JP2024030025A - Removal method of gangue and phosphorus in iron ore and manufacturing method of iron - Google Patents
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 95
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 76
- 239000011574 phosphorus Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 48
- 235000011187 glycerol Nutrition 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 31
- 230000009467 reduction Effects 0.000 description 16
- 239000007790 solid phase Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 6
- 229910052598 goethite Inorganic materials 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005456 ore beneficiation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052585 phosphate mineral Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910006540 α-FeOOH Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- -1 gangue Chemical compound 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- 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
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Abstract
Description
本発明は、鉄鉱石中の脈石及びリンの除去方法、及び鉄の製造方法に関する。 The present invention relates to a method for removing gangue and phosphorus from iron ore, and a method for producing iron.
鉄鉱石の品位を高める（脈石を低減する）方法として、選鉱が知られている。選鉱としては、例えば磁力選鉱、浮遊選鉱、及び重力選鉱が知られている。選鉱は山元（資源国）で行われることが多い。 Ore beneficiation is known as a method of increasing the quality of iron ore (reducing gangue). As ore beneficiation, for example, magnetic ore beneficiation, flotation, and gravity beneficiation are known. Ore processing is often carried out in Yamamoto (resource-rich countries).
ところで、近年、脈石のみならず、リンの濃度が高い鉄鉱石が産出されるようになってきており、このような鉄鉱石の脈石及びリン濃度を低減する技術が強く求められてきた。このような課題に対して、比較的低温で反応を進められるアルカリ水熱反応が提案されている（非特許文献１）。アルカリ水熱反応は、概略的には、鉄鉱石にアルカリ水溶液を加え、密閉容器内で加熱するという技術である。 Incidentally, in recent years, not only gangue but also iron ore with a high phosphorus concentration has been produced, and there has been a strong demand for a technology to reduce the gangue and phosphorus concentration of such iron ore. To address these issues, an alkaline hydrothermal reaction that can proceed at a relatively low temperature has been proposed (Non-Patent Document 1). Alkaline hydrothermal reaction is a technique in which an aqueous alkaline solution is added to iron ore and heated in a closed container.
非特許文献１に開示された技術によれば、鉄鉱石中の脈石及びリン濃度を低減することができる。しかし、本発明者らが非特許文献１に開示された技術についてさらに検討を進めたところ、さらなる改善の余地があることが判明した。 According to the technique disclosed in Non-Patent Document 1, gangue and phosphorus concentration in iron ore can be reduced. However, when the present inventors further investigated the technology disclosed in Non-Patent Document 1, it became clear that there was room for further improvement.
本発明は、上記課題を解決するためになされたものであり、その目的とするところは、鉄鉱石の脈石及びリン濃度をさらに低減することが可能な、新規かつ改良された鉄鉱石中の脈石及びリンの除去方法及び鉄の製造方法を提供することにある。 The present invention has been made to solve the above problems, and its purpose is to provide a new and improved iron ore in which the gangue and phosphorus concentration of iron ore can be further reduced. An object of the present invention is to provide a method for removing gangue and phosphorus, and a method for producing iron.
上記課題を解決するために、本発明のある観点によれば、リンを０．１０質量％以上０．２５質量％以下で含有する鉄鉱石に、濃度が３Ｍ以上５Ｍ以下のＮａＯＨ水溶液を加えて、密閉容器内において２００℃以上３００℃以下で１０分以上加熱することを特徴とする、鉄鉱石中の脈石及びリンの除去方法が提供される。 In order to solve the above problems, according to one aspect of the present invention, an aqueous NaOH solution having a concentration of 3M or more and 5M or less is added to iron ore containing phosphorus at 0.10% by mass or more and 0.25% by mass or less. Provided is a method for removing gangue and phosphorus from iron ore, which comprises heating at 200° C. or higher and 300° C. or lower for 10 minutes or more in a closed container.
本発明の他の観点によれば、リンを０．１０質量％以上０．２５質量％以下で含有する鉄鉱石に、濃度が３Ｍ以上５Ｍ以下のＮａＯＨ水溶液とグリセリンを加えて、密閉容器内において２００℃以上３００℃以下で１０分以上加熱することを特徴とする、鉄鉱石中の脈石及びリンの除去方法が提供される。 According to another aspect of the present invention, an aqueous NaOH solution and glycerin having a concentration of 3M to 5M and glycerin are added to iron ore containing phosphorus in an amount of 0.10% by mass to 0.25% by mass, and the mixture is stored in a closed container. Provided is a method for removing gangue and phosphorus from iron ore, which comprises heating at 200° C. or higher and 300° C. or lower for 10 minutes or more.
ここで、鉄鉱石に対して、４０質量％以上７０質量％以下の含有量となるようにグリセリンを加えてもよい。 Here, glycerin may be added to the iron ore so that the content is 40% by mass or more and 70% by mass or less.
本発明の他の観点によれば、上記の鉄鉱石中の脈石及びリンの除去方法により脈石及びリンを除去した鉄鉱石を還元して鉄を製造することを特徴とする、鉄の製造方法が提供される。 According to another aspect of the present invention, iron production is characterized in that iron is produced by reducing iron ore from which gangue and phosphorus have been removed by the above method for removing gangue and phosphorus from iron ore. A method is provided.
本発明の上記課題によれば、鉄鉱石の脈石及びリン濃度をさらに低減することが可能となる。 According to the above-mentioned problems of the present invention, it becomes possible to further reduce the gangue and phosphorus concentration of iron ore.
＜１．本発明者らによる検討＞
まず、本発明者らが行った検討について説明する。本発明者らは、非特許文献１に開示されたアルカリ水熱反応に着目した。そして、どのような条件下であれば鉄鉱石から多くの脈石及びリンを除去できるかについて検討した。
<1. Investigation by the present inventors>
First, the studies conducted by the present inventors will be explained. The present inventors focused on the alkaline hydrothermal reaction disclosed in Non-Patent Document 1. We then investigated under what conditions a large amount of gangue and phosphorus could be removed from iron ore.
本発明者らは、異なる化学組成を有する複数種類の鉄鉱石を準備した（表１）。粉末Ｘ線回析（ＸＲＤ）分析によれば、ＡＬＹとＡＬＲはα－ＦｅＯＯＨ、ＷＡＬとＡ、Ｂ、Ｃはα－ＦｅＯＯＨとＦｅ２Ｏ３であった。Ｄ、ＥはＦｅ２Ｏ３であった。 The present inventors prepared multiple types of iron ores with different chemical compositions (Table 1). According to powder X-ray diffraction (XRD) analysis, ALY and ALR were α-FeOOH, and WAL and A, B, and C were α-FeOOH and Fe 2 O 3 . D and E were Fe2O3 .
表１におけるＴ．Ｆｅ、ＳｉＯ２、Ａｌ２Ｏ３、ＳｉＯ２＋Ａｌ２Ｏ３、Ｐの濃度（質量％）は化学分析により特定した。Ｔ．Ｆｅは鉄成分、ＳｉＯ２、Ａｌ２Ｏ３は脈石成分、Ｐはリンである。ＬＯＩは強熱減量（質量％）であり、鉄鉱石中の結晶水の含有量を示す。吸着Ｐ（質量％）はゲーサイトに賦存しているリンであり、本検討では、このようなリンをゲーサイトに化学吸着したリンとした。吸着リンの濃度はＭＬＡ（Ｍｉｎｅｒａｌ Ｌｉｂｅｒａｔｉｏｎ Ａｎａｌｙｓｉｓ）により定量した。残りのリンはリン酸塩鉱物として存在するか、酸化鉄（ヘマタイト等）に固溶していたりする。アルカリ水熱反応では、主にゲーサイトに化学吸着したリンを除去する。表１に示す質量％は、鉄鉱石の質量に対する質量％を示す。表１によれば、ＯｒｅＡ～Ｄはリンを０．１０～０．２５質量％と多く含むが、その大半が吸着リンとなっている。つまり、リンを０．１０～０．２５質量％と多く含む鉄鉱石は、アルカリ水熱反応で除去可能な吸着リンを多く含む傾向にある。このような傾向は特に豪州産の鉄鉱石で顕著である。 T. in Table 1. The concentrations (mass %) of Fe, SiO 2 , Al 2 O 3 , SiO 2 +Al 2 O 3 , and P were determined by chemical analysis. T. Fe is an iron component, SiO 2 and Al 2 O 3 are gangue components, and P is phosphorus. LOI is loss on ignition (mass%) and indicates the content of water of crystallization in iron ore. Adsorbed P (mass%) is phosphorus present in goethite, and in this study, such phosphorus was treated as phosphorus chemically adsorbed to goethite. The concentration of adsorbed phosphorus was determined by MLA (Mineral Liberation Analysis). The remaining phosphorus exists as phosphate minerals or is dissolved in iron oxides (such as hematite). In the alkaline hydrothermal reaction, phosphorus chemically adsorbed on goethite is mainly removed. The mass % shown in Table 1 indicates the mass % based on the mass of iron ore. According to Table 1, Ore A to D contain a large amount of phosphorus at 0.10 to 0.25% by mass, most of which is adsorbed phosphorus. In other words, iron ore containing a large amount of phosphorus (0.10 to 0.25% by mass) tends to contain a large amount of adsorbed phosphorus that can be removed by an alkaline hydrothermal reaction. This trend is particularly noticeable in Australian iron ore.
次に、表１に示す各鉄鉱石を用いてアルカリ水熱反応を行った。具体的には、まず、ＳＵＳ３１６製の反応器（外径２５ｍｍ）に鉄鉱石約４．０ｇと５ＭのＮａＯＨ水溶液３．５ｍＬを投入し、圧力計やバルブを備え付けた経路に接続した。ここで、鉄鉱石は粒径４．０ｍｍ以下に分級したものを用いた。具体的には、鉄鉱石を目開き４ｍｍの篩に掛け、篩から落下した鉄鉱石をアルカリ水熱反応に供した。 Next, an alkaline hydrothermal reaction was performed using each iron ore shown in Table 1. Specifically, first, approximately 4.0 g of iron ore and 3.5 mL of 5M NaOH aqueous solution were charged into a reactor made of SUS316 (outer diameter 25 mm), and the reactor was connected to a path equipped with a pressure gauge and a valve. Here, the iron ore used was classified to a particle size of 4.0 mm or less. Specifically, iron ore was passed through a sieve with an opening of 4 mm, and the iron ore that fell through the sieve was subjected to an alkaline hydrothermal reaction.
その後、バルブを介して反応器内に高純度Ｈｅを導入し、加圧状態でリークチェックを行なった。反応器内を充分Ｈｅでパージした後、反応器内を常圧のＨｅ雰囲気にしてバルブを閉じた。反応器は２５０℃または３００℃に保持された流動砂浴に入れ、３０分以上保持した。この時のゲージ圧の変化は０－４ＭＰａの範囲にあった。保持時間が終了した後、反応器を流動砂浴から取り出し、水で急冷した。反応器内の固体（固相）と液体はろ過により分離回収した。回収した固相は、温水にてろ液がｐＨ６になるまで繰り返し洗浄を行なった。ついで、アルカリ水熱反応後の固相中の各成分（鉄、脈石、リン）の含有量を化学分析により特定し、以下の数式（１）、（２）により鉄回収率（％）、脱脈石率（％）、脱リン率（％）を求めた。 Thereafter, high-purity He was introduced into the reactor via a valve, and a leak check was performed under pressure. After the inside of the reactor was sufficiently purged with He, the inside of the reactor was made into a normal pressure He atmosphere and the valve was closed. The reactor was placed in a fluidized sand bath maintained at 250°C or 300°C for 30 minutes or more. The change in gauge pressure at this time was in the range of 0-4 MPa. After the holding time expired, the reactor was removed from the fluidized sand bath and quenched with water. The solid (solid phase) and liquid in the reactor were separated and recovered by filtration. The recovered solid phase was washed repeatedly with warm water until the pH of the filtrate reached 6. Next, the content of each component (iron, gangue, phosphorus) in the solid phase after the alkaline hydrothermal reaction was determined by chemical analysis, and the iron recovery rate (%) was calculated using the following formulas (1) and (2). The gangue removal rate (%) and phosphor removal rate (%) were determined.
数式（１）、（２）において、Ｗａはアルカリ水熱反応後の固相の質量であり、Ｗｂはアルカリ水熱反応前の鉄鉱石の質量であり、Ｆａはアルカリ水熱反応後の固相中の鉄濃度（質量％）であり、Ｆｂはアルカリ水熱反応前の鉄鉱石中の鉄濃度（質量％）である。 In formulas (1) and (2), Wa is the mass of the solid phase after the alkaline hydrothermal reaction, Wb is the mass of the iron ore before the alkaline hydrothermal reaction, and Fa is the mass of the solid phase after the alkaline hydrothermal reaction. Fb is the iron concentration (mass %) in the iron ore before the alkaline hydrothermal reaction.
数式（２）を用いて脱脈石率を求める場合、Ｐａはアルカリ水熱反応後の固相中の全脈石濃度（質量％）であり、Ｐｂはアルカリ水熱反応前の鉄鉱石中の全脈石濃度（質量％）である。数式（２）を用いて脱リン率を求める場合、Ｐａはアルカリ水熱反応後の固相中のリン濃度（質量％）であり、Ｐｂはアルカリ水熱反応前の鉄鉱石中のリン濃度（質量％）である。結果を表２及び図１に示す。図１の横軸はアルカリ水熱反応前の鉄鉱石中のリン濃度（質量％）であり、縦軸は脱リン率（％）である。点Ｐ１はＡＬＹのリン濃度及び脱リン率の相関を示し、点Ｐ２はＡＬＲのリン濃度及び脱リン率の相関を示す。点Ｐ３～Ｐ８はＷＡＬ～ＯｒｅＥのリン濃度及び脱リン率の相関を示す。 When determining the gangue removal rate using formula (2), Pa is the total gangue concentration (mass%) in the solid phase after the alkaline hydrothermal reaction, and Pb is the total gangue concentration (mass%) in the iron ore before the alkaline hydrothermal reaction. Total gangue concentration (mass%). When calculating the dephosphorization rate using formula (2), Pa is the phosphorus concentration (mass%) in the solid phase after the alkaline hydrothermal reaction, and Pb is the phosphorus concentration (mass%) in the iron ore before the alkaline hydrothermal reaction. mass%). The results are shown in Table 2 and Figure 1. The horizontal axis of FIG. 1 is the phosphorus concentration (% by mass) in the iron ore before the alkaline hydrothermal reaction, and the vertical axis is the dephosphorization rate (%). Point P1 shows the correlation between the phosphorus concentration and dephosphorization rate of ALY, and point P2 shows the correlation between the phosphorus concentration and dephosphorization rate of ALR. Points P3 to P8 show the correlation between phosphorus concentration and dephosphorization rate from WAL to OreE.
ＡＬＹ、ＡＬＲはリン濃度の低い高結晶水鉱石であり、これらの脱リン率は高い。しかし、もともとリン濃度が低い（＜０．１０質量％）ので、コストをかけて脱リン処理をする意味合いが低い。 ALY and ALR are highly crystalline water ores with low phosphorus concentration, and their dephosphorization rates are high. However, since the phosphorus concentration is originally low (<0.10% by mass), there is little significance in dephosphorizing it at high cost.
リン濃度が高い鉄鉱石は埋蔵量も豊富であり、脱リン処理をして有効活用化する意味合いは大きい。表２及び図１によれば、リン濃度が０．１～０．２５質量％の鉄鉱石にアルカリ水熱処理をすることで、効率の良い脱リン処理が出来ることが分かった。 Iron ore, which has a high phosphorus concentration, has abundant reserves, and it has great significance to dephosphorize it and make effective use of it. According to Table 2 and FIG. 1, it was found that efficient dephosphorization can be achieved by subjecting iron ore having a phosphorus concentration of 0.1 to 0.25% by mass to alkaline hydrothermal treatment.
リン濃度の高い鉄鉱石の方が、含有脈石量が低く、高い脱脈石率を示す。リン濃度が０．１質量％以上の鉄鉱石にアルカリ水熱処理をすると、６０％以上の高い脱脈石率を示した。アルカリ水熱処理による鉄回収率は鉄鉱石の種類に依らず高く、８０％以上であった。 Iron ore with a higher phosphorus concentration has a lower gangue content and a higher gangue removal rate. When iron ore with a phosphorus concentration of 0.1% by mass or more was subjected to alkaline hydrothermal treatment, it showed a high gangue removal rate of 60% or more. The iron recovery rate by alkaline hydrothermal treatment was high, regardless of the type of iron ore, and was over 80%.
なお、リン濃度が０．１質量％未満だと、上述した高結晶水鉱石を除き、リンの多くがＦｅ２Ｏ３と共存するリン酸塩鉱物として存在することになり、アルカリ水熱反応による脱リン性が劣る。リン濃度が０．１質量％以上の鉄鉱石では、リンの多くがゲーサイトに化学吸着したリンとなる。アルカリ水熱反応では、吸着リンの反応性が高く、したがってリン濃度が０．１質量％以上となる場合に脱リン率が向上する。さらに、脈石成分（ＳｉＯ２、Ａｌ２Ｏ３）もアルカリ水溶液に溶出し、脱脈石率も向上する。一方、リン濃度が０．２５質量％を超えると、アルカリ水熱反応の反応性に対して、初期のリン含有量が過剰となり、脱リン率が低下する。 Note that if the phosphorus concentration is less than 0.1% by mass, most of the phosphorus will exist as phosphate minerals coexisting with Fe 2 O 3 , except for the highly crystalline water ore mentioned above, and the Poor dephosphorization properties. In iron ore with a phosphorus concentration of 0.1% by mass or more, most of the phosphorus becomes phosphorus chemically adsorbed to goethite. In the alkaline hydrothermal reaction, the reactivity of adsorbed phosphorus is high, and therefore the dephosphorization rate is improved when the phosphorus concentration is 0.1% by mass or more. Furthermore, gangue components (SiO 2 , Al 2 O 3 ) are also eluted into the alkaline aqueous solution, and the gangue removal rate is also improved. On the other hand, when the phosphorus concentration exceeds 0.25% by mass, the initial phosphorus content becomes excessive with respect to the reactivity of the alkaline hydrothermal reaction, and the dephosphorization rate decreases.
そこで、本発明者らは、アルカリ水熱反応による脱リン及び脱脈石の対象となる鉄鉱石を、リン含有量０．１～０．２５質量％の鉄鉱石とした。また、アルカリ水熱反応の反応温度を２００～３００℃とし、反応時間を１０分以上、好ましくは３０分以上とした。反応温度が２００℃未満では、アルカリ水熱の反応速度が十分に早くなく、アルカリ水熱処理に多大な時間がかかってしまうので望ましくなく、反応温度が３００℃超では、反応速度は十分に早いものの、反応温度２００℃の時と大差ないばかりか、加温に多大なエネルギーが必要となるので、望ましくないからである。また、反応時間が１０分未満では、アルカリ水熱反応が十分に進行しないからである。反応時間の上限値は特に制限されないが、例えば、工業的には３時間以内であってもよい。 Therefore, the present inventors selected iron ore with a phosphorus content of 0.1 to 0.25% by mass as the target of dephosphorization and gangue removal by an alkaline hydrothermal reaction. Further, the reaction temperature of the alkaline hydrothermal reaction was set to 200 to 300°C, and the reaction time was set to 10 minutes or more, preferably 30 minutes or more. If the reaction temperature is less than 200°C, the reaction rate of alkaline hydrothermal treatment will not be fast enough and the alkaline hydrothermal treatment will take a long time, which is undesirable. If the reaction temperature exceeds 300°C, although the reaction rate is sufficiently fast, This is because not only is there not much difference from the reaction temperature of 200° C., but also a large amount of energy is required for heating, which is not desirable. Further, if the reaction time is less than 10 minutes, the alkaline hydrothermal reaction will not proceed sufficiently. The upper limit of the reaction time is not particularly limited, but may be, for example, within 3 hours industrially.
次に、本発明者らは、ＮａＯＨ水溶液の濃度について検討した。具体的には、ＮａＯＨ水溶液の濃度を２～６Ｍと変動させて上述したアルカリ水熱反応を行った。鉄鉱石はＯｒｅＡを用いた。その結果を表３に示す。 Next, the present inventors investigated the concentration of the NaOH aqueous solution. Specifically, the above-described alkaline hydrothermal reaction was performed while varying the concentration of the NaOH aqueous solution from 2 to 6M. OreA was used as the iron ore. The results are shown in Table 3.
表３によれば、ＮａＯＨ水溶液の濃度が３～５Ｍとなる場合に、脱脈石率及び脱リン率が６０％以上となる。他の鉱石種（Ｂ～Ｄ）に対しても同様の結果が得られた。なお、ＮａＯＨ水溶液の濃度が３Ｍ未満となる場合、どの鉄鉱石種に対しても十分な（６０％以上の）脱脈石率、脱リン率が得られなかった。一方、ＮａＯＨ水溶液の濃度が５Ｍを超えると、アルカリ水熱反応後の鉄鉱石（固相）中にＮａが０．１２％超残留して好ましくない。このような高Ｎａの鉄鉱石を用いて焼結鉱を製造すると、焼結鉱の還元粉化性（ＲＤＩ）が悪化（４０％以上）する。なお、ＲＤＩは、ＪＩＳ Ｍ ８７２０で規定される焼結鉱の還元粉化指数である。焼結鉱５００ｇを、５５０℃でＣＯ－３０％（Ｎ２－７０％）のガスで３０分還元し、冷却後に所定の回転粉化処理を行った後の粉率（２．８ｍｍ以下）で表される。洗浄を強化して残留Ｎａを低減させる方法もあるが、焼結鉱の生産性が著しく低下するので好ましくない。 According to Table 3, when the concentration of the NaOH aqueous solution is 3 to 5M, the gangue removal rate and dephosphorization rate are 60% or more. Similar results were obtained for other ore types (B to D). Note that when the concentration of the NaOH aqueous solution was less than 3M, a sufficient gangue removal rate (60% or more) and dephosphorization rate could not be obtained for any type of iron ore. On the other hand, if the concentration of the NaOH aqueous solution exceeds 5M, more than 0.12% of Na will remain in the iron ore (solid phase) after the alkaline hydrothermal reaction, which is not preferable. When sintered ore is produced using such high Na iron ore, the reduction pulverizability (RDI) of the sintered ore deteriorates (40% or more). Note that RDI is a reduction pulverization index of sintered ore specified in JIS M 8720. 500 g of sintered ore was reduced with CO-30% (N 2 -70%) gas at 550°C for 30 minutes, and after cooling, the powder ratio (2.8 mm or less) was obtained after performing the specified rotary powdering process. expressed. Although there is a method of reducing residual Na by strengthening cleaning, it is not preferable because the productivity of the sintered ore is significantly reduced.
次に、本発明者らは、アルカリ水熱反応に添加する物質について検討した。この結果、本発明者らは、上述したアルカリ水熱反応において、鉄鉱石にグリセリンを添加することで、高い還元率が得られることを見出した。グリセリンの添加濃度は、内数で４０～７０質量％が好ましい。この場合、高い還元率に加えて、高い脱リン率、脱脈石率が得られる。グリセリンの添加濃度はグリセリン、鉄鉱石、及びＮａＯＨの合計質量に対する質量割合である。 Next, the present inventors studied substances to be added to an alkaline hydrothermal reaction. As a result, the present inventors discovered that a high reduction rate can be obtained by adding glycerin to iron ore in the above-mentioned alkaline hydrothermal reaction. The concentration of glycerin added is preferably 40 to 70% by mass. In this case, in addition to a high reduction rate, a high dephosphorization rate and a high gangue removal rate can be obtained. The concentration of glycerin added is a mass ratio to the total mass of glycerin, iron ore, and NaOH.
本発明者らは、このような結果が得られた理由を以下の様に考えている。すなわち、まず、グリセリンとＮａＯＨが反応し、Ｈ２とＨ２Ｏが生成する（化学式１）。さらに、過剰なグリセリンが分解して、Ｈ２を発生する（化学式２）。これらの反応で生成したＨ２によって、共存する鉄鉱石が還元される（化学式３）。
Ｃ３Ｈ５（ＯＨ）３＋ＮａＯＨ＝ＣＨ３ＣＨ（ＯＨ）ＣＯＯＮａ＋Ｈ２＋Ｈ２Ｏ （化学式１）
Ｃ３Ｈ５（ＯＨ）３＝ ＣＨ３ＣＨ（ＯＨ）ＣＯＯＨ＋Ｈ２ （化学式２）
Ｆｅ２Ｏ３＋３Ｈ２＝２Ｆｅ＋３Ｈ２Ｏ （化学式３）
The present inventors believe that the reason why such results were obtained is as follows. That is, first, glycerin and NaOH react to generate H 2 and H 2 O (chemical formula 1). Furthermore, excess glycerin decomposes to generate H2 (chemical formula 2). The coexisting iron ore is reduced by H 2 generated by these reactions (chemical formula 3).
C3H5 (OH) 3 +NaOH= CH3CH (OH)COONa+ H2 + H2O ( Chemical formula 1)
C3H5 (OH) 3 = CH3CH (OH) COOH + H2 (chemical formula 2)
Fe2O3 + 3H2 =2Fe+ 3H2O (chemical formula 3)
表４は５ＭのＮａＯＨ水溶液に６５質量％のグリセリンを添加してアルカリ水熱反応を行った結果を示す。表４において、還元率は、アルカリ水熱反応前試料のＴ．Ｆｅ、Ｍ．Ｆｅ、ＦｅＯの化学分析から求まる被還元酸素量と、アルカリ水熱反応後試料のＴ．Ｆｅ、Ｍ．Ｆｅ、ＦｅＯの化学分析値から求まる残存酸素量を測定して、被還元酸素量に対する除去された酸素量の比率から求めた。 Table 4 shows the results of an alkaline hydrothermal reaction by adding 65% by mass of glycerin to a 5M NaOH aqueous solution. In Table 4, the reduction rate is the T.I. of the sample before alkaline hydrothermal reaction. Fe, M. The amount of reduced oxygen determined from the chemical analysis of Fe and FeO, and the T.I. of the sample after the alkaline hydrothermal reaction. Fe, M. The amount of residual oxygen determined from the chemical analysis values of Fe and FeO was measured and determined from the ratio of the amount of oxygen removed to the amount of oxygen to be reduced.
表４によれば、リン含有量が０．１質量％未満のＷＡＬは低い還元率であった。一方、高結晶水鉱石であるＡＬＹとＡＬＲは高い還元率を示した。リン含有量が０．１質量％以上の鉄鉱石は高い還元率を示した。これは以下の理由によると考えられる。すなわち、上記のようにリン含有率が高い鉄鉱石中にはゲーサイト吸着リンが多く、アルカリ水熱反応で脱リンされやすいので、脱リンに消費されるＮａＯＨ量が少なくてすむ。その分、グリセリンと反応してＨ２を生じやすく還元が進む。このため、リン含有量が０．１質量％以上の鉄鉱石は高い還元率を示すと考えられる。ただし、過度にリン含有量が高い（０．２５重量％超）と、ＮａＯＨのほとんどが脱リンで消費されてしまい、グリセリンと反応してＨ２を発生する量が限定されてしまうために還元率は８０％未満となった。 According to Table 4, WAL with a phosphorus content of less than 0.1% by mass had a low reduction rate. On the other hand, ALY and ALR, which are highly crystalline water ores, showed high reduction rates. Iron ore with a phosphorus content of 0.1% by mass or more showed a high reduction rate. This is considered to be due to the following reasons. That is, as described above, iron ore with a high phosphorus content has a large amount of phosphorus adsorbed on goethite and is easily dephosphorized by an alkaline hydrothermal reaction, so the amount of NaOH consumed for dephosphorization can be reduced. Therefore, it is easier to react with glycerin to generate H 2 and the reduction progresses. Therefore, iron ore with a phosphorus content of 0.1% by mass or more is considered to exhibit a high reduction rate. However, if the phosphorus content is excessively high (more than 0.25% by weight), most of the NaOH will be consumed in dephosphorization, and the amount of H2 generated by reaction with glycerin will be limited, resulting in reduced reduction. The rate was less than 80%.
本発明者らは、グリセリンの好ましい濃度について検討した。具体的には、本発明者らは、グリセリンの添加濃度を３５～７５質量％として上述したアルカリ水熱反応を行った。鉄鉱石はＯｒｅＡを使用した。結果を表５に示す。 The present inventors investigated the preferred concentration of glycerin. Specifically, the present inventors conducted the above-mentioned alkaline hydrothermal reaction with the added concentration of glycerin ranging from 35 to 75% by mass. OreA was used as the iron ore. The results are shown in Table 5.
表５によれば、グリセリンの濃度がいずれの場合であっても、高い還元率が得られた。特に、グリセリンの添加濃度が４０～７０質量％となる場合に高い脱脈石率、脱リン率、還元率が得られた。他の鉱石種（Ｂ～Ｄ）でも同様の結果が得られた。グリセリンの濃度が４０質量％未満だと、Ｈ２発生量が不十分となり、還元率が低下して８０％以下となる。ただし、７０％の還元率は実用上十分な値である。グリセリンの濃度が７０質量％を超えると、ＮａＯＨを優先的に消費してしまい、脱脈石率、脱リン率が低下して６０％未満となる。ただし、還元率は１００％と非常に高い値となった。 According to Table 5, a high reduction rate was obtained regardless of the glycerin concentration. In particular, high gangue removal rate, dephosphorization rate, and reduction rate were obtained when the concentration of glycerin added was 40 to 70% by mass. Similar results were obtained for other ore types (B to D). If the concentration of glycerin is less than 40% by mass, the amount of H 2 generated will be insufficient and the reduction rate will decrease to 80% or less. However, a reduction rate of 70% is a practically sufficient value. When the concentration of glycerin exceeds 70% by mass, NaOH is consumed preferentially, and the gangue removal rate and dephosphorization rate decrease to less than 60%. However, the return rate was extremely high at 100%.
以上により、リンを０．１０～０．２５質量％で含有する鉄鉱石に、濃度が３～５ＭのＮａＯＨ水溶液を加えて、密閉容器内で２００～３００℃で１０分以上、好ましくは加熱することで、鉄鉱石の脈石及びリン濃度をさらに低減することが可能となる。具体的には、脱リン率、脱脈石率ともに６０％以上に達する。これに加えて、密閉容器内にＮａＯＨ水溶液を添加する際に、更にグリセリンを添加することで、高い還元率の鉄を得ることができる。グリセリンの添加濃度は、好ましくは内数で４０～７０質量％である。この場合、鉄鉱石の還元率が８０％以上に達する。 As described above, an aqueous NaOH solution with a concentration of 3 to 5 M is added to iron ore containing 0.10 to 0.25 mass% of phosphorus, and the mixture is preferably heated in a closed container at 200 to 300°C for 10 minutes or more. This makes it possible to further reduce the gangue and phosphorus concentration of iron ore. Specifically, both the dephosphorization rate and the gangue removal rate reach 60% or more. In addition to this, by further adding glycerin when adding the NaOH aqueous solution into the sealed container, iron with a high reduction rate can be obtained. The concentration of glycerin added is preferably 40 to 70% by mass. In this case, the reduction rate of iron ore reaches 80% or more.
＜２．鉄鉱石中の脈石及びリンの除去方法＞
次に、鉄鉱石中の脈石及びリンの除去方法について説明する。上述したように、本実施形態に係る鉄鉱石中の脈石及びリンの除去方法は、リンを０．１０～０．２５質量％で含有する鉄鉱石に、濃度が３～５ＭのＮａＯＨ水溶液を加えて、密閉容器内で２００～３００℃で１０分以上、好ましくは３０分以上加熱するというものである。密閉容器内は、不活性ガス（Ｈｅ等）を充填することが好ましい。これにより、鉄鉱石の脈石及びリン濃度をさらに低減することが可能となる。本実施形態では、密閉容器内にＮａＯＨ水溶液を添加する際に、更にグリセリンを添加することが好ましい。これにより、高い還元率の鉄を得ることができる。グリセリンの好ましい添加濃度は内数で４０～７０質量％である。なお、アルカリ水熱反応後の固相を十分に洗浄すれば固相にアルカリ成分が残留せず、その後に高炉に使用しても問題ない。また、本実施形態に係る鉄鉱石中の脈石及びリンの除去方法は、バッチ式で行われてもよいし、ＮａＯＨ水溶液を循環させるような流通式で行われてもよい。
<2. Method for removing gangue and phosphorus in iron ore>
Next, a method for removing gangue and phosphorus from iron ore will be explained. As described above, the method for removing gangue and phosphorus from iron ore according to the present embodiment involves adding a NaOH aqueous solution with a concentration of 3 to 5M to iron ore containing 0.10 to 0.25% by mass of phosphorus. In addition, it is heated in a closed container at 200 to 300°C for 10 minutes or more, preferably 30 minutes or more. The inside of the closed container is preferably filled with an inert gas (such as He). This makes it possible to further reduce the gangue and phosphorus concentration of iron ore. In this embodiment, when adding the NaOH aqueous solution into the closed container, it is preferable to further add glycerin. Thereby, iron with a high reduction rate can be obtained. The preferred addition concentration of glycerin is 40 to 70% by mass. Note that if the solid phase after the alkaline hydrothermal reaction is sufficiently washed, no alkaline components will remain in the solid phase, and there will be no problem even if it is used in a blast furnace after that. Further, the method for removing gangue and phosphorus from iron ore according to the present embodiment may be performed in a batch method or in a flow method in which an aqueous NaOH solution is circulated.
＜３．鉄の製造方法＞
本実施形態に係る鉄の製造方法は、上述した鉄鉱石中の脈石及びリンの除去方法により脈石及びリンを除去した鉄鉱石を還元して鉄を製造するというものである。鉄の製造方法は特に制限されないが、例えば鉄鉱石を用いて焼結鉱を製造し、この焼結鉱を高炉に装入することで鉄を製造してもよい。
<3. Iron manufacturing method>
The method for producing iron according to the present embodiment is to produce iron by reducing iron ore from which gangue and phosphorus have been removed by the above-described method for removing gangue and phosphorus from iron ore. Although the method for producing iron is not particularly limited, for example, iron may be produced by producing sintered ore using iron ore and charging the sintered ore into a blast furnace.
以上、添付図面を参照しながら本発明の好適な実施形態について詳細に説明したが、本発明はかかる例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、これらについても、当然に本発明の技術的範囲に属するものと了解される。 Although preferred embodiments of the present invention have been described above in detail with reference to the accompanying drawings, the present invention is not limited to such examples. It is clear that a person with ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea stated in the claims. It is understood that these also naturally fall within the technical scope of the present invention.
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