JPH0153330B2 - - Google Patents
Info
- Publication number
- JPH0153330B2 JPH0153330B2 JP57080107A JP8010782A JPH0153330B2 JP H0153330 B2 JPH0153330 B2 JP H0153330B2 JP 57080107 A JP57080107 A JP 57080107A JP 8010782 A JP8010782 A JP 8010782A JP H0153330 B2 JPH0153330 B2 JP H0153330B2
- Authority
- JP
- Japan
- Prior art keywords
- cao
- weight
- steel
- refining agent
- present
- 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
Links
- 229910000831 Steel Inorganic materials 0.000 claims description 22
- 239000010959 steel Substances 0.000 claims description 22
- 238000007670 refining Methods 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 34
- 239000000292 calcium oxide Substances 0.000 description 17
- 235000012255 calcium oxide Nutrition 0.000 description 17
- 239000002994 raw material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Description
本発明は石灰質鉄鋼精錬剤、さらに詳しくは、
CaO−Al2O3を主成分とし脱硫、脱りん、脱酸等
の作用を有し、かつ溶鋼の水素吸収を防止した石
灰質鉄鋼精錬剤に関する。
最近の鉄鋼製品、特に大径鋼管、高圧容器用鋼
材、海洋鋼材、構造用線材等については、品質の
高級化が要望されているので、鉄鋼製品の靭性お
よび強度に優れた高張力鋼を得るため、通常溶鋼
に種々の精錬剤を添加して清浄化処理する操作が
行なわれている。この処理には従来より取り鍋炉
外精錬法が用いられ、溶鋼を処理する際には次の
如き精錬剤が用いられている。
(1) CaOを主体とする物とフツ化物との混合物。
(2) CaOを主体とする物にハロゲン化物を添加し
て焼成した焼結物。
(3) CaOを主体とする物にフツ化物を添加し、電
融した溶融物。
しかしながら、これら精錬剤はCaOを主体とし
ているため、精錬剤の保存および使用時において
吸湿が大きく、その結果、溶鋼中への水素吸収が
大きくなり、鋼の品質向上を阻害するため、耐吸
湿性の点で大きな欠点がある。またこの精錬剤は
ハロゲン化物を含んでいるため、作業環境が悪化
したり、ライニング溶損量が大になるなどの問題
があつた。
本発明者等はこのような精錬剤の欠点を除去せ
んとして種々研究を行つた結果、CaOは大気中の
水分と速やかに反応するのに対し、3CaO・
Al2O3は水と接触すると速やかに反応して水和物
を生成するが、大気中の水分とは反応しにくいこ
とを知見した。本発明はかかる知見に基づくもの
であつて、石灰質原料粉末およびアルミナ質原料
粉末とをそれぞれCaO、Al2O3およびSiO2が特定
量になるように混合し、この混合物を特定温度範
囲に焼成してCaC結晶粒子の周囲を3CaO・
Al2O3を主とした液相成分で被覆し、焼成物の耐
吸湿性を向上せしめんとしたものである。
すなわち、本発明に係る石灰質鉄鋼精錬剤は、
成分比がCaO60〜85重量％、Al2O310〜35重量
％、SiO23重量％以下であるクリンカであつて、
CaO結晶粒子の周囲に3CaO・Al2O3からなる被
覆が形成されてなることを特徴とする。
次に本発明者等が行つた実験例の一例を示す。
石灰質原料として石灰石、アルミナ質原料として
ボーキサイトを用い、何れも88μ篩残分が10重量
％以下になるように粉砕して得た粉末を第１表の
割合になるように混合したものを、水を媒体とし
てペレタイザーで直径10〜15mmに成球した後乾燥
し、小型ロータリーキルンで1350〜1400℃でクリ
ンカを造つた。
The present invention provides a calcareous steel refining agent, more specifically,
The present invention relates to a calcareous steel refining agent containing CaO-Al 2 O 3 as a main component, which has desulfurization, dephosphorization, deoxidation, etc. effects, and which prevents hydrogen absorption in molten steel. Recently, there is a demand for higher quality steel products, especially large diameter steel pipes, steel materials for high-pressure vessels, marine steel materials, structural wire rods, etc., so we can obtain high-tensile steel with excellent toughness and strength for steel products. Therefore, various refining agents are usually added to molten steel for cleaning. Conventionally, a ladle out-of-furnace refining method has been used for this treatment, and the following refining agents have been used when treating molten steel. (1) A mixture of substances mainly composed of CaO and fluorides. (2) A sintered product made by adding a halide to a material mainly composed of CaO and firing it. (3) A molten product made by adding fluoride to a substance mainly composed of CaO and melting it by electricity. However, since these refining agents are mainly composed of CaO, they absorb a lot of moisture during storage and use.As a result, hydrogen absorption into the molten steel increases, impeding the improvement of steel quality. There are major drawbacks in this respect. Furthermore, since this refining agent contains halides, there have been problems such as deteriorating the working environment and increasing the amount of lining erosion. The present inventors conducted various studies in an attempt to eliminate these drawbacks of refining agents, and found that while CaO reacts quickly with moisture in the atmosphere, 3CaO.
It was discovered that Al 2 O 3 reacts quickly when it comes into contact with water to form hydrates, but it is difficult to react with moisture in the atmosphere. The present invention is based on this knowledge, and involves mixing calcareous raw material powder and alumina raw material powder so that CaO, Al 2 O 3 and SiO 2 are in specific amounts, respectively, and firing this mixture to a specific temperature range. and surrounding the CaC crystal particles with 3CaO・
It is coated with a liquid phase component mainly consisting of Al 2 O 3 to improve the moisture absorption resistance of the fired product. That is, the calcareous steel refining agent according to the present invention is
A clinker whose component ratio is 60 to 85% by weight of CaO, 10 to 35% by weight of Al2O3 , and 3% by weight of SiO2 ,
It is characterized by a coating made of 3CaO.Al 2 O 3 formed around CaO crystal particles. Next, an example of an experiment conducted by the present inventors will be shown.
Using limestone as the calcareous raw material and bauxite as the alumina raw material, the powder obtained by pulverizing them so that the residue on an 88 μ sieve is 10% by weight or less is mixed in the proportions shown in Table 1, and then mixed with water. The balls were formed into balls with a diameter of 10 to 15 mm using a pelletizer as a medium, dried, and clinker was produced at 1350 to 1400°C in a small rotary kiln.
【表】
次に斯くして造つたクリンカの研磨面を
EPMA（エレクトロン、プローブ、マイクロアナ
ライザー）で元素分析したところ、クリンカ中の
Al成分はCaO結晶粒子を被覆していることが確
認された。またクリンカの粉末をＸ線回折により
その構成鉱物を同定したところ、検出された鉱物
はCaOと3CaO・Al2O3であることが認められた。
クリンカ（径10〜15mm）を相対湿度80％、温度
20℃の大気中に放置したところ、重量増加率は添
付図面に示すように小さく耐吸湿性に優れている
ことを認めた。なお図面には比較のため従来の市
販の精錬剤（CaOを主体とするものにフツ化物を
添加し電融した溶融物を径10〜15mmに破砕したも
の）の吸湿量も併記した。
このクリンカを粉砕して１mm以下の粒度に調整
し、マグネシアルツボ内で高周波溶融した1600℃
の低硫溶鋼に対し、アルゴンガスと共に0.5重量
％添加し、10分間処理したところ第２表に示す如
き結果を得た。[Table] Next, the polished surface of the clinker made in this way is
Elemental analysis using EPMA (Electron, Probe, Micro Analyzer) revealed that
It was confirmed that the Al component covered the CaO crystal particles. When the constituent minerals of the clinker powder were identified by X-ray diffraction, the detected minerals were found to be CaO and 3CaO・Al 2 O 3 . Clinker (10-15 mm diameter) at 80% relative humidity and temperature
When it was left in the air at 20°C, the weight increase rate was small as shown in the attached drawing, and it was found to have excellent moisture absorption resistance. For comparison, the drawing also shows the amount of moisture absorbed by a conventional commercially available refining agent (a molten product made by adding fluoride to CaO and crushing it into pieces of 10 to 15 mm in diameter). This clinker was crushed and adjusted to a particle size of 1 mm or less, and then melted at high frequency in a magnesia crucible at 1600℃.
When 0.5% by weight of argon gas was added to low sulfur molten steel and treated for 10 minutes, the results shown in Table 2 were obtained.
【表】
第２表より本発明によるクリンカは脱硫効果お
よび脱りん効果が大なることが認められた。
本発明において、CaO成分が60重量％未満の場
合には、精錬剤の主目的である脱硫、脱りん等の
溶鋼の清浄化効果が低下し、また85重量％を超え
ると、3CaO・Al2O3によるCaO結晶粒子の被覆
作用が乏しくなるので、充分なる耐吸湿性を有す
る精錬剤を得ることが難かしい。さらにまた
Al2O3成分が10重量％未満の場合には、3CaO・
Al2O3によるCaO結晶粒子の被覆作用が乏しくな
るため耐吸湿性が悪化し、また35重量％を超える
と相対的に主剤であるCaO成分が減少するため、
溶鋼の清浄化効果が低下する。最後に、SiO2成
分が３重量％を超えると、溶鋼の清浄効果が低下
するばかりでなく耐吸湿性が悪化するので好まし
くない。
石灰質原料としては、通常の石灰石、生石灰、
消石灰等が使用され、アルミナ質原料としては、
ボーキサイト、礬土頁岩、バイヤー法アルミナ、
アルミニウム残渣あるいは粘土等が使用される。
但し、精錬剤中のSiO2が３重量％以下になるよ
うにSiO2含有量の少ない原料を選択しなければ
ならない。
上述の各原料は88μ篩分が10重量％以下になる
ように粉砕したものを使用することが好ましい。
原料粉末の焼成は粉状のままで焼成しても、また
成形したものを焼成しても良い。
本発明における混合原料の焼成温度は1300〜
1450℃であり、加熱炉としてはロータリーキル
ン、反射炉等が使用出来るが、ロータリーキルン
を採用すれば、連続的に大量生産しうるので工業
上経済的である。
本発明の精錬剤は大気中の水分に対して水和し
にくいから、本発明の精錬剤を使用すれば鋼のＨ
ピツクアツプが無く、靭性および強度の優れた高
張力鋼を造ることができる。[Table] From Table 2, it was confirmed that the clinker according to the present invention has a large desulfurization effect and dephosphorization effect. In the present invention, when the CaO content is less than 60% by weight, the cleaning effect of molten steel such as desulfurization and dephosphorization, which is the main purpose of the refining agent, decreases, and when it exceeds 85% by weight, 3CaO・Al 2 Since the coating effect of CaO crystal particles with O 3 becomes poor, it is difficult to obtain a refining agent with sufficient moisture absorption resistance. Yet again
If the Al 2 O 3 component is less than 10% by weight, 3CaO・
Moisture absorption resistance deteriorates because the coating effect of Al 2 O 3 on CaO crystal particles becomes poor, and if it exceeds 35% by weight, the CaO component, which is the main ingredient, decreases relatively.
The cleaning effect of molten steel decreases. Finally, if the SiO 2 component exceeds 3% by weight, it is not preferable because it not only reduces the cleaning effect of molten steel but also deteriorates moisture absorption resistance. Calcareous raw materials include ordinary limestone, quicklime,
Slaked lime etc. are used, and as alumina raw materials,
Bauxite, shale, Bayer process alumina,
Aluminum residue or clay is used.
However, raw materials with low SiO 2 content must be selected so that SiO 2 in the refining agent is 3% by weight or less. It is preferable to use the above-mentioned raw materials that have been pulverized so that the 88μ sieve content is 10% by weight or less.
The raw material powder may be fired either as a powder or as a shaped product. The firing temperature of the mixed raw materials in the present invention is 1300~
The temperature is 1450°C, and a rotary kiln, reverberatory furnace, etc. can be used as the heating furnace, but if a rotary kiln is used, it is industrially economical because it allows continuous mass production. Since the refining agent of the present invention is difficult to hydrate with moisture in the atmosphere, if the refining agent of the present invention is used, the H
There is no pick-up and high tensile strength steel with excellent toughness and strength can be produced.
図面は、本発明の鉄鋼精錬剤の粒径10〜15mmの
ものと市販の精錬剤（CaOを主体とするものにフ
ツ化物を添加し電融した溶融物）の粒径10〜15mm
のものとを相対湿度80％、温度20℃の大気中に放
置した場合における重量増加率を示す線図であ
る。
図において１……本発明の鉄鋼精錬剤、２……
市販の精錬剤。
The drawing shows the particle size of the steel refining agent of the present invention with a particle size of 10 to 15 mm and the particle size of a commercially available refining agent (a molten product made by adding fluoride to a substance mainly composed of CaO and electro-melting it) with a particle size of 10 to 15 mm.
FIG. 2 is a diagram showing the weight increase rate when the sample is left in the atmosphere at a relative humidity of 80% and a temperature of 20°C. In the figure, 1... the steel refining agent of the present invention, 2...
Commercially available refining agent.
Claims (1)
量％、SiO23重量％以下であるクリンカであつ
て、CaO結晶粒子の周囲に3CaO・Al2O3からな
る被覆が形成されてなることを特徴とする石灰質
鉄鋼精錬剤。1 A clinker whose component ratio is 60 to 85% by weight of CaO, 10 to 35% by weight of Al 2 O 3 , and 3% by weight of SiO 2 or less, and a coating consisting of 3CaO・Al 2 O 3 is formed around CaO crystal particles. A calcareous steel refining agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57080107A JPS58197210A (en) | 1982-05-14 | 1982-05-14 | Calcareous refining agent for steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57080107A JPS58197210A (en) | 1982-05-14 | 1982-05-14 | Calcareous refining agent for steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58197210A JPS58197210A (en) | 1983-11-16 |
| JPH0153330B2 true JPH0153330B2 (en) | 1989-11-14 |
Family
ID=13708954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57080107A Granted JPS58197210A (en) | 1982-05-14 | 1982-05-14 | Calcareous refining agent for steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58197210A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0382714U (en) * | 1989-12-15 | 1991-08-22 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5413300B2 (en) * | 2010-05-07 | 2014-02-12 | 新日鐵住金株式会社 | Mineral-containing molten steel desulfurization flux |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5258011A (en) * | 1975-11-08 | 1977-05-13 | Sumitomo Metal Ind Ltd | Dephosphorizing agent for iron refining |
| JPS52114513A (en) * | 1976-03-24 | 1977-09-26 | Hitachi Ltd | Slag for refining in ladies |
| JPS5458613A (en) * | 1977-10-19 | 1979-05-11 | Kobe Steel Ltd | Steel refining flux |
| JPS54131521A (en) * | 1978-04-04 | 1979-10-12 | Showa Denko Kk | Antidigestive calcic smelting agent for steel |
| JPS5677317A (en) * | 1979-11-28 | 1981-06-25 | Denki Kagaku Kogyo Kk | High calcareous iron and steel refining agent |
-
1982
- 1982-05-14 JP JP57080107A patent/JPS58197210A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5258011A (en) * | 1975-11-08 | 1977-05-13 | Sumitomo Metal Ind Ltd | Dephosphorizing agent for iron refining |
| JPS52114513A (en) * | 1976-03-24 | 1977-09-26 | Hitachi Ltd | Slag for refining in ladies |
| JPS5458613A (en) * | 1977-10-19 | 1979-05-11 | Kobe Steel Ltd | Steel refining flux |
| JPS54131521A (en) * | 1978-04-04 | 1979-10-12 | Showa Denko Kk | Antidigestive calcic smelting agent for steel |
| JPS5677317A (en) * | 1979-11-28 | 1981-06-25 | Denki Kagaku Kogyo Kk | High calcareous iron and steel refining agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0382714U (en) * | 1989-12-15 | 1991-08-22 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58197210A (en) | 1983-11-16 |
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