JP6326904B2 - Phosphate fertilizer raw material and method for producing the same - Google Patents
Phosphate fertilizer raw material and method for producing the same Download PDFInfo
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本発明は、肥料効果の高いりん酸肥料原料とその製造方法に関する。 The present invention relates to a phosphate fertilizer raw material having a high fertilizer effect and a method for producing the same.
我が国は降水量が多いので、土壌は、ミネラル分が流出して、酸性化し易い。そのため、植物を生育する際に使用するりん酸肥料には、土壌中のりん酸濃度だけでなく、同時に、土壌ｐＨも増加させる塩基性りん酸肥料が広く使用されている。 In Japan, there is a lot of precipitation, so the soil tends to acidify due to the outflow of minerals. Therefore, basic phosphate fertilizers that increase not only the phosphate concentration in soil but also the soil pH are widely used as phosphate fertilizers used when growing plants.
現在、塩基性りん酸肥料としては、アルカリ分を多く含む溶成りん酸肥料（りん酸濃度は２０％前後で、りん含有鉱物相は、ガラス相。燐鉱石と酸化マグネシウムを融解及び混合して、ジェット水流で急冷して製造。）が、肥料効果が高いので、最も多く利用されている。 At present, the basic phosphate fertilizer is a soluble acid fertilizer containing a large amount of alkali (phosphoric acid concentration is around 20%, the phosphorus-containing mineral phase is a glass phase. Melting and mixing phosphate ore and magnesium oxide. , Manufactured by quenching with a jet water stream)), but it is most often used because of its high fertilizer effect.
しかし、溶成りん酸肥料を製鋼スラグから製造すると、結晶化を促進するＦｅＯが製鋼スラグから不可避的に混入するので、肥料効果が低下する。 However, when a soluble acid fertilizer is produced from steelmaking slag, FeO that promotes crystallization is inevitably mixed from the steelmaking slag, so the fertilizer effect is reduced.
過去には、非特許文献１に示すように、トーマス製鋼法の副産物であるトーマスりん肥が、塩基性りん酸肥料（りん酸濃度は２０％前後）として利用されてきた。 In the past, as shown in Non-Patent Document 1, Thomas phosphorus fertilizer, a byproduct of the Thomas steelmaking method, has been used as a basic phosphate fertilizer (phosphoric acid concentration is around 20%).
トーマスりん肥は、りん濃度が１．７〜２．１％程度の溶銑に石灰を添加し、空気を吹き込んで脱りんを行った際に生成するスラグを原料とする肥料で、りん含有鉱物相は、Ｃａ3（ＰＯ4）2−Ｃａ2ＳｉＯ4固溶体相、５ＣａＯ・ＳｉＯ2・Ｐ2Ｏ5相、又は、７ＣａＯ・２ＳｉＯ2・Ｐ2Ｏ5相（以下総称して「固溶体」という。）であり、肥料効果は優れている。 Thomas Phosphorus Fertilizer is a fertilizer made from slag produced when dephosphorization is performed by adding lime to hot metal with a phosphorus concentration of about 1.7-2.1%. Is a Ca 3 (PO 4 ) 2 —Ca 2 SiO 4 solid solution phase, 5CaO · SiO 2 · P 2 O 5 phase, or 7CaO · 2SiO 2 · P 2 O 5 phase (hereinafter collectively referred to as “solid solution”). The fertilizer effect is excellent.
しかし、トーマス製鋼法は衰退し、現在、製鋼法として使われていないため、トーマスりん肥は製造されていない。 However, the Thomas steelmaking method has declined and is not currently used as a steelmaking method.
高炉から出銑された溶銑には、不純物として、約０．１％のりんが含まれているが、りんは、製鋼工程で、フラックス添加と酸素吹込みで酸化されて、製鋼スラグとして排出される。 The hot metal discharged from the blast furnace contains about 0.1% phosphorus as an impurity. Phosphorus is oxidized by flux addition and oxygen blowing in the steelmaking process and discharged as steelmaking slag. The
特許文献１に示すように、製鋼スラグのりん酸濃度は１〜４質量％程度であり、りん酸肥料として十分な濃度ではないが、製鋼スラグは、フラックス由来のＣａＯや、溶銑から酸化除去されたＳｉＯ2を多量に含んでいるので、石灰原やケイ酸肥料として利用されている。 As shown in Patent Document 1, the phosphoric acid concentration of steelmaking slag is about 1 to 4% by mass, which is not a sufficient concentration as a phosphate fertilizer, but steelmaking slag is oxidized and removed from flux-derived CaO and hot metal. Since it contains a large amount of SiO 2 , it is used as lime raw material or silicic acid fertilizer.
現在でも、りん酸肥料の原料のりん鉱石の全量を輸入に依存している我が国では、所要量のりん酸を含む製鋼スラグは、有用なりん酸肥料資源である。 Even today, steelmaking slag containing the required amount of phosphoric acid is a useful phosphate fertilizer resource in Japan, which relies on imports for the entire amount of phosphate ore, the raw material for phosphate fertilizer.
そして、特許文献２〜４に示すように、製鋼スラグ中のりん酸を濃縮して高りん酸スラグを製造し、製鋼スラグをりん酸肥料化する取組みが、これまで幾つかなされている。 And as shown to patent documents 2-4, the approach which concentrates the phosphoric acid in steelmaking slag, manufactures high phosphoric acid slag, and makes steelmaking slag into phosphoric acid fertilizer has been made until now.
例えば、特許文献４には、燐含有の製鋼スラグを還元処理し、燐を０．５質量％以上含む高燐高マンガン銑鉄を製造し、順次、マンガン処理、脱燐処理を行って、燐濃度が０．１０質量％以下の溶銑を製造するとともに、脱燐処理で生成したスラグを燐酸肥料原料として使用することが開示されている。
For example, in
上記燐酸肥料原料は、塩基度０．５〜２．０、Ｐ2Ｏ5１５％以上、ＭｎＯ８％以下で、りん含有鉱物相はＣａ3（ＰＯ4）2相と想定しているが、その肥料効果は不明である。 The phosphate fertilizer raw material has a basicity of 0.5 to 2.0, P 2 O 5 of 15% or more and MnO of 8% or less, and the phosphorus-containing mineral phase is assumed to be a Ca 3 (PO 4 ) 2 phase. The fertilizer effect is unknown.
りん酸肥料の原料のりん鉱石を海外から輸入している我が国では、溶銑中のりんはりん酸肥料資源として有用であるが、製鋼スラグを原料としてりん酸肥料を製造する際、結晶化を促進する酸化鉄がりん酸肥料へ混入するのは不可避である。そのため、製鋼スラグを原料とするりん酸肥料の肥料効果は安定しない。 In Japan, where phosphate ore, the raw material for phosphate fertilizer, is imported from overseas, phosphorus in hot metal is useful as a phosphate fertilizer resource, but it promotes crystallization when producing phosphate fertilizer from steelmaking slag. It is inevitable that iron oxide to be mixed into phosphate fertilizer. Therefore, the fertilizer effect of the phosphate fertilizer made from steelmaking slag is not stable.
また、製鋼スラグから高りん酸肥料を製造する場合、固溶体相が析出するりん酸濃度には上限があり、それ以上のりん酸濃度では肥料効果が下がるという問題が有った。 Moreover, when manufacturing a high-phosphate fertilizer from steelmaking slag, there existed a problem that there existed an upper limit in the phosphoric acid density | concentration which a solid solution phase precipitates, and the fertilizer effect fell with the phosphoric acid density | concentration beyond it.
それ故、製鋼スラグを原料とするりん酸濃度が高くかつ肥料効果の高いりん酸肥料原料や、その製造方法は、現状では確立されていない。酸化鉄を含むけれど、りん酸濃度が高く、肥料効果が高いりん酸肥料とその製造方法の開発が望まれている。 Therefore, a phosphoric acid fertilizer raw material having a high phosphoric acid concentration and a high fertilizer effect using steelmaking slag as a raw material and a manufacturing method thereof have not been established at present. Development of a phosphoric acid fertilizer that contains iron oxide but has a high phosphoric acid concentration and a high fertilizer effect and its manufacturing method is desired.
そこで、本発明は、上記現状を踏まえ、製鋼スラグを原料とするりん酸肥料原料の肥料効果を高めることを課題とし、該課題を解決する、酸化鉄を含むが、りん酸濃度が高く、肥料効果が高いりん酸肥料原料と、その製造方法を提供することを目的とする。 In view of the above, the present invention has an object to improve the fertilizer effect of a phosphate fertilizer raw material using steelmaking slag as a raw material, and solves the problem. It aims at providing the phosphate fertilizer raw material with a high effect, and its manufacturing method.
一般に、りん酸肥料原料中にＣａ3（ＰＯ4）2相（以下「Ｃ3Ｐ相」ということがある。）が存在すると、肥料効果は向上せず、Ｃ3Ｐ相とＣａ2ＳｉＯ4相の固溶体が存在すると、肥料効果は向上する。そこで、本発明者らは、Ｃ3Ｐ相と、Ｃａ2ＳｉＯ4相中のＳｉに着目し、上記課題を解決する手法について鋭意検討した。 Generally, if a Ca 3 (PO 4 ) 2 phase (hereinafter sometimes referred to as “C 3 P phase”) is present in a phosphate fertilizer raw material, the fertilizer effect is not improved, and the C 3 P phase and Ca 2 SiO 4 are not improved. The fertilizer effect is improved when a solid solution of the phase is present. Therefore, the present inventors paid attention to the C 3 P phase and the Si in the Ca 2 SiO 4 phase, and intensively studied a method for solving the above problem.
その結果、りん酸肥料原料に、Ｓｉを所要量固溶したＣ3Ｐ相が所要量含まれていると、肥料効果の指標である可溶性りん酸率が著しく高まることを見いだした。 As a result, it has been found that when a required amount of C 3 P phase in which a required amount of Si is dissolved in the phosphate fertilizer raw material is contained, the soluble phosphate ratio, which is an index of fertilizer effect, is remarkably increased.
また、製鋼スラグからりん酸肥料原料を製造する際、りん酸肥料原料の組成及び冷却速度を制御することにより、可溶性りん酸率が著しく高いりん酸肥料原料を製造できることを見いだした。 Moreover, when manufacturing the phosphate fertilizer raw material from steelmaking slag, it discovered that the phosphate fertilizer raw material with a remarkably high soluble phosphate rate could be manufactured by controlling the composition and cooling rate of a phosphate fertilizer raw material.
本発明は、上記知見に基づいてなされたもので、その要旨は以下のとおりである。 This invention was made | formed based on the said knowledge, and the summary is as follows.
（１）ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５質量％以上、及び、Ｓｉが１〜５質量％固溶するＣａ3（ＰＯ4）2相を１０〜４３．８質量％含有する
ことを特徴とするりん酸肥料原料。
(1) A Ca 3 (PO 4 ) 2 phase in which CaO, SiO 2 , P 2 O 5 , and iron oxide (in terms of Fe) total 55 mass% or more and Si is dissolved in 1 to 5 mass%. 10 to 43.8 wt% phosphate fertilizer raw material and having free.
（２）ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５質量％以上、及び、Ｓｉが１〜５質量％固溶するＣａ3（ＰＯ4）2相を１０〜４３．８質量％含有し、塩基度α（＝ＣａＯ／ＳｉＯ2）が０．８〜２．０で、かつ、りん酸濃度が（−６α2＋２７α−６）（α：塩基度）質量％超、４０質量％以下である
ことを特徴とするりん酸肥料原料。
(2) Ca 3 (PO 4 ) 2 phase in which CaO, SiO 2 , P 2 O 5 and iron oxide (in terms of Fe) total 55 mass% or more and Si is dissolved in 1 to 5 mass%. 10 to 43.8 wt% have containing, in basicity α (= CaO / SiO 2) is 0.8 to 2.0, and phosphoric acid concentration (-6α 2 + 27α-6) (α: basicity ) A phosphate fertilizer raw material characterized by being more than 40% by weight and 40% by weight or less.
（３）前記（１）又は（２）に記載のりん酸肥料原料を製造する製造方法において、
ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５％質量以上含有し、塩基度α（＝ＣａＯ／ＳｉＯ2）が０．８〜２．０で、かつ、りん酸濃度が（−６α2＋２７α−６）（α：塩基度）％超、４０質量％以下の製鋼スラグであって、転炉脱りんスラグを溶融し、還元剤及び改質剤として、微粉炭、Ａｌ 2 Ｏ 3 源、ＳｉＯ 2 源を添加して製造した高りん溶銑に、フラックスを添加し酸素を吹き込んで、脱りん処理を施して製造したりん酸含有スラグを、１０００℃以上１７００℃以下に加熱して溶融し、次いで、冷却速度１５℃／分以上で冷却する
ことを特徴とするりん酸肥料原料の製造方法。
(3) In the manufacturing method for manufacturing the phosphate fertilizer raw material according to (1) or (2),
CaO, SiO 2 , P 2 O 5 , and iron oxide (Fe conversion) are contained in a total of 55% by mass or more, the basicity α (= CaO / SiO 2 ) is 0.8 to 2.0, and Steelmaking slag having a phosphoric acid concentration of more than (−6α 2 + 27α-6) (α: basicity)% and 40% by mass or less, melting converter dephosphorization slag, and using fine powder as a reducing agent and modifier Phosphoric acid-containing slag produced by adding a flux and blowing oxygen into a high phosphorus hot metal produced by adding charcoal, an Al 2 O 3 source, and an SiO 2 source to a phosphoric acid-containing slag produced at 1000 ° C. or higher and 1700 ° C. A method for producing a phosphate fertilizer raw material, which is heated and melted below, and then cooled at a cooling rate of 15 ° C./min or more.
本発明によれば、酸化鉄を含むが、りん酸濃度が高く、肥料効果が高いりん酸肥料原料とその製造方法を提供することができる。 According to the present invention, it is possible to provide a phosphate fertilizer raw material containing iron oxide but having a high phosphate concentration and a high fertilizer effect, and a method for producing the same.
以下、本発明について説明する。 The present invention will be described below.
本発明のりん酸肥料原料（以下「本発明肥料原料」ということがある。）は、
ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５質量％以上、及び、Ｓｉが１〜５質量％固溶するＣａ3（ＰＯ4）2相を１０〜４３．８質量％含有する
ことを特徴とする。
The phosphate fertilizer raw material of the present invention (hereinafter sometimes referred to as “the present fertilizer raw material”)
The total amount of CaO, SiO 2 , P 2 O 5 , and iron oxide (in terms of Fe) is 55 mass% or more, and the Ca 3 (PO 4 ) 2 phase in which Si is 1 to 5 mass% is dissolved in 10 to 43 and having .8 weight% free.
また、本発明肥料原料は、
ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５質量％以上、及び、Ｓｉが１〜５質量％固溶するＣａ3（ＰＯ4）2相を１０〜４３．８質量％含有し、塩基度α（＝ＣａＯ／ＳｉＯ2）が０．８〜２．０で、かつ、りん酸濃度が（−６α2＋２７α−６）（α：塩基度）質量％超、４０質量％以下である
ことを特徴とする。
The fertilizer raw material of the present invention is
The total amount of CaO, SiO 2 , P 2 O 5 , and iron oxide (in terms of Fe) is 55 mass% or more, and the Ca 3 (PO 4 ) 2 phase in which Si is 1 to 5 mass% is dissolved in 10 to 43 a .8% by weight containing, in basicity α (= CaO / SiO 2) is 0.8 to 2.0, and phosphoric acid concentration (-6α 2 + 27α-6) (α: basicity) weight% It is more than 40 mass%, It is characterized by the above-mentioned.
本発明のりん酸肥料原料の製造方法（以下「本発明製造方法」ということがある。）は、本発明肥料原料の製造方法において、
ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５％質量以上含有し、塩基度α（＝ＣａＯ／ＳｉＯ2）が０．８〜２．０で、かつ、りん酸濃度が（−６α2＋２７α−６）（α：塩基度）％超、４０質量％以下の製鋼スラグであって、転炉脱りんスラグを溶融し、還元剤及び改質剤として、微粉炭、Ａｌ 2 Ｏ 3 源、ＳｉＯ 2 源を添加して製造した高りん溶銑に、フラックスを添加し酸素を吹き込んで、脱りん処理を施して製造したりん酸含有スラグを、１０００℃以上１７００℃以下に加熱して溶融し、次いで、冷却速度１５℃／分以上で冷却する
ことを特徴とする。
The method for producing a phosphate fertilizer raw material of the present invention (hereinafter sometimes referred to as “the present invention production method”) is a method for producing a fertilizer raw material of the present invention.
CaO, SiO 2 , P 2 O 5 , and iron oxide (Fe conversion) are contained in a total of 55% by mass or more, the basicity α (= CaO / SiO 2 ) is 0.8 to 2.0, and Steelmaking slag having a phosphoric acid concentration of more than (−6α 2 + 27α-6) (α: basicity)% and 40% by mass or less, melting converter dephosphorization slag, and using fine powder as a reducing agent and modifier Phosphoric acid-containing slag produced by adding a flux and blowing oxygen into a high phosphorus hot metal produced by adding charcoal, an Al 2 O 3 source, and an SiO 2 source to a phosphoric acid-containing slag produced at 1000 ° C. or higher and 1700 ° C. It is characterized by being heated and melted below, and then cooled at a cooling rate of 15 ° C./min or more.
まず、植物育成用のりん酸肥料の原料（りん酸肥料原料）として使用可能なりん酸含有スラグの製造について説明する。図１に、製鋼工程において、りん酸含有スラグを製造する工程の一例を示す。 First, production of phosphoric acid-containing slag that can be used as a raw material for phosphoric acid fertilizer for plant growth (phosphoric acid fertilizer raw material) will be described. FIG. 1 shows an example of a process for producing phosphoric acid-containing slag in the steelmaking process.
図１に示すように、製鋼工程においては、高炉で製造した溶銑を転炉に移送し、溶銑の上にスラグを形成し、酸素源を吹き込んで、溶銑とスラグの反応で、溶銑の脱りん処理S01を行う。 As shown in FIG. 1, in the steelmaking process, the hot metal produced in a blast furnace is transferred to a converter, slag is formed on the hot metal, an oxygen source is blown, and the hot metal and slag are reacted to remove phosphorus from the hot metal. Process S01 is performed.
脱りん処理S01によって生成した転炉脱りんスラグ４１を転炉から排出し、その後、転炉内の溶銑の上に、再度、スラグを形成し、酸素源を吹き込んで、脱炭処理S02を行う。脱炭処理S02で得られた溶鋼に2次製錬S03を施した後、連続鋳造S04で鋼片を製造する。
The
脱りん処理S01後、転炉から排出された転炉脱りんスラグ４１は、溶銑中のりんが酸化したりん酸ととともに、多量の鉄分を含んでいる。そこで、転炉脱りんスラグ４１から鉄やりん等の有価元素を回収するために、転炉脱りんスラグ４１に還元・改質処理S11を施す。
After the dephosphorization treatment S01, the
還元・改質処理S11においては、転炉脱りんスラグ４１を溶融し、還元剤及び改質剤として、微粉炭、Ａｌ2Ｏ3源、ＳｉＯ2源を添加して、りんを多く含有する高りん溶銑４２を製造する。
In the reduction / reformation treatment S11, the
高りん溶銑４２のＣｒ含有量が多い場合には、高りん溶銑４２に脱Ｃｒ処理S12を施す。次に、高りん溶銑４２に、生石灰やＳｉＯ2などを原料とするフラックスを添加し酸素を吹き込んで、脱りん処理S13を施して、植物育成用のりん酸肥料の原料（りん酸肥料原料）として使用可能なりん酸含有スラグ５０を製造する。
When the Cr content of the high phosphorus
なお、脱りん処理S13によって脱りんされた溶銑５１は、高炉で製造した溶銑とともに転炉へ供給される。
The
りん酸肥料原料は、ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄と、Ｃａ3（ＰＯ4）2相を含むものであるが、本発明肥料原料は、ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５質量％以上、及び、Ｓｉが１〜５質量％固溶するＣａ3（ＰＯ4）2相（Ｃａ3Ｐ相）を１０〜４３．８質量％含むことを特徴とする。
The phosphate fertilizer raw material includes CaO, SiO 2 , P 2 O 5 , iron oxide, and Ca 3 (PO 4 ) 2 phase. The fertilizer raw material of the present invention includes CaO, SiO 2 , P 2 O 5. In addition, the total amount of iron oxide (in terms of Fe) is 55% by mass or more, and the Ca 3 (PO 4 ) 2 phase (Ca 3 P phase) in which 1 to 5% by mass of Si is dissolved is 10 to 43.8%. and wherein the% including Mukoto.
本発明肥料原料中の主成分の“ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）”は合計で５５質量％以上とする。５５質量％未満であると、上記以外の成分とりん酸が化合物を形成し、りん酸含有鉱物相の生成を制御することができなくなる。好ましくは６５質量％以上である。 “CaO, SiO 2 , P 2 O 5 , and iron oxide (Fe conversion)” as the main components in the fertilizer raw material of the present invention is 55% by mass or more in total. If it is less than 55% by mass, components other than the above and phosphoric acid form a compound, and the production of the phosphoric acid-containing mineral phase cannot be controlled. Preferably it is 65 mass% or more.
製鋼スラグから製造したりん酸肥料原料は、本来的にＣ3Ｐ相を含んでいるが、本発明肥料原料においては、Ｓｉが１〜５質量％固溶するＣ3Ｐ相を１０〜４３．８質量％存在させる。Ｓｉが１〜５質量％固溶するＣ3Ｐ相が１０〜４３．８質量％存在すると、肥料効果が顕著に向上する。この点が、本発明者らが見いだし、本発明肥料原料の基礎とする知見である。
The phosphate fertilizer raw material manufactured from steelmaking slag inherently contains a C 3 P phase. However, in the fertilizer raw material of the present invention, a C 3 P phase in which 1 to 5 mass% of Si is dissolved is 10 to 43. 8 to Zaisa wt% exist. When Si is C 3 P phase solid solution 1-5% by weight is 10 to 43.8 wt% exists, the fertilizer effect is remarkably improved. This is the finding that the present inventors have found and the basis of the fertilizer raw material of the present invention.
ここで、Ｓｉが１〜５％固溶するＣ3Ｐ相と肥料効果の相関について説明する。 Here, the correlation between the C 3 P phase in which Si is dissolved in 1 to 5% and the fertilizer effect will be described.
本発明者らは、Ｃａ3（ＰＯ4）2とＣａ2ＳｉＯ4を所定量秤量し、湿式で混合した後、混合粉の圧粉体を製造した。圧粉体を、１２００〜１６００℃で２時間焼成し、その後、冷却速度１５℃／分で冷却して、実験的に、りん酸肥料原料を製造し、Ｘ線構造解析（ＸＲＤ）で、生成した鉱物相を評価した。結果を表１に示す。 The present inventors weighed a predetermined amount of Ca 3 (PO 4 ) 2 and Ca 2 SiO 4 and mixed them in a wet manner, and then manufactured a green compact of the mixed powder. The green compact is fired at 1200-1600 ° C. for 2 hours and then cooled at a cooling rate of 15 ° C./min to experimentally produce a phosphate fertilizer raw material, which is generated by X-ray structural analysis (XRD). The mineral phase was evaluated. The results are shown in Table 1.
表１に示すように、Ｃ3Ｐ相のＳｉ濃度が５質量％以下であると、Ｃ3Ｐ相の単相での生成が確認され、Ｃ3Ｐ相のＳｉ濃度が５質量％を超えると、Ｃ3Ｐ相の他、固溶体相（Ｃａ5ＳｉＰ2Ｏ12）の生成が確認された。この結果から、Ｃ3Ｐ相のＳｉ濃度は５質量％までしか高めることができないことが解る。 As shown in Table 1, when the Si concentration of the C 3 P phase is 5% by mass or less, formation of the C 3 P phase in a single phase is confirmed, and the Si concentration of the C 3 P phase exceeds 5% by mass. In addition to the C 3 P phase, formation of a solid solution phase (Ca 5 SiP 2 O 12 ) was confirmed. From this result, it can be seen that the Si concentration of the C 3 P phase can only be increased to 5% by mass.
次に、肥料効果を、可溶性りん酸率（＝可溶性りん酸濃度／全りん酸濃度に対する割合）で、Ｃ3Ｐ相のＳｉ濃度との相関で評価した。結果を表１と図２に示す。 Next, the fertilizer effect was evaluated based on the correlation with the Si concentration of the C 3 P phase at the soluble phosphoric acid ratio (= ratio of soluble phosphoric acid concentration / total phosphoric acid concentration). The results are shown in Table 1 and FIG.
表１及び図２から、Ｃ3Ｐ相のＳｉ濃度が１％未満であると、可溶性りん酸率が小さく、肥料効果が低いことが解る。即ち、Ｃ3Ｐ相中にＳｉを１質量％以上固溶させることにより、Ｃ3Ｐ相の可溶性りん酸濃度が著しく高めることができることが解る。 From Table 1 and FIG. 2, it can be seen that when the Si concentration of the C 3 P phase is less than 1%, the soluble phosphoric acid ratio is small and the fertilizer effect is low. That, C 3 by solid solution Si 1 mass% or more P phase, the soluble phosphate concentration of C 3 P phase it can be seen that it is possible to increase significantly.
一方、Ｃ3Ｐ相のＳｉ濃度が５％を超えると、Ｃ3Ｐ相がＣ3Ｐ相として存在できなくなる（固溶体が生成する）。それ故、Ｃ3Ｐ相のＳｉ濃度は１〜５質量％とする。 On the other hand, when the Si concentration of C 3 P phase exceeds 5%, C 3 P phase is (solid solution is produced) can not exist as a C 3 P phase. Therefore, the Si concentration of the C 3 P phase is 1 to 5% by mass.
次に、本発明肥料原料において、Ｓｉが１〜５質量％固溶するＣａ3（ＰＯ4）2相を１０〜４３．８質量％と規定する理由について説明する。
Next, the reason why the Ca 3 (PO 4 ) 2 phase in which 1 to 5 mass% of Si is dissolved in the fertilizer raw material of the present invention is defined as 10 to 43.8 mass % will be described.
Ｃ3Ｐ相の濃度（りん酸濃度）が１０質量％未満であると肥料効果が低下するわけではない。肥料として使用するときは、単位面積あたりに撒くりん酸量を一定にする必要があるので、施肥量はりん酸濃度に反比例する。それ故、Ｃ3Ｐ相の濃度（りん酸濃度）は高い方が好ましいが、Ｃ3Ｐ相の濃度（りん酸濃度）が低くても、所要の肥料効果は確保できる。 If the concentration of C 3 P phase (phosphoric acid concentration) is less than 10% by mass, the fertilizer effect does not decrease. When used as a fertilizer, it is necessary to make the amount of phosphoric acid per unit area constant, so the amount of fertilizer applied is inversely proportional to the phosphoric acid concentration. Therefore, although it is preferable that the concentration of C 3 P phase (phosphoric acid concentration) is high, the required fertilizer effect can be ensured even if the concentration of C 3 P phase (phosphoric acid concentration) is low.
ただし、りん酸肥料原料として販売するためには、りん酸濃度を５％以上（ク溶性りん酸濃度で３％以上）確保する必要があり、そのため、Ｃ3Ｐ相が１０質量以上ないと、りん酸肥料として登録できない。それ故、Ｃ3Ｐ相は１０質量％以上とする。Ｃａ 3 Ｐ相の上限は、実施例の表４の「Ｃａ 3 Ｐ相の存在比（質量％）」における最大値「４３．８」（発明例８）に基づいて４３．８質量％とする。
However, in order to be sold as phosphate fertilizers, it is necessary to secure phosphoric acid concentration of 5% or more (more than 3% by click-soluble phosphate concentration), therefore, the C 3 P phase is not more than 10 mass, Cannot be registered as phosphate fertilizer. Therefore, the C 3 P phase is 10% by mass or more. The upper limit of the Ca 3 P phase, and 43.8 wt% based on the maximum value "43.8" (Inventive Example 8) in the "abundance of Ca 3 P-phase (mass%)" in Table 4 of Example .
塩基度αとりん酸濃度（質量％）は、Ｃ3Ｐ相の析出に影響するので、本発明者らは、Ｃ3Ｐ相の析出と、塩基度α及びりん酸濃度（質量％）の関係を調査した。 Since the basicity α and the phosphoric acid concentration (mass%) affect the precipitation of the C 3 P phase, the present inventors have determined the precipitation of the C 3 P phase and the basicity α and the phosphoric acid concentration (mass%). The relationship was investigated.
Ｆｅ（酸化物のＦｅ換算）：１０質量％、ＭｎＯ：５質量％、ＭｇＯ：５質量％、Ａｌ2Ｏ3：３質量％で、塩基度αを変えた製鋼スラグ試料を、１６００℃から１５℃／分で冷却して、析出相とりん酸濃度（質量％）を調査した。結果を図３に示す。 A steelmaking slag sample in which the basicity α was changed from 1600 ° C. to 15% with Fe (as oxide Fe equivalent): 10% by mass, MnO: 5% by mass, MgO: 5% by mass, Al 2 O 3 : 3% by mass. After cooling at ° C./min, the precipitated phase and phosphoric acid concentration (mass%) were investigated. The results are shown in FIG.
図３において、○は、Ｓｉが１〜５質量％固溶したＣ3Ｐ相（Ｓｉ固溶Ｃ3Ｐ相）が析出した場合を示し、■は、固溶体操が析出した場合を示し、×は、Ｃ3Ｐ相（単相）が析出した場合を示す。塩基度（＝ＣａＯ／ＳｉＯ2）が０．８〜２．０であると、Ｓｉ固溶Ｃ3Ｐ相が析出し、肥料効果が向上する。 In FIG. 3, ◯ indicates a case where a C 3 P phase (Si solid solution C 3 P phase) in which 1 to 5% by mass of Si is dissolved is precipitated, ■ indicates a case where a solid solution operation is precipitated, and × Indicates a case where a C 3 P phase (single phase) is precipitated. When the basicity (= CaO / SiO 2 ) is 0.8 to 2.0, the Si solid solution C 3 P phase is precipitated, and the fertilizer effect is improved.
塩基度αが、０．８未満又は２．０超であるとＳｉが固溶していないＣ3Ｐ相（単相）が析出し、肥料効果が低下する。それ故、本発明肥料原料において、塩基度α（＝ＣａＯ／ＳｉＯ2）は０．８〜２．０が好ましい。なお、塩基度αの調整は、脱りん処理時、生石灰やＳｉＯ2の添加量を調整して行う。 If the basicity α is less than 0.8 or more than 2.0, a C 3 P phase (single phase) in which Si is not dissolved is precipitated, and the fertilizer effect is reduced. Therefore, in the fertilizer raw material of the present invention, the basicity α (= CaO / SiO 2 ) is preferably 0.8 to 2.0. The basicity α is adjusted by adjusting the amount of quicklime and SiO 2 added during the dephosphorization process.
さらに、本発明者らは、図３において、Ｓｉ固溶Ｃ3Ｐ相が析出する臨界線を求めた。その結果、図３の点線で示す通り、Ｓｉ固溶Ｃ3Ｐ相は、りん酸濃度が（−６α2＋２７α−６）質量％を超えると存在できることが解った。それ故、本発明肥料原料において、りん酸濃度は（−６α2＋２７α−６）（α：塩基度）％超が好ましい。 Furthermore, the present inventors determined the critical line in which the Si solid solution C 3 P phase precipitates in FIG. As a result, as indicated by the dotted line in FIG. 3, it was found that the Si solid solution C 3 P phase can exist when the phosphoric acid concentration exceeds (−6α 2 + 27α-6) mass%. Therefore, in the fertilizer raw material of the present invention, the phosphoric acid concentration is preferably more than (−6α 2 + 27α-6) (α: basicity)%.
りん酸濃度が（−６α2＋２７α−６）質量％未満であると、固溶体相が生成し、Ｓｉが固溶したＣ3Ｐ相が生成し難くなる。一方、りん酸濃度が４０質量％を超えると、Ｃａ3Ｍｇ3Ｐ4Ｏ16相が析出し肥料効果が低下する。それ故、本願発明肥料原料のりん酸濃度は（−６α2＋２７α−６）質量％超、４０質量％以下が好ましい。より好ましくは（−６α2＋２７α−６）質量％超、３５質量％以下である。 When the phosphoric acid concentration is less than (−6α 2 + 27α-6) mass%, a solid solution phase is generated, and a C 3 P phase in which Si is dissolved is difficult to generate. On the other hand, when the phosphoric acid concentration exceeds 40% by mass, the Ca 3 Mg 3 P 4 O 16 phase is precipitated and the fertilizer effect is lowered. Therefore, the phosphoric acid concentration of the fertilizer raw material of the present invention is preferably more than (−6α 2 + 27α-6) mass% and 40 mass% or less. More preferably, it is more than (−6α 2 + 27α-6) mass% and not more than 35 mass%.
次に、本発明製造方法について説明する。 Next, the manufacturing method of the present invention will be described.
まず、ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５％質量以上含有する製鋼スラグであって、転炉脱りんスラグを溶融し、還元剤及び改質剤として、微粉炭、Ａｌ 2 Ｏ 3 源、ＳｉＯ 2 源を添加して製造した高りん溶銑に、フラックスを添加し酸素を吹き込んで、脱りん処理を施して製造したりん酸含有スラグを、１０００℃以上１７００℃以下に加熱して溶融する。
First, a steelmaking slag containing 55% by mass or more of CaO, SiO 2 , P 2 O 5 and iron oxide (Fe conversion) in total, melting the converter dephosphorization slag, reducing agent and modifier As a high-phosphorus molten iron produced by adding pulverized coal, Al 2 O 3 source and SiO 2 source, flux is added and oxygen is blown, and phosphoric acid-containing slag produced by dephosphorization treatment is added at 1000 ° C. it melted by heating below 1700 ° C. or higher.
加熱温度が１０００℃未満であると、製鋼スラグが溶融せずに所望の鉱物相を得られない可能性があるので、１０００℃以上とする。好ましくは１１００℃以上である。 If the heating temperature is less than 1000 ° C, the steelmaking slag may not melt and a desired mineral phase may not be obtained. Preferably it is 1100 degreeC or more.
加熱温度が１７００℃を超えると、設備上の問題で製造できないので、１７００℃以下とする。好ましくは１６００℃以下である。 If the heating temperature exceeds 1700 ° C., it cannot be produced due to equipment problems. Preferably it is 1600 degrees C or less.
次に、溶融状態の製鋼スラグを、冷却速度１５℃／分以上で冷却する。この冷却で、本発明肥料原料中に、Ｓｉが１〜５質量％固溶したＣ3Ｐ相（Ｓｉ固溶Ｃ3Ｐ相）を生成させることができる。 Next, the molten steelmaking slag is cooled at a cooling rate of 15 ° C./min or more. By this cooling, a C 3 P phase (Si solid solution C 3 P phase) in which 1 to 5% by mass of Si is dissolved in the fertilizer raw material of the present invention can be generated.
表２に、各種成分組成の製鋼スラグ試料を、１５００〜１６００℃に加熱して溶融し、所要の冷却速度で冷却して、生成するりん酸鉱物相と、生成したＣ3Ｐ相のＳｉ濃度（質量％）を調査した結果を示す。なお、表２中、“ｔ．Ｆｅ”は、酸化鉄の組成をＦｅに換算した組成である。 In Table 2, steelmaking slag samples of various composition are heated to 1500-1600 ° C. and melted, cooled at a required cooling rate, and the resulting phosphate mineral phase and the Si concentration of the generated C 3 P phase The result of having investigated (mass%) is shown. In Table 2, “t.Fe” is a composition in which the composition of iron oxide is converted to Fe.
冷却速度が１５℃／分未満であると、試料Ｎｏ．１５及び１６に示すように、Ｃ3Ｐ相が析出しても、Ｃ3Ｐ相のＳｉ濃度は１質量％未満である。 When the cooling rate was less than 15 ° C./minute, the sample No. As shown in 15 and 16, even if the C 3 P phase is precipitated, the Si concentration of the C 3 P phase is less than 1% by mass.
冷却速度が１５℃／分の試料Ｎｏ．１０〜１３においては、Ｓｉが１〜５質量％の範囲で固溶したＣ3Ｐ相が析出している。冷却速度が５０℃／分の試料Ｎｏ．１７においても、Ｓｉが１〜５質量％の範囲で固溶したＣ3Ｐ相が析出している。 Sample No. with a cooling rate of 15 ° C./min. In 10 to 13, Si is C 3 P phase solid solution in the range of 1 to 5 mass% is precipitated. Sample No. with a cooling rate of 50 ° C./min. In C17, a C 3 P phase in which Si is dissolved in the range of 1 to 5% by mass is precipitated.
試料Ｎｏ．７〜９では、冷却速度が１５℃／分でも、Ｓｉが固溶したりん酸鉱物相が析出していないが、これは、りん酸濃度が低いために、図３に示すように、固溶体相が析出する領域であるからである。また、Ｎｏ．１４では、りん濃度が高すぎるために、別の鉱物相であるＣａ3Ｍｇ3Ｐ4Ｏ16が析出している。 Sample No. 7 to 9, even though the cooling rate was 15 ° C./min, the phosphate mineral phase in which Si was dissolved was not precipitated. This is because the phosphate concentration is low, as shown in FIG. It is because it is an area | region which precipitates. No. In No. 14, since the phosphorus concentration is too high, another mineral phase, Ca 3 Mg 3 P 4 O 16, is precipitated.
ここで、図４に、冷却速度（℃／分）とＣ3Ｐ相のＳｉ濃度（質量％）の関係を示す。１０００℃以上１７００℃以下に加熱して溶融状態にある製鋼スラグを、１５℃／分以上の冷却速度で冷却すると、Ｓｉが１〜５質量％の範囲で固溶したＣ3Ｐ相を析出させることができる。 Here, FIG. 4 shows the relationship between the cooling rate (° C./min) and the Si concentration (mass%) of the C 3 P phase. When steelmaking slag in a molten state is heated to 1000 ° C. or higher and 1700 ° C. or lower and cooled at a cooling rate of 15 ° C./min or higher, a C 3 P phase in which Si is dissolved in a range of 1 to 5% by mass is precipitated. be able to.
製鋼スラグの塩基度α（＝ＣａＯ／ＳｉＯ2）は、特に制約されないが、０．８〜２．０であると、Ｓｉが１〜５質量％の範囲で固溶したＣ3Ｐ相が析出し易い。それ故、製鋼スラグの塩基度αは０．８〜２．０が好ましい。 The basicity α (= CaO / SiO 2 ) of the steelmaking slag is not particularly limited, but when it is 0.8 to 2.0, a C 3 P phase in which Si is dissolved in the range of 1 to 5% by mass is precipitated. Easy to do. Therefore, the basicity α of the steelmaking slag is preferably 0.8 to 2.0.
また、製鋼スラグのりん酸濃度は、（−６α2＋２７α−６）質量％超、４０質量％以下が好ましい。 Further, the phosphoric acid concentration of the steelmaking slag is preferably more than (−6α 2 + 27α-6) mass% and 40 mass% or less.
次に、本発明の実施例について説明するが、実施例での条件は、本発明の実施可能性及び効果を確認するために採用した一条件例であり、本発明は、この一条件例に限定されるものではない。本発明は、本発明の要旨を逸脱せず、本発明の目的を達成する限りにおいて、種々の条件を採用し得るものである。 Next, examples of the present invention will be described. The conditions in the examples are one example of conditions used for confirming the feasibility and effects of the present invention, and the present invention is based on this one example of conditions. It is not limited. The present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
（実施例１）
Ｃａ3（ＰＯ4）2とＣａ2ＳｉＯ4を所定量秤量し、湿式で混合した後、混合粉の圧粉体を製造した。圧粉体を、１２００〜１６００℃で２時間焼成し、その後、冷却速度１５℃／分で冷却して、Ｘ線構造解析（ＸＲＤ）で、生成した鉱物相を解析し、また、その後、可溶性りん酸率を評価した。
Example 1
A predetermined amount of Ca 3 (PO 4 ) 2 and Ca 2 SiO 4 was weighed and mixed in a wet manner, and then a green compact of mixed powder was produced. The green compact is fired at 1200 to 1600 ° C. for 2 hours, then cooled at a cooling rate of 15 ° C./min, and the generated mineral phase is analyzed by X-ray structural analysis (XRD). The phosphoric acid rate was evaluated.
可溶性りん酸率が０．５未満の試料は×、０．５以上０．７未満の試料は○、０．７以上は◎として、りん酸肥料としての性能を評価した。結果を表３に示す。 Samples having a soluble phosphoric acid ratio of less than 0.5 were evaluated as “×”, samples of 0.5 or more and less than 0.7 were evaluated as “◯”, and samples of 0.7 or more were evaluated as “◎”. The results are shown in Table 3.
比較例１では、Ｃ3Ｐ相がＳｉを含有しないので、評価は×である。これに対し、発明例１〜３では、Ｓｉ濃度が１〜５質量％のＣ3Ｐ相が確認され、かつ、評価が◎である。なお、参考例２と３では、評価は◎であるものの、固溶体相の析出が確認された。 In Comparative Example 1, since the C 3 P phase does not contain Si, the evaluation is x. On the other hand, in Invention Examples 1 to 3, a C 3 P phase having a Si concentration of 1 to 5% by mass is confirmed, and the evaluation is ◎. In Reference Examples 2 and 3, although the evaluation was ◎, precipitation of a solid solution phase was confirmed.
（実施例２）
表４に示す成分組成の製鋼スラグ試料を、１５００〜１６００℃に加熱して溶融し、次いで、所要の冷却速度で冷却して、りん酸肥料原料を製造した。りん酸肥料原料中に生成したりん酸鉱物相と、生成したＣ3Ｐ相のＳｉ濃度（質量％）と存在比率、可溶性りん酸率を、併せて表４に示す。
(Example 2)
A steelmaking slag sample having the component composition shown in Table 4 was heated to 1500 to 1600 ° C to melt, and then cooled at a required cooling rate to produce a phosphate fertilizer raw material. Table 4 shows the Si concentration (mass%), the abundance ratio, and the soluble phosphoric acid ratio of the phosphate mineral phase generated in the phosphate fertilizer raw material and the generated C 3 P phase.
可溶性りん酸率が０．５未満の試料は×、０．５以上０．７未満の試料は○、０．７以上は◎として、りん酸肥料としての性能を評価した。Ｃ3Ｐ相のＳｉ濃度（質量％）は、Ｘ線による結晶相解析と、ＳＥＭ−ＥＤＳで測定した。なお、表４中、“ｔ．Ｆｅ”は、酸化鉄の組成をＦｅに換算した組成である。発明例４〜７及び８では、評価が◎である。 Samples having a soluble phosphoric acid ratio of less than 0.5 were evaluated as “×”, samples of 0.5 or more and less than 0.7 were evaluated as “◯”, and samples of 0.7 or more were evaluated as “◎”. The Si concentration (% by mass) of the C 3 P phase was measured by X-ray crystal phase analysis and SEM-EDS. In Table 4, “t.Fe” is a composition in which the composition of iron oxide is converted to Fe. In invention examples 4-7 and 8, evaluation is (double-circle).
（実施例３）
Ｃ3Ｐ相のＳｉ濃度の差異による肥料効果の違いを確認するため、ヒロシマ菜を育て、生育が良かったものを◎、全く生育しなかったものを×として評価した。結果を表５に示す。
(Example 3)
In order to confirm the difference in fertilizer effect due to the difference in the Si concentration of the C 3 P phase, Hiroshima vegetables were grown and evaluated as を for those that grew well, and × for those that did not grow at all. The results are shown in Table 5.
本発明肥料原料を用いた発明例８では、評価が◎である。 In Invention Example 8 using the fertilizer raw material of the present invention, the evaluation is ◎.
前述したように、本発明によれば、酸化鉄を含むが、りん酸濃度が高く、肥料効果が高いりん酸肥料原料とその製造方法を提供することができる。よって、本発明は、鉄鋼産業及び植物育成産業において利用可能性が高いものである。 As described above, according to the present invention, it is possible to provide a phosphate fertilizer raw material that contains iron oxide but has a high phosphate concentration and a high fertilizer effect, and a method for producing the same. Therefore, the present invention has high applicability in the steel industry and the plant breeding industry.
S00 高炉
S01 溶銑の脱りん処理
S02 脱炭処理
S03 ２次製錬
S04 連続鋳造
S00 Blast furnace
S01 Dephosphorization of hot metal
S02 Decarburization treatment
S03 Secondary smelting
S04 Continuous casting
S11 還元・改質処理
S12 脱Ｃｒ処理
S13 脱りん処理
４１ 転炉脱りんスラグ
４２ 高りん溶銑
５０ りん酸含有スラグ
５１ 溶銑
S11 Reduction / reformation treatment
S12 Cr removal treatment
Claims (3)
ことを特徴とするりん酸肥料原料。 The total amount of CaO, SiO 2 , P 2 O 5 , and iron oxide (in terms of Fe) is 55 mass% or more, and the Ca 3 (PO 4 ) 2 phase in which Si is 1 to 5 mass% is dissolved in 10 to 43 phosphate fertilizer raw material and having .8 weight% free.
ことを特徴とするりん酸肥料原料。 The total amount of CaO, SiO 2 , P 2 O 5 , and iron oxide (in terms of Fe) is 55 mass% or more, and the Ca 3 (PO 4 ) 2 phase in which Si is 1 to 5 mass% is dissolved in 10 to 43 a .8% by weight containing, in basicity α (= CaO / SiO 2) is 0.8 to 2.0, and phosphoric acid concentration (-6α 2 + 27α-6) (α: basicity) weight% Phosphoric fertilizer raw material characterized by being over 40% by mass.
ＣａＯ、ＳｉＯ2、Ｐ2Ｏ5、及び、酸化鉄（Ｆｅ換算）を合計で５５％質量以上含有し、塩基度α（＝ＣａＯ／ＳｉＯ2）が０．８〜２．０で、かつ、りん酸濃度が（−６α2＋２７α−６）（α：塩基度）％超、４０質量％以下の製鋼スラグであって、転炉脱りんスラグを溶融し、還元剤及び改質剤として、微粉炭、Ａｌ2Ｏ3源、ＳｉＯ2源を添加して製造した高りん溶銑に、フラックスを添加し酸素を吹き込んで、脱りん処理を施して製造したりん酸含有スラグを、１０００℃以上１７００℃以下に加熱して溶融し、次いで、冷却速度１５℃／分以上で冷却する
ことを特徴とするりん酸肥料原料の製造方法。 In the manufacturing method which manufactures the phosphate fertilizer raw material of Claim 1 or 2,
CaO, SiO 2 , P 2 O 5 , and iron oxide (Fe conversion) are contained in a total of 55% by mass or more, the basicity α (= CaO / SiO 2 ) is 0.8 to 2.0, and Steelmaking slag having a phosphoric acid concentration of more than (−6α 2 + 27α-6) (α: basicity)% and 40% by mass or less, melting converter dephosphorization slag, and using fine powder as a reducing agent and modifier Phosphoric acid-containing slag produced by adding a flux and blowing oxygen into a high phosphorus hot metal produced by adding charcoal, an Al 2 O 3 source, and an SiO 2 source to a phosphoric acid-containing slag produced at 1000 ° C. or higher and 1700 ° C. A method for producing a phosphate fertilizer raw material, which is heated and melted below, and then cooled at a cooling rate of 15 ° C./min or more.
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