Fluorinated compound removing agent

Abstract

The present invention provides a fluorinated compound removal agent that removes a fluorinated compound, particularly phosphorus trifluoride (PF3), from exhaust gas. The above object is achieved by a fluorinated compound removal agent comprising 20 to 80% by weight of calcium (Ca) calculated as CaO, and 10 to 55% by weight of iron (Fe) calculated as Fe2O3 or 30 to 80% by weight of manganese (Mn) calculated as MnO, wherein the % by weight is based on the weight of the fluorinated compound removal agent.

Description

Technical Field

[0001] This invention relates to fluoride compound removers and their manufacturing methods. Background Technology

[0002] Fluorinated compounds used in semiconductor manufacturing processes, etc., need to be removed before being released into the atmosphere.

[0003] Patent document 1 discloses a fluorine-containing gas removal agent comprising alumina and alkaline earth metal compounds.

[0004] Patent document 2 discloses a halide gas treatment agent containing a compound selected from at least one of alkali metal chlorides, alkaline earth metal chlorides and alkali metal fluorides, which is composed of calcium oxide or magnesium oxide prepared by firing under a nitrogen atmosphere.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: WO2018-230121

[0008] Patent Document 2: JPH09-267027 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The object of the present invention is to provide a fluorinated compound remover that can effectively remove fluorinated compounds.

[0011] Methods for solving problems

[0012] One embodiment is a fluoride removal agent comprising 20-80% by weight of calcium (Ca) calculated as CaO and 10-55% by weight of iron (Fe) calculated as Fe2O3 or 30-80% by weight of manganese (Mn) calculated as MnO, wherein the weight percentage is based on the weight of the fluoride removal agent.

[0013] Another embodiment is a method for manufacturing the above-mentioned fluoride compound remover, which includes: a step of mixing a calcium compound and an iron compound or a manganese compound; and a step of drying the mixture.

[0014] Another embodiment is a method for removing fluorinated compounds, which includes: a step of placing the fluorinated compound remover in a container; and a step of introducing a gas containing fluorinated compounds into the container.

[0015] The fluoride removal agent according to the present invention can effectively remove fluoride compounds.

[0016] It should be noted that in this specification, the fluoride compound remover is also referred to simply as the "remover". Detailed Implementation

[0017] Fluoride removal agents contain Ca and either Fe or Mn. Based on the weight of the fluoride removal agent, Ca is calculated as CaO, which is 20–80% by weight; Fe is calculated as Fe₂O₃, which is 10–55% by weight; and Mn is calculated as MnO, which is 30–80% by weight.

[0018] Regarding Ca, based on the weight of the fluoride removal agent, calculated as CaO, in one embodiment it is 22-80% by weight, in another embodiment it is 25-80% by weight, in another embodiment it is 26-80% by weight, in another embodiment it is 27-80% by weight, in another embodiment it is 28-80% by weight, in another embodiment it is 29-80% by weight, in another embodiment it is 30-80% by weight, in another embodiment it is 36-80% by weight, in another embodiment it is 38-80% by weight, in another embodiment it is 40-80% by weight, in another embodiment it is 42-80% by weight, in another embodiment it is 22-75% by weight, in another embodiment it is 25-75% by weight, in another embodiment it is 25-73% by weight, in another embodiment it is... In one embodiment, the weight percentage is 25–70% by weight; in another embodiment, it is 30–70% by weight; in another embodiment, it is 25–68% by weight; in another embodiment, it is 25–64% by weight; in another embodiment, it is 25–60% by weight; in another embodiment, it is 25–58% by weight; in another embodiment, it is 22–75% by weight; in another embodiment, it is 25–75% by weight; in another embodiment, it is 28–73% by weight; in another embodiment, it is 31–70% by weight; in another embodiment, it is 34–68% by weight; in another embodiment, it is 38–64% by weight; in another embodiment, it is 38–52% by weight; in another embodiment, it is 40–60% by weight; in another embodiment, it is 42–58% by weight; and in another embodiment, it is 45–53% by weight.

[0019] In one embodiment, some or all of the Ca contained in the above-mentioned fluoride compound remover is present as calcium hydroxide. In another embodiment, all of the Ca contained in the above-mentioned fluoride compound remover is present as calcium hydroxide.

[0020] Regarding Fe, based on the weight of the fluoride removal agent, calculated as Fe2O3, it is 11-55% by weight in one embodiment, 13-55% by weight in another embodiment, 14-55% by weight in another embodiment, 15-55% by weight in another embodiment, 17-55% by weight in another embodiment, 19-55% by weight in another embodiment, 20-55% by weight in another embodiment, 21-55% by weight in another embodiment, 12-54% by weight in another embodiment, 25-53% by weight in another embodiment, 25-52% by weight in another embodiment, and 25-55% by weight in another embodiment. 1% by weight, in another embodiment 22-50% by weight, in another embodiment 23-49% by weight, in another embodiment 25-48% by weight, in another embodiment 27-46% by weight, in another embodiment 28-45% by weight, in another embodiment 29-43% by weight, in another embodiment 30-55% by weight, in another embodiment 30-52% by weight, in another embodiment 30-48% by weight, in another embodiment 30-45% by weight, in another embodiment 31-41% by weight, in another embodiment 32-40% by weight, in another embodiment 33-39% by weight.

[0021] In one embodiment, some or all of the Fe contained in the above-mentioned fluoride compound remover exists as ferric hydroxide and / or ferric oxide. In another embodiment, some or all of the Fe contained in the above-mentioned fluoride compound remover exists as ferric hydroxide and ferric oxide. In another embodiment, all of the Fe contained in the above-mentioned fluoride compound remover exists as ferric hydroxide and ferric oxide. In another embodiment, all of the Fe contained in the above-mentioned fluoride compound remover exists as ferric hydroxide or ferric oxide. In one embodiment, the ferric hydroxide is selected from Fe(OH)2, Fe(OH)3, and combinations thereof. In another embodiment, the ferric hydroxide comprises Fe(OH)3. In another embodiment, the ferric hydroxide is Fe(OH)3. In one embodiment, the ferric oxide is selected from FeO, Fe3O4, Fe2O3, and combinations thereof. In another embodiment, the ferric oxide comprises Fe2O3. In another embodiment, the ferric oxide is Fe2O3.

[0022] Regarding Mn, based on the weight of the fluoride removal agent, calculated as MnO, in one embodiment it is 35-79% by weight, in another embodiment it is 36-79% by weight, in another embodiment it is 39-79% by weight, in another embodiment it is 43-79% by weight, in another embodiment it is 45-79% by weight, in another embodiment it is 48-79% by weight, in another embodiment it is 50-79% by weight, in another embodiment it is 38-77% by weight, in another embodiment it is 36-69% by weight, in another embodiment it is 39-69% by weight, in another embodiment it is 43-69% by weight, in another embodiment it is 45-69% by weight, in another embodiment it is 45-64% by weight, in another embodiment it is 48-62% by weight, in another embodiment it is 45-60% by weight, in another embodiment it is 38-75% by weight, in another embodiment In one embodiment, the weight percentage is 38–74% by weight; in another embodiment, it is 38–73% by weight; in another embodiment, it is 41–73% by weight; in another embodiment, it is 43–73% by weight; in another embodiment, it is 45–73% by weight; in another embodiment, it is 48–73% by weight; in another embodiment, it is 50–72% by weight; in another embodiment, it is 50–70% by weight; in another embodiment, it is 50–67% by weight; in another embodiment, it is 50–65% by weight; in another embodiment, it is 50–63% by weight; in another embodiment, it is 50–61% by weight; in another embodiment, it is 50–59% by weight; in another embodiment, it is 50–58% by weight; in another embodiment, it is 50–56% by weight; in another embodiment, it is 50–55% by weight; in another embodiment, it is 50–54% by weight; and in another embodiment, it is 50–53% by weight.

[0023] In one embodiment, some or all of the Mn contained in the above-mentioned fluoride compound remover is present as a manganese oxide. In another embodiment, all of the Mn contained in the above-mentioned fluoride compound remover is present as a manganese oxide. In one embodiment, the manganese oxide is selected from MnO, Mn3O4, Mn2O3, MnO2, MnO3, Mn2O7, and combinations thereof. In another embodiment, the manganese oxide comprises MnO and / or MnO2. In another embodiment, the manganese oxide is MnO2.

[0024] The aforementioned fluoride removal agent contains Ca and Fe or Mn. Those skilled in the art can add other components without substantially altering the desired properties of the fluoride removal agent. In one embodiment, the fluoride removal agent may contain additional components besides Ca and Fe or Mn. In one embodiment, the additional component is sulfur (S), magnesium (Mg), and silicon (Si). Regarding this additional component, based on the weight of the fluoride removal agent and calculated by oxide, it is less than 20% by weight in one embodiment, and less than 19% by weight, less than 18% by weight, less than 17% by weight, less than 16% by weight, less than 15% by weight, and less than 14% by weight in another embodiment.

[0025] In one embodiment, the fluoride removal agent contains water. The water content in the fluoride removal agent is 1–20% by weight, based on the weight of the fluoride removal agent; in another embodiment, it is 5–18% by weight; in yet another embodiment, it is 7–17% by weight; and in still another embodiment, it is 10–16% by weight. It is known that calcium-containing removal agents improve their removal capacity by containing water.

[0026] In one embodiment, the fluoride removal agent is free of alkali metals. In another embodiment, the alkali metal comprises at least lithium (Li), sodium (Na), or potassium (K). It is known that the removal capacity is improved by adding an alkali metal, particularly potassium, to a removal agent containing calcium hydroxide. However, alkali metals react with carbon dioxide in the air to form insoluble carbonates, which can reduce the removal capacity, thus requiring proper storage management from manufacturing to use. Therefore, the absence of alkali metals reduces the burden of storage management and provides a removal agent with stable removal capacity. In another embodiment, the fluoride removal agent is potassium-free.

[0027] The term "free of" means that the fluoride compound remover is substantially free of the component, excluding cases where the fluoride compound remover unintentionally contains substances that will be the target, such as contaminants. In one embodiment, the alkali metal content is 1% by weight or less based on the weight of the fluoride compound remover; in another embodiment, it is 0.5% by weight or less; in another embodiment, it is 0.2% by weight or less; in another embodiment, it is 0.1% by weight or less; in another embodiment, it is 0.05% by weight or less; and in another embodiment, it is 0.01% by weight or less.

[0028] In one embodiment, the fluorinated compound is an organofluorine compound (PFC) and / or an inorganic fluorinated compound. In one embodiment, the organofluorine compound (PFC) comprises a perfluoroalkyl compound and / or a polyfluoroalkyl compound. In another embodiment, the organofluorine compound (PFC) is selected from CHF3, CH2F2, CH3F, CF4, C2F6, C4F8, NF3, SF6, C3HF5, and mixtures thereof. In another embodiment, the fluorinated compound comprises an inorganic fluorinated compound. In one embodiment, the inorganic fluorinated compound is selected from phosphorus trifluoride (PF3), silicon tetrafluoride (SiF4), arsenic trifluoride (AsF3), boron trifluoride (BF3), sulfur hexafluoride (SF6), tungsten hexafluoride (WF6), molybdenum hexafluoride (MOF6), chlorine trifluoride (ClF3), silicon tetrafluoride (SiF4), nitrogen trifluoride (NF3), sulfur hexafluoride (SF6), and combinations thereof. In another embodiment, the inorganic fluorinated compound comprises phosphorus trifluoride (PF3). In another embodiment, the fluorinated compound is phosphorus trifluoride (PF3). In another embodiment, the fluorinated compound remover is a phosphorus trifluoride (PF3) remover.

[0029] The composition of this fluoride removal agent can be determined using methods known to those skilled in the art, such as elemental analysis based on fluorescence X-ray analysis (XRF analysis). For example, it can be determined using a fluorescence X-ray spectrometer (manufactured by Rigaku Corporation, model ZSX Primus II).

[0030] The specific surface area (SA) of the remover is 10 to 500 m² in one embodiment. 2 / g, in another embodiment, is 22–420m 2 / g, in another embodiment, is 37–345m 2 / g, in another embodiment, is 51–280m 2 / g, in another embodiment, is 60–200m 2 / g, in another embodiment, is 70–160m 2 / g, in another embodiment, is 20–85m 2 / g, in another embodiment, is 25–68m 2 / g, in another embodiment, is 30–55m 2 / g. Specific surface area can be determined according to JIS Z8830:2013 using the BET (1 point) method, for example, using a specific surface area measuring device (Macsorb (registered trademark) HMmodel-1201, MOUNTECH Co. Ltd.).

[0031] The remover is porous in one embodiment. In one embodiment, the pore volume (PV) is 0.05–3.0 ml / g, 0.08–2.2 ml / g, 0.11–1.8 ml / g, 0.28–0.8 ml / g, 0.35–0.7 ml / g, and 0.40–0.6 ml / g. The pore volume can be measured, for example, using an automated mercury porosimeter (AutoPore V9620, Micromeritics).

[0032] The bulk density of the remover is 0.1–3.0 g / ml in one embodiment, 0.3–2.7 g / ml in another embodiment, 0.4–1.8 g / ml in another embodiment, 0.5–1.3 g / ml in another embodiment, 0.4–1.2 g / ml in another embodiment, and 0.6–0.95 g / ml in another embodiment.

[0033] There is no limitation on the shape of the fluoride removal agent. The fluoride removal agent can be of any shape as long as it achieves sufficient removal capacity and strength of the fluoride. In one embodiment, the fluoride removal agent may be amorphous, such as fragmented. In another embodiment, the fluoride removal agent is selected from granular, cylindrical, spherical, or amorphous shapes and combinations thereof. In another embodiment, the fluoride removal agent is cylindrical. In one embodiment, the cross-section of the fluoride removal agent is selected from circular, elliptical, polygonal, rectangular, multi-lobed, and combinations thereof.

[0034] There are no particular limitations on the size of the fluoride removal agent. The size of the fluoride removal agent can be any size, as long as it can sufficiently remove the fluoride and achieve sufficient strength. The diameter of the cross-section of the fluoride removal agent is 0.5–10.0 mm in one embodiment, 0.6–8.7 mm in another, 0.7–7.2 mm in another, 0.8–6.5 mm in another, 1.0–5.7 mm in another, 1.0–4.8 mm in another, 1.1–3.2 mm in another, and 1.2–2.5 mm in another. When the cross-section is elliptical or rectangular, the diameter refers to the major axis. When the cross-section is multi-lobed or polygonal, the diameter refers to the diameter of the circumcircle.

[0035] The length of the fluoride removal agent is 1.0–30.0 mm in one embodiment, 2.2–24.0 mm in another embodiment, 2.7–19.0 ​​mm in another embodiment, 3.2–14.0 mm in another embodiment, 3.8–12.0 mm in another embodiment, 4.2–10.0 mm in another embodiment, and 5.0–8.0 mm in another embodiment.

[0036] If the fluoride remover is in an irregular shape, such as a broken piece, a sieve can be used to make its size uniform to some extent. In one embodiment, if it is irregular, a sieve with a mesh size of about 0.8 to 6 mm can be used.

[0037] The method for manufacturing the aforementioned fluoride compound remover includes a step of mixing a calcium compound with an iron compound or a manganese compound, and a step of drying the mixture.

[0038] In one embodiment, the calcium compound is selected from calcium carbonate, calcium oxide, calcium hydroxide, calcium sulfate, calcium phosphate, calcium hydride, and combinations thereof. In another embodiment, the calcium compound is selected from calcium carbonate, calcium oxide, calcium hydroxide, and combinations thereof. In another embodiment, the calcium compound comprises calcium hydroxide. In yet another embodiment, the calcium compound is calcium hydroxide.

[0039] In one embodiment, the iron compound is selected from iron oxide, iron hydroxide, and mixtures thereof. In another embodiment, the iron compound comprises iron oxide or iron hydroxide. In another embodiment, the iron compound comprises iron oxide and iron hydroxide. In another embodiment, the iron compound is iron oxide and iron hydroxide. In yet another embodiment, the iron compound comprises iron oxide.

[0040] The above-mentioned calcium compound and iron or manganese compound are mixed with water to obtain a mixture. The amount of water can be adjusted in a manner suitable for molding or according to the type of raw materials. In one embodiment, the amount of water in the mixture is 2 to 50 parts by weight relative to 100 parts by weight of materials other than water.

[0041] In one embodiment, the manufacturing method described above may include a step of shaping the resulting mixture. In one embodiment, the manufacturing method includes: a step of extruding the mixture using a matrix with orifices of the desired shape prior to a drying step, or a step of pulverizing the dried mixture after the drying step to shape it into an amorphous form. In another embodiment, the manufacturing method includes a step of extruding the mixture using a matrix with orifices of the desired shape prior to a drying step.

[0042] In the process of drying the mixture, the drying temperature is 60–200°C in one embodiment, 70–170°C in another embodiment, and 100–150°C in yet another embodiment. The drying time is 5 minutes to 5 hours in one embodiment, 10 minutes to 2 hours in another embodiment, and 1 to 5 hours in yet another embodiment.

[0043] The above drying process can be performed using a dryer. Dryers such as mesh belt ovens, rotary dryers, infrared heating dryers, and hot air circulating dryers can be used.

[0044] The method for removing fluorinated compounds includes: placing the aforementioned removing agent in a container; and introducing a gas containing fluorinated compounds into the container.

[0045] In one embodiment, the container comprises a fixed bed, a moving bed, a fluidized bed, or a combination thereof of a removal agent. In another embodiment, the container comprises a fixed bed of removal agents. In one embodiment, the removal agent placed within the container can be a fixed bed, a moving bed, a fluidized bed, or a combination thereof. In another embodiment, the removal agent placed within the container is a fixed bed.

[0046] For example, in cases where the remover is dried before use, water can be added to the remover before placing it in a container. In one embodiment, the process of adding water to the remover is included. In one embodiment, the water is added by spraying.

[0047] In one embodiment, the remover placed in the container may be a fixed bed, a moving bed, a fluidized bed, or a combination thereof. In another embodiment, the remover placed in the container is a fixed bed.

[0048] In one embodiment, the container is a reaction vessel. In another embodiment, the container is a SUS-made reaction vessel; in yet another, a cylindrical reaction vessel; and in still another, a cylindrical SUS-made reaction vessel. In one embodiment, the container has an inlet and an outlet for gas introduction. In one embodiment, there may be multiple containers, allowing the outlet of one container to be connected to the inlet of another.

[0049] In one embodiment, the container has an inlet and an outlet for gas. In another embodiment, there may be multiple containers, allowing the outlet of one container to be connected to the inlet of another container.

[0050] The concentration of fluorinated compounds in the gas introduced into the container containing the purging agent is 0.01 to 10% by volume in one embodiment, 0.05 to 8% by volume in another embodiment, 0.1 to 5% by volume in another embodiment, 0.4 to 3% by volume in another embodiment, 0.8 to 2.5% by volume in another embodiment, 0.8 to 1.9% by volume in another embodiment, and 0.8 to 1.5% by volume in yet another embodiment.

[0051] In the process of introducing a gas containing a fluorinated compound into the container, the gas space velocity (GHSV) is 100–1000 h⁻¹ in one embodiment. -1 In another embodiment, it is 110–850h. -1 In another embodiment, it is 120–650 h. -1 In another embodiment, it is 150–550 h. -1 In another embodiment, it is 180–250 h. -1 .

[0052] The temperature at which the gas comes into contact with the removing agent is 10–70°C in one embodiment, 15–55°C in another embodiment, and 20–40°C in yet another embodiment. The temperature inside the container can be adjusted to obtain the desired temperature. In another embodiment, the gas can also be introduced at room temperature without adjusting the temperature inside the container.

[0053] The pressure at which the gas comes into contact with the removing agent is 500–2000 hPa in one embodiment, 600–1600 hPa in another, 700–1400 hPa in yet another, and 900–1300 hPa in still another. The pressure inside the container can be adjusted to obtain the desired pressure. In another embodiment, the gas can also be introduced at atmospheric pressure without adjusting the pressure inside the container.

[0054] In one embodiment, the remover can remove fluoride compounds from the gas without supplying water from outside the reaction system. In one embodiment, the method for removing fluoride compounds from the gas can be applied as a gas purification process, such as treating fluoride-containing gases in semiconductor manufacturing processes or treating exhaust gases in chemical plants.

[0055] Example

[0056] Iron powder and calcium hydroxide powder were measured and mixed using a kneader while water was added to obtain a mixture. The composition of the iron powder was Fe2O3: 64%, SO3: 15%, CaO: 15%, MgO: 4.0%, and MnO: 2%. The mixture was extruded into cylindrical shapes (approximately 1.6 mm in diameter and 6 mm in length). The resulting molded bodies were dried in an electric dryer maintained at 120°C for 2 hours to obtain the removal agent. The composition of each removal agent was analyzed using a fluorescence X-ray spectrometer (XRF, manufactured by Rigaku Corporation, model ZSXPrimus II). The results calculated based on the oxides of each component are shown in Table 1.

[0057] Measurement

[0058] According to JlSZ8830:2013, the specific surface area (SA) of the remover was determined using the BET (1-point) method based on nitrogen adsorption at liquid nitrogen temperature, using a specific surface area measuring device (Macsorb (registered trademark) HMmodel-1201, MOUNTECH CO.Ltd.). The pore volume (PV) of the remover was determined using an automated mercury porosimeter (AutoPore V9620, Micromeritics). The results of the specific surface area (SA) and pore volume (PV) measurements are shown in Table 1.

[0059] The removal rate of PF3 gas by the above-mentioned remover was determined as follows. 20 ml of the remover was packed into a cylindrical SUS reactor (inner diameter 2.1 cm, height 500 mm) with an inlet at the top and an outlet at the bottom, forming a fixed bed (bulk density: 0.75 g / ml). For the remover, water spray was used, and it was left to stand for one day. The moisture content was approximately 14%. Nitrogen gas was introduced from the inlet of the reaction vessel at atmospheric pressure, room temperature (approximately 25°C), and a space velocity (GHSV) of 200 h⁻¹. -1 The nitrogen gas was introduced downwards. After 30 minutes, the nitrogen was switched to feed gas. This feed gas was nitrogen containing 1.0 vol% PF3. The exhaust gas from the reactor outlet was measured using a suction gas detector (CDS-7, Gas Detection Unit PS-7, Shin Cosmos Electric Co., Ltd.) until 1 ppm PF3 was detected, at which point the feed gas was kept flowing continuously. After the feed gas started flowing, the time until PF3 was detected in the exhaust gas from the reactor outlet was measured, which was defined as the PF3 gas treatment time. The PF3 gas treatment time and the PF3 gas removal amount calculated by GHSV are shown in Table 1.

[0060] [Table 1]

[0061] result

[0062] Regarding the amount of PF3 gas removed, compared with the remover that does not contain iron oxide (Comparative Example 1), the remover containing both calcium oxide and iron oxide is improved (Examples 1-3), while the remover containing 14.6% by weight of calcium oxide and 59.1% by weight of iron oxide (Comparative Example 2) is reduced.

[0063] Next, the removal rate of PF3 gas was investigated using a removal agent containing manganese (Mn) instead of iron (Fe). The removal agent was prepared in the same manner as in Example 1, except that the composition is shown in Table 2. Manganese oxide powder (98% purity) with manganese oxide as the main component was used as the manganese raw material. For the obtained removal agent, the composition calculated by oxide, the specific surface area (SA), the pore volume (PV), and the PF3 gas removal rate (L / kg) were determined using the same method as in Example 1. The results are shown in Table 2.

[0064] [Table 2]

[0065] result

[0066] Regarding the removal of PF3 gas, even removal agents containing 51% and 72% MnO by weight increased (Examples 4 and 5).

[0067] Further implementation methods are described below, which can be implemented with any combination of numbers as long as they do not contradict the theory or technology.

[0068] Implementation Method 1. A fluoride removal agent comprising 20-80% by weight of calcium (Ca) calculated as CaO and 10-55% by weight of iron (Fe) calculated as Fe2O3 or 30-80% by weight of manganese (Mn) calculated as MnO, wherein the weight percentage is based on the weight of the fluoride removal agent.

[0069] Implementation Method 2. The fluoride removal agent according to Implementation Method 1, wherein part or all of the calcium (Ca) is present as calcium hydroxide.

[0070] Implementation Method 3. A fluoride removal agent according to Implementation Method 1 or 2, wherein part or all of the iron (Fe) is present as ferric hydroxide and / or ferric oxide, and part or all of the manganese (Mn) is present as manganese oxide.

[0071] Embodiment 4. A fluoride removal agent according to any one of Embodiments 1 to 3, comprising 22 to 80% by weight of calcium (Ca) calculated as CaO.

[0072] Embodiment 5. A fluoride compound remover according to any one of Embodiments 1 to 4, comprising 25 to 80% by weight of calcium (Ca) calculated as CaO.

[0073] Embodiment 6. A fluoride removal agent according to any one of Embodiments 1 to 4, comprising 30 to 80% by weight of calcium (Ca) calculated as CaO.

[0074] Embodiment 7. A fluoride removal agent according to any one of Embodiments 1 to 6, comprising 20 to 55% by weight of iron (Fe) calculated as Fe2O3.

[0075] Embodiment 8. A fluoride removal agent according to any one of Embodiments 1 to 6, comprising 25 to 48% by weight of iron (Fe) calculated as Fe2O3.

[0076] Embodiment 9. A fluoride compound remover according to any one of Embodiments 1 to 8, comprising 35 to 79% by weight of manganese (Mn) calculated as MnO.

[0077] Embodiment 10. A fluoride removal agent according to any one of Embodiments 1 to 8, comprising 45 to 73% by weight of manganese (Mn) calculated as MnO.

[0078] Embodiment 11. The fluoride removal agent according to any one of Embodiments 1 to 10, which is free of potassium (K).

[0079] Embodiment 12. The fluoride removal agent according to any one of Embodiments 1 to 11, which does not contain alkali metals.

[0080] Embodiment 13. The fluoride compound remover according to any one of Embodiments 1 to 12 is a phosphorus trifluoride (PF3) remover.

[0081] Implementation Method 14. A fluoride removal agent comprising 30-70% by weight of calcium (Ca) calculated as CaO and 30-55% by weight of iron (Fe) calculated as Fe2O3 or 48-62% by weight of manganese (Mn) calculated as MnO, wherein the weight percentage is based on the weight of the fluoride removal agent.

[0082] Implementation Method 15. A fluoride removal agent comprising 30-80% by weight of calcium (Ca) calculated as CaO and 20-55% by weight of iron (Fe) calculated as Fe2O3, wherein the weight percentage is based on the weight of the fluoride removal agent.

[0083] Implementation Method 16. A fluoride removal agent comprising 30-70% by weight of calcium (Ca) calculated as CaO and 30-55% by weight of iron (Fe) calculated as Fe2O3, wherein the weight percentage is based on the weight of the fluoride removal agent.

[0084] Implementation Method 17. A fluoride removal agent comprising 38-52% by weight of calcium (Ca) calculated as CaO and 48-62% by weight of manganese (Mn) calculated as MnO, wherein the weight percentage is based on the weight of the fluoride removal agent.

[0085] Embodiment 18. A method for manufacturing the fluoride compound remover according to Embodiment 1, comprising: a step of mixing a calcium compound and an iron compound or a manganese compound, and a step of drying the mixture.

[0086] Embodiment 19. A method for removing fluorinated compounds, comprising: a step of placing a fluorinated compound removing agent according to Embodiment 1 in a container, and a step of introducing a gas containing fluorinated compounds into the container.

[0087] Implementation Method 20. The method according to Implementation Method 19, wherein the fluorinated compound is phosphorus trifluoride (PF3).

[0088] Implementation Method 21. A phosphorus trifluoride (PF3) remover comprising 20-80% by weight of calcium (Ca) calculated as CaO and 10-55% by weight of iron (Fe) calculated as Fe2O3 or 30-80% by weight of manganese (Mn) calculated as MnO, wherein the weight percentage is based on the weight of the phosphorus trifluoride (PF3) remover.

[0089] Embodiment 22. The method for manufacturing the PF3 remover described in Embodiment 21 includes a step of mixing a calcium compound and an iron compound or a manganese compound, and a step of drying the mixture.

[0090] Embodiment 23. A method for removing PF3, comprising: a step of placing the PF3 removing agent according to Embodiment 21 in a container, and a step of introducing a gas containing PF3 into the container.

Claims

1. A fluoride removal agent comprising 20–80% by weight calcium (Ca) calculated as CaO, and 10–55% by weight iron (Fe) calculated as Fe₂O₃ or 30–80% by weight manganese (Mn) calculated as MnO, wherein, This weight percentage is based on the weight of the fluoride removal agent.

2. The fluoride compound remover according to claim 1, wherein, Calcium (Ca) exists in part or all as calcium hydroxide.

3. The fluoride compound remover according to claim 1, wherein, Iron (Fe) exists in part or all as ferric hydroxide and / or ferric oxide, and manganese (Mn) exists in part or all as manganese oxide.

4. The fluoride removal agent according to claim 1, comprising 30 to 80% by weight of calcium (Ca) calculated as CaO.

5. The fluoride removal agent according to claim 1, comprising 20 to 55% by weight of iron (Fe) calculated as Fe2O3.

6. The fluoride removal agent according to claim 1, comprising 35 to 79% by weight of manganese (Mn) calculated as MnO.

7. The fluoride removal agent according to claim 1, wherein it is free of potassium (K).

8. The fluoride compound remover according to claim 1 is a phosphorus trifluoride (PF3) remover.

9. A method for manufacturing the fluoride compound remover according to claim 1, comprising: The process of mixing calcium compounds with iron compounds or manganese compounds, and the process of drying the mixture.

10. A method for removing fluorinated compounds, comprising: The steps of placing the fluorinated compound remover of claim 1 in a container and introducing a gas containing fluorinated compounds into the container.

11. The method according to claim 10, wherein, The fluorinated compound is phosphorus trifluoride (PF3).

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