JP2011256411A - Method for treating steel slag - Google Patents
Method for treating steel slag Download PDFInfo
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- JP2011256411A JP2011256411A JP2010129881A JP2010129881A JP2011256411A JP 2011256411 A JP2011256411 A JP 2011256411A JP 2010129881 A JP2010129881 A JP 2010129881A JP 2010129881 A JP2010129881 A JP 2010129881A JP 2011256411 A JP2011256411 A JP 2011256411A
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- slag
- organic acid
- high iron
- acid solution
- steelmaking
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- 239000002893 slag Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910000831 Steel Inorganic materials 0.000 title abstract description 9
- 239000010959 steel Substances 0.000 title abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- 150000007524 organic acids Chemical class 0.000 claims abstract description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 10
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- 238000009628 steelmaking Methods 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 10
- 229910052918 calcium silicate Inorganic materials 0.000 description 10
- 235000012241 calcium silicate Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000007885 magnetic separation Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- GAISRYMZAXLPHD-UHFFFAOYSA-N 2-hydroxybenzoic acid;methanol Chemical compound OC.OC(=O)C1=CC=CC=C1O GAISRYMZAXLPHD-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910001719 melilite Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Furnace Details (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
Description
本発明は、製鋼工程で大量に副生する製鋼スラグの処理方法に関する。 The present invention relates to a method for treating steelmaking slag that is by-produced in large quantities in a steelmaking process.
製鋼産業においては、種々のプロセスや設備によって、また、製造する鋼種によって様々な組成や性状を有するスラグが副生する。例えば、銑鉄を調製するプロセスで用いる高炉からは高炉スラグが、銑鉄から製鋼するプロセスで用いる溶銑予備処理設備、転炉、及び電気炉からは、それぞれ、溶銑予備処理スラグ、転炉スラグ、及び電気炉スラグが副生する。そして、高炉スラグには水砕スラグ及び徐冷スラグがあり、溶銑予備処理スラグには、脱珪スラグ、脱リンスラグ、脱硫スラグ、及び脱炭スラグがあり、電気炉スラグにも酸化期スラグと還元期スラグが存在する。また、鋼種の違いで、普通炭素鋼、極低炭素鋼、特殊合金鋼、及びステンレス鋼等がある。 In the steelmaking industry, slag having various compositions and properties is produced as a by-product by various processes and facilities and by the steel type to be manufactured. For example, blast furnace slag from the blast furnace used in the process of preparing pig iron, hot metal pretreatment equipment, converter, and electric furnace used in the process of steelmaking from pig iron, respectively, hot metal pretreatment slag, converter slag, and electric Furnace slag is by-produced. The blast furnace slag includes granulated slag and slow-cooled slag. The hot metal pretreatment slag includes desiliconized slag, dephosphorized slag, desulfurized slag, and decarburized slag. Period slag exists. Also, there are ordinary carbon steel, ultra-low carbon steel, special alloy steel, stainless steel, etc., depending on the type of steel.
上記スラグのうち、高炉より副生する高炉水砕スラグは、セメント・コンクリート用混和材や路盤材等として利用されている。また、高炉水砕スラグ以外の製鋼スラグをセメント用混和材として使用することも提案されている（特許文献１）。 Among the slags, granulated blast furnace slag produced as a by-product from the blast furnace is used as a cement / concrete admixture or roadbed material. It has also been proposed to use steelmaking slag other than blast furnace granulated slag as an admixture for cement (Patent Document 1).
しかしながら、高炉水砕スラグ以外の製鋼スラグはメーカー及びロットにより組成、物性が大きく異なるために、これをセメント混和材として使用するとセメント組成物の品質変動が大きくなる虞があり、現状では充分に再利用されているとは言えず、埋立処分も多い状況にある。そのため、高炉水砕スラグ以外の製鋼スラグを有効利用できる処理方法が求められている。
なお、本発明でいう製鋼スラグとは、製鋼プロセスで生じるスラグの総称であり、具体的には溶銑予備処理スラグ、転炉スラグ、電気炉スラグ、溶融還元炉スラグ、二次精錬スラグやステンレススラグを指すものであり、高炉水砕スラグ及び高炉徐冷スラグは含まない。
However, the composition and physical properties of steelmaking slag other than blast furnace granulated slag vary greatly depending on the manufacturer and lot, so using this as a cement admixture may increase the quality of the cement composition. It cannot be said that it is being used, and there are many landfill disposals. Therefore, the processing method which can utilize effectively steelmaking slag other than blast furnace granulated slag is calculated | required.
The steelmaking slag as used in the present invention is a general term for slag generated in the steelmaking process. Specifically, hot metal pretreatment slag, converter slag, electric furnace slag, smelting reduction furnace slag, secondary refining slag, and stainless slag. It does not include blast furnace granulated slag and blast furnace annealed slag.
本発明者らは、斯かる実情に鑑み、鋭意検討した結果、製鋼スラグを有機酸溶液で処理することにより、Fe2O3含有量が多い高鉄含有物を回収できることを見いだし、本発明を完成させたものである。
すなわち、本発明は、製鋼スラグを有機酸溶液中で攪拌後、固液分離して、Fe2O3含有量が40質量％以上である高鉄含有物を回収することを特徴とする製鋼スラグの処理方法である（請求項１）。
上記高鉄含有物は、製鋼原料、セメントクリンカー用原料及び／又はコンクリート用混和材として使用することができる。
As a result of intensive studies in view of such circumstances, the present inventors have found that high iron content containing a large amount of Fe 2 O 3 can be recovered by treating steelmaking slag with an organic acid solution, and It has been completed.
That is, the present invention is a steelmaking slag characterized in that the steelmaking slag is stirred in an organic acid solution and then solid-liquid separated to recover a high iron-containing material having an Fe 2 O 3 content of 40% by mass or more. (Claim 1).
The high iron-containing material can be used as a steelmaking raw material, a raw material for cement clinker and / or an admixture for concrete.
本発明では、製鋼スラグから高鉄含有物を回収し、該高鉄含有物は製鋼原料やセメントクリンカー用原料などとして使用することができるので、従来、有効利用が困難であった製鋼スラグの有効利用を可能とし、埋め立て処分量を大幅に減少することができる。 In the present invention, high iron content is recovered from steelmaking slag, and the high iron content can be used as a steelmaking raw material or a raw material for cement clinker. It can be used and landfill disposal volume can be greatly reduced.
以下、本発明について詳細に説明する。
本発明で対象とする製鋼スラグは、溶銑予備処理スラグ、転炉スラグ、電気炉スラグ、溶融還元炉スラグ、二次精錬スラグやステンレススラグである。これらのスラグは、CaO、Fe2O3、SiO2を主要な化学成分とし、その他に、Al2O3、MnO、MgO、P2O5等を含んでいる。また、化合物としては、ビーライト、メリライト、ウスタイト、カルシウムフェライトなどを主要化合物として含んでいる。
Hereinafter, the present invention will be described in detail.
Steelmaking slag targeted in the present invention is hot metal pretreatment slag, converter slag, electric furnace slag, smelting reduction furnace slag, secondary refining slag, and stainless steel slag. These slags contain CaO, Fe 2 O 3 and SiO 2 as main chemical components, and additionally contain Al 2 O 3 , MnO, MgO, P 2 O 5 and the like. The compounds include belite, melilite, wustite, calcium ferrite and the like as main compounds.
製鋼スラグ中の鉄は、金属鉄として粒径100μｍ以上の塊で存在する他に、ビーライトの間隙を埋めるようにウスタイト、カルシウムフェライトとして存在しているので、製鋼スラグから高鉄含有物を回収するには、製鋼スラグ中のビーライトを選択的に除去する必要がある。そのために、本発明においては、製鋼スラグを有機酸溶液中で攪拌することにより、製鋼スラグ中のビーライトを有機酸溶液に溶解させて除去する。
上記有機酸としては、サリチル酸、ピクリン酸、マレイン酸等を使用することができるが、ビーライトを選択的に溶解できることや攪拌処理時間の短縮等の観点から、有機酸としてはサリチル酸を使用することが好ましい。
有機酸溶液の溶媒としては、メタノール、エタノール、アセトン、トルエン等を使用することができるが、ビーライトを選択的に溶解できることや攪拌処理時間の短縮等の観点から、有機酸溶液の溶媒としてはメタノールを使用することが好ましい。
The iron in steelmaking slag exists as lump with a particle size of 100μm or more as metallic iron, and also exists as wustite and calcium ferrite so as to fill the gap of belite, so high iron content is recovered from steelmaking slag. Therefore, it is necessary to selectively remove belite in the steelmaking slag. For this purpose, in the present invention, steelmaking slag is stirred in an organic acid solution, so that belite in the steelmaking slag is dissolved in the organic acid solution and removed.
Salicylic acid, picric acid, maleic acid, and the like can be used as the organic acid, but salicylic acid can be used as the organic acid from the viewpoint of selective dissolution of belite and shortening of the stirring time. Is preferred.
As the solvent for the organic acid solution, methanol, ethanol, acetone, toluene, and the like can be used. From the viewpoint of selective dissolution of belite and shortening of the stirring treatment time, the solvent for the organic acid solution is Preference is given to using methanol.
有機酸溶液の濃度(溶質(有機酸)の質量／溶媒の体積)は、10kg/m3以上が好ましく、15kg/m3以上がより好ましく、20kg/m3以上が特に好ましい。有機酸溶液の濃度が10kg/m3未満では、製鋼スラグの攪拌処理に時間がかかるうえ、ビーライトの溶解量も少なくなりFe2O3含有量が40質量％以上である高鉄含有物を回収することが困難になる虞がある。
なお、有機酸溶液の濃度の上限は飽和濃度であるが、有機酸溶液の濃度を高くしても高鉄含有物中の鉄含有量は大きく増えず、薬剤コストが増大することに加えて、固液分離後の液分(有機酸溶液)からカルシウムや珪素やリン等を回収することが困難になる。従って、有機酸溶液の濃度は、150kg/m3以下が好ましく、100kg/m3以下がより好ましく、70kg/m3以下が特に好ましい。
The concentration of the organic acid solution (solute (volume / weight of solvent in the organic acid)) is, 10 kg / m 3 or more, more preferably at least 15kg / m 3, 20kg / m 3 or more is particularly preferable. At concentrations of less than 10 kg / m 3 of organic acid solution, it takes time to stirring treatment of steel slag, a high iron-containing material that dissolved amount less and less Fe 2 O 3 content of belite is 40 wt% or more It may be difficult to collect.
The upper limit of the concentration of the organic acid solution is a saturated concentration, but even if the concentration of the organic acid solution is increased, the iron content in the high iron content does not increase greatly, and in addition to the increase in drug cost, It becomes difficult to recover calcium, silicon, phosphorus, and the like from the liquid (organic acid solution) after solid-liquid separation. Therefore, the concentration of the organic acid solution is preferably 150 kg / m 3 or less, more preferably 100 kg / m 3 or less, particularly preferably 70 kg / m 3.
有機酸溶液に対する製鋼スラグの添加量は、有機酸溶液1m3に対して5〜150kgが好ましく、10〜120kgがより好ましく、10〜120kgが特に好ましい。有機酸溶液1m3に対して製鋼スラグの添加量が5kg未満では、製鋼スラグの処理効率が低下する。一方、有機酸溶液1m3に対して製鋼スラグの添加量が150kgを超えると、ビーライトの溶解量が少なくなりFe2O3含有量が40質量％以上である高鉄含有物を回収することが困難になる虞がある。
なお、本発明においては、攪拌処理時間の短縮等の観点から、製鋼スラグをジョークラッシャーなどを用いて2.0ｍｍ以下、より好ましくは1.2mm以下に粗砕した後、有機酸溶液中で攪拌することが好ましい。さらにはボールミルなどを用いてブレーン比表面積2000cm2/g以上に粉砕した後に有機酸溶液中で攪拌することが特に好ましい。
攪拌時間としては10〜120分間（より好ましくは15〜90分間、特に好ましくは20〜60分間）が好ましい。攪拌時間が10分間未満では、ビーライトの溶解量が少なくなりFe2O3含有量が40質量％以上である高鉄含有物を回収することが困難になる虞がある。攪拌時間が120分間を超えると、製鋼スラグの処理効率が低下する。
なお、攪拌は、慣用の攪拌装置を使用して行なうことができる。
The amount of steelmaking slag added to the organic acid solution is preferably 5 to 150 kg, more preferably 10 to 120 kg, and particularly preferably 10 to 120 kg with respect to 1 m 3 of the organic acid solution. When the amount of steelmaking slag added is less than 5 kg with respect to 1 m 3 of the organic acid solution, the processing efficiency of the steelmaking slag decreases. On the other hand, the amount of steel slag to the organic acid solution 1 m 3 is more than 150 kg, the dissolved amount is small Fe 2 O 3 content of belite is recovery of high iron-containing material which is a 40% by mass or more May become difficult.
In the present invention, from the viewpoint of shortening the stirring time, etc., the steelmaking slag is roughly crushed to 2.0 mm or less, more preferably 1.2 mm or less using a jaw crusher, and then stirred in the organic acid solution. Is preferred. Further, it is particularly preferable to use a ball mill or the like to grind to a brain specific surface area of 2000 cm 2 / g or more and then stir in the organic acid solution.
The stirring time is preferably 10 to 120 minutes (more preferably 15 to 90 minutes, particularly preferably 20 to 60 minutes). If the stirring time is less than 10 minutes, the dissolved amount of belite is reduced, and it may be difficult to recover the high iron content having an Fe 2 O 3 content of 40% by mass or more. When the stirring time exceeds 120 minutes, the processing efficiency of steelmaking slag decreases.
Stirring can be performed using a conventional stirring device.
製鋼スラグを有機酸溶液中で攪拌後、固液分離して、Fe2O3含有量が多い高鉄含有物を回収する。固液分離の方法としては、ろ過や遠心分離等を行なえば良い。
本発明においては、回収した高鉄含有物の有効利用を図るために、高鉄含有物中のFe2O3含有量は40質量％以上であることが好ましく、43質量％以上であることがより好ましく、45質量％以上であることが特に好ましい。
なお、品位の悪い鉄鋼石では、Fe2O3含有量が40〜45質量％程度のものもある。
Steelmaking slag is stirred in an organic acid solution and then solid-liquid separated to recover high iron content with a high Fe 2 O 3 content. As a solid-liquid separation method, filtration, centrifugation, or the like may be performed.
In the present invention, in order to effectively use the recovered high iron content, the content of Fe 2 O 3 in the high iron content is preferably 40% by mass or more, and 43% by mass or more. More preferably, it is particularly preferably 45% by mass or more.
In addition, some steel stones with poor quality have a Fe 2 O 3 content of about 40 to 45% by mass.
本発明においては、上記高鉄含有物中のFe2O3含有量を高めるために、該高鉄含有物を磁選処理や比重選別処理することは差し支えない。磁選処理や比重選別処理を行なうことにより、高鉄含有物中のFe2O3含有量を50質量％以上にまで高めることが可能になる。
磁選処理や比重選別処理後の残渣は、未処理の製鋼スラグと混合して、再度本願発明の処理をすれば良い。
なお、磁選処理装置としては、ドラム型、プーリー型、吊り下げ型、対極型などの磁選処理装置を使用することができる。比重選別処理装置としては、乾式の風力型、エアスクリーン型、湿式の重力沈降型、比重液型、遠心力式などの比重選別処理装置を使用することができる。
In the present invention, in order to increase the Fe 2 O 3 content in the high iron content, the high iron content may be subjected to magnetic separation treatment or specific gravity separation treatment. By performing the magnetic separation process and the specific gravity selection process, the Fe 2 O 3 content in the high iron content material can be increased to 50% by mass or more.
The residue after the magnetic separation process and the specific gravity selection process may be mixed with untreated steelmaking slag and processed again according to the present invention.
In addition, as a magnetic separation processing apparatus, a magnetic separation processing apparatus such as a drum type, a pulley type, a suspension type, or a counter electrode type can be used. As the specific gravity sorting processing device, a specific gravity sorting processing device such as a dry wind type, an air screen type, a wet gravity sedimentation type, a specific gravity liquid type, or a centrifugal force type can be used.
上記回収した高鉄含有物は、製鋼原料、セメントクリンカー用原料や、コンクリート用混和材として使用することができるが、本発明においては、製鋼原料として使用することがより好ましい。その理由は、(1)製鋼スラグは、Mn、MgやCr（セメントクリンカー用原料やコンクリート用混和材としては望ましくない成分）を含んでおり、該Mn、MgやCrはウスタイトに非常に多く固溶しているので、Mn、MgやCrは高鉄含有物中に多く含まれることになること、また、(2)製鋼スラグは、リン（製鋼原料としては望ましくない成分）を含んでおり、該リンはほぼ全量がビーライトに固溶しているので、高鉄含有物中のリン含有量が少なくなること、からである。
なお、Mn、MgやCr含有量の少ない高鉄含有物は、セメントクリンカー用原料やコンクリート（特に重量コンクリート）用混和材として使用できることは言うまでもない。該高鉄含有物をセメントクリンカー用原料として使用する場合は鉄原料として使用することができ、石灰石、生石灰、消石灰などのCaO原料、珪石、粘土などのSiO2原料や粘土、石炭灰などのAl2O3原料と併用して使用し、成分調整すれば良い。
The recovered high iron-containing material can be used as a steelmaking raw material, a cement clinker raw material, or a concrete admixture, but in the present invention, it is more preferably used as a steelmaking raw material. The reason is as follows: (1) Steelmaking slag contains Mn, Mg and Cr (undesirable ingredients for cement clinker raw materials and concrete admixtures), and Mn, Mg and Cr are very much solid in wustite. Because it melts, Mn, Mg and Cr will be contained in high iron content, and (2) Steelmaking slag contains phosphorus (an undesirable component for steelmaking raw materials) This is because almost all of the phosphorus is dissolved in belite, so that the phosphorus content in the high iron content is reduced.
Needless to say, a high iron content with a low content of Mn, Mg and Cr can be used as a raw material for cement clinker or an admixture for concrete (particularly heavy concrete). When using the high-iron-containing material as a raw material for cement clinker can be used as a source of iron, limestone, burnt lime, CaO raw material such as slaked lime, silica, SiO 2 raw material or clay such as clay, Al, such as coal ash Use it in combination with 2 O 3 raw material and adjust the ingredients.
なお、上記固液分離して得られる液分(有機酸溶液)中には、カルシウムや珪素やリンが比較的多く含まれている。本発明においては、上記固液分離して得られる液分(有機酸溶液)から、これらの有効成分を回収することができる。
特にリンは枯渇が懸念されている元素であり、本技術によりリンが濃縮した有機酸溶液からリンを回収することが資源の有効利用の面から好ましい。リンの回収方法として蒸発乾固させた後、有機酸を燃焼により除去する方法、溶液に水酸化カルシウム、硫酸バンドなどを添加して凝集沈殿させる方法、吸着剤やキレートによりリンを選択的に吸着させる方法等が上げられる。
Note that the liquid (organic acid solution) obtained by solid-liquid separation contains a relatively large amount of calcium, silicon, and phosphorus. In the present invention, these active ingredients can be recovered from the liquid (organic acid solution) obtained by solid-liquid separation.
In particular, phosphorus is an element that is feared to be depleted, and it is preferable from the viewpoint of effective use of resources to recover phosphorus from an organic acid solution in which phosphorus is concentrated by this technique. As a recovery method of phosphorus, after evaporating to dryness, removing organic acid by combustion, adding calcium hydroxide, sulfuric acid band, etc. to the solution and aggregating and precipitating, selective adsorption of phosphorus by adsorbent and chelate The method of making it go up.
次に、実施例を挙げて本発明をさらに説明するが、本発明は、これら実施例により限定されるものではない。
１．使用転炉スラグ
使用した転炉スラグの化学成分(質量％)は、CaO:42.1％、Fe2O3:26.7％、SiO2:16.2％、MgO:4.4％、MnO:4.6％、P2O5:2.2％、Al2O3:2.2％である。
上記転炉スラグをブレーン比表面積3000cm2/gに粉砕したものを使用した。
EXAMPLES Next, although an Example is given and this invention is further demonstrated, this invention is not limited by these Examples.
1. Used converter slag The chemical composition (mass%) of the used converter slag is CaO: 42.1%, Fe 2 O 3 : 26.7%, SiO 2 : 16.2%, MgO: 4.4%, MnO: 4.6%, P 2 O 5 : 2.2%, Al 2 O 3 : 2.2%.
The converter slag was pulverized to a brain specific surface area of 3000 cm 2 / g.
２．実施例１
サリチル酸(試薬)とメタノール(試薬)を使用して、サリチル酸メタノール溶液(濃度:40g/1000cm3)を調製した。該サリチル酸メタノール溶液1000cm3に対して、上記転炉スラグ粉末を20g添加して、20℃で60分間攪拌した後、固液分離(ろ過)した。
得られた固形分(高鉄含有物)の化学成分(質量％)は、CaO:23.1％、Fe2O3:44.5％、SiO2:10.8％、MgO:7.8％、MnO:6.9％、P2O5:1.7％、Al2O3:3.2％であった。
なお、固形分(高鉄含有物)の回収率は54質量％であった。
2. Example 1
A salicylic acid methanol solution (concentration: 40 g / 1000 cm 3 ) was prepared using salicylic acid (reagent) and methanol (reagent). 20 g of the above converter slag powder was added to 1000 cm 3 of the salicylic acid methanol solution, and the mixture was stirred at 20 ° C. for 60 minutes, followed by solid-liquid separation (filtration).
The resulting chemical composition of solids (high iron-containing material) (mass%), CaO: 23.1%, Fe 2 O 3: 44.5%, SiO 2: 10.8%, MgO: 7.8%, MnO: 6.9%, P 2 O 5 : 1.7% and Al 2 O 3 : 3.2%.
The recovery rate of solid content (high iron content) was 54% by mass.
３．実施例２
サリチル酸(試薬)とメタノール(試薬)を使用して、サリチル酸メタノール溶液(濃度:150g/1000cm3)を調製した。該サリチル酸メタノール溶液1000cm3に対して、上記転炉スラグ粉末を25g添加して、20℃で60分間攪拌した後、固液分離(ろ過)した。
得られた固形分(高鉄含有物)の化学成分(質量％)は、CaO:21.1％、Fe2O3:46.2％、SiO2:10.4％、MgO:7.6％、MnO:7.1％、P2O5:1.7％、Al2O3:3.7％であった。
なお、固形分(高鉄含有物)の回収率は38質量％であった。
3. Example 2
A salicylic acid methanol solution (concentration: 150 g / 1000 cm 3 ) was prepared using salicylic acid (reagent) and methanol (reagent). 25 g of the above converter slag powder was added to 1000 cm 3 of the salicylic acid methanol solution, and the mixture was stirred at 20 ° C. for 60 minutes, followed by solid-liquid separation (filtration).
The chemical composition (mass%) of the obtained solid content (high iron content) is CaO: 21.1%, Fe 2 O 3 : 46.2%, SiO 2 : 10.4%, MgO: 7.6%, MnO: 7.1%, P 2 O 5 : 1.7% and Al 2 O 3 : 3.7%.
The recovery rate of the solid content (high iron content) was 38% by mass.
４．比較例１
10％塩酸1000cm3に対して、上記転炉スラグ粉末を20g添加して、20℃で60分間攪拌した後、固液分離(ろ過)した。
得られた固形分の化学成分(質量％)は、CaO:4.0％、Fe2O3:14.4％、SiO2:68.6％、MgO:1.1％、MnO:1.4％、P2O5:0.3％、Al2O3:1.3％であった。
なお、固形分の回収率は11質量％であった。
4). Comparative Example 1
20 g of the above converter slag powder was added to 1000 cm 3 of 10% hydrochloric acid, and the mixture was stirred at 20 ° C. for 60 minutes, followed by solid-liquid separation (filtration).
The chemical content (% by mass) of the solid content was CaO: 4.0%, Fe 2 O 3 : 14.4%, SiO 2 : 68.6%, MgO: 1.1%, MnO: 1.4%, P 2 O 5 : 0.3% Al 2 O 3 : 1.3%.
The solids recovery rate was 11% by mass.
実施例１〜２に示すように、本願の処理方法によると、転炉スラグからFe2O3含有量が40質量％以上である高鉄含有物を回収できることが分かる。
一方、有機酸溶液以外の酸を使用した比較例１では、高鉄含有物を回収することができなかった。
As shown in Examples 1 and 2, it can be seen that according to the treatment method of the present application, a high iron-containing material having an Fe 2 O 3 content of 40% by mass or more can be recovered from the converter slag.
On the other hand, in Comparative Example 1 using an acid other than the organic acid solution, the high iron content could not be recovered.
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| CN108504799A (en) * | 2018-05-15 | 2018-09-07 | 鞍钢股份有限公司 | Method for reducing FeO content in final slag in molten converter slag modification |
| JP2018149538A (en) * | 2017-03-13 | 2018-09-27 | 株式会社三井Ｅ＆Ｓホールディングス | Molten slag processing method, silica raw material, high specific surface area silica, mesoporous silica and silica manufacturing method |
| JP2021155300A (en) * | 2020-03-27 | 2021-10-07 | 住友大阪セメント株式会社 | Manufacturing method of cement raw material |
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| JP2018149538A (en) * | 2017-03-13 | 2018-09-27 | 株式会社三井Ｅ＆Ｓホールディングス | Molten slag processing method, silica raw material, high specific surface area silica, mesoporous silica and silica manufacturing method |
| JP7027672B2 (en) | 2017-03-13 | 2022-03-02 | Ｊｆｅ環境テクノロジー株式会社 | Molten slag treatment method, mesoporous silica production method, and silica production method |
| CN108504799A (en) * | 2018-05-15 | 2018-09-07 | 鞍钢股份有限公司 | Method for reducing FeO content in final slag in molten converter slag modification |
| CN108504799B (en) * | 2018-05-15 | 2019-08-27 | 鞍钢股份有限公司 | Method for reducing FeO content in final slag in molten converter slag modification |
| JP2021155300A (en) * | 2020-03-27 | 2021-10-07 | 住友大阪セメント株式会社 | Manufacturing method of cement raw material |
| JP7294207B2 (en) | 2020-03-27 | 2023-06-20 | 住友大阪セメント株式会社 | Cement raw material manufacturing method |
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