JP4942954B2 - Method for processing fluorine-containing steelmaking slag - Google Patents
Method for processing fluorine-containing steelmaking slag Download PDFInfo
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- JP4942954B2 JP4942954B2 JP2005203337A JP2005203337A JP4942954B2 JP 4942954 B2 JP4942954 B2 JP 4942954B2 JP 2005203337 A JP2005203337 A JP 2005203337A JP 2005203337 A JP2005203337 A JP 2005203337A JP 4942954 B2 JP4942954 B2 JP 4942954B2
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- 239000002893 slag Substances 0.000 title claims description 132
- 239000011737 fluorine Substances 0.000 title claims description 122
- 229910052731 fluorine Inorganic materials 0.000 title claims description 122
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 121
- 238000009628 steelmaking Methods 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 25
- 238000012545 processing Methods 0.000 title description 5
- 239000010883 coal ash Substances 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 10
- 238000003672 processing method Methods 0.000 claims description 9
- 241001062472 Stokellia anisodon Species 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000010828 elution Methods 0.000 description 21
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 238000006477 desulfuration reaction Methods 0.000 description 15
- 230000023556 desulfurization Effects 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 229910004261 CaF 2 Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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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
Description
本発明は、フッ素含有製鋼スラグを処理してフッ素の溶出を抑制するための方法に関する。 The present invention relates to a method for treating fluorine-containing steelmaking slag to suppress fluorine elution.
製鋼プロセスから排出されるスラグの中には、脱燐剤や脱硫剤の添加が原因でフッ素を含有するものがあり、中には土壌環境基準で規定されている環境庁告示４６号試験（サンプルを２ｍｍ以下に粉砕して水中で６時間振盪し、その水中に溶出したフッ素濃度を計る方法）で測定されたフッ素濃度が基準濃度以上になるものもあり、これらをそのまま土壌に戻すことができない。
このため、フッ素の溶出を抑制する方法が多く提案されている。
Some slag discharged from the steelmaking process contains fluorine due to the addition of dephosphorization and desulfurization agents. In some cases, the fluorine concentration measured by crushing to 2 mm or less, shaking in water for 6 hours, and measuring the fluorine concentration eluted in the water) exceeds the reference concentration, and these cannot be returned to the soil as they are .
For this reason, many methods for suppressing elution of fluorine have been proposed.
例えば、フッ素含有スラグとアルミナ含有スラグを事前に混合し、この混合スラグを水中に浸し、その水中にＣａイオンとＡｌイオンが溶出して、ＣａＯ−Ａｌ2 Ｏ3 −Ｈ2 Ｏの化合物が生成する際に、フッ素イオンが、生成した化合物に取り込まれ、フッ素が化合物中に安定に固定されることにより、フッ素の溶出を抑制する方法がある( 例えば、非特許文献１参照) 。 For example, fluorine-containing slag and alumina-containing slag are mixed in advance, and the mixed slag is immersed in water, and Ca ions and Al ions are eluted in the water to form a compound of CaO—Al 2 O 3 —H 2 O. In this case, there is a method in which fluorine ions are taken into the generated compound and fluorine is stably fixed in the compound to suppress elution of fluorine (for example, see Non-Patent Document 1).
しかしながら、前記した方法を工業的レベルで活用しようとすると、前記両スラグのフッ素及びアルミナの含有量は種々変化するために、溶出するイオンバランスを適正に保つための両スラグの事前配合が事実上難しいという問題が生じていた。
また、大量の両スラグを均一に混合することが極めて難しいため、フッ素含有スラグの偏在を完全に無くすには無理があり、部分的にフッ素溶出基準を超える溶出が起こる可能性が懸念されることから、有効なものではなかった。
However, if the above-described method is used at an industrial level, the contents of fluorine and alumina in both slags vary, so it is practically necessary to pre-blend both slags in order to maintain the proper ion balance. There was a difficult problem.
In addition, since it is extremely difficult to uniformly mix a large amount of both slags, it is impossible to completely eliminate the uneven distribution of fluorine-containing slag, and there is a concern that elution that partially exceeds the fluorine elution standard may occur. Therefore, it was not effective.
本発明はかかる事情に鑑みてなされたもので、製鉄所内の設備を用いて安価で、かつ、確実にフッ素含有製鋼スラグを処理して、フッ素の溶出抑制を工業的レベルで実行可能なものとするフッ素含有製鋼スラグの処理方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and is inexpensive and reliably processing fluorine-containing steelmaking slag using equipment in an ironworks, and can suppress fluorine elution at an industrial level. An object of the present invention is to provide a method for treating fluorine-containing steelmaking slag.
本発明は前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、フッ素含有製鋼スラグと石炭灰を高炉から排出された溶融状態の高炉滓に同時に添加して溶融し、これを冷却固化して、フッ素濃度が２．５質量％以下のフッ素含有高炉滓とすることを特徴とするフッ素含有製鋼スラグの処理方法である。
また、手段２は、前記手段１において、前記フッ素含有製鋼スラグは、粒度が０．２ｍｍ以下であることを特徴とするフッ素含有製鋼スラグの処理方法である。
更に、手段３は、前記手段１又は２において、前記フッ素含有製鋼スラグと前記石炭灰を造粒し、２０ｍｍ以下の造粒物として、前記溶融状態の高炉滓に添加することを特徴とするフッ素含有製鋼スラグの処理方法である。
The present invention has been made in order to solve the above-mentioned problems. The
Means 2 is the processing method of fluorine-containing steelmaking slag according to the
Furthermore,
本発明のフッ素含有製鋼スラグの処理方法は、フッ素含有製鋼スラグと石炭灰を、溶融状態の高炉滓に同時に添加して溶解し、フッ素が溶出しない鉱物組成に転換して、フッ素含有製鋼スラグからのフッ素の溶出を確実に抑制することができる状態で高炉滓に含有させるので、高炉滓としての用途及び使用量を制限することなく、フッ素含有製鋼スラグを多量に処理することが可能となり、この分野にもたらす効果は極めて大きい。 The method for treating fluorine-containing steelmaking slag according to the present invention comprises adding fluorine-containing steelmaking slag and coal ash to a molten blast furnace smelt at the same time, and converting to a mineral composition that does not elute fluorine. Fluorine-containing steelmaking slag can be processed in large quantities without restricting the use and amount of use as a blast furnace so that the elution of fluorine can be reliably suppressed. The effect on the field is extremely large.
続いて、添付した図面を参照しつつ、本発明を具体化した実施の形態につき説明し、本発明の理解に供する。
ここで、図１は冷却固化後の高炉滓中のフッ素濃度と環境庁告示４６号試験における水中でのフッ素溶出量との関係を示す説明図、図２は本発明の一実施の形態に係るフッ素含有製鋼スラグの処理方法を適用する高炉滓処理設備の平面図である。
Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention.
Here, FIG. 1 is an explanatory diagram showing the relationship between the fluorine concentration in the blast furnace after cooling and solidification and the fluorine elution amount in water in the Environmental Agency Notification No. 46 test, and FIG. 2 relates to one embodiment of the present invention. It is a top view of the blast furnace slag processing equipment to which the processing method of fluorine-containing steelmaking slag is applied.
図２に示すように、本発明の一実施の形態に係るフッ素含有製鋼スラグの処理方法は、高炉１０から排出された溶融状態の高炉滓( 以下、溶融高炉滓とも言う) に、フッ素含有製鋼スラグ（以下、製鋼スラグ又は製鋼滓ともいう）と石炭灰を同時に添加して溶解し、これを冷却して固化し、フッ素濃度が２．５質量％以下のフッ素含有高炉滓として、このフッ素含有高炉滓からのフッ素の溶出を抑制する方法である。
まず、一実施の形態に係るフッ素含有製鋼スラグの処理方法を適用する高炉滓処理設備１１について説明した後、製鋼スラグ中のフッ素の処理方法について説明する。
As shown in FIG. 2, the method for treating fluorine-containing steelmaking slag according to one embodiment of the present invention is applied to a molten blast furnace slag discharged from the blast furnace 10 (hereinafter also referred to as a molten blast furnace slag). Slag (hereinafter also referred to as steel slag or steel slag) and coal ash are added and dissolved simultaneously, and this is cooled and solidified to form a fluorine-containing blast furnace slag having a fluorine concentration of 2.5% by mass or less. This is a method for suppressing the elution of fluorine from the blast furnace.
First, after explaining the blast furnace
図２に示すように、高炉滓処理設備１１は、高炉１０の出銑口１２から排出される溶銑及び溶融高炉滓を流す大樋１３と、この大樋１３に接続された滓樋１４とを有している。この大樋１３の途中には、大樋１３の上側を仕切るスキンマー１５が設けられ、また大樋１３と滓樋１４との接続部分には、滓樋１４の下側を仕切るスキンマー１６が設けられ、大樋１３の下側を流れる溶銑を大樋１３の下流側へ、大樋１３の上側を流れる溶融高炉滓を滓樋１４へとそれぞれ送っている。
滓樋１４の下流側は、溶融高炉滓に含まれる溶銑を分離する流銑鍋１７に接続され、この溶融高炉滓が、流銑鍋１７から水砕設備１８、又は放流ピット（徐冷ピットの一例）１９へ送られる。なお、水砕設備１８又は放流ピット１９への溶融高炉滓の供給は、各場所へ供給の切替えが可能な切替樋（水砕及び放流樋）２０を介して行われる。
As shown in FIG. 2, the blast furnace
The downstream side of the
まず、上記した高炉１０から排出された溶融高炉滓に、フッ素含有製鋼スラグと石炭灰を同時に添加する。
フッ素含有製鋼スラグと石炭灰の同時添加は、大樋１３（Ａ点）、滓樋１４（Ｂ点）、及び流銑鍋１７（Ｃ点）のいずれか１箇所又は複数箇所で行うことが好ましい。なお、フッ素含有製鋼スラグと石炭灰の同時添加は、上記のＡ点〜Ｃ点に限らず、高炉１０から高炉滓の水砕設備１８又は高炉滓の放流ピット１９に至るまでの経路の１箇所又は複数箇所で添加することができる。
First, fluorine-containing steelmaking slag and coal ash are simultaneously added to the molten blast furnace slag discharged from the
The simultaneous addition of fluorine-containing steelmaking slag and coal ash is preferably performed at any one or a plurality of locations in the large bowl 13 (point A), the bowl 14 (point B), and the fluted pan 17 (point C). In addition, simultaneous addition of fluorine-containing steelmaking slag and coal ash is not limited to the above points A to C, but one place on the path from the
添加するフッ素含有製鋼スラグとしては、例えば、溶銑脱燐スラグ、溶銑脱硫スラグ、転炉スラグ、及び溶鋼脱硫スラグのいずれか１又は２以上がある。溶銑脱燐スラグは、溶銑にＣａＦ2 を含む脱燐剤を添加して脱燐処理した後に発生するスラグであり、溶銑脱硫スラグは、同じく溶銑にＣａＦ2 を含む脱硫剤を添加して脱硫処理した後に発生するスラグであり、転炉スラグは、転炉吹錬で脱燐を促進するためにＣａＦ2 を炉内に添加した後に発生するスラグであり、溶鋼脱硫スラグは、転炉から出鋼した後の溶鋼にＣａＦ2 を含む脱硫剤を添加して脱硫処理した後に発生するスラグである。
ここで、フッ素含有製鋼スラグ（フッ素含有溶銑脱燐滓及びフッ素含有溶鋼脱硫滓）と石炭灰の化学成分の一例を表１に示す。なお、フッ素含有製鋼スラグと石炭灰を同時添加する溶融高炉滓（添加前溶融高炉滓）の化学成分の一例を表２に示す。
Examples of the fluorine-containing steelmaking slag to be added include one or more of hot metal dephosphorization slag, hot metal desulfurization slag, converter slag, and molten steel desulfurization slag. Hot metal dephosphorization slag is slag generated after adding dephosphorization agent containing CaF 2 to hot metal and dephosphorization treatment. Hot metal desulfurization slag is also desulfurization treatment by adding desulfurization agent containing CaF 2 to hot metal The converter slag is generated after adding CaF 2 to the furnace to promote dephosphorization by converter blowing, and the molten steel desulfurization slag is discharged from the converter. This is slag generated after desulfurization treatment by adding a desulfurization agent containing CaF 2 to the molten steel after being processed.
Here, Table 1 shows an example of the chemical components of fluorine-containing steelmaking slag (fluorine-containing molten steel dephosphorization and fluorine-containing molten steel desulfurization) and coal ash. In addition, Table 2 shows an example of chemical components of a molten blast furnace slag (melting blast furnace slag before addition) in which fluorine-containing steel slag and coal ash are added simultaneously.
前記したように、高炉１０から排出された溶融高炉滓に、前記した位置（Ａ点〜Ｃ点のいずれか1 箇所又は複数箇所）で、フッ素含有製鋼スラグと石炭灰を同時に添加し、その後冷却固化した高炉滓からのフッ素溶出量を環境基準値である０．８ｍｇ／Ｌ（リットル）以下に低減する。ここで、フッ素の溶出量を低減するメカニズムについて説明する。
フッ素含有製鋼スラグと石炭灰を同時にＣａＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 が主成分の溶融高炉滓に添加すると、溶融高炉滓中のＣａＯとＳｉＯ2 が、フッ素含有製鋼スラグ中のフッ素及び石炭灰中のわずかなフッ素と反応して、３ＣａＯ・２ＳｉＯ2 ・ＣａＦ2 （鉱物相名：カスピダイン）の形態を示す安定鉱物相を生成する。
この鉱物相は、極めて安定で分解しにくいため、この鉱物相構造の中に取り込まれたフッ素は容易に分解せず、溶出しない。即ち、製造したフッ素含有高炉滓を水中にどんなに晒しても、フッ素の溶出量は極めて低い値に抑えられると解される。
As described above, fluorine-containing steelmaking slag and coal ash are simultaneously added to the molten blast furnace slag discharged from the
When fluorine-containing steelmaking slag and coal ash are simultaneously added to the molten blast furnace slag containing CaO-SiO 2 —Al 2 O 3 as the main components, CaO and SiO 2 in the molten blast furnace slag become fluorine and coal ash in the fluorine-containing steelmaking slag. It reacts with a small fluorine in, 3CaO · 2SiO 2 · CaF 2 ( mineral phases name: Kasupidain) to produce a stable mineral phases showing the embodiment.
Since this mineral phase is extremely stable and difficult to decompose, fluorine incorporated into this mineral phase structure does not easily decompose and does not elute. In other words, it can be understood that the amount of fluorine elution can be suppressed to a very low value, no matter how much the produced fluorine-containing blast furnace is exposed to water.
なお、溶融高炉滓に添加する際に石炭灰を同時添加する方法は、製鋼スラグが４０質量％以上６０質量％以下のＣａＯを含み、その融点が添加する溶融高炉滓の温度より高いため、溶融高炉滓にフッ素含有製鋼スラグのみを添加しても容易に溶解せず未溶解が残ることを解決するために着想した方法である。これにより、石炭灰の主成分であるＳｉＯ2 とＡｌ2 Ｏ3 がフッ素含有製鋼スラグの主成分であるＣａＯと混ざり合い、添加物の融点を下げて添加物を溶融高炉滓に容易に溶解できる。 In addition, the method of adding coal ash simultaneously when adding to the molten blast furnace slag is because the steelmaking slag contains 40 mass% or more and 60 mass% or less of CaO, and its melting point is higher than the temperature of the molten blast furnace slag to be added. This method was conceived to solve the problem that even if only fluorine-containing steel slag is added to the blast furnace soot, it does not dissolve easily and remains undissolved. Thereby, SiO 2 and Al 2 O 3 which are main components of coal ash are mixed with CaO which is a main component of fluorine-containing steelmaking slag, and the melting point of the additive can be lowered to easily dissolve the additive in the molten blast furnace. .
ここで、表１記載の２種類のフッ素含有製鋼スラグと石炭灰を使って、フッ素含有製鋼スラグと石炭灰を同時に添加して溶解し、冷却して固化した後の新規化合物の生成によって、フッ素溶出挙動がどの程度低減するかを確認するための基礎実験を行った結果について説明する。
実験は、高炉１０から排出した表２に示す化学成分を有した高炉滓を小型の坩堝にて３００ｇ溶解し、そこにフッ素含有製鋼スラグと石炭灰の重量比率を種々振らせ、溶融高炉滓の重量に対して３０質量％である９０ｇに揃えて両者を同時に添加した後、添加物溶解後の製鋼スラグを冷却し固化してフッ素含有量の異なる高炉滓を製造し、この各冷却高炉滓のフッ素溶出量を前記環境庁告示４６号試験に準じて測定した。この結果を図１に示す。
Here, by using two types of fluorine-containing steelmaking slag and coal ash listed in Table 1, fluorine-containing steelmaking slag and coal ash are simultaneously added and dissolved, and after cooling and solidification, fluorine is produced. The results of a basic experiment for confirming how much the elution behavior is reduced will be described.
In the experiment, 300 g of the blast furnace slag having the chemical components shown in Table 2 discharged from the
図１から明らかなように、含有フッ素濃度が２．５質量％以下の高炉滓は、フッ素溶出量が前記基準濃度である０．８ｍｇ／Ｌ以下を満足する。
なお、高炉滓中のフッ素濃度とは、該高炉滓に含まれるあらゆる形態のフッ素の総量（トータルフッ素量）である。
As is apparent from FIG. 1, the blast furnace furnace having a fluorine concentration of 2.5% by mass or less satisfies the reference concentration of 0.8 mg / L or less.
The fluorine concentration in the blast furnace slag is the total amount (total fluorine amount) of all forms of fluorine contained in the blast furnace slag.
ここで、溶融高炉滓へのフッ素含有製鋼スラグと石炭灰の同時添加の総量は、溶融高炉滓の３０質量％以下であることが好ましい。これは、フッ素含有製鋼スラグと石炭灰の同時添加の総量が溶融高炉滓の３０質量％を超える場合、添加量が多くなり過ぎて溶融高炉滓の熱が奪われ、上記メカニズムが進行する前に溶融高炉滓の温度が低下して添加物が溶解できずに未溶解のまま残ることもあり、添加物中のフッ素の一部が前記した安定鉱物相に取り込まれないため、冷却固化した後の高炉滓から前記基準濃度以上のフッ素が溶出してしまうことも考えられるためである。 Here, the total amount of simultaneous addition of fluorine-containing steelmaking slag and coal ash to the molten blast furnace slag is preferably 30% by mass or less of the molten blast furnace slag. This is because when the total amount of fluorine-containing steelmaking slag and coal ash added simultaneously exceeds 30% by mass of the molten blast furnace slag, the added amount becomes too large and the heat of the molten blast furnace slag is deprived, before the above mechanism proceeds. Since the temperature of the molten blast furnace iron is lowered and the additive cannot be dissolved and remains undissolved, a part of the fluorine in the additive is not taken into the stable mineral phase. This is because it is considered that fluorine having a reference concentration or more is eluted from the blast furnace soot.
また、高炉滓へのフッ素含有製鋼スラグ及び石炭灰の同時添加の方法としては、例えば、フッ素含有製鋼スラグと石炭灰を溶融高炉滓の上方から同時に落とし込む方法、フッ素含有製鋼スラグと石炭灰の混合粉体を一緒に溶融高炉滓中に吹き込む（インジェクション）方法、又はフッ素含有製鋼スラグと石炭灰を造粒して造粒物とし溶融高炉滓の上方から落とし込む方法があるが、粉体のままで上方投入する場合は発塵があり、これを集塵処理する設備が必要となり不経済になると共に、フッ素含有製鋼スラグと石炭灰が均一に添加できず偏在した形で添加される懸念がある。また、混合粉体を溶融高炉滓に吹き込む方法では、均一添加という点では有利であるが、粉体を吹き込む装置にコストがかかることから、簡易な設備でフッ素含有製鋼スラグと石炭灰の均一添加が可能な造粒添加による方法が好ましい。 In addition, as a method of simultaneous addition of fluorine-containing steelmaking slag and coal ash to the blast furnace slag, for example, a method of dropping fluorine-containing steelmaking slag and coal ash simultaneously from above the molten blast furnace slag, a mixture of fluorine-containing steelmaking slag and coal ash There is a method of injecting the powder together into the molten blast furnace slag (injection), or a method of granulating fluorine-containing steel slag and coal ash into a granulated product and dropping it from above the molten blast furnace slag. When it is introduced upward, dust is generated, and equipment for collecting the dust is required, which is uneconomical, and there is a concern that fluorine-containing steelmaking slag and coal ash cannot be uniformly added and are added in an unevenly distributed form. In addition, the method of blowing the mixed powder into the molten blast furnace is advantageous in terms of uniform addition, but since the apparatus for blowing the powder is costly, uniform addition of fluorine-containing steelmaking slag and coal ash with simple equipment It is preferable to use a granulation addition method.
また、フッ素含有製鋼スラグの粒径は、ロッドミル等の破砕機で破砕して０．２ｍｍ以下にすることが好ましい。
これは、粒径が０．２ｍｍを超えると、フッ素含有製鋼スラグと石炭灰の混合粉体のまま溶融高炉滓に吹き込む場合、サイズが大き過ぎて粉体搬送に障害が出やすいし、均一混合もしにくくなる。また、フッ素含有製鋼スラグと石炭灰の混合物を造粒して添加する場合も、フッ素含有製鋼スラグが０．２ｍｍ以下の粒子であれば、造粒し易くなって好ましい。
一方、フッ素含有製鋼スラグの粒径の下限値については規定していないが、破砕コストの面から０．０５ｍｍ程度である。
なお、石炭灰（フライアッシュ）は、通常０．１ｍｍ以下の微粉が大半であることから粉砕する必要はない。
The particle size of the fluorine-containing steelmaking slag is preferably 0.2 mm or less by crushing with a crusher such as a rod mill.
This is because if the particle size exceeds 0.2 mm, when the mixed powder of fluorine-containing steelmaking slag and coal ash is blown into the molten blast furnace slag, the size is too large and obstacles to powder conveyance are likely to occur, and uniform mixing If it becomes difficult. Moreover, also when granulating and adding the mixture of fluorine-containing steelmaking slag and coal ash, if a fluorine-containing steelmaking slag is a particle | grain of 0.2 mm or less, it will become easy to granulate and is preferable.
On the other hand, the lower limit of the particle size of the fluorine-containing steelmaking slag is not specified, but is about 0.05 mm from the viewpoint of crushing cost.
In addition, since coal ash (fly ash) usually has most fine powder of 0.1 mm or less, it is not necessary to grind | pulverize.
フッ素含有製鋼スラグと石炭灰の造粒物のサイズは２０ｍｍ以下にすることが好ましい。即ち、２０ｍｍを超えた大きな造粒物では、添加した造粒物が溶融高炉滓中に完全に溶解できずに未溶解分が残り、溶融高炉滓が冷却固化した後に、その部分からフッ素が溶出する場合があるからである。
なお、造粒する方法は、例えば、パンペレタイザー、押出成型、又は混練造粒を同時に行う混練造粒機など、２０ｍｍ以下の造粒物が製造できる方法であれば、いずれを使用しても構わない。
一方、造粒物の粒径の下限値については規定していないが、溶融高炉滓に添加した際における発塵の面から５ｍｍ程度である。
このように、本発明の処理方法で製造した高炉滓は、例えば、セメント用原料、又はコンクリート用骨材（粗骨材又は細骨材）に使用することが好ましい。
The size of the granulated product of fluorine-containing steel slag and coal ash is preferably 20 mm or less. That is, in a large granulated product exceeding 20 mm, the added granulated product cannot be completely dissolved in the molten blast furnace slag, and the undissolved part remains, and after the molten blast furnace slag has cooled and solidified, fluorine is eluted from that part. Because there is a case to do.
Any granulation method may be used as long as it can produce a granulated product of 20 mm or less, such as a pan pelletizer, extrusion molding, or a kneading granulator that performs kneading granulation simultaneously. Absent.
On the other hand, although the lower limit value of the particle size of the granulated product is not specified, it is about 5 mm from the surface of dust generation when added to the molten blast furnace.
Thus, it is preferable to use the blast furnace iron manufactured by the processing method of the present invention as, for example, a raw material for cement or an aggregate for concrete (coarse aggregate or fine aggregate).
以下、本発明の実施例について詳細に説明する。
前記表１に示したフッ素含有溶銑脱燐滓又はフッ素含有溶鋼脱硫滓と石炭灰を、以下に示す表３の条件で添加物と成し、表４の方法で溶融高炉滓に添加して冷却固化した後、高炉滓からのフッ素溶出量を前記環境庁告示４６号試験に準じて測定した。
Examples of the present invention will be described in detail below.
Fluorine-containing hot metal dephosphorization slag or fluorine-containing molten steel desulfurization slag and coal ash shown in Table 1 above are made into additives under the conditions shown in Table 3 below, and added to the molten blast furnace slag by the method shown in Table 4 for cooling. After solidification, the amount of fluorine eluted from the blast furnace was measured according to the Environmental Agency Notification No. 46 test.
表３、表４から分かるように、実施例１〜８は、フッ素含有溶鋼脱硫滓又はフッ素含有溶銑脱燐滓を石炭灰と共に、溶融高炉滓へ同時に添加して溶解し、冷却固化した後の高炉滓中のフッ素濃度を２．５質量％以下としているので、高炉滓からのフッ素溶出量が環境基準値の０．８ｍｇ／Ｌ以下に抑えられている。特に、実施例１〜５は、更に、フッ素含有溶鋼脱硫滓又はフッ素含有溶銑脱燐滓の最大粒径を０．２ｍｍとし、溶融高炉滓への添加物を造粒した場合はその造粒物の最大径を２０ｍｍとしたものであり、これにより高炉滓からのフッ素溶出量を０．５ｍｇ／Ｌより低い値に抑えることができた。 As can be seen from Tables 3 and 4, Examples 1 to 8 were obtained by simultaneously adding and melting fluorine-containing molten steel desulfurization slag or fluorine-containing molten iron desulfurization slag together with coal ash to the molten blast furnace slag and cooling and solidifying it. Since the fluorine concentration in the blast furnace soot is 2.5 mass% or less, the fluorine elution amount from the blast furnace soot is suppressed to an environmental standard value of 0.8 mg / L or less. In particular, in Examples 1 to 5, when the maximum particle size of the fluorine-containing molten steel desulfurization iron or fluorine-containing molten iron dephosphorization iron is 0.2 mm, and the additive to the molten blast furnace iron is granulated, the granulated product The maximum diameter was set to 20 mm, and the fluorine elution amount from the blast furnace was able to be suppressed to a value lower than 0.5 mg / L.
なお、実施例６のように、最大粒径が０．２ｍｍを超えた（０．２５ｍｍ）フッ素含有溶鋼脱硫滓を使用した場合、実施例１〜５と比較してフッ素溶出量が若干高くなった。これは、フッ素含有製鋼スラグの粉体と石炭灰との混合の不均一性に起因するものと推定される。
また、実施例７のように、最大径が２０ｍｍを超えた（２７ｍｍ）造粒物を使用した場合、実施例１〜５と比較してフッ素溶出量が若干高くなった。これは、高炉滓が冷却固化するまでに完全に高炉滓に溶けきれず未溶解分が残ったためであると推定される。
更に、実施例８のように、最大粒径が０．２ｍｍを超えた（０．２１ｍｍ）フッ素含有溶銑脱燐滓を使用して、最大径が２０ｍｍを超えた（２５ｍｍ）造粒物を製造し使用した場合、実施例１〜５と比較してフッ素溶出量が若干高くなった。
しかし、いずれの場合においても、冷却固化した後の高炉滓中のフッ素濃度を２．５質量％以下としているので、高炉滓からのフッ素溶出量が環境基準値の０．８ｍｇ／Ｌ以下に抑えられている。
In addition, when the fluorine-containing molten steel desulfurization slag having a maximum particle size exceeding 0.2 mm (0.25 mm) was used as in Example 6, the fluorine elution amount was slightly higher than in Examples 1 to 5. It was. This is presumed to be due to non-uniformity of mixing of the powder of fluorine-containing steelmaking slag and coal ash.
In addition, as in Example 7, when a granulated product having a maximum diameter exceeding 20 mm (27 mm) was used, the fluorine elution amount was slightly higher than in Examples 1-5. It is presumed that this is because the blast furnace slag was not completely dissolved in the blast furnace slag until the blast furnace slag solidified and an undissolved portion remained.
Further, as in Example 8, a granulated product having a maximum diameter exceeding 20 mm (25 mm) is produced using a fluorine-containing hot metal dephosphorizing iron having a maximum particle diameter exceeding 0.2 mm (0.21 mm). When used, the fluorine elution amount was slightly higher than in Examples 1-5.
However, in any case, the fluorine concentration in the blast furnace slag after cooling and solidification is 2.5% by mass or less, so the amount of fluorine leaching from the blast furnace slag is suppressed to 0.8 mg / L or less of the environmental standard value. It has been.
一方、比較例では、冷却固化した後のフッ素濃度が２．５質量％超（２．７１質量％）となる大量のフッ素含有製鋼スラグを、溶融高炉滓に添加しているため、製造した高炉滓からのフッ素溶出量が環境基準値より高くなった。
以上のことから、本発明のフッ素含有製鋼スラグの処理方法を使用することで、フッ素による環境への負荷を低減でき、しかもフッ素含有製鋼スラグの処理を低コストで実施できることを確認できた。
On the other hand, in the comparative example, since a large amount of fluorine-containing steelmaking slag having a fluorine concentration after cooling and solidification exceeding 2.5% by mass (2.71% by mass) is added to the molten blast furnace blast furnace, Fluorine elution from soot was higher than the environmental standard value.
From the above, it was confirmed that by using the method for treating a fluorine-containing steelmaking slag according to the present invention, it was possible to reduce the environmental load due to fluorine and to carry out the treatment of the fluorine-containing steelmaking slag at a low cost.
以上、本発明を、一実施の形態を参照して説明してきたが、本発明は何ら上記した実施の形態に記載の構成に限定されるものではなく、特許請求の範囲に記載されている事項の範囲内で考えられるその他の実施の形態や変形例も含むものである。例えば、前記したそれぞれの実施の形態や変形例の一部又は全部を組合せて本発明のフッ素含有製鋼スラグの処理方法を構成する場合も本発明の権利範囲に含まれる。 As described above, the present invention has been described with reference to one embodiment. However, the present invention is not limited to the configuration described in the above embodiment, and is described in the claims. Other embodiments and modifications conceivable within the scope of the above are also included. For example, a case where the processing method for fluorine-containing steel slag of the present invention is configured by combining some or all of the above-described embodiments and modifications is also included in the scope of the right of the present invention.
１０：高炉、１１：高炉滓処理設備、１２：出銑口、１３：大樋、１４：滓樋、１５、１６：スキンマー、１７：流銑鍋、１８：水砕設備、１９：放流ピット（徐冷ピット）、２０：切替樋 10: Blast furnace, 11: Blast furnace dredging facility, 12: Outlet, 13: Daegu, 14: Dredging, 15, 16: Skinmer, 17: Floating pan, 18: Granulation facility, 19: Discharge pit Cold pit), 20: Switching 樋
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