JP5515638B2 - Sulfur / Ca-containing slag treatment method - Google Patents
Sulfur / Ca-containing slag treatment method Download PDFInfo
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- JP5515638B2 JP5515638B2 JP2009251157A JP2009251157A JP5515638B2 JP 5515638 B2 JP5515638 B2 JP 5515638B2 JP 2009251157 A JP2009251157 A JP 2009251157A JP 2009251157 A JP2009251157 A JP 2009251157A JP 5515638 B2 JP5515638 B2 JP 5515638B2
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- 239000002893 slag Substances 0.000 title claims description 79
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 63
- 229910052717 sulfur Inorganic materials 0.000 title claims description 63
- 239000011593 sulfur Substances 0.000 title claims description 63
- 238000000034 method Methods 0.000 title claims description 25
- 239000002904 solvent Substances 0.000 claims description 66
- 239000011575 calcium Substances 0.000 claims description 55
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 40
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 21
- 239000001569 carbon dioxide Substances 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- 238000007664 blowing Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 7
- 238000006477 desulfuration reaction Methods 0.000 claims description 6
- 230000023556 desulfurization Effects 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Furnace Details (AREA)
Description
本発明は、硫黄・Ｃａ含有スラグである脱硫スラグの硫黄含有量とＣａ含有量を低減するための処理方法に関する。 The present invention relates to a treatment method for reducing the sulfur content and Ca content of desulfurized slag , which is sulfur / Ca-containing slag .
従来、鉄鋼スラグ（鉄鋼製造プロセスで発生するスラグ）は、コンクリート骨材や路盤材料、港湾土木材料などの土木材料として広く利用されている。この鉄鋼スラグのなかで、脱硫スラグなどの硫黄含有スラグを路盤材料として利用する場合、特に水の存在する環境下で使用すると、硫黄（黄水）が流出して環境に悪影響を与えるおそれがある。従来、このような問題の対策として、（a）強制エージング（例えば、水蒸気エージング）を施して硫黄成分の酸化を促進させ、硫黄成分が溶出しにくいスラグとする方法、（b）スラグを水に浸漬し若しくはスラグに散水することにより硫黄成分を抽出し、スラグ中の硫黄含有量を低減する方法（例えば、特許文献１）、などが行われている。 Conventionally, steel slag (slag generated in a steel manufacturing process) has been widely used as a civil engineering material such as a concrete aggregate, a roadbed material, and a harbor civil engineering material. Among these steel slags, when sulfur-containing slag such as desulfurized slag is used as roadbed material, especially when used in an environment where water exists, sulfur (yellow water) may flow out and adversely affect the environment. . Conventionally, as a countermeasure against such a problem, (a) a method of applying forced aging (for example, steam aging) to promote oxidation of sulfur components to make slag in which sulfur components hardly dissolve, (b) slag into water The method (for example, patent document 1) etc. which extract a sulfur component by immersing or sprinkling to slag and reducing the sulfur content in slag are performed.
しかし、（a）の方法では、エージングの際に生じる排水中に硫黄成分が溶出する問題があり、排水処理に手間とコストがかかる。また、（b）の方法では、硫黄成分を効率的に抽出することができず、大部分の硫黄成分がスラグに残存してしまうので、硫黄成分を除去したスラグの利用も含めた有効な対策にはなり得ない。
また、一般に硫黄含有スラグは水溶性Ｃａ成分（アルカリ成分）も含有しているが、このような水溶性Ｃａ成分も水の存在する環境下で流出して環境に悪影響を与えるおそれがあり、その対策が望まれる。
However, in the method (a), there is a problem that the sulfur component is eluted in the wastewater generated during aging, and the wastewater treatment takes time and cost. In addition, in the method (b), sulfur components cannot be extracted efficiently, and most of the sulfur components remain in the slag, so effective measures including the use of slag from which sulfur components have been removed are included. It cannot be.
In general, sulfur-containing slag also contains a water-soluble Ca component (alkaline component), but such a water-soluble Ca component may also flow out in the presence of water and adversely affect the environment. Countermeasures are desired.
したがって本発明の目的は、脱硫スラグの硫黄含有量と水溶性Ｃａ含有量を効果的に低減することができるスラグ処理方法を提供することにある。
また、本発明の他の目的は、硫黄含有量と水溶性Ｃａ含有量が効果的に低減された脱硫黄・Ｃａ処理スラグ等の製造方法を提供することにある。
Accordingly, an object of the present invention is to provide a slag treatment method capable of effectively reducing the sulfur content and water-soluble Ca content of desulfurized slag .
Another object of the present invention is to provide a method for producing desulfurized / Ca-treated slag and the like in which the sulfur content and the water-soluble Ca content are effectively reduced.
本発明者らは、脱硫スラグを浸漬した溶媒中に二酸化炭素を吹き込み、且つ溶媒を特定のｐＨに調整することで、スラグに含まれる硫黄成分と水溶性Ｃａ成分を溶媒中に効率的に抽出し、脱硫スラグの硫黄含有量と水溶性Ｃａ含有量を効果的に低減できること、しかも、抽出されたＣａ成分の一部または全部を二酸化炭素と反応させて炭酸カルシウムとして固定し、回収できることを見出した。
本発明はこのような知見に基づきなされたもので、以下を要旨とするものである。
The present inventors efficiently extract the sulfur component and water-soluble Ca component contained in the slag into the solvent by blowing carbon dioxide into the solvent in which the desulfurized slag is immersed and adjusting the solvent to a specific pH. And the sulfur content and water-soluble Ca content of the desulfurized slag can be effectively reduced, and the extracted Ca component can be fixed and recovered as calcium carbonate by reacting part or all of the extracted Ca component with carbon dioxide. It was.
The present invention has been made on the basis of such findings and has the following gist.
［1］工程（Ａ）として、脱硫スラグを溶媒に浸漬し、該溶媒中に二酸化炭素を吹き込み、且つ溶媒をｐＨ４〜１０に調整することで、脱硫スラグに含まれる硫黄成分とＣａ成分を溶媒中に抽出するとともに、該抽出されたＣａ成分を前記二酸化炭素と反応させて炭酸カルシウムを生成させ、該炭酸カルシウムを処理済みスラグとともに回収する工程を有することを特徴とする硫黄・Ｃａ含有スラグの処理方法。
［2］上記［1］の処理方法において、さらに、溶媒に抽出された硫黄成分を回収する工程（Ｂ）を有することを特徴とする硫黄・Ｃａ含有スラグの処理方法。
［3］上記［2］の処理方法において、工程（Ｂ）を経た溶媒を工程（Ａ）に循環させることを特徴とする硫黄・Ｃａ含有スラグの処理方法。
[1] As step (A), desulfurization slag is immersed in a solvent, carbon dioxide is blown into the solvent, and the solvent is adjusted to
[2] The processing method of [1], further comprising a step (B) of recovering a sulfur component extracted in a solvent, and a processing method for sulfur / Ca-containing slag.
[3] A method for treating sulfur / Ca-containing slag, characterized in that in the treatment method of [2], the solvent that has undergone step (B) is circulated to step (A).
［4］工程（Ａ）として、脱硫スラグを溶媒に浸漬し、該溶媒中に二酸化炭素を吹き込み、且つ溶媒をｐＨ４〜１０に調整することで、脱硫スラグに含まれる硫黄成分とＣａ成分を溶媒中に抽出するとともに、該抽出されたＣａ成分を前記二酸化炭素と反応させて炭酸カルシウムを生成させ、該炭酸カルシウムを処理済みスラグとともに回収する工程を有し、該工程で脱硫黄・Ｃａ処理スラグを得ることを特徴とする脱硫黄・Ｃａ処理スラグ等の製造方法。
［5］上記［4］の製造方法において、さらに、溶媒に抽出された硫黄成分を回収する工程（Ｂ）を有し、該工程の回収物として硫黄含有原料を得ることを特徴とする脱硫黄・Ｃａ処理スラグ等の製造方法。
［6］上記［5］の製造方法において、工程（Ｂ）を経た溶媒を工程（Ａ）に循環させることを特徴とする脱硫黄・Ｃａ処理スラグ等の製造方法。
[4] As the step (A), the sulfur component and the Ca component contained in the desulfurized slag are removed by immersing the desulfurized slag in a solvent, blowing carbon dioxide into the solvent, and adjusting the solvent to pH 4-10. And extracting the Ca component with the carbon dioxide to produce calcium carbonate, and recovering the calcium carbonate together with the treated slag. In this step, desulfurized and Ca-treated slag A method for producing desulfurized / Ca-treated slag, etc.
[5] The method according to [4], further comprising a step (B) of recovering a sulfur component extracted in a solvent, and obtaining a sulfur-containing raw material as a recovered product of the step -Manufacturing methods, such as Ca processing slag.
[6] A method for producing desulfurized / Ca-treated slag or the like, characterized in that in the production method of [5], the solvent that has undergone step (B) is circulated to step (A).
本発明の処理方法によれば、脱硫スラグに含まれる硫黄成分とＣａ成分を溶媒中に効率的に抽出し、硫黄含有量と水溶性Ｃａ含有量を効果的に低減させることができる。また、本発明の製造方法によれば、硫黄成分とＣａ成分が効果的に低減された脱硫黄・Ｃａ処理スラグを製造することができ、さらに、スラグから抽出された硫黄成分による有用原料を製造することもできる。 According to the treatment method of the present invention, the sulfur component and the Ca component contained in the desulfurized slag can be efficiently extracted into the solvent, and the sulfur content and the water-soluble Ca content can be effectively reduced. Moreover, according to the production method of the present invention, it is possible to produce a desulfurized / Ca-treated slag in which the sulfur component and the Ca component are effectively reduced, and further produce a useful raw material from the sulfur component extracted from the slag. You can also
本発明が処理対象とするのは脱硫スラグ（溶銑予備処理スラグ）である。脱硫スラグは硫黄とＣａを含有し、硫黄含有量が０．５mass％以上であり、硫黄含有量が０．５mass％以上のスラグが特に上述したような問題を生じやすい。脱硫スラグは硫黄含有量が多く、利材化しにくい面があるので、本発明は有用性が高い。 The subject of the present invention is desulfurization slag (hot metal pretreatment slag). The desulfurized slag contains sulfur and Ca, the sulfur content is 0.5 mass% or more, and the slag having a sulfur content of 0.5 mass% or more is particularly likely to cause the above-described problems . Since the desulfurization slag has many sulfur content, it is difficult to interest material of the surface, the present invention has high usefulness.
本発明法は、工程Ａとして、脱硫スラグを溶媒に浸漬し、この溶媒中に二酸化炭素を吹き込み、且つ溶媒をｐＨ４〜１０に調整することで、スラグに含まれる硫黄成分とＣａ成分を溶媒中に抽出するとともに、この抽出されたＣａ成分を前記二酸化炭素と反応させて炭酸カルシウムを生成させ、この炭酸カルシウムを処理済みスラグとともに回収する工程を有する。また、この工程Ａに加えて、溶媒に抽出された硫黄成分を回収する工程Ｂを有することが好ましく、この場合、工程Ｂを経た溶媒を工程Ａに循環させることが好ましい。
In the method of the present invention, as step A, desulfurized slag is immersed in a solvent, carbon dioxide is blown into the solvent, and the solvent is adjusted to
本発明では、必要に応じて破砕処理、磁選処理を施したスラグを処理対象とするが、硫黄成分とＣａ成分の抽出を効率的に行うため、スラグ粒度は粒径０．５ｍｍ以下の割合が１５質量％以上、より好ましくは３０質量％以上であることが望ましい。
また、工程Ａでの液／固比（水溶液／スラグの質量比）は、３以上、１００以下が好ましい。液／固比が３未満では、溶媒が不足することから硫黄抽出効率が低下する。一方、液／固比が１００を超えると抽出設備などが大きくなり、コスト面で不利となる。
In the present invention, slag that has been subjected to crushing treatment and magnetic separation treatment as necessary is treated, but in order to efficiently extract the sulfur component and the Ca component, the slag particle size has a particle size of 0.5 mm or less. It is desirable that the content be 15% by mass or more, more preferably 30% by mass or more.
Moreover, the liquid / solid ratio (mass ratio of aqueous solution / slag) in step A is preferably 3 or more and 100 or less. If the liquid / solid ratio is less than 3, the solvent is insufficient and the sulfur extraction efficiency decreases. On the other hand, if the liquid / solid ratio exceeds 100, the extraction equipment becomes large, which is disadvantageous in terms of cost.
図１は、本発明の一実施形態を示すものである。この実施形態は、スラグに含まれる硫黄成分とＣａ成分を溶媒中に抽出する工程Ａと、溶媒に抽出された硫黄成分を回収する工程Ｂを有する。図において、１は工程Ａを行う抽出処理槽、２は工程Ｂを行う回収処理槽である。抽出処理槽１内の溶媒は、流路３a，３bを通じて、回収処理槽２を経て抽出処理槽１へと循環（返送）され、この系内で循環使用される。
FIG. 1 shows an embodiment of the present invention. This embodiment has the process A which extracts the sulfur component and Ca component which are contained in slag in a solvent, and the process B which collect | recovers the sulfur component extracted by the solvent. In the figure, 1 is an extraction processing tank for performing step A, and 2 is a recovery processing tank for performing step B. The solvent in the extraction processing tank 1 is circulated (returned) to the extraction processing tank 1 through the
前記工程Ａでは、抽出処理槽１内に入れられた溶媒（通常は水）に脱硫スラグを投入・浸漬し、この溶媒中にガス吹込手段５から二酸化炭素を吹き込み、且つこの溶媒がｐＨ４〜１０になるように調整する。溶媒がｐＨ１０を超えると硫黄成分、Ｃａ成分の抽出率が低下する。また、本発明では抽出されたＣａ成分を溶媒中の二酸化炭素と反応させて炭酸カルシウムとして固定し、この炭酸カルシウムを処理済みスラグとともに回収するものであるが、溶媒がｐＨ４未満では、生成した炭酸カルシウムが溶解してしまうので好ましくない。また、溶媒がｐＨ４未満では、硫黄成分やＣａ成分以外のスラグ成分も溶解してしまうおそれがある。
脱硫スラグは所定の時間溶媒中に浸漬されるが、その間、溶媒は上記ｐＨに維持されることが好ましい。
溶媒中に吹き込む二酸化炭素としては、ＣＯ２ガス、ＣＯ２含有ガスのいずれを用いてもよい。
In the step A, desulfurized slag is introduced and immersed in a solvent (usually water) placed in the extraction treatment tank 1, carbon dioxide is blown into the solvent from the gas blowing means 5, and the solvent has a pH of 4 to 10. Adjust so that When a solvent exceeds pH 10, the extraction rate of a sulfur component and Ca component will fall. Further, in the present invention, the extracted Ca component is reacted with carbon dioxide in the solvent to fix it as calcium carbonate, and this calcium carbonate is recovered together with the treated slag. This is not preferable because calcium dissolves. Moreover, when the solvent is less than
While the desulfurized slag is immersed in the solvent for a predetermined time, it is preferable that the solvent be maintained at the above pH during that time.
As carbon dioxide blown into the solvent, either CO 2 gas or CO 2 containing gas may be used.
脱硫スラグを溶媒中に浸漬し、この溶媒に二酸化炭素を吹き込むとともに、溶媒のｐＨを上記の範囲に調整・維持することにより、スラグに含まれる硫黄成分とＣａ成分が溶媒中に効率的に抽出される。また、抽出されたＣａ成分が溶媒中の二酸化炭素と反応して炭酸カルシウムとして固定される。そして、この炭酸カルシウムが処理済みスラグととともに回収される。
通常、本発明で使用する溶媒は水であり、この溶媒ｐＨの調整は、基本的に二酸化炭素の吹き込みにより行い、必要に応じて二酸化炭素の吹き込み量の調整や吹き込み中断を行う。但し、この二酸化炭素の吹き込みと併用して、例えば、強酸＋弱塩基、弱酸（補助的に強酸）、ｐＨ緩衝液などでｐＨを調整することもできる。したがって、この場合の溶媒は、例えば、（a）強酸＋弱塩基の水溶液、（b）弱酸水溶液、（c）ｐＨ緩衝剤水溶液、などである。
By immersing desulfurized slag in a solvent, blowing carbon dioxide into this solvent, and adjusting and maintaining the pH of the solvent within the above range, the sulfur component and Ca component contained in the slag are efficiently extracted into the solvent. Is done. Further, the extracted Ca component reacts with carbon dioxide in the solvent and is fixed as calcium carbonate. And this calcium carbonate is collect | recovered with processed slag.
Usually, the solvent used in the present invention is water, and the pH of the solvent is basically adjusted by blowing carbon dioxide, and the amount of blowing carbon dioxide is adjusted or the blowing is interrupted as necessary. However, in combination with the blowing of carbon dioxide, the pH can be adjusted with, for example, a strong acid + a weak base, a weak acid (auxiliarily a strong acid), a pH buffer solution, or the like. Therefore, the solvent in this case is, for example, (a) a strong acid + weak base aqueous solution, (b) a weak acid aqueous solution, (c) a pH buffer aqueous solution, or the like.
上記（a）の水溶液では、強酸として塩酸、硝酸などの１種以上を、弱塩基としてアンモニア、アミン類（例えば、ジエタノールアミンなど）などの１種以上を、それぞれ用いることができる。また、上記（b）の弱酸水溶液では、弱酸として、酢酸、クエン酸、リン酸などの１種以上を用いることができる。また、上記（c）のｐＨ緩衝剤水溶液は、目的とするｐＨを安定化させるために有効であり、酢酸系、リン酸系などのｐＨ緩衝剤が利用できる。但し、単独でｐＨを下げる効果は比較的小さいため、上述した他の酸などとの併用が望ましい。 In the aqueous solution (a), one or more kinds such as hydrochloric acid and nitric acid can be used as the strong acid, and one or more kinds such as ammonia and amines (for example, diethanolamine) can be used as the weak base. In the weak acid aqueous solution (b), one or more of acetic acid, citric acid, phosphoric acid and the like can be used as the weak acid. The aqueous pH buffer solution (c) is effective for stabilizing the target pH, and acetic acid and phosphoric acid pH buffers can be used. However, since the effect of lowering the pH by itself is relatively small, the combined use with the above-mentioned other acids is desirable.
抽出処理槽１内の溶媒は、脱硫スラグが浸漬された状態で撹拌手段４で撹拌してもよい。処理が完了したスラグと上述した炭酸カルシウムは槽外に排出され、炭酸カルシウムを含む脱硫黄・Ｃａ処理済みのスラグとして回収される。このスラグは、例えば、土木材料や骨材などに利材化される。
抽出処理槽１内の溶媒は、流路３aを通じて回収処理槽２に適宜移送され、ここで硫黄成分の回収が行われる。この回収処理槽２において溶媒の硫黄成分を回収するために、例えば石灰が投入され、硫黄成分と反応させて石膏などとして沈降させ、この沈降物を回収する。回収処理槽２内の溶媒は、石灰が投入された状態で撹拌手段６で撹拌してもよい。ここで回収された沈降物は、硫黄含有原料（例えば石膏原料）として利材化することができる。なお、抽出処理槽１から回収処理槽２への溶媒の移送や、回収処理槽２での溶媒の処理および沈降物の回収は、バッチ式、連続式のいずれでもよい。
The solvent in the extraction processing tank 1 may be stirred by the stirring means 4 in a state where the desulfurized slag is immersed. The treated slag and the above-described calcium carbonate are discharged out of the tank and recovered as desulfurized and Ca-treated slag containing calcium carbonate. For example, this slag is used as a civil engineering material or an aggregate.
The solvent in the extraction processing tank 1 is appropriately transferred to the
回収処理槽２内の溶媒は、流路３bを通じて抽出処理槽１に適宜返送され、循環使用される。なお、この抽出処理槽１への水溶液の返送は、バッチ式、連続式のいずれでもよい。
また、本発明の製造方法では、上述した工程Ａにおいて、脱硫黄・Ｃａ処理されたスラグが製造され、このスラグはそのまま或いは適当な処理を加えて土木材料、その他の材料に利用される。また、工程Ｂにおいては、回収物として硫黄含有原料（例えば石膏原料）が製造される。
The solvent in the
Moreover, in the manufacturing method of this invention, in the process A mentioned above, the desulfurization and Ca-treated slag is manufactured, and this slag is used for civil engineering materials and other materials as they are or after appropriate treatment. In Step B, a sulfur-containing raw material (for example, a gypsum raw material) is produced as a recovered product.
溶媒（水）を入れた容器内に０．５ｍｍ篩下の脱硫スラグを投入・浸漬し、表１に示す条件でＣＯ２含有ガス（ＣＯ２濃度：２０vol％）を吹き込みつつ、３０分間撹拌した。液／固比：６０とし、処理時間中、ｐＨが一定となるようにＣＯ２含有ガスの吹き込みを適宜中断した。
処理完了後、容器の内容物をろ過し、液相（溶媒）と固相（処理済みスラグ＋炭酸カルシウム）を分離回収し、硫黄成分の抽出率、炭酸カルシウムとして析出したＣａ量を測定した。硫黄成分の抽出率とは、スラグ中に含まれていた硫黄に対する溶媒に溶解した硫黄の割合（質量％）である。
溶媒ｐＨなどの試験条件、処理後の硫黄成分の抽出率、炭酸カルシウムとして析出したＣａ量を表１に示す。これによれば、本発明例では、スラグ中の硫黄成分とＣａ成分が選択的に溶解し、且つ溶媒中への硫黄成分とＣａ成分の抽出が効率的になされ、また、抽出されたＣａ成分は炭酸カルシウムとして適切に析出していることが判る。
The desulfurized slag of 0.5 mm below the sieve was put in and immersed in a container containing the solvent (water), and stirred for 30 minutes while blowing CO 2 -containing gas (CO 2 concentration: 20 vol%) under the conditions shown in Table 1. . The liquid / solid ratio was set to 60, and the blowing of the CO 2 -containing gas was appropriately interrupted so that the pH became constant during the treatment time.
After completion of the treatment, the contents of the container were filtered, the liquid phase (solvent) and the solid phase (treated slag + calcium carbonate) were separated and recovered, and the sulfur component extraction rate and the amount of Ca deposited as calcium carbonate were measured. The extraction rate of the sulfur component is a ratio (mass%) of sulfur dissolved in the solvent with respect to sulfur contained in the slag.
Table 1 shows the test conditions such as the solvent pH, the extraction rate of the sulfur component after the treatment, and the amount of Ca deposited as calcium carbonate. According to this, in the present invention example, the sulfur component and the Ca component in the slag are selectively dissolved, the sulfur component and the Ca component are efficiently extracted into the solvent, and the extracted Ca component It can be seen that is appropriately deposited as calcium carbonate.
１ 抽出処理槽
２ 回収処理槽
３a，３b 流路
４ 撹拌手段
５ ガス吹込手段
６ 撹拌手段
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| JP5983537B2 (en) * | 2012-05-29 | 2016-08-31 | Ｊｆｅスチール株式会社 | Method for removing sulfur from slag containing sulfur |
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| WO2019107115A1 (en) * | 2017-11-30 | 2019-06-06 | 日新製鋼株式会社 | Method for eluting calcium from steel-making slag, method for collecting calcium from steel-making slag, and device for eluting calcium from steel-making slag |
| WO2019107116A1 (en) * | 2017-11-30 | 2019-06-06 | 日新製鋼株式会社 | Method for eluting calcium from steel-making slag, method for collecting calcium from steel-making slag, and device for eluting calcium from steel-making slag |
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