WO2025013527A1 - リン酸塩の製造方法 - Google Patents

リン酸塩の製造方法 Download PDF

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Publication number
WO2025013527A1
WO2025013527A1 PCT/JP2024/021853 JP2024021853W WO2025013527A1 WO 2025013527 A1 WO2025013527 A1 WO 2025013527A1 JP 2024021853 W JP2024021853 W JP 2024021853W WO 2025013527 A1 WO2025013527 A1 WO 2025013527A1
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WO
WIPO (PCT)
Prior art keywords
phosphorus
phosphate
containing liquid
acid
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/021853
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English (en)
French (fr)
Japanese (ja)
Inventor
泰武 矢埜
久宏 松永
克則 ▲高▼橋
茂 杉山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
University of Tokushima NUC
Original Assignee
JFE Steel Corp
University of Tokushima NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JFE Steel Corp, University of Tokushima NUC filed Critical JFE Steel Corp
Priority to KR1020257041286A priority Critical patent/KR20260008133A/ko
Priority to EP24839423.1A priority patent/EP4711331A1/en
Priority to JP2024562271A priority patent/JPWO2025013527A1/ja
Publication of WO2025013527A1 publication Critical patent/WO2025013527A1/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
    • C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/36—Aluminium phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for producing phosphates.
  • phosphorus While phosphorus is used in a wide range of fields, including agriculture, food, medicine, and industry, it is a resource that is unevenly distributed around the world, and is only produced in a limited number of countries, including China, the United States, and Morocco.
  • the phosphorus resources circulating in Japan are phosphorus products such as yellow phosphorus and crude phosphoric acid, and the raw material for these, phosphate rock, and the entire supply is imported.
  • the phosphorus concentration of molten iron tapped from a blast furnace is about 0.1% by mass, and the phosphorus concentration in steelmaking slag produced by subjecting this molten iron to conventional general treatments (dephosphorization treatment, decarburization refining) is as low as about 5% by mass at most, calculated as P2O5 .
  • dephosphorization treatment, decarburization refining is as low as about 5% by mass at most, calculated as P2O5 .
  • Patent Document 1 discloses a method for recovering phosphorus in the form of phosphates (i.e., producing phosphates) from dephosphorization slag, a type of steelmaking slag.
  • Patent Document 1 The method described in Patent Document 1 is a very complicated method consisting of many steps, and it may take a long time to obtain the desired phosphate. Furthermore, Patent Document 1 essentially describes only a method for producing calcium phosphate.
  • the present invention has been made in consideration of the above points, and aims to provide a method for producing phosphate that can easily produce the desired phosphate.
  • 1 is a flowchart showing the flow of a method for producing a phosphate according to the present embodiment.
  • 1 is a graph showing the relationship between the pH of a phosphorus-containing liquid and the amount of iron phosphate produced for each temperature of the phosphorus-containing liquid.
  • 1 is a graph showing the relationship between the pH of a phosphorus-containing liquid and the amount of aluminum phosphate produced for each temperature of the phosphorus-containing liquid.
  • 1 is an XRD pattern of the precipitate of Example 1.
  • FIG. 1 is a flow chart showing the flow of the method for producing a phosphate according to the present embodiment.
  • the method for producing a phosphate according to the present embodiment is a method for recovering phosphorus from a starting material in the form of a target phosphate (e.g., at least one selected from the group consisting of iron phosphate and aluminum phosphate), and includes an acid leaching step (S1) and a precipitation step (S2) in this order.
  • a target phosphate e.g., at least one selected from the group consisting of iron phosphate and aluminum phosphate
  • S1 acid leaching step
  • S2 precipitation step
  • ⁇ Acid leaching step (S1)> components contained in the starting material are leached with acid to obtain a phosphorus-containing liquid. Specifically, for example, acid is added to the starting material, the mixture is stirred, and then filtered. As a result, a residue (I) and a leachate (A) are obtained. The leachate (A) is the phosphorus-containing liquid.
  • the acid used in the acid leaching step (S1) may be at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and organic acids (e.g., citric acid), with nitric acid or hydrochloric acid being preferred, and nitric acid being more preferred.
  • the concentration of the acid is not particularly limited, but is preferably 0.1 to 1.5M, and more preferably 0.3 to 0.8M.
  • pH is measured in accordance with JIS Z8802:2011 "pH measurement method" (hereinafter the same).
  • the temperature when measuring pH is 25°C unless otherwise specified.
  • the leaching time is preferably 0.4 to 0.5 h because the contents of P, Fe, and Al in the obtained phosphorus-containing liquid are high to a certain extent and the contents of other elements (such as Mg) are not too high. This tendency remains the same even when scaled up.
  • ⁇ Precipitation Step (S2)> an alkali is added to the phosphorus-containing liquid obtained in the acid leaching step (S1) to obtain a precipitate containing phosphate. Specifically, for example, an alkali is added to the phosphorus-containing liquid, and then the liquid is filtered. This results in a precipitate (II) and a filtrate (B). The precipitate (II) is the precipitate.
  • Examples of the alkali used in the precipitation step (S2) include sodium hydroxide, potassium hydroxide, calcium hydroxide, and aqueous ammonia (NH 4 OH). Among these, ammonia water is preferred because it does not contain unnecessary cations.
  • the concentration of the aqueous ammonia is not particularly limited, but is preferably from 20 to 40% by mass, and more preferably from 25 to 35% by mass.
  • the inventors adjusted the pH of the phosphorus-containing liquid by adding ammonia water (concentration: 28% by mass) as an alkali to the phosphorus-containing liquid at a temperature of 25°C or 50°C, and confirmed the amount of precipitate that formed (amount of precipitate produced). Specifically, they confirmed the amount of iron phosphate and aluminum phosphate produced in the precipitate. The results are shown in Figures 2 and 3.
  • Fig. 2 is a graph showing the relationship between the pH of the phosphorus-containing liquid and the amount of iron phosphate produced for each temperature of the phosphorus-containing liquid.
  • Fig. 3 is a graph showing the relationship between the pH of the phosphorus-containing liquid and the amount of aluminum phosphate produced for each temperature of the phosphorus-containing liquid. The findings obtained from FIG. 2 and FIG. 3 will be described.
  • the amount of iron phosphate (FePO4.2H2O ) produced is large, but as the pH increases, the amount of iron phosphate produced decreases and instead the amount of iron hydroxide produced (not shown in FIG. 2) increases.
  • the amount of aluminum phosphate ( AlPO4.2H2O ) produced gradually increases as the pH increases, reaching a maximum at a pH of 4 to 5. However, at a pH above 5, the amount of aluminum phosphate produced decreases, and instead, the amount of aluminum hydroxide produced (not shown in Figure 3) increases.
  • the temperature of the phosphorus-containing liquid is raised to 50°C, and then an alkali is added to adjust the pH to 4.
  • an alkali is added to adjust the pH to 4.
  • iron phosphate being obtained as the phosphate (however, the precipitate that is produced contains compounds other than phosphate, such as aluminum hydroxide).
  • an additional raw material may be added to the phosphorus-containing liquid as necessary.
  • the additional raw material is preferably selected according to the target phosphate and the content of each element (the element constituting the target phosphate) in the phosphorus-containing liquid.
  • iron phosphate FePO4
  • a phosphoric acid liquid whose concentration has been adjusted is added as an additional raw material so that the molar ratio of Fe to P in the phosphorus-containing liquid is 1:1. This allows Fe and P to react with each other without any excess, and the purity of the iron phosphate contained in the precipitate can be increased.
  • Example 1 First, in the acid leaching step (S1), steelmaking slag having a particle size of 355 ⁇ m or less was added to nitric acid (concentration: 0.5 M) and then stirred for 0.4 h to obtain a phosphorus-containing liquid. Next, in the precipitation step (S2), ammonia water (concentration: 28% by mass) was added to the phosphorus-containing liquid kept at 25° C. while stirring at 200 rpm to adjust the pH to 4, and a precipitate was generated. More specifically, the pH of the phosphorus-containing liquid was increased by adding ammonia water, and the solution was stirred for 0.5 h from the point when the pH became constant, and then allowed to stand for 0.5 h.
  • S1 steelmaking slag having a particle size of 355 ⁇ m or less was added to nitric acid (concentration: 0.5 M) and then stirred for 0.4 h to obtain a phosphorus-containing liquid.
  • S2 ammonia water (concentration: 28%
  • Fig. 4 is an XRD pattern of the precipitate of Example 1. From the XRD pattern shown in Fig. 4, it was found that aluminum phosphate (AlPO 4 ) was obtained as the phosphate contained in the precipitate.
  • Example 2 In the precipitation step (S2), the pH of the phosphorus-containing liquid at a temperature of 25° C. was adjusted to 3. Except for this, the same procedure as in Example 1 was followed to generate a precipitate. As a result, it was found that iron phosphate (FePO 4 ) was obtained as the phosphate contained in the precipitate.
  • FePO 4 iron phosphate
  • Example 3 In the precipitation step (S2), the pH of the phosphorus-containing liquid at a temperature of 50° C. was adjusted to 3. Except for this, the same procedure as in Example 1 was followed to generate a precipitate. As a result, it was found that the precipitate contained iron phosphate (FePO 4 ). The precipitate also contained iron hydroxide and aluminum hydroxide.
  • Example 4 In the precipitation step (S2), the pH of the phosphorus-containing liquid at 25° C. was adjusted to 3.5. Except for this, the precipitation was carried out in the same manner as in Example 1. As a result, it was found that the phosphates contained in the precipitate were aluminum phosphate (AlPO 4 ) and iron phosphate (FePO 4 ) in a molar ratio of 3:1.
  • Example 5 In the precipitation step (S2), the pH of the phosphorus-containing liquid at 25° C. was adjusted to 3, but before that, a phosphoric acid solution with an adjusted concentration was added as an additional raw material so that the molar ratio of Fe to P contained in the phosphorus-containing liquid was 1:1. Otherwise, a precipitate was generated in the same manner as in Example 1. As a result, it was found that iron phosphate (FePO 4 ) was obtained as the phosphate contained in the precipitate. Furthermore, analysis of the filtrate revealed that the content of Fe and P was zero. In other words, the purity of the iron phosphate contained in the precipitate could be increased.
  • FePO 4 iron phosphate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
PCT/JP2024/021853 2023-07-12 2024-06-17 リン酸塩の製造方法 Pending WO2025013527A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020257041286A KR20260008133A (ko) 2023-07-12 2024-06-17 인산염의 제조 방법
EP24839423.1A EP4711331A1 (en) 2023-07-12 2024-06-17 Method for producing phosphate
JP2024562271A JPWO2025013527A1 (https=) 2023-07-12 2024-06-17

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JP2023-114247 2023-07-12
JP2023114247 2023-07-12

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001130903A (ja) * 1999-08-23 2001-05-15 Nkk Plant Engineering Corp リン酸塩回収方法
JP2011020892A (ja) * 2009-07-15 2011-02-03 Ryoko Lime Industry Co Ltd ろ過・沈降性に優れたアモルファスリン酸アルミニウムの製造方法
JP2016172654A (ja) * 2015-03-16 2016-09-29 地方独立行政法人 岩手県工業技術センター リン酸鉄の回収方法
WO2016199896A1 (ja) * 2015-06-11 2016-12-15 久夫 大竹 被処理水中のリンの回収システム、被処理水中のリンの回収方法、肥料及び肥料原料並びに黄リン原料
JP2020018951A (ja) * 2018-07-30 2020-02-06 日本製鉄株式会社 鉄鋼スラグからリン酸塩を回収する方法
JP2022150640A (ja) 2021-03-26 2022-10-07 株式会社北匠 リン化合物の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001130903A (ja) * 1999-08-23 2001-05-15 Nkk Plant Engineering Corp リン酸塩回収方法
JP2011020892A (ja) * 2009-07-15 2011-02-03 Ryoko Lime Industry Co Ltd ろ過・沈降性に優れたアモルファスリン酸アルミニウムの製造方法
JP2016172654A (ja) * 2015-03-16 2016-09-29 地方独立行政法人 岩手県工業技術センター リン酸鉄の回収方法
WO2016199896A1 (ja) * 2015-06-11 2016-12-15 久夫 大竹 被処理水中のリンの回収システム、被処理水中のリンの回収方法、肥料及び肥料原料並びに黄リン原料
JP2020018951A (ja) * 2018-07-30 2020-02-06 日本製鉄株式会社 鉄鋼スラグからリン酸塩を回収する方法
JP2022150640A (ja) 2021-03-26 2022-10-07 株式会社北匠 リン化合物の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUGIYAMA SHIGERU, HSIAO LI-HAO, TOKUNAGA TAIZO, HASHIMOTO TAKUMI, HABARA MASAKI, SHIMODA NAOHIRO, LIU JHY-CHERN, ABE SEIICHI, YAMA: "PHOSPHORUS RECOVERY FROM SEWAGE-SLUDGE MOLTEN SLAG USING A COMBINATION OF ACID-DISSOLUTION, ALKALI-PRECIPITATION, AND ION-EXCHANGE", PHOSPHORUS RESEARCH BULLETIN, TOKYO, JP, vol. 38, no. 0, 1 January 2022 (2022-01-01), JP , pages 60 - 66, XP093261036, ISSN: 0918-4783, DOI: 10.3363/prb.38.60 *

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KR20260008133A (ko) 2026-01-15
TW202517577A (zh) 2025-05-01
JPWO2025013527A1 (https=) 2025-01-16
EP4711331A1 (en) 2026-03-18

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