25, 3-20, 3-15, 3-10, 3-9, 3-8, 3-7, 3-6, 3-5, 3-4, 4-25, 4-20, 4-15, 4-10, 4- In some aspects, the bioactive glass contains substantially no or no Na2O.

[0050] In some aspects, the bioactive glass comprises KO in an amount of 0 wt% or greater than 0 wt%. In some aspects, the bioactive glass comprises KO in an amount of 5 wt% or less. In some aspects, the bioactive glass comprises KO in an amount (wt%) of: 0-5, 0-4.5, 0-4, 0-3.5, 0-3, 0-2.5, 0-2, 0-1.5, 0-1, 0-0.5, >0-5, >0-4.5, >0-4, >0-3.5, >0-3, >0-2.5, >0-2, >0-1.5, >0-1, >0-0.5, 0.5-5, 0.5-4.5, 0.5-4, 0.5-3.5, 0.5-3, 0.5-2.5, 0.5-2, 0.5-1.5, 0.5-1, 1-5, 1 In some aspects, the bioactive glass contains substantially no or no K2O.

[0051] In some aspects, the bioactive glass comprises Li2O in an amount of 0 wt% or greater than 0 wt%. In some aspects, the bioactive glass comprises Li2O in an amount of 5 wt% or less. In some aspects, the bioactive glass comprises Li2O in an amount (wt%) of: 0-5, 0-4.5, 0-4, 0-3.5, 0-3, 0-2.5, 0-2, 0-1.5, 0-1, 0-0.5, >0-5, >0-4.5, >0-4, >0-3.5, >0-3, >0-2.5, >0-2, >0-1.5, >0-1, >0-0.5, 0.5-5, 0.5-4.5, 0.5-4, 0.5-3.5, 0.5-3, 0.5-2.5, 0.5-2, 0.5-1.5, 0.5-1, 1-5, In some aspects, the bioactive glass contains substantially no or no Li2O.

[0052] In some aspects, the bioactive glass comprises MgO. In some aspects, the inclusion of MgO can improve the liquidus of the precursor glass to avoid devitrification during the forming process. In some aspects, the amount of MgO included in the bioactive glass is 0 wt% or greater than 0 wt%. In some aspects, the amount of MgO included in the bioactive glass is 10 wt% or less. In some aspects, the amount of MgO included in the bioactive glass (wt%) is: 0-10, 0-9, 0-8, 0-7, 0-6, 0-5, 0-4, 0-3, 0-2, 0-1, >0-10, >0-9, >0-8, >0-7, >0-6, >0-5, >0-4, >0-3, >0-2, >0-1, 1-10, 1-9, 1-8, 1-7, 1-6, 1-5, 1-4, 1-3, 1- 2, 2-10, 2-9, 2-8, 2-7, 2-6, 2-5, 2-4, 2-3, 3-10, 3-9, 3-8, 3-7, 3-6, 3-5, 3-4, 4-10, 4-9, 4-8, 4-7, 4-6, 4-5, 5-10, 5-9, 5-8, 5-7, 5-6, 6-10, 6-9, 6-8, 6-7, 7-10, 7-9, 7-8, 8-10, 8-9, or 9-10. In some aspects, the bioactive glass is substantially free of or free of MgO.

[0053] In some aspects, the bioactive glass comprises F - The amount of F is 0 wt % or greater than 0 wt %. In some aspects, the bioactive glass comprises F - In some aspects, the bioactive glass comprises F -The amount (weight %) is: 0-10, 0-9, 0-8, 0-7, 0-6, 0-5, 0-4.5, 0-4, 0-3.5, 0-3, 0-2.5, 0-2, 0-1.5, 0-1, 0-0.5, 0-0.1, >0-10, >0-9, >0-8, >0-7, >0-6, >0-5, >0-4.5, >0-4, >0-3.5, >0-3, >0-2.5, >0-2, >0-1.5, >0-1, >0-0.5, >0-0.4, >0-0.3, >0-0.2, >0-0.1, >0-0.01, 0.01-10, 0.01-9, 0.01-8, 0.01-7, 0.01-6, 0.01- 5, 0.01-4.5, 0.01-4, 0.01-3.5, 0.01-3, 0.01-2.5, 0.01-2, 0.01-1.5, 0.01-1, 0.01-0.5, 0.01-0.4, 0.01-0.3, 0.01-0.2, 0.01-0.1, 0.1-10, 0.1-9, 0 .1-8, 0.1-7, 0.1-6, 0.1-5, 0.1-4.5, 0.1-4, 0.1-3.5, 0.1-3, 0.1-2.5, 0.1-2, 0.1-1.5, 0.1-1, 0.1-0.5, 0.1-0.4, 0.1-0.3, 0.1-0.2, 0.2-10, 0.2-9, 0 .2-8, 0.2-7, 0.2-6, 0.2-5, 0.2-4.5, 0.2-4, 0.2-3.5, 0.2-3, 0.2-2.5, 0.2-2, 0.2-1.5, 0.2-1, 0.2-0.5, 0.2-0.4, 0.2-0.3, 0.3-10, 0.3-9, 0.3-8, 0.3 -7,0.3-6,0.3-5,0.3-4.5,0.3-4,0.3-3.5,0.3-3,0.3-2.5,0.3-2,0.3-1.5,0.3-1,0.3-1.5,0.3-0.4,0.4-10,0.4-9,0.4-8,0.4-7,0.4-6,0.4-5,0 .4-4.5, 0.4-4, 0.4-3.5, 0.4-3, 0.4-2.5, 0.4-2, 0.4-1.5, 0.4-1, 0.4-0.5, 0.5-10, 0.5-9, 0.5-8, 0.5-7, 0.5-6, 0.5-5, 0.5-4.5, 0.5-4, 0.5-3.5, 0.5 -3, 0.5-2.5, 0.5-2, 0.5-1.5, 0.5-1, 1-10, 1-9, 1-8, 1-7, 1-6, 1-5, 1-4.5, 1-4, 1-3.5, 1-3, 1-2.5, 1-2, 1-1.5, 1.5-10, 1.5-9, 1.5-8, 1.5-7, 1.5-6, 1.5-5, 1.5-4.5, 1.5-4, 1.5-3.5, 1.5-3, 1.5-2.5, 1.5-2, 2-10, 2-9, 2-8, 2-7, 2-6, 2-5, 2-4.5, 2-4, 2-3.5, 2-3, 2-2.5, 2.5-10, 2.5-9, 2.5-8, 2.5-7, 2.5-6, 2.5-5, 2.5-4.5, 2.5-4, 2.5-3.5, 2.5-3, 3-10, 3-9, 3-8, 3-7, 3-6, 3-5, 3-4.5, 3 -4, 3-3.5, 3.5-10, 3.5-9, 3.5-8, 3.5-7, 3.5-6, 3.5-5, 3.5-4.5, 3.5-4, 4-10, 4-9, 4-8, 4-7, 4-6, 4-5, 4-4.5, 4.5-10, 4.5-9, 4.5-8, 4.5-7, 4.5-6, 4.5-5, 5-10, 5-9, 5-8, 5-7, 5-6, 6-10, 6-9, 6-8, 6-7, 7-10, 7-9, 7-8, 8-10, 8-9, or 9-10. In some aspects, the bioactive glass is substantially free of or free of F. - .

[0054] In some aspects, the bioactive glasses disclosed herein have any suitable average particle size. The average particle size can be measured by suitable techniques such as dynamic light scattering (DLS), which will be known to those skilled in the art. In some aspects, the bioactive glasses disclosed herein have an average particle size of at least 1 μm. In some aspects, the bioactive glasses disclosed herein have an average particle size of 5000 μm or less (i.e., 5 mm or less). In some aspects, the bioactive glasses disclosed herein have an average particle size (μm) of 1-5000, 1-4000, 1-3000, 1-2000, 1-1000, 1-800, 1-600, 1-400, 1-200, 1-100, 1-80, 1-60, 1-50, 1-40, 1-30, 1-20, 1-10, 1-8, 1-6, 1-4, 1-2, 2-5000, 2-4000, 2-3000, 2-2000, 2-1000, 2-800, 2-600, 2-400, 2-200, 2-100, 2-80, 2-60, 2-50, 2-40, 2-30, 2-20, 2-10, 2-8, 2-6, 2-4, 4-5000, 4-4000, 4-3000, 4-2000, 4-1000, 4-800, 4-600, 4-400, 4-200, 4-100, 4-80, 4-60, 4-50, 4-40, 4-30, 4-20, 4-10, 4-8, 4-6, 6-5000, 6-4000, 6-3000, 6-2000, 6-1000, 6-800, 6-600, 6-400, 6-20 0,6-100,6-80,6-60,6-50,6-40,6-30,6-20,6-10,6-8,8-5000,8-4000,8-3000,8-2000,8-1000,8-800,8-600,8-400,8-200,8-100,8-80,8-60,8-50,8-40,8-30,8-20,8-10,10-5000,10-4000,10-3000,10-2000,10-1000,10-800,10-600,10-400,10-2 00, 10-100, 10-80, 10-60, 10-50, 10-40, 10-30, 10-20, 20-5000, 20-4000, 20-3000, 20-2000, 20-1000, 20-800, 20-600, 20-400, 20-200, 20-100, 20-80, 20-60, 20-50, 20-40, 20-30, 30-5000, 30-4000, 30-3000, 30-2000, 30-1000, 30-800, 30-600, 30-400,30-200, 30-100, 30-80, 30-60, 30-50, 30-40, 40-5000, 40-4000, 40-3000, 40-2000, 40-1000, 40-800, 40-600, 40-400, 40-200, 40-100, 40-80, 40-60, 40-50, 50-5000, 50-4000, 50-3000, 50-2000, 50-1000, 50-800, 50-600, 50-400, 50- 200, 50-100, 50-80, 50-60, 60-5000, 60-4000, 60-3000, 60-2000, 60-1000, 60-800, 60-600, 60-400, 60-200, 60-100, 60-80, 80-5000, 80-4000, 80-3000, 80-2000, 80-1000, 80-800, 80-600, 80-400, 80-200, 80-100, 100-5000, 100-400 0,100-3000,100-2000,100-1000,100-800,100-600,100-400,100-200,200-5000,200-4000,200-3000,200-2000,200-1000,200-800,200-600,200-400,400-5000,400-4000,400-3000,400-2000,400-1000,400-800,400-600,600- 5000, 600-4000, 600-3000, 600-2000, 600-1000, 600-800, 800-5000, 800-4000, 800-3000, 800-2000, 800-1000, 1000-5000, 1000-4000, 1000-3000, 1000-2000, 2000-5000, 2000-4000, 2000-3000, 3000-5000, 3000-4000, or 4000-5000. ,

[0055] In some aspects, the method further comprises collecting the fluorspar. In some aspects, the method further comprises refining the collected fluorspar to purify the fluorspar to a higher purity than before refining. In some aspects, the refining results in a fluorspar having a purity of at least 90% by weight, based on the total weight of the pure fluorspar. In some aspects, the collecting can be any suitable collecting technique, such as collecting a bioactive glass having fluorspar precipitates and / or crystallites thereon, and / or subjecting a bioactive glass containing fluorspar to the contact with the bioactive glass. -Any fluorspar precipitates and / or crystallites in solid form in the fluid are filtered. In some aspects, refining can include filtering, cycloning (e.g., hydrocycloning), or other manipulation techniques that can selectively separate fluorspar from non-fluorspar materials (e.g., bioactive glass). In some aspects, refining includes crushing, grinding, shearing and / or size reduction steps to remove and / or separate fluorspar from other non-fluorspar materials (e.g., bioactive glass).

[0056] In some aspects, refining provides fluorspar having a purity of at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt%.

[0057] In some aspects, the disclosed fluorspar has a purity of at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt%. In some aspects, fluorspar having such purity is produced by the methods disclosed herein.

[0058] In some aspects, disclosed are bioactive glasses formed by the methods disclosed herein, wherein the bioactive glass comprises a fluorite crystalline phase located on an outer surface of the bioactive glass. In some aspects, disclosed are bioactive glasses formed by the methods disclosed herein, wherein the bioactive glass is in a composition comprising fluorite.

[0059] In some aspects, the contacting step of the method comprises a filter medium comprising bioactive glass, wherein the filter medium comprises at least one of: sand, gravel, charcoal, polymer particles, and ceramic particles. The filter medium is the same as described elsewhere herein.

[0060] In some aspects, filter media are disclosed that include: bioactive glass that includes calcium, and at least one of: sand, gravel, charcoal, polymer particles, and ceramic particles. In some aspects, the filter media includes: bioactive glass that includes calcium, and at least one of: sand, gravel, charcoal, polymer particles, ceramic particles, Ca(OH)2, CaCO3 (e.g., calcite, amorphous, or mixtures thereof), and non-glass CaO. In some aspects, the filter media is used to remove calcium from a liquid containing F. - The aqueous fluid forms fluorspar. The bioactive glass contained in the filter media is the same as the bioactive glass described elsewhere herein.

[0061] In some aspects, the filter media is characterized by at least one of the following:

[0062] Sand is present and has an average particle size of 1 micron to 5 mm;

[0063] Grit is present and has an average particle size of 1 micron to 5 mm;

[0064] The presence of charcoal has an average particle size of 1 micron to 5 mm;

[0065] Polymer particles are present and have an average particle size of 1 micron to 5 mm;

[0066] Ceramic particles are present and have an average particle size of 1 micron to 5 mm.

[0067] In some aspects, the average particle size of sand, gravel, charcoal, polymer particles and ceramic particles can independently have any suitable average particle size. The average particle size can be measured by a suitable technique (e.g., dynamic light scattering (DLS)), which will be known to those skilled in the art. In some aspects, the average particle size of sand, gravel, charcoal, polymer particles and ceramic particles can independently be at least 1 μm. In some aspects, the average particle size of sand, gravel, charcoal, polymer particles and ceramic particles can independently be 5000 μm or less (i.e., 5 mm or less). In some aspects, the average particle size of sand, gravel, charcoal, polymer particles, and ceramic particles can independently be (μm): 1-5000, 1-4000, 1-3000, 1-2000, 1-1000, 1-800, 1-600, 1-400, 1-200, 1-100, 1-80, 1-60, 1-50, 1-40, 1-30, 1-20, 1-10, 1-8, 1-6, 1-4, 1-2, 2-5000, 2-4000, 2-3000, 2-2000, 2-1000, 2-800, 2-6 00, 2-400, 2-200, 2-100, 2-80, 2-60, 2-50, 2-40, 2-30, 2-20, 2-10, 2-8, 2-6, 2-4, 4-5000, 4-4000, 4-3000, 4-2000, 4-1000, 4-800, 4-600, 4-400, 4-200, 4-100, 4-80, 4-60, 4-50, 4-40, 4-30, 4-20, 4-10, 4-8, 4-6, 6-5000, 6-4000, 6-3000, 6-20 00, 6-1000, 6-800, 6-600, 6-400, 6-200, 6-100, 6-80, 6-60, 6-50, 6-40, 6-30, 6-20, 6-10, 6-8, 8-5000, 8-4000, 8-3000, 8-2000, 8-1000, 8-800, 8-600, 8-400, 8-200, 8-100, 8-80, 8-60, 8-50, 8-40, 8-30, 8-20, 8-10, 10-5000, 10-4000, 10-300 0,10-2000,10-1000,10-800,10-600,10-400,10-200,10-100,10-80,10-60,10-50,10-40,10-30,10-20,20-5000,20-4000,20-3000,20-2000,20-1000,20-800,20-600,20-400,20-200,20-100,20-80,20-60,20-50,20-40,20-30,30-5000,30-4000,30-3000,30-2000,30-1000,30-800,30-600,30-400,30-200,30-100,30-80,30-60,30-50,30-40,40-5000,40-4000,40-3000,40-2000,40-1000,40-800,40-600,40-400,40-200,40-100,40-80,40-60,40-50,50-5000,50-4000,50-3000, 50-2000, 50-1000, 50-800, 50-600, 50-400, 50-200, 50-100, 50-80, 50-60, 60-5000, 60-4000, 60-3000, 60-2000, 60-1000, 60-800, 60-600, 60-400, 60-200, 60-100, 60-80, 80-5000, 80-4000, 80-3000, 80-2000, 80-1000, 80-800, 80-600, 80-400, 80-2 00, 80-100, 100-5000, 100-4000, 100-3000, 100-2000, 100-1000, 100-800, 100-600, 100-400, 100-200, 200-5000, 200-4000, 200-3000, 200-2000, 200-1000, 200-800, 200-600, 200-400, 400-5000, 400-4000, 400-3000, 400-2000, 400-1000, 400-800 , 400-600, 600-5000, 600-4000, 600-3000, 600-2000, 600-1000, 600-800, 800-5000, 800-4000, 800-3000, 800-2000, 800-1000, 1000-5000, 1000-4000, 1000-3000, 1000-2000, 2000-5000, 2000-4000, 2000-3000, 3000-5000, 3000-4000, or 4000-5000. ,

[0068] In some aspects, the polymer particles of the filter media include: polyolefins, polyacrylates, polystyrene, polyethylene terephthalate, cellulose acetate, or any combination thereof. In some aspects, examples of polyolefins include: polyethylene, polypropylene, ultra-high molecular weight polyethylene, high molecular weight polyethylene, high density polyethylene, high density cross-linked polyethylene, cross-linked polyethylene, medium density polyethylene, linear low density polyethylene, low density polyethylene, very low density polyethylene, chlorinated polyethylene, or any combination thereof. In some aspects, examples of polyacrylates include: polyacrylates, polymethacrylates, polymethacrylate (methyl) esters (PMMA), or any combination thereof. In some aspects, the polymer particles of the filter media have a melting temperature (Tm) greater than 25°C (this includes, for example, polyethylene, which has a Tm of more than 100°C). Suitable Tm (°C) is: greater than 30, greater than 50, greater than 75, greater than 100, greater than 125, greater than 150, or greater than 175. Alternatively or additionally, suitable Tm (°C) is: less than 200, less than 175, less than 150, less than 125, less than 100, less than 75, less than 50 or less than 30. Any of the foregoing open ranges for Tm can be combined to form closed ranges, for example: 25-200, 50-125, 75-175, etc.

[0069] In some aspects, the ceramic particles of the filter media include: alumina, zirconia, ceria-stabilized zirconia, silica microspheres, or any combination thereof.

[0070] In some aspects, the alumina includes a high alumina content (e.g., at least 98 wt. %, such as at least 99 wt. % Al2O3). An exemplary composition of a high alumina content alumina is: Al2O3 99.7 wt. %, MgO 0.15 wt. %, trace materials 0.15 wt. % (e.g., trace materials can be SiO2, CaO and / or FeO, etc.). In some aspects, the alumina includes a reduced alumina content (e.g., at least 91 wt. %, such as at least 92 wt. % Al2O3). An exemplary composition of a reduced alumina content alumina is: Al2O3 92.3 wt. %, SiO2 2.55 wt. %, MgO 2.45 wt. %, CaO 2.10 wt. %, trace materials 0.6 wt. % (e.g., trace materials can be FeO, Na2O and / or K2O, etc.).

[0071] In some aspects, the zirconium oxide comprises high content zirconium oxide (e.g., at least 99 wt % ZrO2). An exemplary high content zirconium oxide composition is: ZrO2 99.1 wt %, 0.9 wt % trace materials. In some aspects, the zirconium oxide is stabilized by cerium. An exemplary composition of cerium stabilized zirconium oxide is: ZrO2 83 wt %, CeO2 17 wt %.

[0072] In some aspects, disclosed are filters comprising the filter media disclosed herein. In some aspects, the filter comprises: a filter body, an inlet, an outlet, and a filter media disposed in the filter body between the inlet and the outlet. In some aspects, the structure of the filter and the filter media achieves a filter comprising F - The aqueous fluid passes through the filter (from the inlet, through the filter media, and out of the outlet). In some aspects, the inclusion of at least one of sand, gravel, charcoal, polymer particles, and ceramic particles promotes the formation of F-containing - Aqueous fluids pass through the filter media without clogging for a commercially viable amount of time before any need for filter media replacement (eg, due to a drop in flow rate caused by significant fluorspar formation on the bioactive glass).

[0073] In some aspects, disclosed are methods for making the filters disclosed herein, the methods comprising inserting a filter media into a filter body. In some aspects, the methods place the filter media between an inlet and an outlet of the filter body.

[0074] In some aspects, disclosed are methods for making the filter media disclosed herein, the methods comprising combining the bioactive glass disclosed herein with at least one of the following: sand, gravel, charcoal, polymer particles, and ceramic particles.

[0075] Various embodiments are contemplated herein, some of which are described in the following paragraphs. It is expressly contemplated that any aspect or portion thereof may be combined to form a combination. The phrase "any other aspect herein" refers to any numbered aspect herein, or any aspect or aspects disclosed elsewhere herein.

[0076] Aspect 1: A method of obtaining a - A method for forming fluorspar from an aqueous fluid, the method comprising:

[0077] Bioactive glass containing calcium and F - Aqueous fluid contact; and

[0078] Forming fluorite.

[0079] Aspect 2: The method of aspect 1 or any other aspect of the present invention, wherein the compound comprises F - Fluid contains F - The amount is at least 1 ppm, by mass, based on the F-containing - The total mass of the fluid.

[0080] Aspect 3: The method of aspect 1 or aspect 2 or any other aspect herein, wherein the compound comprises F - Fluid contains F- The amount is at least 500 ppm, by mass, based on the F-containing - The total mass of the fluid.

[0081] Aspect 4: The method of any one of aspects 1-3 or any other aspect herein, wherein the method comprises - F in aqueous fluids - Concentrations are reduced to 1 ppm or less, by mass, based on F-containing materials in contact with bioactive glass. - The total mass of the fluid.

[0082] Aspect 5: The method of any one of aspects 1-4 or any other aspect herein, wherein the compound comprises F - The fluid is substantially free of at least one of: a buffer, saliva, and a simulated body fluid.

[0083] Aspect 6: The method of any one of Aspects 1-5 or any other aspect herein, wherein the method is performed in a water treatment plant or a residential home.

[0084] Aspect 7: The method of any one of aspects 1-6 or any other aspect herein, wherein the fluorspar formed is a F-containing - A precipitate or crystalline phase in a fluid, as a precipitate or crystalline phase located on an outer surface of a bioactive glass, or any combination thereof.

[0085] Aspect 8: The method of any of Aspects 1-7 or any other aspect herein, wherein at least a portion of the bioactive glass dissolves during the method to release calcium ions into the F-containing - In fluid.

[0086] Aspect 9: The method of any of Aspects 1-8, or any other aspect herein, wherein fluorspar is formed within 1 day of contacting as determined by XRD analysis.

[0087] Aspect 10: The method of any of Aspects 1-9 or any other aspect herein, wherein no crystalline phase other than fluorspar is detected by XRD analysis within 7 days of contacting.

[0088] Aspect 11: The method of any of Aspects 1-10 or any other aspect herein, wherein the contacting comprises causing the F-containing - The fluid flows through or in one or more containers comprising the bioactive glass.

[0089] Aspect 12: The method of any of Aspects 1-11 or any other aspect herein, wherein the contacting comprises causing the F-containing - The fluid passes through a filter medium containing bioactive glass.

[0090] Aspect 13: The method of any of Aspects 1-12 or any other aspect herein, wherein the method is substantially free of CaCO3, Ca(OH)2, non-glass CaO, or any combination thereof.

[0091] Aspect 14: The method of any of Aspects 1-13 or any other aspect herein, wherein the bioactive glass comprises:

[0092] SiO2;

[0093] CaO; and

[0094] P2O5.

[0095] Aspect 15: The method of any of Aspects 1-14 or any other aspect herein, wherein the bioactive glass comprises:

[0096] 25-55 wt% SiO2;

[0097] 20-55 wt% CaO; and

[0098] 5-20 wt% P2O5.

[0099] Aspect 16: The method of any of Aspects 1-15 or any other aspect herein, wherein the bioactive glass comprises at least one of:

[0100] 0-10 wt% ZrO2;

[0101] 0-25 wt% Na2O;

[0102] 0-10 wt% MgO;

[0103] 0-5 wt% K2O;

[0104] 0-5 wt% F - ;or

[0105] Any combination thereof.

[0106] Aspect 17: The method of any of Aspects 1-16 or any other aspect herein, wherein the bioactive glass is substantially free of F - .

[0107] Aspect 18: The method of any of Aspects 1-17, or any other aspect herein, wherein the bioactive glass has an average particle size of 1 micron to 5 mm.

[0108] Aspect 19: The method of any of Aspects 1-18 or any other aspect herein, further comprising collecting fluorspar and refining to provide pure fluorspar having a purity of at least 90 wt %, based on the total weight of the pure fluorspar.

[0109] Aspect 20: The method of any of Aspects 1-19 or any other aspect herein, wherein contacting comprises a filter medium comprising bioactive glass, wherein the filter medium comprises at least one of: sand, gravel, charcoal, polymer particles, and ceramic particles.

[0110] Aspect 21: A bioactive glass formed by the method of any of Aspects 1-20 or any other aspect herein, wherein the bioactive glass comprises a fluorite crystalline phase located on an outer surface of the bioactive glass.

[0111] Aspect 22: A method of preparing a - Aqueous fluid forming fluorite filter medium, the filter medium comprising:

[0112] Bioactive glass comprising calcium; and

[0113] At least one of the following: sand, gravel, charcoal, polymer particles, and ceramic particles.

[0114] Aspect 23: The filter medium of Aspect 22 or any other aspect herein, wherein the bioactive glass comprises:

[0115] SiO2;

[0116] CaO; and

[0117] P2O5.

[0118] Aspect 24: The filter medium of Aspect 22 or Aspect 23 or any other aspect herein, wherein the bioactive glass comprises:

[0119] 25-55 wt% SiO2;

[0120] 20-45 wt% CaO; and

[0121] 5-20 wt% P2O5.

[0122] Aspect 25: The filter medium of any of Aspects 22-24 or any other aspect herein, wherein the bioactive glass comprises:

[0123] 0-10 wt% ZrO2;

[0124] 0-25 wt% Na2O;

[0125] 0-5 wt% MgO;

[0126] 0-5 wt% K2O;

[0127] 0-5 wt% F - ;or

[0128] Any combination thereof.

[0129] Aspect 26: The filter medium of any of Aspects 22-25 or any other aspect herein, comprising a fluorite crystalline phase positioned on an outer surface of the bioactive glass.

[0130] Aspect 27: The filter medium of any of Aspects 22-26 or any other aspect herein, wherein the bioactive glass is substantially free of F - .

[0131] Aspect 28: The filter medium of any of Aspects 22-27 or any other aspect herein, wherein the bioactive glass has a particle size of 1 micron to 5 mm.

[0132] Aspect 29: The filter medium of any of Aspects 22-28 or any other aspect herein, wherein at least one of the following requirements is met:

[0133] Sand is present and has an average particle size of 1 micron to 5 mm;

[0134] Grit is present and has an average particle size of 1 micron to 5 mm;

[0135] The presence of charcoal has an average particle size of 1 micron to 5 mm;

[0136] Polymer particles are present and have an average particle size of 1 micron to 5 mm;

[0137] Ceramic particles are present and have an average particle size of 1 micron to 5 mm.

[0138] Aspect 30: The filter medium of any of Aspects 22-29 or any other aspect herein,

[0139] Wherein, polymer particles are present and include: polyolefin, polyacrylate, polystyrene, polyethylene terephthalate, cellulose acetate, or any combination thereof.

[0140] Aspect 31: The filter medium of any of Aspects 22-30 or any other aspect herein,

[0141] Wherein, ceramic particles are present and include: alumina, zirconia, cerium-stabilized zirconia, silica microspheres, or any combination thereof.

[0142] Aspect 32: A filter comprising the filter media of any of Aspects 22-31 or any other aspect herein.

[0143] Aspect 33: The filter of Aspect 32 or any other aspect herein, comprising a filter body, an inlet, an outlet, and a filter media disposed in the filter body between the inlet and the outlet.

[0144] Aspect 34: A method of making the filter of Aspect 32 or Aspect 33 or any other aspect herein, comprising inserting a filter media into a filter body.

[0145] Aspect 35: A method of making the filter media of any of Aspects 22-34 or any other aspect herein, comprising combining the bioactive glass with at least one of: sand, gravel, charcoal, polymer particles, and ceramic particles.

[0146] Aspect 36: A combination of any two or more of the preceding aspects or any portion(s) thereof.

[0147] Example

[0148] The following examples illustrate non-limiting aspects of the disclosure and are not intended to limit the scope of the disclosure or the claims.

[0149] This example demonstrates that by immersing - Fluorspar is formed on bioactive glass in aqueous fluids.

[0150] Glass compositions having the compositions and densities shown in Table 1 were prepared by melting at temperatures below 1400° C. (e.g., below 1200° C.) Such low melting temperatures allow melting in smaller commercial glass jars if desired.

[0151] Table 1

[0152] (weight%) *45S5 1 2 3 4 5 6 7 8 9 <![CDATA[SiO2]]> 45.0 29.5 53.6 47.6 33.45 33.3 31.4 33.4 30.4 31.4 CaO 24.5 42.5 33.1 31.8 42.5 42.5 42.5 42.5 42.5 42.5 <![CDATA[P2O5]]> 6.0 19.5 5.8 5.6 15.5 15.5 17.5 15.5 18.5 17.5 <![CDATA[ZrO2]]> 0.0 4.0 0.0 7.7 4 4 4 4 4 4 <![CDATA[Na2O]]> 24.5 0.0 1.6 1.6 0 0 0 0 0 0 MgO 0.0 4.5 1.8 1.7 4.5 4.5 4.5 4.5 4.5 4.5 <![CDATA[K2O]]> 0.0 0.0 4.0 3.9 0 0 0 0 0 0 <![CDATA[F - ]]> 0 0 0 0 0.05 0.2 0.1 0.1 0.1 0.1 **density 2.71 2.99 2.75 2.87 -- -- -- -- -- --

[0153] *45S5 Haleon is a company with the characteristics of Technical Brand sales.

[0154] **g / cm 3

[0155] Table 1 (continued)

[0156] (weight%) 10 11 12 13 14 15 <![CDATA[SiO2]]> 33.4 35.4 42 41 40 38 CaO 42.5 42.5 42.5 42.5 42.5 42.5 <![CDATA[P2O5]]> 15.5 13.5 6 6 8 10 <![CDATA[ZrO2]]> 4 4 4 4 4 4 <![CDATA[Na2O]]> 0 0 0 0 0 0 MgO 4.5 4.5 4.5 4.5 4.5 4.5 <![CDATA[K2O]]> 0 0 0 0 0 0 <![CDATA[F - ]]> 0.1 0.1 1 2 1 1 **density -- -- -- -- -- --

[0157] **g / cm 3

[0158] 45S5 and compositions #1 to #3 shown in Table 1 were immersed in a solution containing about 9000 ppm of fluoride ions (presented as dissolved sodium fluoride in 0.05 mol / L tris(hydroxy)aminomethane buffer solution) and adjusted to a pH of 7.9 with hydrochloric acid. RTThe solutions contained 2.02 wt% NaF, 0.61 wt% tris(hydroxy)aminomethane, and 0.18 wt% HCl in water. For each experiment, 2.0 g of bioactive glass was immersed in these solutions at 37°C for up to 7 days. Prior to immersion, each glass was ground to a particle size of <10 microns. The results are shown in Table 1. Figure 1-4 shown.

[0159] Figure 1-2 XRD spectra of 45S5 and Example compositions #1 to #3 are shown after immersion in fluoride ion solution for up to 7 days. Fluorite ( Figure 1 ). Figure 2 Composition #3 is shown soaked for 1, 4, and 7 days, with the highlighted sample bioactive glass exposed to F - Fluorspar was quickly formed (within 1 day) from the aqueous fluid.

[0160] Figure 3-4 SEM image showing particles of glass composition #3 after immersion in fluoride ion solution for 7 days, 10k magnification ( Figure 3 ) and 25k magnification ( Figure 4 ). The images show the formation of nano-sized fluorite precipitates or crystallites on the surface of the glass particles, identified by XRD.

[0161] It will be understood that the various aspects or embodiments disclosed may relate to specific features, elements or steps described in conjunction with a particular aspect or embodiment. It will also be understood that although specific features, elements or steps are described in conjunction with a particular aspect or embodiment, different aspects or embodiments may be interchanged or combined with each other in various combinations or permutations not shown.

[0162] As used herein, the term "and / or" when used to list two or more items means that any one of the listed items can be used alone, or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B, and / or C, the composition can contain only A; only B; only C; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B, and C.

[0163] Although the transitional term "comprising" may be used to disclose various features, elements, or steps of a particular aspect or embodiment, it is to be understood that this implies including alternative aspects or embodiments that may be described using the transitional terms "consisting of," "consisting essentially of." Thus, for example, implicit alternative aspects or embodiments for an apparatus comprising A+B+C include aspects or embodiments of the apparatus consisting of A+B+C and aspects or embodiments of the apparatus consisting essentially of A+B+C.

[0164] The positions of elements referred to herein (e.g., "top," "bottom," "above," "below," "first," "second," etc.) are merely used to describe the orientation of the various elements in the drawings. It should be noted that the orientation of the various elements may be different according to other exemplary embodiments, and such variations are intended to be included in the present disclosure. Furthermore, these relational terms are merely used to distinguish one entity or behavior from another, without necessarily requiring or implying any actual such relationship or order between such entities or behaviors.

[0165] As used herein, the terms "approximately," "about," "substantially," and similar terms are intended to have the broad meanings generally agreed upon and accepted by those skilled in the art for use with the subject matter to which the present disclosure pertains. Those skilled in the art who read the present disclosure should understand that these terms are intended to describe certain features described and claimed without limiting these features to the precise numerical ranges provided. Therefore, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or variations of the subject matter described and claimed are considered to be within the scope of the present invention as described in the appended claims.

[0166] As used herein, "optional" or "optionally" etc. are intended to indicate that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not occur. Unless otherwise stated, the indefinite article "a" or "an" and the corresponding definite article "the" used herein mean "at least one" or "one or more". It is also to be understood that the various features disclosed in the specification and drawings can be used in any and all combinations.

[0167] For substantially any plural and / or singular terms used herein, those skilled in the art may appropriately convert from the plural to the singular and / or from the singular to the plural as appropriate as applicable to the context and / or application. For clarity, various singular / plural arrangements may be explicitly described herein.

[0168] Unless otherwise stated, all compositions are expressed as weight percentages (wt%) of the batch. It will be appreciated by those skilled in the art that various melt components (e.g., silicon, alkaline or alkaline-based materials, boron, etc.) may undergo different volatilization levels (e.g., as a function of vapor pressure, melting time and / or melting temperature) during the melting of the components. Therefore, the values ​​of the weight percentages of the batches for such components are intended to include ±0.5 wt % of the values ​​of these components in the final melted product. In view of the above, substantial compositional equivalence between the final product and the batch composition is expected.

[0169] It is obvious to those skilled in the art that various modifications and changes can be made to the present disclosure without departing from the scope and spirit of the present disclosure. Because those skilled in the art can think of various improved combinations, sub-item combinations and changes of the described embodiments that incorporate the spirit and essence of the present disclosure, it should be considered that this document includes all the contents within the scope of the attached claims and their equivalents.

Claims

1. A kind of - A method for forming fluorspar from an aqueous fluid, the method comprising: Bioactive glass containing calcium and F - Aqueous fluid contact; as well as Forming fluorite.

2. The method of claim 1, wherein: Contains F - Fluid contains F - The amount is at least 1 ppm, by mass, based on the F-containing - The total mass of the fluid.

3. The method of claim 1, wherein: Contains F - Fluid contains F - The amount is at least 500 ppm, by mass, based on the F-containing - The total mass of the fluid.

4. The method of claim 1, wherein: This method will contain F - F in aqueous fluids - Concentrations are reduced to 1 ppm or less, by mass, based on F-containing materials in contact with bioactive glass. - The total mass of the fluid.

5. The method of claim 1, wherein: Contains F - The fluid is substantially free of at least one of: a buffer, saliva, and a simulated body fluid.

6. The method of claim 1, wherein: The method is carried out at a water treatment plant or in a residential home.

7. The method of claim 1, wherein: The fluorite formed is a kind of - A precipitate or crystalline phase in a fluid, as a precipitate or crystalline phase located on an outer surface of a bioactive glass, or any combination thereof.

8. The method of claim 1, wherein: At least a portion of the bioactive glass dissolves during the process thereby releasing calcium ions into the F-containing - In fluid.

9. The method of claim 1, wherein: Fluorspar was formed within 1 day of contact, as determined by XRD analysis.

10. The method according to any one of claims 1 to 9, wherein: Within 7 days of contact, no other crystalline phases than fluorspar were detected by XRD analysis.

11. The method according to any one of claims 1 to 9, wherein: Contact includes making F - The fluid flows through or in one or more containers comprising the bioactive glass.

12. The method according to any one of claims 1 to 9, wherein: Contact includes making F - The fluid flows through the filter media containing the bioactive glass.

13. The method according to any one of claims 1 to 9, wherein: The method is substantially free of CaCO3, Ca(OH)2, non-glass CaO, or any combination thereof.

14. The method according to any one of claims 1 to 9, wherein: Bioactive glass contains: SiO2; CaO; and P2O5.

15. The method according to any one of claims 1 to 9, wherein: Bioactive glass contains: 25-55 wt% SiO2; 20-55 wt% CaO; and 5-20 wt% P2O5.

16. The method of claim 15, wherein: The bioactive glass comprises at least one of the following: 0-10 wt% ZrO2; 0-25 wt% Na2O; 0-10 wt% MgO; 0-5 wt% K2O; 0-5 wt% F - ;or Any combination thereof.

17. The method of claim 15, wherein: Bioactive glass contains almost no F - .

18. The method according to any one of claims 1 to 9, wherein: The bioactive glass has an average particle size of 1 micron to 5 mm.

19. The method of any one of claims 1 to 9, further comprising collecting fluorspar and refining to provide pure fluorspar having a purity of at least 90% by weight, based on the total weight of the pure fluorspar.

20. The method of any one of claims 1 to 9, wherein: The contacting includes a filter media comprising bioactive glass, wherein the filter media comprises at least one of the following: sand, gravel, charcoal, polymer particles, and ceramic particles.

21. A bioactive glass formed by the method of any one of claims 1 to 9, wherein: The bioactive glass includes a fluorite crystalline phase located on an outer surface of the bioactive glass.

22. A kind of - Aqueous fluid forming fluorite filter medium, the filter medium comprising: Bioactive glass comprising calcium; and At least one of the following: sand, gravel, charcoal, polymer particles, and ceramic particles.

23. The filter medium of claim 22, wherein: Bioactive glass contains: SiO2; CaO; and P2O5.

24. The filter medium of claim 22, wherein: Bioactive glass contains: 25-55 wt% SiO2; 20-45 wt% CaO; and 5-20 wt% P2O5.

25. The filter medium of any one of claims 22-24, wherein: Bioactive glass contains: 0-10 wt% ZrO2; 0-25 wt% Na2O; 0-5 wt% MgO; 0-5 wt% K2O; 0-5 wt% F - ;or Any combination thereof.

26. The filter medium of any one of claims 22-24, comprising a fluorite crystalline phase positioned on an outer surface of the bioactive glass.

27. The filter medium of any one of claims 22-24, wherein: Bioactive glass contains almost no F - .

28. The filter medium of any one of claims 22-24, wherein: Bioactive glass has a particle size ranging from 1 micron to 5 mm.

29. The filter medium of any one of claims 22-24, wherein: Meet at least one of the following requirements: Sand is present and has an average particle size of 1 micron to 5 mm; Grit is present and has an average particle size of 1 micron to 5 mm; The presence of charcoal has an average particle size of 1 micron to 5 mm; Polymer particles are present and have an average particle size of 1 micron to 5 mm; Ceramic particles are present and have an average particle size of 1 micron to 5 mm.

30. The filter medium of any one of claims 22-24, in, Polymeric particles are present and include polyolefins, polyacrylates, polystyrene, polyethylene terephthalate, cellulose acetate, or any combination thereof.

31. The filter medium of any one of claims 22-24, in, Ceramic particles are present and include: alumina, zirconia, ceria-stabilized zirconia, silica microspheres, or any combination thereof.

32. A filter comprising the filter medium of any one of claims 22-24.

33. The filter of claim 32, comprising: A filter body, an inlet, an outlet, and a filter medium disposed in the filter body between the inlet and the outlet.

34. A method of making the filter of claim 32 comprising inserting filter media into a filter body.

35. A method of making the filter media of any one of claims 22-24, comprising combining the bioactive glass with at least one of the following: sand, gravel, charcoal, polymer particles, and ceramic particles.

Images