JP4436153B2 - Blast furnace slag reformer and its reforming method - Google Patents
Blast furnace slag reformer and its reforming method Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims description 72
- 238000002407 reforming Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 claims description 48
- 239000010883 coal ash Substances 0.000 claims description 45
- 239000003607 modifier Substances 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 8
- 239000004071 soot Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000002440 industrial waste Substances 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000000292 calcium oxide Substances 0.000 description 26
- 235000012255 calcium oxide Nutrition 0.000 description 25
- 230000005484 gravity Effects 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000010583 slow cooling Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2400/00—Treatment of slags originating from iron or steel processes
- C21B2400/02—Physical or chemical treatment of slags
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Manufacture Of Iron (AREA)
- Furnace Details (AREA)
Description
本発明は、冷却固化した高炉滓を改質するための改質材及び改質方法に関するものである。 The present invention relates to a reforming material and a reforming method for reforming a cooled and solidified blast furnace furnace.
従来より、溶鉱炉から排出された溶融高炉滓は、徐冷して固める徐冷滓、或いは溶融状態の高炉滓に水を掛けて急冷し水砕にする処理が行われている。
前者の徐冷滓の用途として主に路盤材に利用されていたが、徐冷滓は気孔が多く比重も小さいので、緻密で比重が高くて硬い徐冷滓（徐冷高炉滓）が求められていた。
また、後者の水砕に関しては、主にセメント原料として利用されていたが、新しい用途として「砂代替」としての硬質水砕の造り込み技術が望まれていた。すなわち、気泡が少なく緻密で比重の高い水砕が求められていた。これらの問題に対し、火力発電所等から排出される産業廃棄物である石炭灰（通称フライアッシュと呼ばれ、ＳｉＯ2 とＡｌ2 Ｏ3 を主成分とする）を溶融高炉滓に添加して改質し、高炉徐冷滓或いは高炉水砕を人工土木用骨材として活用する試みも考えられている。
Conventionally, the molten blast furnace slag discharged from the blast furnace has been gradually cooled and solidified, or a molten blast furnace slag is rapidly cooled by watering and crushed.
Although the former was used mainly for roadbed materials as a slow cooling kit, the slow cooling kit has many pores and small specific gravity, so a dense, high specific gravity, hard annealing kit (slow cooling blast furnace kit) is required. It was.
In addition, the latter water granulation has been mainly used as a raw material for cement, but as a new application, a technique for building in hard water granulation as “sand substitute” has been desired. That is, there has been a demand for water granulation with less bubbles and high density. To solve these problems, coal ash (commonly called fly ash, mainly composed of SiO 2 and Al 2 O 3 ), which is industrial waste discharged from thermal power plants, is added to the molten blast furnace slag. Attempts have also been made to modify and use blast furnace slow cooling or granulated blast furnace as an aggregate for artificial civil engineering.
この例としては、特許文献１、特許文献２に提案されているように、石炭灰単身（粉体）を大樋の溶銑中にインジェクションして、溶銑の熱を利用しながら溶銑の上に浮かんだ溶融高炉滓に石炭灰を溶かし込んで、徐冷滓や水砕を作る方法がある。また、特許文献３に提案されているように、石炭灰にＣａＯ含有物質を混合して塩基度を高めてから溶融高炉滓に添加する方法がある。
As an example of this, as proposed in
しかし、特許文献１及び２に提案されている方法では、溶融高炉滓に石炭灰単身で添加しているために石炭灰の塊が添加場所の耐火物、例えば樋や鍋に付着成長して、添加操業を著しく阻害し、付着した石炭灰主体の焼結状付着物（以下焼結体とも称す）は溶融高炉滓に全く溶けなくなる問題が生じ、操業上安定した石炭灰の添加が困難で、高炉滓の改質が継続して行えないものであった。また、たとえ、オペレーターが付着した焼結体を突き落としつつ添加したとしても、高炉滓が冷却固化した後でも突き落とした塊状の焼結体は異物として高炉滓に混じり、赤色或いは黒色を呈して用途側から敬遠されるのに加えて、高炉滓の粉砕工程でこれら塊状焼結体は粉化して粒度調整に支障をきたすなど、品質上の課題も生じていた。更に、特許文献３に提案されている方法では、塩基度を上げる目的からＣａＯ含有物を多量添加せねばならず、添加した後の溶融高炉滓の温度が下がって添加物の未溶解が生じたり、スラグの粘性が上がって添加後のスラグが樋等の耐火物に付着して操業上の障害になるなどの課題が生じていた。
However, in the methods proposed in
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手段１は、冷却固化される前の溶融高炉滓に添加される改質材であって、石炭灰と換算ＣａＯ量を３０質量％以上含有するＣａ含有物の混合粉粒体であり、前記Ｃａ含有物中の換算ＣａＯ量（Ｃａ含有物中のＣａ分をＣａＯに換算した量）を前記石炭灰の重量に対して５〜６０質量％になるように配合したことを特徴とする高炉滓の改質材である。
また、手段２は、前記Ｃａ含有物がダスト、鉄鋼スラグ、及び産業廃棄物のいずれかである手段１の高炉滓の改質材である。
手段３は、溶融高炉滓に改質材を添加した後、冷却固化して高炉滓とするに際して、溶融高炉滓に対して手段１又は２に記載の改質材を１〜３０質量％添加した後、冷却して徐冷滓又は水砕とする高炉滓の改質方法である。
手段４は、前記溶融高炉滓に前記改質材を１カ所又は複数カ所で添加し、かつ、その添加する１カ所当たりの添加量が１０質量％以下である手段３記載の高炉滓の改質方法である。
The present invention has been made to solve the above problems, and
Moreover, it means 2, the Ca-containing substance Hurghada strike a steel slag, and industrial modifier of blast furnace slag means 1 is either waste.
前記Ｃａ含有物としては、生石灰、生石灰ダスト（生石灰製造プラントから発生するダスト）、石灰石、石膏等建築廃材、製糖業から排出される漂白処理後スラッジ（ＣａＣＯ3 ）、鉄鋼業から排出される溶銑脱燐滓、溶銑脱珪滓、転炉滓、電気炉滓、連続鋳造滓、造塊滓及びＣａＯ含有鉱物等があり、そして、それらの粒度は溶解性の点から２ｍｍ以下のものが好ましい。もちろん、これらを複数混合して用いてもよい。
また、上記石炭灰の成分としては、その主成分であるＳｉＯ2 とＡｌ2 Ｏ3 の質量％の和が６５％以上のものが望ましい。何故なら、ＳｉＯ2 とＡｌ2 Ｏ3 のいずれも、高炉滓に溶けて高炉滓の融点を下げる効果が有り、より低い温度で固化するため、固化に至るまでに窒素ガス、亜硫酸ガス等の脱気がより進み、緻密で強固な高炉滓になるからである。
Examples of the Ca-containing material include quick lime, quick lime dust (dust generated from a quick lime production plant), limestone, gypsum and other construction waste, sludge after bleaching treatment (CaCO 3 ) discharged from the sugar industry, and hot metal discharged from the steel industry. There are dephosphorizing iron, hot metal desiliconizing iron, converter iron, electric furnace iron, continuous casting iron, ingot iron, CaO-containing mineral, etc., and the particle size thereof is preferably 2 mm or less from the viewpoint of solubility. Of course, a mixture of these may be used.
As the component of the coal ash, mass% of the sum of SiO 2 and Al 2 O 3 which is a main component is preferable not less than 65%. This is because both SiO 2 and Al 2 O 3 have the effect of lowering the melting point of the blast furnace slag by melting in the blast furnace slag and solidify at a lower temperature, so that nitrogen gas, sulfurous acid gas, etc. are removed before solidification. This is because the spirit is more advanced and it becomes a dense and strong blast furnace.
本発明によれば、改質材の焼結体塊状化を抑制できるので、これら塊状焼結体の耐火物への付着成長及び未溶解等の操業上のトラブルが無く、改質材が容易に溶融高炉滓に添加可能となると共に溶融高炉滓にスムーズに溶解することから、冷却固化後の高炉滓が緻密となり比重が増大して、高炉滓の付加価値が高まり、用途も拡大する等の効果を有するものであり、この分野にもたらす効果は極めて大きい。 According to the present invention, since agglomeration of the sintered body of the reforming material can be suppressed, there are no operational troubles such as adhesion growth and undissolution of the massive sintered body on the refractory, and the reforming material can be easily obtained. Since it can be added to the molten blast furnace slag and melts smoothly into the molten blast furnace slag, the blast furnace slag after cooling and solidification becomes dense, the specific gravity increases, the added value of the blast furnace slag increases, and the use is expanded. The effect brought about in this field is extremely large.
以下、本発明の実施の形態を詳細に説明する。
本発明者らは、石炭灰を単身で溶融高炉滓に添加すると、前記のように石炭灰の耐火物への付着問題が顕在化し、その形態になった石炭灰は溶融高炉滓に溶けなくなるため、その原因を調査にするために、小型坩堝内の溶融高炉滓に石炭灰を単身添加する実験を行った。
この実験は高炉から排出した高炉滓を小型坩堝にて溶解し、そこに表１に示す成分を有する石炭灰を溶融高炉滓の６質量％に相当する量添加して、溶解の様子を観察した。その結果、添加された石炭灰は溶融高炉滓にはなかなか溶けず、塊状に成長して坩堝壁に付着するか溶融高炉滓の上部表面に浮上した儘となった。
Hereinafter, embodiments of the present invention will be described in detail.
When the present inventors add coal ash alone to the molten blast furnace slag, as described above, the problem of adhesion of coal ash to the refractory material becomes obvious, and the coal ash in that form cannot be dissolved in the molten blast furnace slag. In order to investigate the cause, an experiment was conducted in which coal ash was added alone to the molten blast furnace in a small crucible.
In this experiment, the blast furnace slag discharged from the blast furnace was melted in a small crucible, and coal ash having the components shown in Table 1 was added thereto in an amount corresponding to 6% by mass of the molten blast furnace slag, and the state of melting was observed. . As a result, the added coal ash did not readily melt in the molten blast furnace slag, and it grew into a lump and adhered to the crucible wall or became a soot that floated on the upper surface of the molten blast furnace slag.
本発明者らは、この現象のメカニズムを解明するため、添加した石炭灰の未溶解部（坩堝付着部）を採取し、光学顕微鏡調査及びＸ線回折調査を行った。
その光学顕微鏡調査から、この未溶解石炭灰は極めて気孔の多い、「断熱煉瓦」状の形態をしており、更に、Ｘ線回折調査から、未溶解石炭灰中に（１）Ｍｕｌｌｉｔｅ（ムライト、３Ａｌ2 Ｏ3 ・２ＳｉＯ2 ：融点は１９３４℃）及び（２）Ｃｒｉｓｔｏｂａｌｉｔｅ（クリストバライト、ＳｉＯ2 ：融点は１７３４℃）が存在している事が確認された。即ち、石炭灰が溶融高炉滓に添加されると溶融高炉滓の熱で加熱され、上記（１）及び（２）の極めて高融点の結晶体が新たに生成している事が判明した。
In order to elucidate the mechanism of this phenomenon, the present inventors collected an undissolved portion (crucible adhering portion) of the added coal ash, and performed an optical microscope survey and an X-ray diffraction survey.
From the optical microscope investigation, this undissolved coal ash is in the form of “insulated brick” with a lot of pores. Furthermore, from the X-ray diffraction investigation, (1) Mullite (mullite, 3Al 2 O 3 .2SiO 2 : melting point 1934 ° C.) and (2) Cristobalite (Cristobalite, SiO 2 : melting point 1734 ° C.) were present. That is, it was found that when coal ash was added to the molten blast furnace slag, it was heated by the heat of the molten blast furnace slag, and the extremely high melting point crystals of the above (1) and (2) were newly generated.
これらの高融点結晶体（固体）は、石炭灰の一部溶けた融液をバインダーとして焼結反応を起こして焼結体として成長し、耐火物に付着したり、「断熱煉瓦」状の気孔の多い塊状形態となるために伝熱律速（熱がなかなか伝わらない）により上記焼結体の塊が未溶解で残存することが判明した。これら焼結体には上記の極めて融点の高い結晶体が多量に存在するため、この焼結体自身が１５００℃程度の溶融高炉滓にはもはや溶けない強固なものになっている事も判明した。 These high-melting-point crystals (solid) grow as a sintered body by using a melt in which coal ash is partly melted as a binder, grow as a sintered body, adhere to refractories, and form pores in the form of “insulating bricks” Therefore, it was found that the sintered compact lump remains undissolved by heat transfer rate control (heat is not easily transmitted). Since these sintered bodies contain a large amount of the above-mentioned crystals having a very high melting point, it has also been found that the sintered bodies themselves are strong and can no longer be melted in a molten blast furnace at about 1500 ° C. .
そこで、本発明者らは、上記の高融点結晶体が生成しない為の方策を実験、検討を重ねた。この結果、Ｃａ含有物を石炭灰に添加すると該石炭灰が高炉滓にスムーズに溶解し、前記（１）及び（２）を含む焼結体の生成が殆ど認められなくなる事を発見した。
これは、ＣａＯを加える事により改質材の成分がＳｉＯ2 −Ａｌ2 Ｏ3 −ＣａＯの３元系酸化物となるため、石炭灰を単身添加した際に生成したＳｉＯ2 −Ａｌ2 Ｏ3 の２元系酸化物に起因する前記（１）及び（２）の高融点結晶体の生成とそれらの焼結体の成長が抑制される効果によるものと判明した。すなわち、ＣａＯを加えた石炭灰を添加した後に冷却固化した高炉滓には上記焼結体は全く生成しておらず、添加物が溶融高炉滓に均一に溶解していることが、顕微鏡観察により明らかとなった。
また、上記改質材を粒径１ｍｍ〜１０ｍｍ程度の粒状に成形して添加しても、粉体と全く同じように問題無く溶融高炉滓に溶解することも確認した。
なお、Ｃａ含有物のＣａの形態としては、ＣａＯ以外に石灰石に代表されるＣａＣＯ3 、石膏に代表されるＣａＳＯ4 が有るが、これらは溶融高炉滓への添加時の温度では熱分解して形態がＣａＯに変わり、元々ＣａＯの形態のＣａ含有物と同等の効果を発揮する。
Therefore, the present inventors have experimented and studied measures for preventing the above-mentioned high melting point crystal from being formed. As a result, it was discovered that when Ca-containing material is added to coal ash, the coal ash is smoothly dissolved in the blast furnace soot, and the formation of the sintered body containing (1) and (2) is hardly recognized.
This is because, by adding CaO, the component of the modifier becomes a ternary oxide of SiO 2 —Al 2 O 3 —CaO, and thus SiO 2 —Al 2 O 3 produced when coal ash is added alone. It has been found that this is due to the effect of suppressing the formation of the high-melting-point crystals of (1) and (2) and the growth of those sintered bodies due to the binary oxide. That is, the sintered body was not formed at all in the blast furnace slag that had been cooled and solidified after adding the coal ash to which CaO was added, and it was confirmed by microscopic observation that the additive was uniformly dissolved in the molten blast furnace slag. It became clear.
Further, it was confirmed that even when the modifier was added after being formed into granules having a particle size of about 1 mm to 10 mm, it was dissolved in the molten blast furnace without any problem just like the powder.
In addition to CaO, there are CaCO 3 typified by limestone and CaSO 4 typified by gypsum, which are pyrolyzed at the temperature at the time of addition to the molten blast furnace. The form changes to CaO and exhibits the same effect as the Ca-containing material originally in the form of CaO.
また、上記改質材を添加した後に、冷却固化した高炉滓は、気泡が極めて少ない緻密なスラグとなっており、改質材を添加しない従来の高炉滓に比較して比重が重くて硬い強固なスラグになっており、高品質であるし、景観材料等の新規用途としての活用が可能であることが判明した。 In addition, the blast furnace slag that has been cooled and solidified after the addition of the above-mentioned reformer is a dense slag with extremely few bubbles, and has a higher specific gravity and is harder and harder than the conventional blast furnace slag without the addition of a reformer. It has been found that the slag has a high quality and can be used for new uses such as landscape materials.
更に、本発明者らは、Ｃａ含有物による効果発現の条件を明確にするために、石炭灰とＣａ含有物との配合粉粒体（混合粉粒体）である改質材に具備すべき分条件を明らかにするために、前述した小型坩堝を用いて系統的な実験を重ねた。 Furthermore, the present inventors should equip with the modifier which is a compounding granular material (mixed granular material) of coal ash and Ca containing material in order to clarify the conditions of the effect expression by Ca containing material. In order to clarify the minute conditions, systematic experiments were repeated using the small crucible described above.
先ず、石炭灰に配合するＣａ含有物中の換算ＣａＯ量の割合を種々変更した改質材を用いて焼結体の生成状態を確認する実験を行い図１に示す結果を得た。
なお、この際に改質材に使用した石炭灰は上記表１に示す成分と含有量を有するものであり、更に、Ｃａ含有物としては表２に示す成分と含有量を有する溶銑脱燐滓で、この改質材を添加する溶融高炉滓の温度は１４５０℃とした。また、溶融高炉滓に対する改質材の添加量は１０質量％とした。
First, an experiment for confirming the production state of the sintered body was performed using the modifiers in which the ratio of the converted CaO amount in the Ca-containing material to be blended with the coal ash was changed, and the results shown in FIG. 1 were obtained.
The coal ash used for the modifier at this time has the components and contents shown in Table 1 above, and the Ca-containing material contains hot metal dephosphorized iron having the components and contents shown in Table 2. Therefore, the temperature of the molten blast furnace to which this modifier was added was 1450 ° C. Further, the amount of the modifier added to the molten blast furnace slag was 10% by mass.
図１からわかるように、石炭灰に対してＣａ含有物の換算ＣａＯ量の配合割合が５質量％未満だと、石炭灰の中のＳｉＯ2 分とＡｌ2 Ｏ3 分から生成される高融点結晶の焼結体の成長を抑制することができず、坩堝壁への付着或いは塊状のまま溶けずに溶融高炉滓の上面に浮上、残留して未溶解として残る石炭灰の割合が多く、操業上、又は高炉滓の品質上好ましくない。一方、配合割合が６０質量％を超えると、焼結体の塊状化成長は抑制できるが、換算ＣａＯ量過多による改質材の未溶解が生ずる。
従って、石炭灰に対するＣａ含有物の換算ＣａＯ量の配合割合は５〜６０質量％が好ましい。
As can be seen from FIG. 1, when the blending ratio of the Ca content equivalent to Ca ash is less than 5% by mass with respect to coal ash, refractory crystals generated from SiO 2 and Al 2 O 3 in coal ash. It is difficult to suppress the growth of the sintered body, and there is a large proportion of coal ash that remains on the upper surface of the molten blast furnace without adhering to the crucible wall or melting as a lump and remaining undissolved. Or, it is not preferable in terms of the quality of the blast furnace. On the other hand, when the blending ratio exceeds 60% by mass, the agglomeration growth of the sintered body can be suppressed, but the undissolved material of the modifying material due to an excessive amount of converted CaO occurs.
Therefore, the blending ratio of the converted CaO amount of the Ca-containing material to the coal ash is preferably 5 to 60% by mass.
更に、Ｃａ含有物の換算ＣａＯ量が少な過ぎると、多量の改質材を溶融高炉滓に添加する必要も発生することの懸念から、本発明者らは種々のＣａ含有物（例えば、ダスト、鉄鋼スラグ、産業廃棄物等）を使った実験を重ねた。この結果、Ｃａ含有物の換算ＣａＯ量が３０質量％以上含有することが好ましいことが判明した。３０％未満では、改質材中のＣａＯ以外の成分が溶融高炉滓に多量混入するために、改質材を高炉滓に添加した際の温度降下が大きくなるし、本来の石炭灰を主成分とする改質材としての効果が十分に得られず、好ましくない。 Furthermore, since there is a need to add a large amount of a modifier to the molten blast furnace furnace when the converted CaO amount of the Ca-containing material is too small, the present inventors have various Ca-containing materials (for example, dust, Experiments using steel slag, industrial waste, etc.) were repeated. As a result, it has been found that the Ca-containing material preferably has a reduced CaO content of 30% by mass or more. If it is less than 30%, components other than CaO in the reforming material are mixed in a large amount in the molten blast furnace so that the temperature drop when adding the reforming material to the blast furnace becomes large, and the original coal ash is the main component. It is not preferable because the effect as a modifier is not sufficiently obtained.
また、図２は、溶融高炉滓に対する本発明の改質材の添加比率と冷却固化後の高炉滓の比重測定値との関係を示す図である。改質材添加比率が１質量％未満だと、冷却固化後の高炉滓の比重の増加が僅かであるが、１質量％を超えると改質材の効果が発現して比重が大幅に増大する。しかし、改質材の添加比率が３０質量％を超えると、高炉滓の比重は増大する反面、改質材の顕熱による溶融高炉滓の温度低下が著しくなり、操業に支障をきたす。すなわち、高融点結晶体の生成は無いが、低温の為に溶融高炉滓の耐火物への付着残留傾向が強くなり、操業後の耐火物メンテナンスの負荷が大きくなる。従って、溶融高炉滓に対する本発明の改質材添加比率は１〜３０質量％である。
なお、この知見は小型坩堝でのラボテストのみでなく、実炉試験においても全く同様な結果が確認された。
ここで、図２の縦軸は、高炉滓を乾燥した後の嵩比重を測定したものであり、絶乾比重が大きくなる程、それと対応して吸水率も低減するメリットが得られる。
Moreover, FIG. 2 is a figure which shows the relationship between the addition ratio of the modifier of this invention with respect to a molten blast furnace slag, and the specific gravity measured value of the blast furnace slag after cooling solidification. If the modifier addition ratio is less than 1% by mass, the increase in specific gravity of the blast furnace after cooling and solidification is slight, but if it exceeds 1% by mass, the effect of the modifier is manifested and the specific gravity increases significantly. . However, if the addition ratio of the reforming material exceeds 30% by mass, the specific gravity of the blast furnace slag increases, but the temperature of the molten blast furnace slag decreases due to the sensible heat of the reforming material, which hinders operation. That is, although there is no generation of a high melting point crystal, the tendency to adhere to the refractory of the molten blast furnace is increased due to the low temperature, and the load of refractory maintenance after operation increases. Therefore, the modifier addition ratio of the present invention relative to the molten blast furnace is 1 to 30% by mass.
This finding was confirmed not only in a laboratory test using a small crucible but also in an actual furnace test.
Here, the vertical axis in FIG. 2 is obtained by measuring the bulk specific gravity after drying the blast furnace slag, and as the absolute dry specific gravity increases, the merit that the water absorption rate is correspondingly reduced can be obtained.
改質材の添加量が多い場合は、１カ所に集中添加するよりも、溶融高炉滓と改質材の接触面積を大きくするために、改質材を溶融高炉滓中に添加する位置を複数カ所とすることが局部温度低下に伴う耐火物への付着を防止すると共に添加した改質材の溶解を加速させる観点から好ましい。その１カ所当たりの添加量としては、高炉滓に対して１０質量％以下が好ましい。 When there is a large amount of modifier added, multiple locations where modifiers are added to the molten blast furnace slag in order to increase the contact area between the molten blast furnace slag and the modifier rather than concentrated addition at one location. It is preferable from the viewpoint of preventing the adhesion to the refractory accompanying the local temperature drop and accelerating the dissolution of the added modifier. The addition amount per one is preferably 10% by mass or less with respect to the blast furnace.
溶融高炉滓への改質材の添加は、高炉の出銑孔から冷却ピットまでにおいて高炉滓が溶融状態に有る場所ならば、どこを利用しても構わない。例えば、出銑孔からスキンマ（溶銑と高炉滓を分離する装置）までの大樋、分離した後のノロ樋（滓樋）或いは溶融高炉滓中の粒鉄を回収する為の流銑鍋（流銑鉢とも称す）、更に、徐冷滓にする場合はピットへの落ち口やピット内に添加しても構わない。溶融高炉滓を搬送する滓鍋に添加しても構わない。また、これらの場所を複数使用しても構わない。添加方式としては、上方から粉粒状で投入しても良いし、粉体状態でスラグ中に吹き込んでも構わない。 The addition of the modifying material to the molten blast furnace slag may be performed anywhere as long as the blast furnace slag is in a molten state from the blast furnace outlet hole to the cooling pit. For example, a large bowl from the tap hole to the skinma (a device that separates the molten iron and the blast furnace), a non-rolled rice cake (seed) after separation, or a ladle for collecting granular iron in the molten blast furnace cake (fluid) In addition, it may be added to the pit or the pit when it is gradually cooled. You may add to the ladle which conveys a molten blast furnace firewood. A plurality of these locations may be used. As an addition method, it may be added in powder form from above, or may be blown into the slag in a powder state.
以下、本発明の実施例について図３を参照して詳細に説明する。
１．実機での改質材添加方法
溶鉱炉から排出された溶融高炉滓がドライピット或いは水砕設備８に到着するまでの流路に、Ｃａ含有物を混合した石炭灰からなる改質材を添加し、徐冷滓又は水砕にした。高炉１の下部に設けられた出銑口２から溶銑と共に流れ出る溶融高炉滓に対して、図３の黒丸印で示した位置で改質材を添加した。すなわち、大樋３、スキンマ４で溶銑と溶融高炉滓を分離した後の滓樋５、溶融高炉滓中の流銑を回収するための容器である流銑鍋６、水砕設備８の直前の水砕・放流樋７、放流ピット９のピット落ち口１０、そして放流ピット９内のいずれかの場所を、改質材添加量に応じて改質材添加場所とした。
２．溶融高炉滓の化学成分
表３に示す化学成分の溶融高炉滓に上述の如く改質材を添加した。
Hereinafter, an embodiment of the present invention will be described in detail with reference to FIG.
1. Reformer addition method in actual machine Add the reformer made of coal ash mixed with Ca-containing material to the flow path until the molten blast furnace slag discharged from the blast furnace arrives at the dry pit or the
2. Chemical component of molten blast furnace slag As described above, the modifier was added to the molten blast furnace slag having chemical components shown in Table 3.
３．使用した石炭灰の化学成分
表１に記載した成分の石炭灰を使用した。
４．使用したＣａ含有物の化学成分
Ｃａ含有物は、表４の欄外に示す主成分を有するものを使用した。なお、溶銑脱燐滓は表２に記載した成分と同じである。
その結果を具体的に表４、表５に示す。
3. Chemical composition of coal ash used Coal ash having the components described in Table 1 was used.
4). As the chemical component Ca-containing material of the Ca-containing material used, one having the main components shown in the column of Table 4 was used. The hot metal dephosphorization is the same as the components described in Table 2.
The results are specifically shown in Tables 4 and 5.
表４、表５は、本発明例及び比較例を示したものであり、実施例１〜実施例１０は、本発明の条件の範囲内であることから、改質材添加に伴う耐火物への付着物（未溶解焼結体の生成、成長或いは温度低下増大に伴う溶融高炉滓の樋内面或いは流銑鍋内面の耐火物への付着）起因の操業トラブルを惹起すること無く、改質材を継続添加でき、これにより、石炭灰の未溶解比率も低く抑えられ、比重の大きい高炉滓が得られた。なお、実施例８の滓搬送鍋とは、図３の流銑鍋６から流出した溶融高炉滓を収容して、他の場所に搬送する鍋（図示せず）である。
Tables 4 and 5 show examples of the present invention and comparative examples. Examples 1 to 10 are within the range of the conditions of the present invention. Reducing material without causing operational troubles due to deposits (adhering to the refractory on the inner surface of the molten blast furnace or the inner surface of the ladle as the unmelted sintered body forms, grows or decreases in temperature) As a result, the undissolved ratio of coal ash was kept low, and a blast furnace slag with high specific gravity was obtained. In addition, the firewood conveyance pot of Example 8 is a pot (not shown) which accommodates the molten blast furnace fired which flowed out from the floating
一方、比較例１及び比較例５では、改質材の石炭灰へのＣａ含有物中の換算ＣａＯの配合比率が本発明範囲の下限を外れた為に、石炭灰が溶融高炉滓にスムーズに溶融せずに高融点結晶の焼結体が生成し、改質材添加による改質効果が得られず、いずれも比重が小さい高炉滓になってしまった。
比較例２は、比較例１とは逆に石炭灰へのＣａ含有物中換算ＣａＯの配合比率が本発明範囲の上限を外れる多量配合となっているため、焼結体の生成は無いものの改質材を構成する粒子同士が十分に溶け合わず、未溶解物が残留して、改質効果が十分得られず、冷却後の高炉滓の比重は低い値となった。
比較例３は、改質材の溶融高炉滓への添加量が本発明範囲の下限を外れた為に、改質材による改質効果が不足して高炉滓の比重は小さいものであった。
また、比較例４は、比較例３とは逆に改質材の溶融高炉滓への添加量が本発明範囲の上限を外れた為に、該改質材に奪われる顕熱が大きくなり、溶融高炉滓の改質材添加部分の温度が局部的に大きく下がり、改質材は溶けるものの添加後の溶融高炉滓の粘性が上がり、改質材添加後の大樋や流銑鍋の内面耐火物への溶融高炉滓の付着量が増大して、処理後の付着スラグ除去等、煩雑な作業を伴うことになり、操業上の支障が生じた。比較例６は、Ｃａ含有物中の換算ＣａＯ含有量が１０．７質量％と低いため、ＣａＯ以外の成分が溶融高炉滓に多量混入するために、改質材を添加した際の温度降下が大きくなり、操業上の支障をきたし、石炭灰を主成分とする改質材としての効果が十分に得られず、比重は小さい物となった。
On the other hand, in Comparative Example 1 and Comparative Example 5, since the blending ratio of the converted CaO in the Ca-containing material to the coal ash of the reforming material deviated from the lower limit of the scope of the present invention, the coal ash smoothly moved into the molten blast furnace slag. A sintered body of a high melting point crystal was formed without melting, and no reforming effect was obtained by the addition of a modifier, and both became blast furnaces with a low specific gravity.
Contrary to Comparative Example 1, Comparative Example 2 is a large amount of Ca containing compounded CaO to coal ash that is out of the upper limit of the range of the present invention. The particles constituting the material were not sufficiently melted together, undissolved material remained, a sufficient reforming effect was not obtained, and the specific gravity of the blast furnace after cooling was low.
In Comparative Example 3, the amount of the reformer added to the molten blast furnace slag deviated from the lower limit of the range of the present invention, so that the reforming effect by the modifier was insufficient and the specific gravity of the blast furnace slag was small.
Further, in contrast to Comparative Example 3, the amount of modification material added to the molten blast furnace slag deviates from the upper limit of the range of the present invention, so that the sensible heat taken away by the modification material increases. The temperature of the part where the modifier is added in the molten blast furnace drastically decreases locally, but the modifier melts, but the viscosity of the molten blast furnace bowl after the addition increases, and the inner surface refractory of the large bowl and the potato pan after the addition of the modifier The adhesion amount of the molten blast furnace slag increased to a complicated operation such as the removal of the adhered slag after the treatment, resulting in operational problems. In Comparative Example 6, since the converted CaO content in the Ca-containing material is as low as 10.7% by mass, components other than CaO are mixed in a large amount in the molten blast furnace so that the temperature drop when the modifier is added is low. It became large, causing trouble in operation, and the effect as a reformer mainly composed of coal ash was not obtained, and the specific gravity was small.
１：高炉、２：出銑口、３：大樋、４：スキンマ、５：滓樋、６：流銑鍋、７：水砕・放流樋、８：水砕設備、９：放流ピット、１０：ピット放流口 1: Blast furnace, 2: Outlet, 3: Large bowl, 4: Skinma, 5: Fence, 6: Floating pan, 7: Granulation / release basin, 8: Granulation equipment, 9: Discharge pit, 10: Pit outlet
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