JP4571818B2 - Method for reforming steelmaking slag - Google Patents
Method for reforming steelmaking slag Download PDFInfo
- Publication number
- JP4571818B2 JP4571818B2 JP2004125012A JP2004125012A JP4571818B2 JP 4571818 B2 JP4571818 B2 JP 4571818B2 JP 2004125012 A JP2004125012 A JP 2004125012A JP 2004125012 A JP2004125012 A JP 2004125012A JP 4571818 B2 JP4571818 B2 JP 4571818B2
- Authority
- JP
- Japan
- Prior art keywords
- slag
- steelmaking slag
- temperature
- heat treatment
- furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002893 slag Substances 0.000 title claims description 205
- 238000009628 steelmaking Methods 0.000 title claims description 98
- 238000000034 method Methods 0.000 title claims description 52
- 238000002407 reforming Methods 0.000 title claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 98
- 238000002844 melting Methods 0.000 claims description 71
- 230000008018 melting Effects 0.000 claims description 71
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002956 ash Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 239000004567 concrete Substances 0.000 claims description 14
- 238000010583 slow cooling Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000003723 Smelting Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000010801 sewage sludge Substances 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 51
- 238000010521 absorption reaction Methods 0.000 description 42
- 239000002994 raw material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007790 solid phase Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000007654 immersion Methods 0.000 description 9
- 239000010426 asphalt Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000002969 artificial stone Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- -1 solidified bodies Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- 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)
Description
本発明は、上層路盤材、加熱アスファルト混合道路用材、アスファルト舗装用骨材、コンクリート用骨材等の有用な原料、硬化体・固化体原料、底質・海水浄化剤原料、もしくは鉄鋼、非鉄の製錬・精錬工程、廃棄物燃焼溶融炉、灰溶融炉、スラグ溶融炉における原料等に適用することができる改質製鋼スラグ及びその製造方法に関するものである。 The present invention is useful raw materials such as upper layer roadbed materials, heated asphalt mixed road materials, aggregates for asphalt pavement, aggregates for concrete, hardened body / solidified body materials, bottom material / seawater purifier raw materials, or steel, non-ferrous The present invention relates to a modified steelmaking slag that can be applied to raw materials in a smelting and refining process, a waste combustion melting furnace, an ash melting furnace, a slag melting furnace, and a method for manufacturing the same.
製鋼スラグは遊離CaO(以降f・CaOと記載する)を含み、その水和反応時の体積変化から膨脹崩壊性を示す。また、微小な亀裂、開気孔が多いため、吸水率が高く強度が低い。これにより、土木工事用の仮設材、道路の地盤改良材、下層路盤材等の低級用途でしか使用されておらず、より高級用途である上層路盤材、コンクリート用骨材、石材原料等には用いられていない。
しかし、低級用途の需要の低下から在庫が増大しており、発生した製鋼スラグの置き場等の問題も発生している。このため、上層路磐材、コンクリート用骨材、石材原料等、高級用途への有効利用が必要である。従来、スラグ中のf.CaOを減少させるスラグ熱間改質法、エージング法が種々検討されている。
Steelmaking slag contains free CaO (hereinafter referred to as “f · CaO”), and exhibits expansion and disintegration from the volume change during the hydration reaction. Moreover, since there are many fine cracks and open pores, the water absorption is high and the strength is low. As a result, it is used only for low-level applications such as temporary materials for civil engineering, road ground improvement materials, lower-layer roadbed materials, etc., and for higher-grade upper-layer roadbed materials, concrete aggregates, stone materials, etc. Not used.
However, stocks are increasing due to a drop in demand for low-grade applications, and problems such as storage of generated steelmaking slag have also occurred. For this reason, it is necessary to effectively use it for high-grade applications such as upper-layer roadside materials, concrete aggregates, and stone materials. Conventionally, f. Various slag hot reforming methods and aging methods for reducing CaO have been studied.
スラグ熱間改質法は、特許文献1に提案されているように、製鋼スラグに、珪酸含有改質剤、炭素含有還元剤及び鉄スクラップを混合し、該混合物を、酸素ガス含有気体を供給しつつ還元性雰囲気に維持しながら溶融することを特徴とする製鋼スラグの熱間改質法である。
また、エージング法は、特許文献2に提案されているように、製鋼スラグを精錬時の装入副原料のCaO量を50kg/粗鋼ton以下およびスラグ塩基度3.5以下を基準として分別して、これに適合するスラグを放冷固化後、スラグ温度が400〜1000℃の顕熱を保持した状態で40〜100℃の温水槽に投入してf.CaOの水和反応を促進させ安定化処理することを特徴とする方法である。
In addition, as proposed in
しかし、上記スラグ熱間改質法は鉄スクラップを混合するため、1550℃以上に加熱し、該混合物を溶融する必要がある。この溶解に多量の熱と時間を必要とし、処理能力が低い。また還元性雰囲気で酸化鉄、酸化燐、酸化マンガン等の金属酸化物を還元して回収するため、f・CaOが完全にSiO2や低融点金属酸化物と反応しきれずに、改質スラグにはf・CaOが残存していた。
また、上記エージング法は、改質可能なスラグを限定しており、改質できないスラグが約半数程度残存する。スラグの塩基度が高い場合、エージング期間を短くしたときにf・CaOが低減できずにスラグの安定化が不十分となる。また、改質可能なスラグであっても数日以内のエージング期間が必要であり、処理能力が低い。また、100℃以下程度での完全固相反応では、f・CaOが完全にSiO2等と反応しきれずに、スラグの膨脹、粉化を単に軽減することはできるものの、上層路盤材に使用可能なまでに安定化することはできない。また、改質スラグは、砕石等と比較すると吸水率が高く、強度が不十分である。
However, since the slag hot reforming method mixes iron scrap, it must be heated to 1550 ° C. or higher to melt the mixture. This melting requires a large amount of heat and time, and the processing capacity is low. In addition, since metal oxides such as iron oxide, phosphorus oxide, and manganese oxide are reduced and recovered in a reducing atmosphere, f · CaO cannot be completely reacted with SiO 2 or low-melting-point metal oxides. F.CaO remained.
Moreover, the aging method described above limits slag that can be modified, and about half of the slag that cannot be modified remains. If the basicity of the slag is high, f · CaO cannot be reduced when the aging period is shortened, and the stabilization of the slag becomes insufficient. Further, even slag that can be modified requires an aging period of several days or less, and the processing capacity is low. Also, in complete solid-phase reactions at about 100 ° C or less, f · CaO cannot be completely reacted with SiO 2 and the like, and slag expansion and pulverization can be simply reduced, but it can be used for upper roadbed materials. It cannot be stabilized at all. In addition, the modified slag has a high water absorption rate compared with crushed stone and the like, and the strength is insufficient.
すなわち、従来の技術によって製造された改質スラグは、残存したf・CaOを未だ含み、吸水率も高く強度が低いため、上層路盤材等の高級用途、固化体等の原料をはじめ、もしくは鉄鋼・非鉄の製錬・精錬工程等の原料に、有効利用することが不可能であった。
本発明は、このような従来の技術の課題に鑑みてなされたもので、製鋼スラグの改質法を改良し、f・CaOのみならず、吸水率をも減少させる製鋼スラグの改質方法、および改質製鋼スラグを提供することを目的とする。
In other words, the modified slag produced by the conventional technology still contains the remaining f · CaO and has a high water absorption rate and low strength, so it is used for high-grade applications such as upper roadbed materials, raw materials such as solidified bodies, or steel.・ It could not be effectively used as a raw material for non-ferrous smelting and refining processes.
The present invention has been made in view of the problems of the prior art as described above, and is an improved steelmaking slag reforming method that reduces not only f · CaO but also the water absorption rate. And it aims at providing modified steelmaking slag.
本発明の要旨は、以下の通りである。
(1)製鋼スラグにSiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上を含有する物質を添加した物を、溶融温度以上の温度で10分以下熱処理し、熱処理後に10℃/分以下の冷却速度で徐冷処理すること、または熱処理後に850℃〜1100℃で保定処理することを特徴とする製鋼スラグの改質方法。
(2)製鋼スラグを熱処理する際に、溶融温度より10℃以上高い温度で熱処理することを特徴とする(1)に記載の製鋼スラグの改質方法。
(3)前記SiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上を含有する物質として、高炉スラグ、脱珪スラグ、フライアッシュ、廃ガラス、コンクリート廃材、廃レンガ、アルミ灰、アルミドロス、アルミニウム精錬スラグ、都市ゴミ・下水汚泥の焼却灰、灰溶融スラグ、下水汚泥溶融スラグ、カーシュレッダーダスト燃焼灰、転炉ダスト、電炉ダスト、高炉二次灰、天然砂、珪砂、廃棄鋳砂、粘土、土壌、天然砕石、鉄鉱石の1種以上を用いることを特徴とする(1)または(2)に記載の製鋼スラグの改質方法。
(4)製鋼スラグとして、溶銑予備処理スラグ、溶融還元炉スラグ、転炉スラグ、電気炉スラグ、二次精錬スラグまたはステンレス鋼スラグの1種又は2種以上を用いることを特徴とする(1)〜(3)いずれかに記載の製鋼スラグの改質方法。
(5)熱処理、保定処理、もしくは徐冷処理に際し、転炉、電炉、精錬炉、滓鍋、混銑車、ロータリーキルン、焼結機、回転炉床型炉、流動床加熱炉、バッチ式加熱炉、連続式加熱炉、キュポラ炉、コークスベッド式炉の1種又は2種以上を用いることを特徴とする(1)〜(4)いずれかに記載の製鋼スラグの改質方法。
The gist of the present invention is as follows.
(1) A material obtained by adding a material containing at least one of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 to steelmaking slag is heat-treated at a temperature equal to or higher than the melting temperature for 10 minutes or less. A method for reforming a steelmaking slag, characterized by performing a slow cooling treatment at a cooling rate of 10 ° C./min or less after the heat treatment, or a holding treatment at 850 ° C. to 1100 ° C. after the heat treatment.
(2) The steelmaking slag reforming method according to (1), wherein the steelmaking slag is heat-treated at a temperature higher by 10 ° C. or more than the melting temperature when the steelmaking slag is heat-treated.
(3) As a substance containing one or more of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 , blast furnace slag, desiliconized slag, fly ash, waste glass, concrete waste, waste Brick, aluminum ash, aluminum dross, aluminum smelting slag, incineration ash of municipal waste and sewage sludge, ash melting slag, sewage sludge melting slag, car shredder dust combustion ash, converter dust, electric furnace dust, blast furnace secondary ash, natural sand The method for reforming steelmaking slag according to (1) or (2), wherein at least one of silica sand, waste cast sand, clay, soil, natural crushed stone, and iron ore is used.
(4) As the steelmaking slag, one or more of hot metal pretreatment slag, smelting reduction furnace slag, converter slag, electric furnace slag, secondary refining slag or stainless steel slag is used (1) ~ (3) The method for reforming steelmaking slag according to any one of the above.
(5) heat treatment, retaining process, or upon slow cooling process, converter, electric furnace, smelting furnace, Kasunabe, torpedo car, b Tarikirun, sintering machines, rotary hearth furnaces, fluid bed furnaces, a batch type heating furnace The method for reforming steelmaking slag according to any one of (1) to (4), wherein one or more of a continuous heating furnace, a cupola furnace, and a coke bed furnace are used.
本発明による改質製鋼スラグとその製造方法によれば、f・CaOが低く、かつ吸水率の小さい強度が高いスラグを得ることができる。比較的低温で確実な改質が可能となるので処理能力が向上し、改質されたスラグは、上層路盤材、加熱アスファルト混合道路用材、アスファルト舗装用骨材、コンクリート用骨材、コンクリート二次製品用原料、窯業・タイル用原料、人工石材原料用途等の有用な原料に適用することができ、再生資源として高度に有効利用でき、また、経済的効果も大きい。さらに、製鋼スラグの在庫の縮小に伴ない、在庫管理が容易となり、さらにスラグヤードの占有率を小さくできることから、スラグの運搬、払い出し等の作業の負荷が軽減できる。 According to the modified steelmaking slag and the method for producing the same according to the present invention, it is possible to obtain a slag having low f · CaO and high strength with low water absorption. Since it is possible to reliably modify at relatively low temperatures, the processing capacity is improved, and the modified slag is made of upper-layer roadbed materials, heated asphalt mixed road materials, asphalt pavement aggregates, concrete aggregates, concrete secondary It can be applied to useful raw materials such as raw materials for products, ceramics and tiles, and artificial stone materials. It can be used effectively as a recycled resource, and has great economic effects. Furthermore, as the stock of steelmaking slag is reduced, inventory management becomes easier and the occupation rate of the slag yard can be reduced, so that the work load such as slag transportation and dispensing can be reduced.
本発明者らは上記課題を解決するために、製鋼スラグ中のf・CaOを減少させると共に、スラグ中の未滓化の高融点の固相を減少させることで吸水率を低減し、強度を向上させる製鋼スラグの改質法を発明するに至った。
以下にその詳細を説明する。
まず、製鋼スラグを、溶融温度以上の温度で熱処理する方法について説明する。ちなみに、溶融温度の測定方法については後述する。
製鋼スラグを溶融温度以上の温度で熱処理することにより、製鋼スラグ中のf・CaOをSiO2等との反応により低減することができる。同様に未滓化の固相を消滅させることができる。これにより、水浸膨張比を低減し、強度を向上することができ、各用途別の基準を満足することで、さまざまな用途に利用することができる。
In order to solve the above-mentioned problems, the present inventors have reduced the water absorption rate by reducing the f · CaO in the steelmaking slag, and by reducing the unmelted high melting point solid phase in the slag, thereby increasing the strength. The inventors have invented an improved steelmaking slag reforming method.
Details will be described below.
First, a method for heat-treating steelmaking slag at a temperature equal to or higher than the melting temperature will be described. Incidentally, the method for measuring the melting temperature will be described later.
By heat-treating steelmaking slag at a temperature equal to or higher than the melting temperature, f · CaO in the steelmaking slag can be reduced by reaction with SiO 2 or the like. Similarly, the unhatched solid phase can be extinguished. Thereby, a water immersion expansion ratio can be reduced and intensity | strength can be improved, and it can utilize for various uses by satisfy | filling the reference | standard for every use.
製鋼スラグ中のf・CaOを減少させる点については、製鋼スラグにはSiO2が含まれていることに着目し、製鋼スラグ中のf・CaOとSiO2との反応が起こる条件を検討したところ、溶融温度未満で熱処理を行っても、安定してf・CaOを減少させることができないのに対し、溶融温度以上で熱処理すれば安定してf・CaOを減少させることができることを見出した。熱処理前の製鋼スラグの成分としては、塩基度が小さい方が好ましい。ここで、スラグの塩基度とは、スラグ中のCaOとSiO2の質量比(CaO/SiO2)である。すなわち、熱処理前スラグの塩基度が小さいほど、f・CaOに対するSiO2量が多くなるため、反応が促進される。
従って、熱処理前の製鋼スラグの成分を必要に応じて適宜選択して、溶融温度以上で熱処理することで、スラグ中のf・CaOとSiO2との反応が起こって、改質製鋼スラグ中のf・CaOを低減することができる。溶融温度未満で熱処理を行った場合には、熱処理前に未滓化のスラグが固相として残存し、固相として高融点の析出相が残存する場合があるため、SiO2との反応が十分に進行せず、安定してf・CaOを減少させることができない。
The points of reducing the f · CaO in steelmaking slag, where the steelmaking slag Noting that contains SiO 2, was studied the conditions under which the reaction takes place with the f · CaO and SiO 2 in the steelmaking slag It has been found that f · CaO cannot be stably reduced even when heat treatment is performed at a temperature lower than the melting temperature, whereas f · CaO can be stably reduced if heat treatment is performed at or above the melting temperature. As a component of steelmaking slag before heat processing, the one where basicity is smaller is preferable. Here, the basicity of slag is the mass ratio (CaO / SiO 2 ) between CaO and SiO 2 in the slag. That is, the smaller the basicity of the slag before heat treatment, the greater the amount of SiO 2 with respect to f · CaO, so the reaction is accelerated.
Accordingly, the components of the steelmaking slag before heat treatment are appropriately selected as necessary, and the heat treatment at a melting temperature or higher causes the reaction between f · CaO and SiO 2 in the slag to occur, in the modified steelmaking slag. f · CaO can be reduced. When performing heat treatment at below the melting temperature, because it may remain as slag solid phase non dregs of before the heat treatment, the high melting point of the precipitation phase remains as the solid phase, reaction with SiO 2 is sufficiently Therefore, f · CaO cannot be reduced stably.
次に、製鋼スラグ中の吸水率を減少させる点についても、溶融温度以上で熱処理すれば良いことを見出した。さらに、熱処理前スラグの塩基度が小さいほど好ましいことが判明した。これについては、溶融温度以上で熱処理することで、スラグを溶融状態とすることにより、製鋼スラグに存在する未滓化の固相を消滅させることが可能になる。これにより吸水率が減少し、その結果、各製品別の割れ、強度基準を満足することができるようになるものと考えられる。
このことは、従来技術の様な低温処理、固相が残った状態での反応では、製鋼スラグ改質に供される製鋼スラグに多数存在していた亀裂、開気孔を塞ぐことができない状態となることで吸水率が高くなり、強度が低い製鋼スラグとなる。
また、改質時にスラグが溶融状態にならず、固相が残った状態になると、内部に改質前から存在した、表面に連通していない閉気孔が残存することとなり、外部から力を受けた際の亀裂の伝播が容易になり、強度が低い改質製鋼スラグとなる。本発明の様に固相が消失した状態、すなわち液相状態で十分反応を進行させた製鋼スラグでは、吸水率を低減できる反応が起こることを示しているものと考えられる。
また、SiO2は融点を低下させる作用があるため、より低い熱処理温度もしくは同一温度であれば短時間で改質が可能となるため、その点で塩基度が低い方が好ましい。
Next, it has been found that the heat absorption at the melting temperature or higher may be used for reducing the water absorption rate in the steelmaking slag. Furthermore, it was found that the smaller the basicity of the slag before heat treatment, the better. About this, it becomes possible to extinguish the unsolidified solid phase which exists in steelmaking slag by heat-processing above a melting temperature, and making slag into a molten state. As a result, the water absorption rate decreases, and as a result, it is considered that the cracks and strength standards for each product can be satisfied.
This is because the low temperature treatment as in the prior art and the reaction with the solid phase remaining cannot close the cracks and open pores that existed in many steelmaking slags used for steelmaking slag reforming. As a result, the water absorption is increased and the steelmaking slag has a low strength.
In addition, if the slag does not enter the molten state during the reforming and the solid phase remains, closed pores that have existed before the reforming and do not communicate with the surface will remain, and receive external force. Propagation of cracks during heating is facilitated, resulting in a modified steelmaking slag with low strength. It is considered that the steelmaking slag in which the solid phase has disappeared as in the present invention, that is, the steelmaking slag in which the reaction has sufficiently progressed in the liquid phase, indicates that the reaction capable of reducing the water absorption rate occurs.
In addition, since SiO 2 has an action of lowering the melting point, it can be reformed in a short time at a lower heat treatment temperature or the same temperature, and in this respect, a lower basicity is preferable.
従って、熱処理前の製鋼スラグの成分を必要に応じて適宜選択して、溶融温度以上で熱処理することで、改質に供される製鋼スラグを溶融状態とすることにより、改質製鋼スラグ中の吸水率を低減することができる。また、熱処理温度は高いほど、スラグの溶融、均一化が迅速に進むため、改質反応が促進される。
以上の様に、熱処理前の製鋼スラグの成分を必要に応じて適宜選択して、溶融温度以上で所望の時間の熱処理を行うことで、熱処理後スラグ性状をf・CaO≦2.7質量%かつ吸水率≦4.0質量%に改質することができる。ここで、f・CaO≦2.7質量%であれば、改質製鋼スラグが膨張崩壊しても、水浸膨張比1.5%を達成でき、また吸水率≦4.0質量%であれば、さまざまな用途に用いても必要な強度を確保することができる。
また、溶融温度以上の熱処理の所望の時間とは、特に規定するものではなく、熱処理前の製鋼スラグの成分と熱処理温度に応じて、適宜設定すれば良い。
Therefore, the components of the steelmaking slag before heat treatment are appropriately selected as necessary, and the steelmaking slag to be reformed is brought into a molten state by heat treatment at a melting temperature or higher, so that the The water absorption rate can be reduced. Also, the higher the heat treatment temperature, the faster the melting and homogenization of the slag, so that the reforming reaction is promoted.
As described above, the components of the steelmaking slag before heat treatment are appropriately selected as necessary, and heat treatment is performed at a melting temperature or higher for a desired time, so that the slag properties after heat treatment are f · CaO ≦ 2.7% by mass. In addition, the water absorption can be improved to ≦ 4.0% by mass. Here, if f · CaO ≦ 2.7 mass%, even if the modified steelmaking slag expands and collapses, a water immersion expansion ratio of 1.5% can be achieved, and the water absorption ratio ≦ 4.0 mass%. For example, the required strength can be ensured even when used for various purposes.
Further, the desired time for the heat treatment at the melting temperature or higher is not particularly defined, and may be appropriately set according to the components of the steelmaking slag before the heat treatment and the heat treatment temperature.
加熱方法については特に規定されない。具体的には、酸素、酸素ガス含有気体としては空気の使用、酸素富化燃料バーナー、コークス燃焼、電気抵抗加熱、高周波加熱、アーク加熱、マイクロ波加熱等が例示できるが、いずれもスラグを均一に溶融温度以上に熱処理が可能なものであれば良い。
また、熱処理温度の上限は特に規定するものではなくが、コスト等を考慮して、適宜温度を設定すればよいが、スラグの溶融した浴の平均温度として高々1500℃程度とする。さらに、熱処理時間については、所望のスラグ成分に改質できる様に、塩基度や熱処理温度等を考慮して、適宜設定すれば良い。
The heating method is not particularly specified. Specific examples of oxygen and oxygen gas-containing gas include air, oxygen-enriched fuel burner, coke combustion, electric resistance heating, high-frequency heating, arc heating, microwave heating, etc. In addition, any material that can be heat-treated at the melting temperature or higher may be used.
The upper limit of the heat treatment temperature is not particularly specified, and the temperature may be appropriately set in consideration of cost and the like, but the average temperature of the bath in which the slag is melted is about 1500 ° C. at most. Furthermore, the heat treatment time may be appropriately set in consideration of basicity, heat treatment temperature, etc. so that it can be modified to a desired slag component.
スラグ成分の分析には蛍光X線分析(JIS K 0119)を、f・CaOの分析にはエチレングリコール抽出法ICP発光分光分析を用いることができる。f・CaOの分析において同様にf・CaOを抽出する方法としてTBP(トリブロムフェノール)法等があり、抽出が正しくできればいずれの方法を用いてもよい。また、吸水率の測定には、JIS A1109もしくはA1110に規定される試験方法を用いた。 Fluorescence X-ray analysis (JIS K 0119) can be used for analysis of slag components, and ethylene glycol extraction ICP emission spectroscopic analysis can be used for analysis of f · CaO. Similarly, in the analysis of f · CaO, there is a TBP (tribromophenol) method or the like as a method for extracting f · CaO, and any method may be used as long as the extraction can be performed correctly. Moreover, the test method prescribed | regulated to JIS A1109 or A1110 was used for the measurement of a water absorption rate.
次に、製鋼スラグを、溶融温度より10℃以上高い温度で熱処理することにより均一性を向上させることを特徴とする製鋼スラグの改質方法について説明する。製鋼スラグを改質するにあたり、さらにf・CaOを減少させて、厳しい条件であるf・CaO≦0.7質量%かつ吸水率≦4.0質量%を満足させると、各製品群の中でもより高級な用途である上層路盤材、コンクリート骨材等に適用できるようになる。
本発明者らは実験結果から、改質製鋼スラグのf・CaO≦0.7質量%を満足するための熱処理温度は、溶融温度より10℃以上高い温度とすれば、スラグ中の浴中の組成のばらつきが小さくなり、f・CaOとSiO2との反応が促進されやすくなるため、好ましいことがわかった。
すなわち、熱処理前の製鋼スラグの成分を適宜選択して、スラグの溶融温度より10℃以上高い温度で熱処理することで、スラグ中のf・CaOとSiO2との反応がより促進されるため、改質製鋼スラグ中のf・CaO≦0.7質量%が達成されやすい。
Next, a steelmaking slag reforming method characterized by improving the uniformity by heat-treating the steelmaking slag at a temperature higher by 10 ° C. than the melting temperature will be described. In modifying steelmaking slag, if f · CaO is further reduced to satisfy the severe conditions of f · CaO ≦ 0.7 mass% and water absorption ≦ 4.0 mass%, it is more It can be applied to high-grade roadbed materials and concrete aggregates.
From the experimental results, the present inventors have found that the heat treatment temperature for satisfying f · CaO ≦ 0.7 mass% of the modified steelmaking slag is 10 ° C. higher than the melting temperature. It was found preferable because the variation in the composition is reduced and the reaction between f.CaO and SiO 2 is facilitated.
That is, by appropriately selecting the components of the steelmaking slag before the heat treatment and heat-treating at a temperature higher by 10 ° C. or more than the melting temperature of the slag, the reaction between f · CaO in the slag and SiO 2 is further promoted, It is easy to achieve f · CaO ≦ 0.7 mass% in the modified steelmaking slag.
さらに、溶融温度以上の温度で熱処理を行った場合の、改質製鋼スラグにおけるスラグの塩基度と(f・CaO)の関係を検討した結果の一例を図1に示す。ここで、ΔTは熱処理温度から溶融温度を引いたものを意味しており、▲印はΔTが0℃以上10℃未満を示しており、■印はΔTが10℃以上30℃未満を示しており、○印はΔTが30℃以上を示している。熱処理にあたってはすべて図中のΔTの温度に5〜10分程度保持した。保持時間は5分以上であればスラグはほぼ改質されるため、保持時間を5分以上とした。また、10分を超えて保持してもスラグ特性に大きな変化がなくなり、また熱処理のコストが無駄にかかるため、上限を10分程度以下とした。
溶融温度以上の温度で熱処理を行った場合には、改質製鋼スラグの塩基度が3.0以下であればf・CaOを2.7質量%以下にまで低減でき、また更には塩基度が2.5であればf・CaOを0.91質量%にまで低減可能である。
すなわち、溶融温度以上の温度で熱処理を行うと、改質製鋼スラグの塩基度が小さいほど、f・CaOが減少しやすくなる傾向を示すことが判明した
また、溶融温度より10℃以上高い温度で熱処理を行った場合には、改質製鋼スラグの塩基度が2.5以下であればf・CaOを0.7質量%以下にまで低減でき、また更には塩基度が1.2であればf・CaOを0.05質量%にまで低減可能である。すなわち、溶融温度より10℃以上高い温度で熱処理を行うと、改質製鋼スラグの塩基度が同じである場合更に、f・CaOが減少しやすくなる傾向を示すことが判明した。従って、f・CaO≦0.7質量%を達成するためには熱処理温度を溶融温度より10℃以上高い温度とすることが好ましい条件である。熱処理温度が溶融温度より30℃以上高い温度になると、更にf・CaOが減少しやすくなる傾向を示す。
このように、製鋼スラグ中のf・CaOをより減少させるためには、これと反応するSiO2の存在下、熱間(溶融温度より10℃以上高い温度)で反応させることで達成されやすくなる。従って、製鋼スラグ自体にSiO2が多く含まれている様な塩基度が低いものであれば、より短時間の熱処理で製鋼スラグ中のf・CaOを減少させることが可能であるため好ましい。
Furthermore, FIG. 1 shows an example of the result of examining the relationship between the basicity of slag and (f · CaO) in the modified steelmaking slag when heat treatment is performed at a temperature equal to or higher than the melting temperature. Here, ΔT means a value obtained by subtracting the melting temperature from the heat treatment temperature, ▲ indicates ΔT is 0 ° C. or higher and lower than 10 ° C., ■ ■ indicates ΔT is 10 ° C. or higher and lower than 30 ° C. ◯ indicates that ΔT is 30 ° C. or higher. In the heat treatment, the temperature was kept at ΔT in the figure for about 5 to 10 minutes. If the holding time is 5 minutes or longer, the slag is almost modified, so the holding time was 5 minutes or longer. In addition, even if held for more than 10 minutes, there is no significant change in slag characteristics, and the cost of heat treatment is wasted, so the upper limit was made about 10 minutes or less.
When heat treatment is performed at a temperature equal to or higher than the melting temperature, f · CaO can be reduced to 2.7% by mass or less if the basicity of the modified steelmaking slag is 3.0 or less. If it is 2.5, f.CaO can be reduced to 0.91 mass%.
That is, when heat treatment was performed at a temperature higher than the melting temperature, it was found that the smaller the basicity of the modified steelmaking slag, the more likely that f · CaO tends to decrease. When heat treatment is performed, if the basicity of the modified steelmaking slag is 2.5 or less, f · CaO can be reduced to 0.7 mass% or less, and further, if the basicity is 1.2. f · CaO can be reduced to 0.05% by mass. That is, it was found that when heat treatment is performed at a temperature higher by 10 ° C. or more than the melting temperature, f · CaO tends to decrease further when the basicity of the modified steelmaking slag is the same. Therefore, in order to achieve f · CaO ≦ 0.7 mass%, it is a preferable condition that the heat treatment temperature is 10 ° C. higher than the melting temperature. When the heat treatment temperature is higher than the melting temperature by 30 ° C. or more, f · CaO tends to be further reduced.
Thus, in order to further reduce the f · CaO in the steelmaking slag, it is easily achieved by reacting in the presence of SiO 2 that reacts with it in the hot state (temperature higher by 10 ° C. or more than the melting temperature). . Accordingly, it is preferable that the steelmaking slag itself has a low basicity such that a large amount of SiO 2 is contained because f · CaO in the steelmaking slag can be reduced by a shorter heat treatment.
以上のことから、製鋼スラグ中のf・CaOを減少させること及び吸水率を低減させることの両者を満足する方法としては、溶融温度より30℃以上高い温度で熱処理することが、反応効率の面でより好ましい。また、一般に温度が高いほど、スラグの粘性は低下するので、スラグの均一性を高める目的で、溶融温度より50℃以上高い温度で熱処理しても良い。
熱処理に際して、製鋼スラグの塩基度が低く、処理時間は長い程、より反応は促進される。但し、熱処理時間については、所望のスラグ成分に改質できる様に、塩基度や熱処理温度等を考慮して、適宜設定すれば良く、特に規定するものではないが、生産性・コストの面から10分程度が好ましい。また、熱処理温度は高ければ高い程、より短時間で処理が完了するため望ましいが、溶融温度との差が大きくなると改善効果が小さくなっていくだけでなく、溶融温度から温度を高くし、100℃以上にすることは費用を要するので、コストの観点から必要最低限の温度で熱処理することが好ましい。
From the above, as a method of satisfying both of reducing f · CaO in steelmaking slag and reducing water absorption, heat treatment at a temperature higher by 30 ° C. or more than the melting temperature is an aspect of reaction efficiency. And more preferable. In general, the higher the temperature, the lower the viscosity of the slag. Therefore, heat treatment may be performed at a temperature higher by 50 ° C. than the melting temperature for the purpose of improving the uniformity of the slag.
In the heat treatment, the lower the basicity of the steelmaking slag and the longer the treatment time, the more the reaction is promoted. However, the heat treatment time may be appropriately set in consideration of basicity, heat treatment temperature, etc. so that it can be modified to a desired slag component, and is not particularly specified, but from the viewpoint of productivity and cost. About 10 minutes is preferable. Further, the higher the heat treatment temperature is, the more preferable it is because the treatment can be completed in a shorter time. However, when the difference from the melting temperature is increased, not only the improvement effect is reduced, but also the temperature is increased from the melting temperature to 100 ° C. Since the above is expensive, it is preferable to perform the heat treatment at the minimum necessary temperature from the viewpoint of cost.
ここで、溶融温度とは図3に示すように、耐火物の支持台の上に白金箔を載せ、その上に2〜3gのスラグを微粉砕し、プレスにて直径1cmの円柱状に成形した後、一定の昇温速度で昇温し、スラグが溶融し、液滴高さが1/2になった時点の温度を測定し求めた。この方法で測定したスラグの溶融温度では試料が液滴となっており、均一な液体状態となっており、未溶解状態の固相もしくは、固相として析出する析出相は見られず、均一な溶融状態となっている。
鉄と鋼 Vol.88(2002)No2 p51〜58に記されているように、FactSage等の市販の計算ソフトを用いて、スラグ組成より溶融温度を算出することも可能であるが、一般に、上述のような実際の測定値とは差異が生ずるので、市販の計算ソフトを用いて溶融温度を評価するためには、事前に測定値との比較を実施しておくことが必要である。
Here, as shown in FIG. 3, the melting temperature is obtained by placing a platinum foil on a refractory support, finely pulverizing 2 to 3 g of slag, and forming it into a cylindrical shape with a diameter of 1 cm using a press. Then, the temperature was raised at a constant rate of temperature rise, and the temperature at the time when the slag melted and the droplet height became ½ was measured and determined. At the melting temperature of the slag measured by this method, the sample is droplets and is in a uniform liquid state, and there is no solid phase in the undissolved state or a precipitated phase that precipitates as a solid phase. It is in a molten state.
Iron and steel Vol. 88 (2002) No2 p51-58, it is possible to calculate the melting temperature from the slag composition using commercially available calculation software such as FactSage. Since it differs from the measured value, it is necessary to compare with the measured value in advance in order to evaluate the melting temperature using commercially available calculation software.
一方、上層路盤材、コンクリート骨材等高級用途に適用するための条件の1つである吸水率を、より低減しやすい方法について検討した。その結果、改質製鋼スラグの吸水率を低減する条件として、図2に示す様に、熱処理により改質後の塩基度が同じであっても、その後の冷却において、冷却速度が110℃/分以上の急冷を行った場合と比較すると、冷却速度が10℃/分以下の徐冷を行った場合は、改質製鋼スラグの吸水率を低減できており、冷却速度を低減することが有効なことが分かった。
本発明者らがさらに研究を進めたところ、図2に示すように製鋼スラグを溶融温度以上の温度で熱処理した後、10℃/分以下の冷却速度で徐冷することにより、
(1)熱処理前、熱処理後に残存する気泡の脱泡、破泡が10℃/分以下の冷却速度で徐冷処理することにより促進されること、
(2)スラグ温度が溶融温度未満となって、凝固冷却される際に発生する製鋼スラグ中の亀裂の発生を抑制し、なおかつ微細な亀裂の修復が起こること
を見出し、吸水率をさらに低下させることができることが分かった。
また、10℃/分以下の冷却速度で徐冷することにより脱泡、破泡が顕著となり、吸水率改善の効果が大きく、その際の温度範囲は特に限定するものではない。但し、熱処理温度から1100℃までの間の温度範囲で10℃/分以下の冷却速度で徐冷することにより、特に脱泡、破泡が顕著となり、吸水率改善の効果が大きいため好ましい。冷却速度の下限は特に規定するものではない。
また、850℃〜1100℃の温度範囲で保定処理を行うことにより、凝固冷却される際に発生する製鋼スラグ中の亀裂の発生を抑制し、なおかつ微細な亀裂の修復が起こるが、保定時間は特に規定するものではないが、20分以上保定すると、その効果が発揮され易くなるため好ましい。保定時間は長いほど好ましいので、操業上の支障がない範囲であれば、上限値は特に規定するものではない。
熱処理温度からの徐冷処理方法としては、加熱炉・回転炉床・流動床等で実施でき加熱している炉内で徐冷処理を行うことができる。また、スラグ凝固後の温度域で10℃/分以下の冷却速度で徐冷処理を行う方法としては、製鋼スラグ搬送用鋼滓鍋に保温蓋を装着し、場合によっては一部熱補償することで実施することができる。また、保定処理同様、加熱炉・回転炉床・流動床炉等を活用して、所定の冷却速度を確保できる程度に加熱・保温することで実施できる。
On the other hand, we investigated a method that makes it easier to reduce water absorption, which is one of the conditions for high-grade applications such as upper-layer roadbed materials and concrete aggregates. As a result, as a condition for reducing the water absorption rate of the modified steelmaking slag, as shown in FIG. 2, even if the basicity after the modification by heat treatment is the same, the cooling rate is 110 ° C./min in the subsequent cooling. Compared with the case of the above rapid cooling, when the cooling rate is 10 ° C./min or less, the water absorption rate of the modified steelmaking slag can be reduced, and it is effective to reduce the cooling rate. I understood that.
As a result of further research by the inventors, as shown in FIG. 2, after steelmaking slag was heat-treated at a temperature higher than the melting temperature, it was gradually cooled at a cooling rate of 10 ° C./min or less.
(1) Before and after heat treatment, defoaming and breaking of bubbles remaining after heat treatment are promoted by slow cooling treatment at a cooling rate of 10 ° C./min or less,
(2) Slag temperature is lower than the melting temperature, suppressing the generation of cracks in steelmaking slag that occurs when solidified and cooled, and found that fine cracks are repaired, further reducing the water absorption rate I found out that I could do it.
Further, by slowly cooling at a cooling rate of 10 ° C./min or less, defoaming and foam breaking become remarkable, and the effect of improving the water absorption rate is great, and the temperature range at that time is not particularly limited. However, slow cooling at a cooling rate of 10 ° C./min or less in the temperature range from the heat treatment temperature to 1100 ° C. is particularly preferable because defoaming and bubble breaking become remarkable and the effect of improving the water absorption rate is great. The lower limit of the cooling rate is not particularly specified.
In addition, by performing a holding treatment in the temperature range of 850 ° C. to 1100 ° C., the occurrence of cracks in the steelmaking slag that occurs when solidified and cooled is suppressed, and the repair of fine cracks occurs, but the holding time is Although not particularly specified, holding for 20 minutes or more is preferable because the effect is easily exhibited. The longer the holding time is, the better. Therefore, the upper limit is not particularly specified as long as there is no problem in operation.
As a method of slow cooling treatment from the heat treatment temperature, it can be carried out in a heating furnace, a rotary hearth, a fluidized bed or the like, and the slow cooling treatment can be performed in a heating furnace. In addition, as a method of performing slow cooling at a cooling rate of 10 ° C./min or less in the temperature range after slag solidification, a heat insulation lid is attached to the steel slag pan for steelmaking slag conveyance, and in some cases, partial heat compensation is performed. Can be implemented. Moreover, it can implement by heating and heat-maintaining to the extent which can ensure a predetermined | prescribed cooling rate using a heating furnace, a rotary hearth, a fluidized bed furnace, etc. similarly to a retention process.
次に、製鋼スラグにSiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上を含有する物質を添加した物を熱処理する方法について説明する。
塩基度の低い製鋼スラグを改質する場合は、上述の通り熱処理を行うだけでも良いが、塩基度の高い製鋼スラグを改質する場合は、SiO2源が不足するため、これを補うためにSiO2源を添加して熱処理することで、f・CaOの低減を実施できるため、好ましい。
SiO2の添加量は、所望とする製鋼スラグ中のf.CaOに応じて、適宜SiO2を添加して熱処理すれば良い。その上、前述の通りSiO2には製鋼スラグ組成域において、融点を低下させる効果があるため、SiO2源を添加することで固相率を低減して、改質を行うことが可能である。
Next, a method for heat-treating a steelmaking slag added with a material containing one or more of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 will be described.
When reforming steelmaking slag with low basicity, it is only necessary to perform heat treatment as described above. However, when modifying steelmaking slag with high basicity, the SiO 2 source is insufficient, so that this can be compensated. It is preferable to add a SiO 2 source and perform heat treatment because f · CaO can be reduced.
The amount of SiO 2 added is the desired f. Depending on CaO, SiO2 may be added as appropriate and heat treated. In addition, as described above, since SiO 2 has an effect of lowering the melting point in the steelmaking slag composition region, it is possible to perform reforming by reducing the solid phase ratio by adding the SiO 2 source. .
また、Al2O3、FeO、Fe2O3、P2O5はそれぞれ、f・CaOと反応してf.CaOの低減を実施でき、さらに融点を低下させる効果があるため、上記と同様の効果を得ることができるため、添加することが好ましい。特に、FeOは酸化反応によりFe2O3になるものもあり、その際に発熱するため、この熱を熱処理時の反応に有効利用できるという作用もある。さらに、SiO2、Al2O3、FeO、Fe2O3、P2O5の複数種を含有する物質を添加して、同様に熱処理することでも良い。
従って、製鋼スラグ中には低融点金属酸化物、例えばFeO、MnO、Al2O3、SiO2が含まれているが、更にSiO2、Al2O3を加え、熱処理することで、改質製鋼スラグの吸水率をより低減でき、強度の向上を達成できる。また、同じスラグ組成であれば、温度が高い程、固相が少なくなり液相が増加するため、処理後スラグの吸水率はより小さくなる。しかし、反応温度を高くするには加熱が必要で、加熱処理コストが大きくなるため、可能な限り低い温度で反応させることがコスト的にも重要である。
以上の様に、SiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上を含有する物質を添加することが好ましく、添加量や熱処理時間は実験等で適宜設定すれば良い。
Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 each react with f · CaO to cause f. Since CaO can be reduced and the melting point is further lowered, the same effect as described above can be obtained. In particular, FeO may be converted to Fe 2 O 3 by an oxidation reaction, and heat is generated at that time, so that this heat can be effectively used for the reaction during the heat treatment. Further, a material containing plural kinds of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 may be added and similarly heat-treated.
Therefore, the steelmaking slag contains low melting point metal oxides such as FeO, MnO, Al 2 O 3 and SiO 2, but it is further modified by adding heat treatment with SiO 2 and Al 2 O 3. The water absorption rate of the steelmaking slag can be further reduced and the strength can be improved. Moreover, if it is the same slag composition, since a solid phase decreases and a liquid phase increases, so that temperature is high, the water absorption rate of a post-process slag becomes smaller. However, heating is required to raise the reaction temperature, and the heat treatment cost increases. Therefore, it is important in terms of cost to react at the lowest possible temperature.
As described above, it is preferable to add a substance containing one or more of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 , and the addition amount and heat treatment time are appropriately set by experiments or the like. Just do it.
実際に溶融温度以上で熱処理を実施する方法としては、大きく三つの方法がある。
一つ目は、事前に製鋼スラグの溶融温度測定を実施し、組成と溶融温度との関係を求め、求めた温度以上で熱処理を行う。
二つ目は、所定の熱処理温度で溶融温度以上となるように、製鋼スラグ組成に必要なSiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上の量を求め、それを添加して熱処理を行う。
三つ目は製鋼スラグにある程度のSiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上を添加し、そのときの溶融温度を事前に測定した、スラグ組成と溶融温度との関係を求め、その温度以上で熱処理を行うという方法である。求めた温度が熱処理温度以上であれば、再度SiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上を添加することを繰り返し、溶融温度以上のスラグ組成となった場合、熱処理を行えば良い。
There are three main methods for actually carrying out the heat treatment at the melting temperature or higher.
First, the melting temperature of steelmaking slag is measured in advance, the relationship between the composition and the melting temperature is determined, and heat treatment is performed at a temperature equal to or higher than the determined temperature.
Secondly, at least one amount of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 required for the steelmaking slag composition is set so that the temperature is equal to or higher than the melting temperature at a predetermined heat treatment temperature. Find it, add it and heat-treat.
The third is the addition of a certain amount of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , P 2 O 5 to steelmaking slag, and the melting temperature at that time was measured in advance. In this method, the relationship with the melting temperature is obtained, and the heat treatment is performed at the temperature or higher. If the obtained temperature is equal to or higher than the heat treatment temperature, the addition of one or more of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , and P 2 O 5 is repeated to obtain a slag composition that is higher than the melting temperature. In such a case, heat treatment may be performed.
次に、前記SiO2、Al2O3、FeO、Fe2O3、P2O5の1種以上を含有する物質について説明する。
これらの物質として、高炉スラグ、脱珪スラグ、フライアッシュ(石炭灰)、廃ガラス、コンクリート廃材、廃レンガ、アルミ灰、アルミドロス、アルミニウム精錬スラグ、都市ゴミ・下水汚泥の焼却灰、灰溶融スラグ、下水汚泥溶融スラグ、カーシュレッダーダスト燃焼灰、転炉ダスト、電炉ダスト、高炉二次灰、天然砂、珪砂、廃棄鋳砂、粘土、土壌、天然砕石、鉄鉱石の1種以上を用いることで、今回の改質は可能である。
これらは、一部廃棄物として指定されているものであり、安価に入手できるためコスト的に有利であり、廃棄物処理にもなるため好ましい。それぞれ改質されたスラグに悪影響を与える不純物を含まないものであれば特に限定されるものではない。もちろん、試薬のシリカも使用可能である。
Next, a substance containing one or more of SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 and P 2 O 5 will be described.
These materials include blast furnace slag, desiliconized slag, fly ash (coal ash), waste glass, concrete waste, waste brick, aluminum ash, aluminum dross, aluminum refining slag, incineration ash of municipal waste and sewage sludge, ash molten slag By using one or more of sewage sludge melting slag, car shredder dust combustion ash, converter dust, electric furnace dust, blast furnace secondary ash, natural sand, quartz sand, waste cast sand, clay, soil, natural crushed stone, iron ore This modification is possible.
These are partly designated as wastes, are advantageous in terms of cost because they can be obtained at a low cost, and are preferable because they also become waste disposal. There is no particular limitation as long as it does not contain impurities that adversely affect the modified slag. Of course, the reagent silica can also be used.
本発明に用いられる製鋼スラグは特に限定されるものではなく、溶銑予備処理スラグ、溶融還元炉スラグ、転炉スラグ、電気炉スラグ、二次精錬スラグまたはステンレス鋼スラグ等を使用することができ、既に冷却したものも使用できるが、溶融状態又は半凝固状態で熱量を保有するものを使用すると、本発明において加熱に必要なエネルギーを減少し得るので好ましい。 Steelmaking slag used in the present invention is not particularly limited, and hot metal pretreatment slag, smelting reduction furnace slag, converter slag, electric furnace slag, secondary refining slag, or stainless steel slag can be used. Although an already cooled one can be used, it is preferable to use one having a calorie in a molten state or a semi-solid state because the energy required for heating in the present invention can be reduced.
熱処理に際しては、前記の加熱手段を用いて行えば良い。但し、転炉、電炉、精錬炉、滓鍋、混銑車、高炉排滓工程を用いると、排出された製鋼スラグが高温状態であり、そのままその熱を利用できるため、新たに加熱する温度が小さくなるため好ましい。特に半溶融高炉スラグを滓鍋内に保持して使用すれば、更に加熱が必要なくなり好ましい。転炉の場合、製鋼スラグに対し、ランスを用いて吹き込んだ強制供給が好ましいが、入れ置き、上方投入した改質材の拡散による自然供給でもよい。エージング処理工程を用いると、現状のスラグ処理工程に加熱手段を増工程すればよいので、設備費が少なくてすむため好ましい。
ロータリーキルン、焼結機、回転炉床型炉、流動床加熱炉、バッチ式加熱炉、連続式加熱炉、キュポラ炉、コークスベッド式炉の場合は、凝固した中間温度から常温の製鋼スラグも全量改質することができ、在庫削減にも繋がるため好ましい。
The heat treatment may be performed using the above heating means. However, if the converter, electric furnace, refining furnace, ladle, chaotic car, blast furnace exhaust process is used, the discharged steelmaking slag is in a high temperature state, and the heat can be used as it is. Therefore, it is preferable. In particular, if semi-molten blast furnace slag is used while being held in a ladle, it is preferable because heating is not necessary. In the case of a converter, forced supply in which steel slag is blown by using a lance is preferable, but natural supply by diffusion of the reforming material that has been put in and placed upward may be used. The use of an aging treatment step is preferable because the heating means can be increased in the current slag treatment step, so that the equipment cost can be reduced.
In the case of rotary kilns, sintering machines, rotary hearth furnaces, fluidized bed heating furnaces, batch heating furnaces, continuous heating furnaces, cupola furnaces, coke bed furnaces, the entire amount of steelmaking slag from solidified intermediate temperature to room temperature has been modified. It is preferable because it can improve the quality and lead to inventory reduction.
熱処理後に行う保定・徐冷処理についても、上記の熱処理とほぼ同様の方法で行えば良いが、転炉、電炉等の炉で行う場合、炉内の顕熱を利用して、LPG−酸素、炭材−酸素等の熱源を調整しながら、保定・徐冷処理を行うことができる。
滓鍋、エージング処理工程等で保定・徐冷処理を行う場合、蓋をつけ、もしくは箱で囲んで、バーナー等の加熱装置を用いて加熱しながら、保定・徐冷処理を行うことができる。いずれの場合も、熱処理後の製鋼スラグが高温状態であり、その顕熱を利用することで新たに加熱する温度が小さくなるため好ましい。
The retention and gradual cooling treatment performed after the heat treatment may be carried out by substantially the same method as the above heat treatment, but when performed in a furnace such as a converter or an electric furnace, LPG-oxygen, While maintaining the heat source such as the carbonaceous material-oxygen, the holding / slow cooling treatment can be performed.
When performing the holding / slow cooling treatment in the ladle, the aging treatment step, etc., the holding / slow cooling treatment can be performed while heating using a heating device such as a burner with a lid or enclosed in a box. In any case, the steelmaking slag after the heat treatment is in a high temperature state, and it is preferable because the temperature to be newly heated becomes small by utilizing the sensible heat.
本発明の改質製鋼スラグの性状は、f・CaO≦2.7質量%かつ吸水率≦4.0質量%である。F・ CaO≦2.7質量%であれば、改質製鋼スラグが膨張崩壊しても、水浸膨張比1.5%を達成できる。ここで、水浸膨張比とは、例えばJIS A5015の附属書2で測定される値であり、鐵鋼スラグ協会による製鋼スラグ路盤設計施工指針によれば、上層路盤材等の高級用途に供するには、路盤の膨脹による支持力の低下を防ぐため水浸膨張比1.5%以下とすることが重要である。
中級の用途である加熱アスファルト混合道路用材、アスファルト舗装用骨材については水浸膨張比を2.0%以下とすることで使用可能であるため、本発明の改質製鋼スラグは十分満足できる。
The properties of the modified steel slag of the present invention are f · CaO ≦ 2.7% by mass and water absorption ≦ 4.0% by mass. If F · CaO ≦ 2.7 mass%, even if the modified steelmaking slag expands and collapses, a water immersion expansion ratio of 1.5% can be achieved. Here, the water immersion expansion ratio is, for example, a value measured in
Since the heated asphalt mixed road material and the asphalt pavement aggregate, which are intermediate uses, can be used by setting the water immersion expansion ratio to 2.0% or less, the modified steelmaking slag of the present invention is sufficiently satisfactory.
また、一方吸水率は強度と相関があり、JIS A1109、または A1110で規定されている吸水率3%以下を満足することで、これら高級用途に適用可能である。他のJISで吸水率が規定されていない高級用途においては、吸水率4%以下を満足することで、いずれの用途でも使用できる強度を確保することができる。従って、本発明の示すようにいずれの高級用途向けに於いても吸水率≦4.0質量%が、強度の点で重要である。
さらに、高級用途において安定した使用が可能であるスラグ性状として、本発明の改質スラグのより好ましい性状は、f・CaO≦0.7質量%かつ吸水率≦4.0質量%である。f・CaO≦0.7質量%であれば、水浸膨張比1.0%以下を達成できる。こうして水浸膨張比を低位安定化することでJISの規格は十分満足し、路盤を施工するメーカーにおいても、安定した路盤強度を確保できる改質製鋼スラグとしての安心した使用が可能となる。
実際に上層路盤材に使用されている天然砕石並みの膨脹特性を確保するために、水浸膨張比を最大1%以下でかつ実質平均を0.5%程度に求める場合、f.CaO≦0.5質量%が望ましい。また更に、コンクリート用骨材等に適用する場合、天然砕石並みの、膨脹がほとんど無い状態を求める場合は、f・CaO≦0.2質量%が望ましい。
On the other hand, the water absorption rate has a correlation with the strength, and when the water absorption rate is 3% or less as defined in JIS A1109 or A1110, it can be applied to these high-grade applications. In other high-grade applications where the water absorption rate is not prescribed by other JIS, the strength that can be used in any application can be ensured by satisfying the water absorption rate of 4% or less. Therefore, as shown in the present invention, the water absorption ≦ 4.0% by mass is important in terms of strength in any high-grade application.
Furthermore, as the slag properties that can be used stably in high-grade applications, the more preferable properties of the modified slag of the present invention are f · CaO ≦ 0.7 mass% and water absorption ≦ 4.0 mass%. If f · CaO ≦ 0.7 mass%, a water immersion expansion ratio of 1.0% or less can be achieved. By stabilizing the water immersion expansion ratio at a low level, the JIS standard is sufficiently satisfied, and even manufacturers that make roadbeds can use it safely as modified steelmaking slag that can secure stable roadbed strength.
When the water immersion expansion ratio is at most 1% or less and the real average is about 0.5% in order to ensure the expansion characteristics similar to those of natural crushed stone actually used in upper layer roadbed materials, f. CaO ≦ 0.5% by mass is desirable. Furthermore, when applied to aggregates for concrete or the like, f · CaO ≦ 0.2% by mass is desirable when seeking a state of almost no expansion, similar to natural crushed stone.
このように、f・CaO≦0.7質量%かつ吸水率≦4.0質量%である改質製鋼スラグは、より高級な性状であるため、上層路盤材、加熱アスファルト混合道路用材、アスファルト舗装用骨材、コンクリート用骨材、コンクリート二次製品用原料、窯業・タイル用原料、人工石材原料用途として用いることができる。
また、吸水率は強度と相関があり、いずれの高級用途向けに於いても吸水率≦4.0質量%が、強度の点で好ましい。
As described above, the modified steelmaking slag having f · CaO ≦ 0.7% by mass and water absorption ≦ 4.0% by mass has a higher-grade property, so that the upper layer roadbed material, the heated asphalt mixed road material, the asphalt pavement It can be used as an aggregate for concrete, aggregate for concrete, raw material for concrete secondary products, raw material for ceramics and tiles, and raw material for artificial stone.
Further, the water absorption has a correlation with the strength, and the water absorption ≦ 4.0% by mass is preferable in terms of strength for any high-grade application.
以上説明してきた規格が存在する高級用途以外の、中級用途として、本発明での上記のf・CaO≦2.7質量%かつ吸水率≦4.0質量%である改質製鋼スラグは、鉄鋼・非鉄の製錬・精錬工程、廃棄物燃焼溶融炉、灰溶融炉、スラグ溶融炉において主原料、副原料、耐火物保護剤、助剤、保温材原料、鎮静材原料、もしくは硬化体・固化体原料、底質・海水浄化剤原料として用いることができる。 The modified steelmaking slag having the above-mentioned f · CaO ≦ 2.7 mass% and water absorption ≦ 4.0 mass% in the present invention as an intermediate application other than the high-grade application where the standard described above exists -Non-ferrous smelting and refining processes, waste combustion melting furnaces, ash melting furnaces, slag melting furnaces, main raw materials, auxiliary raw materials, refractory protective agents, auxiliaries, thermal insulation raw materials, sedative raw materials, or hardened bodies / solidification It can be used as a body material, bottom sediment / seawater purification material.
本発明による製鋼スラグの改質法の実施例を示す。
製鋼スラグとして、溶銑予備処理スラグを用いた。表1は本実施例に供した溶銑予備処理スラグ、高炉スラグ、フライアッシュの代表組成分析値を示す。
溶銑予備処理スラグ1は、塩基度が2.1でかつf・CaOが6.8質量%含まれる。また、溶銑予備処理スラグ2は、塩基度が3.5でかつf・CaOが13.7質量%含まれる。この溶銑予備処理スラグにSiO2、Al2O3を含む高炉スラグ、フライアッシュを改質剤として添加した。
溶銑予備処理スラグ1もしくは2と高炉スラグもしくはフライアッシュをあらかじめ混合してからマグネシアるつぼに装入し、黒鉛ルツボを発熱体とした高周波溶解炉を用いて所定の温度まで加熱し、約10分保持した。具体的な実施水準等を表2に示す。尚、溶融温度は図3に示した溶融温度測定方法を用いて測定を行った。
The Example of the modification method of the steelmaking slag by this invention is shown.
As the steelmaking slag, hot metal pretreatment slag was used. Table 1 shows representative composition analysis values of the hot metal pretreatment slag, blast furnace slag, and fly ash used in this example.
The hot
Hot
表2の実施例1〜14は、熱処理温度を溶融温度以上にした場合の実施例である。この結果より、熱処理後のスラグ中のf・CaOの濃度は2.7質量%以下となっており、水和による膨張を呈しない濃度になり、良好に改質されている。また、吸水率も4質量%程度以下まで改質されており、強度が高い改質製鋼スラグが得られている。
また、実施例1〜14では熱処理後の冷却速度が10℃/分以下であったので、熱処理前後に、スラグ中に観察された気泡の脱泡、および破泡が促進されたため、塩基度が高い場合でも吸水率の低減が可能となり、安定して吸水率≦4%達成され、スラグの性状が高級用途に適したものとなっている。また、熱処理後に850℃〜1100℃の温度範囲で保定処理を行った、実施例2,3,7,8に関しては、冷却速度制御に加え、さらに保定処理も実施したところ、保定後のスラグの吸水率の低下が見られ、スラグ性状の更なる高級化が確認された。
これに対し、比較例1〜7はともに熱処理温度が、溶融温度未満であったため、熱処理後スラグのf・CaO濃度が低下せず、吸水率も高かった。
Examples 1 to 14 in Table 2 are examples when the heat treatment temperature is equal to or higher than the melting temperature. From this result, the concentration of f · CaO in the slag after the heat treatment is 2.7% by mass or less, which is a concentration that does not exhibit expansion due to hydration, and is well modified. Moreover, the water absorption is also modified to about 4% by mass or less, and a modified steelmaking slag having high strength is obtained.
In Examples 1 to 14, since the cooling rate after the heat treatment was 10 ° C./min or less, the defoaming and bubble breaking observed in the slag was promoted before and after the heat treatment, so the basicity was Even if it is high, the water absorption can be reduced, the water absorption ≦ 4% can be stably achieved, and the slag properties are suitable for high-grade applications. Moreover, about Example 2,3,7,8 which performed the retention process in the temperature range of 850 degreeC-1100 degreeC after heat processing, in addition to cooling rate control, when the retention process was also implemented, the slag of after retention was implemented. A decrease in water absorption was observed, confirming further upgrading of the slag properties.
On the other hand, since the heat treatment temperature of Comparative Examples 1 to 7 was less than the melting temperature, the f · CaO concentration of the slag after heat treatment did not decrease and the water absorption rate was high.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004125012A JP4571818B2 (en) | 2004-04-21 | 2004-04-21 | Method for reforming steelmaking slag |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004125012A JP4571818B2 (en) | 2004-04-21 | 2004-04-21 | Method for reforming steelmaking slag |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005306654A JP2005306654A (en) | 2005-11-04 |
JP4571818B2 true JP4571818B2 (en) | 2010-10-27 |
Family
ID=35435832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004125012A Expired - Lifetime JP4571818B2 (en) | 2004-04-21 | 2004-04-21 | Method for reforming steelmaking slag |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4571818B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180060386A (en) * | 2016-11-29 | 2018-06-07 | (주)케이텍 | Development of stainless-steel-dust-based concentrate for low-energy Fe-Cr-Ni alloy production |
KR20210084563A (en) | 2018-11-27 | 2021-07-07 | 제이에프이 스틸 가부시키가이샤 | Steel manufacturing method and slag basicity reduction method |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4734167B2 (en) * | 2006-05-08 | 2011-07-27 | 新日本製鐵株式会社 | Steelmaking slag treatment method |
KR100775503B1 (en) * | 2006-06-15 | 2007-11-12 | 주식회사 포스코 | Method for cooling molten pig iron preliminary treatment slag |
EP1988180A1 (en) * | 2007-05-04 | 2008-11-05 | ThyssenKrupp Steel AG | Method for manufacturing stone material from slag and application of stone material manufactured in this manner |
JP5381357B2 (en) * | 2009-06-09 | 2014-01-08 | 新日鐵住金株式会社 | Method of melt reforming steelmaking slag |
JP5565826B2 (en) * | 2009-10-16 | 2014-08-06 | 日新製鋼株式会社 | Abrasive for blasting and method for producing the same |
JP6758107B2 (en) * | 2015-07-06 | 2020-09-23 | 日本製鉄株式会社 | How to handle slag |
JP6955200B2 (en) * | 2017-08-23 | 2021-10-27 | 株式会社大林組 | Manufacturing method of heavy metal adsorbent |
CN110218827A (en) * | 2019-07-09 | 2019-09-10 | 鞍钢股份有限公司 | Molten blast furnace slag conditioning agent and preparation and use methods thereof |
JP2021084092A (en) * | 2019-11-29 | 2021-06-03 | Jfeスチール株式会社 | By-product processing method |
JP2021084091A (en) * | 2019-11-29 | 2021-06-03 | Jfeスチール株式会社 | By-product processing method |
JP6838642B1 (en) * | 2019-12-24 | 2021-03-03 | 宇部興産株式会社 | Admixture for mortar / concrete, hydraulic composition, cement composition and concrete |
CN111718183A (en) * | 2020-05-19 | 2020-09-29 | 余姚市恒祥新型建材有限公司 | Insulating brick and preparation method thereof |
CN114477956B (en) * | 2022-03-02 | 2022-12-16 | 深圳市坤鹏环保建筑废料处理有限公司 | Light construction waste regeneration brick and preparation method thereof |
CN115716738B (en) * | 2022-12-09 | 2023-11-10 | 新源县渣宝环保技术有限公司 | Production process of high-strength steel slag brick |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57140366A (en) * | 1981-02-17 | 1982-08-30 | Gifushi | Manufacture of aggregate from incineration ash |
JPH0497928A (en) * | 1990-08-11 | 1992-03-30 | Chubu Kohan Kk | Manufacture of artificial stone using electric furnace slag as raw material |
JPH06115984A (en) * | 1992-09-29 | 1994-04-26 | Kawasaki Steel Corp | Method for hot modification of steel-manufacturing slag |
JPH082949A (en) * | 1994-06-17 | 1996-01-09 | Joho Sogo Kenkyusho:Kk | Method for modifying steelmaking slag |
JPH10279331A (en) * | 1997-03-31 | 1998-10-20 | Yoshizawa Sekkai Kogyo Kk | Production of useful material from slag of pig iron making and steel making |
JPH11228193A (en) * | 1998-02-19 | 1999-08-24 | Sumitomo Metal Ind Ltd | Molten iron pretreatment slag and its production |
JP4351490B2 (en) * | 2002-08-29 | 2009-10-28 | 新日本製鐵株式会社 | Method for modifying steelmaking slag and modified steelmaking slag |
-
2004
- 2004-04-21 JP JP2004125012A patent/JP4571818B2/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57140366A (en) * | 1981-02-17 | 1982-08-30 | Gifushi | Manufacture of aggregate from incineration ash |
JPH0497928A (en) * | 1990-08-11 | 1992-03-30 | Chubu Kohan Kk | Manufacture of artificial stone using electric furnace slag as raw material |
JPH06115984A (en) * | 1992-09-29 | 1994-04-26 | Kawasaki Steel Corp | Method for hot modification of steel-manufacturing slag |
JPH082949A (en) * | 1994-06-17 | 1996-01-09 | Joho Sogo Kenkyusho:Kk | Method for modifying steelmaking slag |
JPH10279331A (en) * | 1997-03-31 | 1998-10-20 | Yoshizawa Sekkai Kogyo Kk | Production of useful material from slag of pig iron making and steel making |
JPH11228193A (en) * | 1998-02-19 | 1999-08-24 | Sumitomo Metal Ind Ltd | Molten iron pretreatment slag and its production |
JP4351490B2 (en) * | 2002-08-29 | 2009-10-28 | 新日本製鐵株式会社 | Method for modifying steelmaking slag and modified steelmaking slag |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180060386A (en) * | 2016-11-29 | 2018-06-07 | (주)케이텍 | Development of stainless-steel-dust-based concentrate for low-energy Fe-Cr-Ni alloy production |
KR101898938B1 (en) * | 2016-11-29 | 2018-09-14 | (주)케이텍 | Development of stainless-steel-dust-based concentrate for low-energy Fe-Cr-Ni alloy production |
KR20210084563A (en) | 2018-11-27 | 2021-07-07 | 제이에프이 스틸 가부시키가이샤 | Steel manufacturing method and slag basicity reduction method |
Also Published As
Publication number | Publication date |
---|---|
JP2005306654A (en) | 2005-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4351490B2 (en) | Method for modifying steelmaking slag and modified steelmaking slag | |
JP4571818B2 (en) | Method for reforming steelmaking slag | |
JP5408369B2 (en) | Hot metal pretreatment method | |
CN104039987A (en) | Steel slag reduction method | |
JP6164151B2 (en) | Method for refining molten iron using a converter-type refining furnace | |
JP4734167B2 (en) | Steelmaking slag treatment method | |
JP5444883B2 (en) | Modified slag | |
JP3965139B2 (en) | Method for reforming steelmaking slag | |
JP5408379B2 (en) | Hot metal pretreatment method | |
JP3091177B2 (en) | Steelmaking reduction slag reforming method | |
Brandaleze et al. | Treatments and recycling of metallurgical slags | |
JP2021134386A (en) | Method for melting cold iron source with slag reduction | |
TWI843517B (en) | Direct-reduction iron melting method, solid iron and method for producing solid iron, civil engineering and construction material and method for producing civil engineering and construction material, and direct-reduction iron melting system | |
JP5573024B2 (en) | Steelmaking slag treatment method | |
TWI844330B (en) | Direct-reduction iron melting method, solid iron and method for producing solid iron, civil engineering and construction material and method for producing civil engineering and construction material | |
JP5625238B2 (en) | Method for refining molten iron | |
KR20210079354A (en) | Gatan materials and methods using the same | |
JP2021084092A (en) | By-product processing method | |
WO2023204063A1 (en) | Method for melting direct reduction iron, solid iron and method for manufacturing solid iron, material for civil engineering and construction, method for producing material for civil engineering and construction, and system for melting direct reduction iron | |
WO2023204069A1 (en) | Method for melting direct-reduced iron, solid iron and method for producing solid iron, and civil engineering and construction material and method for producing civil engineering and construction material | |
JP7363731B2 (en) | Method for dephosphorizing hot metal and manufacturing method for molten steel | |
JP4288101B2 (en) | Method for melt reforming steelmaking slag | |
JP6947024B2 (en) | Hot metal desulfurization method | |
RU2112070C1 (en) | Method of production of ferrovanadium | |
JP4511909B2 (en) | Steelmaking slag treatment method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060906 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090618 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090623 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090824 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091110 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100112 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100316 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100514 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100803 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100813 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130820 Year of fee payment: 3 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 4571818 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130820 Year of fee payment: 3 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130820 Year of fee payment: 3 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
EXPY | Cancellation because of completion of term |