JP7501475B2 - Ferro-coke manufacturing method - Google Patents
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- 239000000571 coke Substances 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 170
- 229910052742 iron Inorganic materials 0.000 claims description 84
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 46
- 239000003245 coal Substances 0.000 claims description 27
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- -1 secondary amine compound Chemical class 0.000 claims description 4
- 230000009257 reactivity Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 13
- 239000004576 sand Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011338 soft pitch Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004079 vitrinite Substances 0.000 description 1
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Description
本発明は、石炭と鉄鉱石との混合原料を乾留することにより得られるフェロコークスの製造方法に関する。 The present invention relates to a method for producing ferro-coke obtained by carbonizing a mixture of coal and iron ore.
高炉の操業では、石炭をコークス炉で乾留して製造されたコークスが高炉に装入される。高炉内に装入されるコークスには、高炉内の通気性を向上させるためのスペーサーの役割、還元材としての役割、熱源としての役割などがある。近年、コークスの反応性を向上させるという観点から、冶金用のフェロコークスを得る技術が知られている。 In blast furnace operation, coke produced by carbonizing coal in a coke oven is charged into the blast furnace. The coke charged into the blast furnace serves various purposes, including as a spacer to improve the gas permeability inside the furnace, as a reducing agent, and as a heat source. In recent years, technology has been developed to obtain ferro-coke for metallurgy purposes in order to improve the reactivity of coke.
フェロコークスは、主原料となる石炭、鉄鉱石について予め粉砕、乾燥などの調製を行い、その後、数質量％のバインダーとともに混練機内で撹拌、混練した後、ダブルロール式の成型機にて成型物とし、この成型物を乾留炉で乾留して製造される。このようにして製造されるフェロコークスには、高炉の原料として一定以上の品質（強度、反応性）が求められている。 Ferro coke is produced by first preparing the main raw materials, coal and iron ore, by crushing and drying them, then stirring and kneading them in a kneading machine with a few mass percent of binder, forming them into a molded product in a double-roll molding machine, and then carbonizing this molded product in a carbonization furnace. Ferro coke produced in this way is required to have a certain level of quality (strength, reactivity) as a raw material for blast furnaces.
ここで、特許文献１には、鉄原料として磁性鉄（磁鉄鉱）を成分とする砂鉄を用いることで、フェロコークス中のＦｅ周辺における空隙量が少ない高強度のフェロコークスを製造する方法が開示されている。
しかしながら、特許文献１に開示された砂鉄をフェロコークスの原料として用いる場合には、高温まで乾留してフェロコークスを製造しても、磁性鉄を成分とすることから高炉内での還元率が低下し、鉄鉱石との反応性が低下するという問題がある。
However, when the iron sand disclosed in
本発明は、かかる事情を鑑みてなされたもので、強度と反応性とを両立させたフェロコークスの製造方法を提供することを目的とする。 The present invention was made in consideration of these circumstances, and aims to provide a method for producing ferro-coke that combines strength and reactivity.
上記課題を解決する本発明の要旨構成は以下のとおりである。
［１］石炭と鉄鉱石とを混合して混合原料とし、前記混合原料を成型して乾留するフェロコークスの製造方法であって、前記鉄鉱石は、磁鉄鉱の含有率が１２質量％以上８０質量％以下である、フェロコークスの製造方法。
［２］石炭と鉄鉱石とを混合して混合原料とし、前記混合原料を成型して乾留するフェロコークスの製造方法であって、前記鉄鉱石は、ＦｅＯの含有率が３質量％以上２５質量％以下である、フェロコークスの製造方法。
［３］前記ＦｅＯの含有率はＪＩＳ Ｍ ８２１３－１９９５に記載の方法で測定される、［２］に記載のフェロコークスの製造方法。
［４］前記鉄鉱石は、複数の銘柄の鉄鉱石を配合した配合鉄鉱石である、［１］から［３］のいずれか１つに記載のフェロコークスの製造方法。
［５］前記石炭は、芳香環を有する１級もしくは２級アミン系化合物であるＮ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミンを１０質量％添加して測定されるギーセラー最高流動度ＭＦの常用対数値ｌоｇＭＦの値が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下である単味石炭または前記ギーセラー最高流動度ＭＦの常用対数値ｌоｇＭＦの加重平均値が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下である配合炭である、［１］から［４］のいずれか１つに記載のフェロコークスの製造方法。
The gist and configuration of the present invention to solve the above problems are as follows.
[1] A method for producing ferro coke, comprising mixing coal and iron ore to prepare a mixed raw material, molding the mixed raw material, and carbonizing the molded material, wherein the iron ore has a magnetite content of 12% by mass or more and 80% by mass or less.
[2] A method for producing ferro coke, comprising mixing coal and iron ore to prepare a mixed raw material, molding the mixed raw material, and carbonizing the molded product, wherein the iron ore has an FeO content of 3 mass% or more and 25 mass% or less.
[3] The method for producing ferro coke according to [2], wherein the content of FeO is measured by the method described in JIS M 8213-1995.
[4] The method for producing ferro coke according to any one of [1] to [3], wherein the iron ore is a blended iron ore obtained by blending a plurality of brands of iron ore.
[5] The method for producing ferro-coke according to any one of [1] to [4], wherein the coal is a pure coal having a common logarithm of the Gieseler maximum fluidity MF, logMF, measured with the addition of 10 mass% of N,N'-di-2-naphthyl-p-phenylenediamine, which is a primary or secondary amine compound having an aromatic ring, of 1.0 log/ddpm or more and 3.0 log/ddpm or less, or a blended coal having a weighted average value of the common logarithm of the Gieseler maximum fluidity MF, logMF, of 1.0 log/ddpm or more and 3.0 log/ddpm or less.
本発明に係るフェロコークスの製造方法により、強度と反応性とを両立させたフェロコークスの製造が可能となる。 The ferro-coke manufacturing method of the present invention makes it possible to produce ferro-coke that is both strong and highly reactive.
以下、本発明を実施するための方法について説明する。本発明は、石炭と鉄鉱石とを混合して混合原料とし、混合原料を成型して乾留するフェロコークスの製造方法であって、鉄鉱石は磁鉄鉱の含有率が１２質量％以上８０質量％以下である。 The method for carrying out the present invention will be described below. The present invention is a method for producing ferro-coke by mixing coal and iron ore to prepare a mixed raw material, molding the mixed raw material, and carbonizing the molded material. The iron ore has a magnetite content of 12% by mass or more and 80% by mass or less.
砂鉄の主成分である磁鉄鉱は、鉄鉱石にも含まれ、その含有率は鉄鉱石の銘柄により様々である。鉄鉱石における磁鉄鉱の含有率は、フェロコークス製造時の強度や反応性に大きく影響する。本発明の発明者らは、鉄鉱石における磁鉄鉱の含有率に注目し、鉄鉱石中の磁鉄鉱の含有率を調整することで、フェロコークスの強度と反応性を制御することを考えた。 Magnetite, the main component of iron sand, is also found in iron ore, with its content varying depending on the brand of iron ore. The magnetite content in iron ore has a significant effect on the strength and reactivity of ferro coke when it is produced. The inventors of the present invention focused on the magnetite content in iron ore, and conceived of controlling the strength and reactivity of ferro coke by adjusting the magnetite content in the iron ore.
まず、鉄鉱石中の磁鉄鉱の含有率が様々である鉄鉱石を用いてフェロコークスを製造し、その強度と反応性への影響を評価した。その結果、磁鉄鉱の含有率が１２質量％以上８０質量％以下の鉄鉱石を使用すると、強度と反応性とを両立させた高品質なフェロコークスを製造できることが確認できた。 First, ferro-coke was produced using iron ore with various magnetite content ratios, and the effect on strength and reactivity was evaluated. As a result, it was confirmed that high-quality ferro-coke that combines strength and reactivity can be produced by using iron ore with a magnetite content of 12% by mass or more and 80% by mass or less.
また、鉄鉱石における磁鉄鉱以外の残りの鉄の形態は、成分をＦｅ２Ｏ３とする赤鉄鉱や褐鉄鉱である。磁鉄鉱の含有率が１２質量％未満であると、高炉内での軟化溶融温度域での還元が過剰となり、軟化溶融性の低い石炭を用いてフェロコークスを製造した場合は粘結性不足となり強度が十分に発現しない。一方、磁鉄鉱の含有率が８０質量％より高くなると、フェロコークスの反応性が低下する。なお、鉄鉱石中の磁鉄鉱の含有率は粉末ＸＲＤ（粉末Ｘ線解析）で測定できる。 The remaining iron in iron ore other than magnetite is in the form of hematite and limonite , which are composed of Fe2O3 . If the magnetite content is less than 12% by mass, excessive reduction occurs in the thermoplastic temperature range in the blast furnace, and when ferro-coke is produced using coal with low thermoplasticity, the caking property is insufficient and the strength is not sufficient. On the other hand, if the magnetite content is higher than 80% by mass, the reactivity of the ferro-coke decreases. The magnetite content in iron ore can be measured by powder XRD (powder X-ray diffraction).
さらに、鉄鉱石中の磁鉄鉱の含有率を１２質量％以上８０質量％以下とすることで、日本工業規格「ＪＩＳ Ｍ ８８０１ 石炭類の試験方法」に記載されたギーセラープラストメータ法での測定が困難である軟化溶融性の低位な石炭を用いたとしても、強度と反応性とが両立したフェロコークスが製造できる。 Furthermore, by setting the magnetite content in the iron ore to 12% by mass or more and 80% by mass or less, it is possible to produce ferro-coke that has both strength and reactivity, even when using coal with low thermoplasticity that is difficult to measure using the Gieseler plastometer method described in the Japanese Industrial Standard "JIS M 8801 Testing methods for coals."
具体的には、特許文献２に記載されている「芳香環を有する１級もしくは２級アミン系化合物であるＮ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミン」を１０質量％添加して軟化溶融特性を向上させた石炭とすることで、ギーセラープラストメータにて測定したギーセラー最高流動度ＭＦの常用対数値（以下、「薬剤添加ｌоｇＭＦ」という。）が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下の範囲内の単味石炭、もしくは、薬剤添加ｌоｇＭＦの加重平均値が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下の範囲内の配合炭を用いることで、強度と反応性とを両立させた高品質なフェロコークスが製造できる。なお、薬剤添加ｌоｇＭＦの上限を３．０ｌｏｇ／ｄｄｐｍ以下とした理由は、高い流動性を有する原料を使用した場合、乾留時にフェロコークスの粒同士が融着するという現象が発生し、炉からの排出不良などのトラブルの原因となるからである。 Specifically, by adding 10% by mass of "N,N'-di-2-naphthyl-p-phenylenediamine, a primary or secondary amine compound having an aromatic ring" as described in Patent Document 2 to produce coal with improved thermoplasticity and melting properties, it is possible to produce a high-quality ferrocoke that combines strength and reactivity by using a single coal whose common logarithm of Gieseler maximum fluidity MF measured with a Gieseler plastometer (hereinafter referred to as "chemically-added logMF") is in the range of 1.0 log/ddpm to 3.0 log/ddpm, or a blended coal whose weighted average value of chemically-added logMF is in the range of 1.0 log/ddpm to 3.0 log/ddpm. The upper limit of the log MF of chemicals added is set at 3.0 log/ddpm or less because, when using raw materials with high fluidity, the ferro coke particles will fuse together during carbonization, causing problems such as poor discharge from the furnace.
また、「ＪＩＳ Ｍ ８２１３－１９９５ 鉄鉱石－けい素定量方法」に記載された「鉄鉱石の成分分析」では、磁鉄鉱の一部がＦｅＯとして検出される。この成分分析の結果を磁鉄鉱の含有率の特定に用いる場合は、「ＪＩＳ Ｍ ８２１３－１９９５」に記載の方法で測定されるＦｅＯの含有率が３質量％以上２５質量％以下である鉄鉱石を用いればよい。 In addition, in the "iron ore composition analysis" described in "JIS M 8213-1995 Iron ore - Silicon Quantitative Method," some of the magnetite is detected as FeO. If the results of this composition analysis are used to determine the magnetite content, iron ore with an FeO content of 3% by mass or more and 25% by mass or less, as measured by the method described in "JIS M 8213-1995," can be used.
なお、本実施形態に係るフェロコークスの製造方法では、鉄鉱石は単味のみならず複数種の銘柄の鉄鉱石を配合した配合鉄鉱石を用いてもよい。この場合には、複数種の鉄鉱石の配合量を調整して、磁鉄鉱の含有率またはＦｅＯの含有率を先述の範囲内に調整すればよい。これにより、磁鉄鉱の含有率が１２質量％以上８０質量％以下を満足しない鉄鉱石であっても、磁鉄鉱を多量に含む他の鉄鉱石と配合し、磁鉄鉱の含有率が１２質量％以上８０質量％以下を満足する配合鉄鉱石とすることで、当該配合鉄鉱石を用いて強度と反応性とを両立させたフェロコークスを製造できる。 In the method for producing ferro coke according to this embodiment, the iron ore may not only be a single component, but may be a blended iron ore containing multiple brands of iron ore. In this case, the blending amounts of the multiple types of iron ore may be adjusted to adjust the magnetite content or FeO content within the aforementioned range. As a result, even if the iron ore does not satisfy the magnetite content of 12% by mass or more and 80% by mass or less, it can be blended with other iron ores containing a large amount of magnetite to produce a blended iron ore containing magnetite that satisfies the magnetite content of 12% by mass or more and 80% by mass or less, and a ferro coke that combines strength and reactivity can be produced using the blended iron ore.
また、磁鉄鉱は、鉄鉱石に含まれるものだけでなく砂鉄やダストに含まれるものであってもよい。磁鉄鉱として砂鉄を用いることで、フェロコークス中のＦｅの周辺の空隙量が少なくなり、フェロコークスの強度をさらに向上できる。一方、砂鉄は鉄鉱石より細かく比表面積が大きいことから、成型時に用いるバインダーの量が鉄鉱石よりも増える場合がある。さらに、一般的に砂鉄は鉄鉱石よりも高価なので、磁鉄鉱を含む鉄鉱石を用いることで、砂鉄を用いることによるコストの上昇を抑制できる。 Magnetite may be contained not only in iron ore but also in iron sand or dust. By using iron sand as magnetite, the amount of voids around the Fe in the ferro coke is reduced, further improving the strength of the ferro coke. On the other hand, since iron sand is finer and has a larger specific surface area than iron ore, the amount of binder used during molding may be greater than that for iron ore. Furthermore, since iron sand is generally more expensive than iron ore, using iron ore containing magnetite can suppress the increase in costs caused by using iron sand.
以下、本実施形態に係るフェロコークスの製造方法を用いて、鉄鉱石中の鉄の形態（磁鉄鉱及びＦｅＯの含有率）と得られたフェロコークスの品質（強度、反応性）との関係を調査した実施例を説明する。実施例にて使用した鉄鉱石に含まれる磁鉄鉱の含有率および「ＪＩＳ Ｍ ８２１３－１９９５」に記載された方法により測定されたＦｅＯの含有率を表１に示す。 Below, an example is described in which the relationship between the form of iron in iron ore (magnetite and FeO content) and the quality (strength, reactivity) of the obtained ferro-coke was investigated using the ferro-coke manufacturing method according to this embodiment. The magnetite content in the iron ore used in the example and the FeO content measured by the method described in "JIS M 8213-1995" are shown in Table 1.
まず、表１に記載した鉄鉱石（Ａ～Ｇ）のうちの１銘柄を粒径３ｍｍ以下の割合が１００％になるように粒度調整し、この粒度調整された１銘柄の鉄鉱石と、粒径２ｍｍ以下の割合が１００％になるように粒度調整した軟化溶融性の低い配合炭（薬剤添加ｌоｇＭＦの加重平均値：１．０ｌоｇ／ｄｄｐｍ）とを３：７の割合で配合した。そして、高速撹拌機内でバインダーとしてアスファルトピッチ、コールタール、軟ピッチをそれぞれ全原料重量に対し２．４質量％、２．０質量％、３．６質量％添加して１６０℃に加熱しながら混練した。ここで、配合炭の特性は、ビトリニット最大反射率Ｒｏ：１．６１、揮発分ＶＭ：１４．４ｍａｓｓ％、灰分：９．６ｍａｓｓ％である。 First, one of the iron ores (A to G) listed in Table 1 was adjusted in particle size so that the proportion of particles with a particle size of 3 mm or less was 100%, and this adjusted iron ore was mixed in a ratio of 3:7 with a low thermoplasticity blended coal (weighted average of chemical-added log MF: 1.0 log/ddpm) whose particle size was adjusted so that the proportion of particles with a particle size of 2 mm or less was 100%. Then, asphalt pitch, coal tar, and soft pitch were added as binders in a high-speed mixer at 2.4 mass%, 2.0 mass%, and 3.6 mass%, respectively, relative to the total raw material weight, and the mixture was kneaded while heating to 160°C. The properties of the blended coal were vitrinite maximum reflectance Ro: 1.61, volatile matter VM: 14.4 mass%, and ash content: 9.6 mass%.
その後、ロールサイズ６５０ｍｍφ×１０４ｍｍの成型機にて、回転数２ｒｐｍ、線圧は１～４ｔｏｎ／ｃｍで成型し、３０ｍｍ×２５ｍｍ×１８ｍｍ（６ｃｍ３）の卵型の成型物とした。そして、得られた成型物をラボスケールの手法（固定層）で乾留した。具体的には、縦２００ｍｍ、横６０ｍｍ、高さ２００ｍｍの乾留缶に成型物を充填し、最大８５０℃のプログラムヒーティングにより４時間２０分かけて乾留した後、窒素雰囲気で冷却した。 The mixture was then molded in a molding machine with a roll size of 650 mmφ×104 mm at a rotation speed of 2 rpm and a linear pressure of 1 to 4 ton/cm to obtain an egg-shaped molded product of 30 mm×25 mm×18 mm (6 cm 3 ). The molded product was then dry-distilled by a laboratory-scale method (fixed bed). Specifically, the molded product was filled into a dry-distillation vessel with a length of 200 mm, a width of 60 mm, and a height of 200 mm, and dry-distilled for 4 hours and 20 minutes by program heating at a maximum temperature of 850° C., and then cooled in a nitrogen atmosphere.
得られたフェロコークスの強度は、日本工業規格「ＪＩＳ Ｋ ２１５１ コークス類」に規定されたドラム試験における１５０回転後の１５ｍｍ篩上の比率である「ＤＩ（１５０／１５）［－］」（以下、単に「ＤＩ」という。）にて評価した。なお、単位［－］は無次元であることを意味する。フェロコークスの反応性は国際規格「ＡＳＴＭ－Ｄ５３４１ コークス反応性指数（ＣＲＩ）と反応後のコークス強度（ＤＩ）を測定するための標準試験方法」に規定されているＣＲＩ（％）にて評価し、強度と反応性に及ぼす鉄鉱石中の鉄の形態（磁鉄鉱及びＦｅＯの含有率）の影響を調査した。 The strength of the obtained ferro-coke was evaluated by "DI (150/15) [-]" (hereinafter simply referred to as "DI"), which is the ratio of the 15 mm sieve size after 150 revolutions in the drum test specified in the Japanese Industrial Standard "JIS K 2151 Cokes". The unit [-] means that it is dimensionless. The reactivity of the ferro-coke was evaluated by CRI (%) specified in the international standard "ASTM-D5341 Standard Test Method for Measuring Coke Reactivity Index (CRI) and Coke Strength after Reaction (DI)", and the effect of the form of iron in the iron ore (magnetite and FeO content) on the strength and reactivity was investigated.
表１の鉄鉱石中の磁鉄鉱の含有率とＤＩ及びＣＲＩとの関係を図１に示す。ここで、ＤＩの下限値を８０とし、ＣＲＩの下限値を４５％とした。ＤＩの下限値である８０は、高炉の通気性に影響を与えないためのフェロコークスの強度の下限値として設定したものである。また、ＣＲＩの下限値である４５％は、フェロコークスを用いることによる還元材低減効果を得るために必要な下限値として設定したものである。なお、ＤＩの上限値を１００とし、ＣＲＩの上限値を１００％とした。 Figure 1 shows the relationship between the magnetite content in the iron ore in Table 1 and the DI and CRI. Here, the lower limit of DI is set to 80, and the lower limit of CRI is set to 45%. The lower limit of DI, 80, is set as the lower limit of the strength of ferro coke so as not to affect the permeability of the blast furnace. The lower limit of CRI, 45%, is set as the lower limit necessary to obtain the reducing agent reduction effect by using ferro coke. The upper limit of DI is set to 100, and the upper limit of CRI is set to 100%.
図１に示す通り、磁鉄鉱の含有率の増加に伴い、ＤＩは上昇しており、磁鉄鉱の含有率が１２質量％以上でＤＩは目標下限値（８０）以上となった。なお、磁鉄鉱の含有率が１２質量％を下回ると（比較例１参照）、ＤＩは目標下限値（８０）を下回った。ＣＲＩは、磁鉄鉱の含有率の増加とともに低下し、磁鉄鉱の含有率が８０質量％を超える範囲（比較例２参照）で目標下限値（４５％）を下回った。以上の結果、鉄鉱石中の磁鉄鉱の含有率が１２質量％以上８０質量％以下の範囲（本発明例１～５）で、高強度かつ高反応性のフェロコークスが製造できることが明らかとなった。 As shown in Figure 1, the DI increased with increasing magnetite content, and when the magnetite content was 12 mass% or more, the DI was equal to or greater than the target lower limit (80). When the magnetite content was below 12 mass% (see Comparative Example 1), the DI was below the target lower limit (80). The CRI decreased with increasing magnetite content, and was below the target lower limit (45%) when the magnetite content was in the range of more than 80 mass% (see Comparative Example 2). As a result of the above, it was revealed that high-strength, highly reactive ferro-coke could be produced when the magnetite content in iron ore was in the range of 12 mass% to 80 mass% (Examples 1 to 5 of the present invention).
次に、表１に記載した通り、日本工業規格「ＪＩＳ Ｍ ８２１３－１９９５」の規定に基づいて分析したＦｅＯの含有率とＤＩ及びＣＲＩとの関係を図２に示す。ここで、図１及び図２に示す通り、磁鉄鉱の含有率とＦｅＯの含有率とは相関がある。そして、図１を用いて述べたように、ＤＩ及びＣＲＩの下限値を考慮すると、フェロコークスの強度と反応性とを両立できるＦｅＯの含有率の範囲は３．０質量％以上２５．０質量％以下（本発明例１～５）であった。 Next, as shown in Table 1, the relationship between the FeO content, DI, and CRI analyzed based on the provisions of the Japanese Industrial Standard "JIS M 8213-1995" is shown in Figure 2. Here, as shown in Figures 1 and 2, there is a correlation between the magnetite content and the FeO content. And, as described using Figure 1, when the lower limit values of DI and CRI are taken into consideration, the range of FeO content that can balance the strength and reactivity of ferro-coke is 3.0 mass% or more and 25.0 mass% or less (Examples 1 to 5 of the present invention).
なお、薬剤添加ｌоｇＭＦの加重平均値が３．０ｌоｇ／ｄｄｐｍである配合炭を、表１に記載した鉄鉱石（Ａ～Ｇ）に配合した場合についても同様に実施したが、図１及び図２を用いて説明した磁鉄鉱及びＦｅＯの含有率と同様の範囲で、高強度かつ高反応性のフェロコークスが製造可能であることを確認した。この結果から、軟化溶融性の低い配合炭を用いた場合でも、鉄鉱石中の磁鉄鉱の含有率又はＦｅＯの含有率を適正な範囲とすることで、高強度かつ高反応性のフェロコークスを製造可能であることを確認した。 The same experiment was also carried out when a coal blend with a weighted average of chemical-added logMF of 3.0 log/ddpm was blended with the iron ores (A to G) listed in Table 1, and it was confirmed that high-strength, highly reactive ferro-coke could be produced within the same range of magnetite and FeO contents as explained using Figures 1 and 2. From these results, it was confirmed that even when a coal blend with low thermoplasticity is used, high-strength, highly reactive ferro-coke can be produced by setting the magnetite content or FeO content in the iron ore within an appropriate range.
続いて、鉄鉱石Ａ～Ｇを混合し、種々の磁鉄鉱の含有率に調整した配合鉄鉱石６種（配合１～６）を使用して、図１及び図２を用いて説明した方法と同様に、ＤＩ及びＣＲＩとの関係を調査した。鉄鉱石Ａ～Ｇの配合割合および磁鉄鉱、ＦｅＯの含有率を表２に示す。 Next, iron ores A to G were mixed and adjusted to various magnetite contents to create six iron ore blends (blends 1 to 6), and the relationship between DI and CRI was investigated in the same manner as described using Figures 1 and 2. The blending ratios of iron ores A to G and the magnetite and FeO contents are shown in Table 2.
配合鉄鉱石（配合１～６）における磁鉄鉱の含有率は５～９０質量％であり、成分分析値のＦｅＯの含有率は２～２９質量％となった。この配合鉄鉱石（配合１～６）及び薬剤添加ｌоｇＭＦの加重平均値が１．０ｌоｇ／ｄｄｐｍである配合炭を用いて製造したフェロコークスの強度（ＤＩ）および反応性（ＣＲＩ）を評価した結果を、図３および図４に示す。 The magnetite content in the iron ore blends (blends 1 to 6) was 5 to 90% by mass, and the FeO content in the component analysis was 2 to 29% by mass. The strength (DI) and reactivity (CRI) of ferro-coke produced using these iron ore blends (blends 1 to 6) and blended coal with a weighted average chemical-added logMF of 1.0 log/ddpm are shown in Figures 3 and 4.
図３は、表２に記載した磁鉄鉱の含有率とＤＩ及びＣＲＩとの関係を示す。図４は、表２に記載したＦｅＯの含有率とＤＩ及びＣＲＩとの関係を示す。図３及び図４のいずれの結果も、図１及び図２と同様の範囲、つまり、鉄鉱石中の磁鉄鉱の含有率が１２質量％以上８０質量％以下である範囲（本発明例６～９）、又は、ＦｅＯの含有率が３．０質量％以上２５．０質量％以下の範囲（本発明例６～９）で、高強度かつ高反応性のフェロコークスが製造可能であることが分かった。 Figure 3 shows the relationship between the magnetite content and the DI and CRI as shown in Table 2. Figure 4 shows the relationship between the FeO content and the DI and CRI as shown in Table 2. The results in both Figures 3 and 4 show that high-strength, highly reactive ferro-coke can be produced in the same range as in Figures 1 and 2, that is, in the range where the magnetite content in iron ore is 12 mass% or more and 80 mass% or less (Examples 6 to 9 of the present invention) or the FeO content is 3.0 mass% or more and 25.0 mass% or less (Examples 6 to 9 of the present invention).
以上の結果から、本発明に係るフェロコークスの製造方法を用いることで、単味の鉄鉱石のみならず配合鉄鉱石でも、高強度かつ高反応性のフェロコークスが製造可能であることが確認できた。また、表１に示した鉄鉱石Ａ、鉄鉱石Ｇのように、単味では磁鉄鉱やＦｅＯの含有率が先述した範囲を満たさない鉄鉱石であっても、配合鉄鉱石とすることで、高強度かつ高反応性のフェロコークスとして製造が可能であることが確認できた。 From the above results, it was confirmed that by using the ferro coke manufacturing method according to the present invention, it is possible to manufacture high-strength, highly reactive ferro coke not only from pure iron ore but also from blended iron ore. It was also confirmed that even if the iron ore, such as iron ore A and iron ore G shown in Table 1, does not satisfy the above-mentioned range of magnetite or FeO content when used purely, it is possible to manufacture high-strength, highly reactive ferro coke by using it as a blended iron ore.
Claims (4)
前記鉄鉱石は、磁鉄鉱の含有率が１２質量％以上８０質量％以下であり、
前記石炭は、芳香環を有する１級もしくは２級アミン系化合物であるＮ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミンを１０質量％添加して測定されるギーセラー最高流動度ＭＦの常用対数値ｌоｇＭＦの値が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下である単味石炭または前記ギーセラー最高流動度ＭＦの常用対数値ｌоｇＭＦの加重平均値が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下である配合炭である、フェロコークスの製造方法。 A method for producing ferro-coke, comprising mixing coal and iron ore to prepare a mixed raw material, molding the mixed raw material, and carbonizing the molded product,
The iron ore has a magnetite content of 12% by mass or more and 80% by mass or less,
The coal is a pure coal having a common logarithm value logMF of the Gieseler maximum fluidity MF, measured by adding 10 mass% of N,N'-di-2-naphthyl-p-phenylenediamine, which is a primary or secondary amine compound having an aromatic ring, of 1.0 log/ddpm or more and 3.0 log/ddpm or less, or a blended coal having a weighted average value of the common logarithm value logMF of the Gieseler maximum fluidity MF of 1.0 log/ddpm or more and 3.0 log/ddpm or less .
前記鉄鉱石は、ＦｅＯの含有率が３質量％以上２５質量％以下であり、
前記石炭は、芳香環を有する１級もしくは２級アミン系化合物であるＮ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミンを１０質量％添加して測定されるギーセラー最高流動度ＭＦの常用対数値ｌоｇＭＦの値が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下である単味石炭または前記ギーセラー最高流動度ＭＦの常用対数値ｌоｇＭＦの加重平均値が１．０ｌｏｇ／ｄｄｐｍ以上３．０ｌｏｇ／ｄｄｐｍ以下である配合炭である、フェロコークスの製造方法。 A method for producing ferro-coke, comprising mixing coal and iron ore to prepare a mixed raw material, molding the mixed raw material, and carbonizing the molded product,
The iron ore has an FeO content of 3% by mass or more and 25% by mass or less,
The coal is a pure coal having a common logarithm value logMF of the Gieseler maximum fluidity MF, measured by adding 10 mass% of N,N'-di-2-naphthyl-p-phenylenediamine, which is a primary or secondary amine compound having an aromatic ring, of 1.0 log/ddpm or more and 3.0 log/ddpm or less, or a blended coal having a weighted average value of the common logarithm value logMF of the Gieseler maximum fluidity MF of 1.0 log/ddpm or more and 3.0 log/ddpm or less .
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