JPH02285018A - Desulfurizing agent for molten pig iron - Google Patents
Desulfurizing agent for molten pig ironInfo
- Publication number
- JPH02285018A JPH02285018A JP1104757A JP10475789A JPH02285018A JP H02285018 A JPH02285018 A JP H02285018A JP 1104757 A JP1104757 A JP 1104757A JP 10475789 A JP10475789 A JP 10475789A JP H02285018 A JPH02285018 A JP H02285018A
- Authority
- JP
- Japan
- Prior art keywords
- desulfurizing agent
- slag
- acetylene
- desulfurization
- pig iron
- 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.)
- Pending
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 14
- 229910000805 Pig iron Inorganic materials 0.000 title abstract 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000005997 Calcium carbide Substances 0.000 abstract description 4
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 30
- 238000006477 desulfuration reaction Methods 0.000 description 22
- 230000023556 desulfurization Effects 0.000 description 22
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 17
- 239000000292 calcium oxide Substances 0.000 description 14
- 235000012255 calcium oxide Nutrition 0.000 description 14
- 239000010436 fluorite Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 235000011116 calcium hydroxide Nutrition 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、溶銑の脱硫剤に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to a desulfurizing agent for hot metal.
従来、卦銑の脱硫剤としては、消石灰（Ｃａ（ＯＨ）２
）％生石灰（Ｃａｂ）及び滓化促進剤からなる（特開昭
６２−１７０４０７号公報）ものが知られている。Conventionally, slaked lime (Ca(OH)2
)% quicklime (Cab) and a slag accelerator (Japanese Unexamined Patent Publication No. 170407/1983) is known.
また、古くから生石灰と螢石の焼成物からなる脱硫剤が
用いられている。In addition, desulfurization agents made of calcined quicklime and fluorite have been used since ancient times.
しかしながら、前者は単なる混合粉末であること、さら
に消石灰の分解吸熱による鋳銑温度の低下などにより、
脱硫効率が不安定である。また、後者においては螢石に
よる生石灰の融点降下は認められるものの、生石灰の焼
成によってＣａＯの活性度が低下し、脱硫性能が低下す
るという欠点があった。However, the former is simply a mixed powder, and the temperature of the cast iron decreases due to the decomposition endotherm of slaked lime.
Desulfurization efficiency is unstable. In the latter case, although it is recognized that the melting point of quicklime is lowered by fluorite, the firing of the quicklime lowers the activity of CaO, resulting in a decrease in desulfurization performance.
本発明の脱硫剤は、アセチレン発生滓とアルカリ土類金
属７ツ化物との造粒焼成物であって、アルカリ土類金Ｊ
ｌｉ７ツ化物を０．５〜５重量％含有してなること’を
特徴とするものである。The desulfurization agent of the present invention is a granulated and fired product of acetylene generation slag and alkaline earth metal heptadide,
It is characterized by containing 0.5 to 5% by weight of li heptadide.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のアセチレン発生滓とは、下記の式に示すカルシ
クムカーバイド（Ｃ”ａＣ２）からアセチレンがス＜Ｃ
５Ｈｓ）を発生させた残滓を意味し、その主成分は消石
灰Ｃａ （０Ｂ）２である。The acetylene generation slag of the present invention refers to acetylene generated from calcium carbide (C''aC2) represented by the following formula.
5Hs), the main component of which is slaked lime Ca(0B)2.
ＣａＣ２＋ ２Ｈ２０→Ｃｊｌ（ＯＨ）２ ＋ Ｃ２Ｈ
２Ｔアルカリ土類金属フッ化物としては、ＣａＦ２、Ｍ
ｇＦ２、ＢａＦ２．８ｒＦ２ の成分を有するもので
ある。CaC2+ 2H20→Cjl(OH)2 + C2H
2T alkaline earth metal fluorides include CaF2, M
It has the following components: gF2, BaF2.8rF2.
通常は、螢石が用いられる。Fluorite is usually used.
本発明は、アセチレン発生滓とアルカリ土類金属フッ化
物とを混合造粒し、これを焼成炉で焼成した脱硫剤であ
る。造粒物の焼成温度は、６００℃〜８００℃であるこ
とが望ましい。焼成温度が６００６Ｃ未満では、アセチ
レン発生環中のＣａ（Ｇ（）２が充分に分解せずに残留
し好ましくない。８００℃を超えると、分解生成したＣ
ａＯが焼結する傾向があるので好ましくない。The present invention is a desulfurizing agent obtained by mixing and granulating acetylene generation slag and an alkaline earth metal fluoride and firing the mixture in a firing furnace. The firing temperature of the granules is preferably 600°C to 800°C. If the firing temperature is less than 6006C, Ca(G()2 in the acetylene generating ring will not be sufficiently decomposed and will remain, which is undesirable. If the firing temperature exceeds 800℃, the decomposed C
This is not preferred because aO tends to sinter.
アルカリ土類金属７ツ化物の含有量は、０．５〜５重量
重量あることが心安である。これが０．５Ｘ量係未満で
は、脱硫剤自身の滓化促進作用が乏しく、結果的には脱
硫性能が低下する。It is safe that the content of the alkaline earth metal heptadide is 0.5 to 5% by weight. When this ratio is less than 0.5X, the desulfurizing agent itself has a poor slag formation promotion effect, resulting in a decrease in desulfurization performance.
また、５重量％を超えると、それ以上の脱硫性能に影響
がなく、さらには相対的に脱硫主剤であるＣａ０分が減
少し、脱硫性能が低下する。Moreover, when it exceeds 5% by weight, there is no effect on further desulfurization performance, and furthermore, Ca0 content, which is the main desulfurization agent, decreases relatively, resulting in a decrease in desulfurization performance.
次に、造粒焼成物の大きさは、０．６〜５ｍが望ましい
。これが０．６未満では、使用に当り飛散ロスが多く、
また排滓等の作業性が悪い。さらに、５ｎを超えると脱
硫剤の単位重量当りの表面積が小さくなり、溶銑との接
触面積が減少する結果、脱硫性能が低下する。Next, the size of the granulated and fired product is preferably 0.6 to 5 m. If this is less than 0.6, there will be a lot of scattering loss during use,
Also, the workability of slag removal etc. is poor. Furthermore, if it exceeds 5n, the surface area per unit weight of the desulfurizing agent decreases, and as a result, the contact area with hot metal decreases, resulting in a decrease in desulfurization performance.
本発明の脱硫剤は、アセチレン発生滓の主成分であるＣ
ａ （ＯＨ）２を焼成して得られたＣａＯが脱硫主剤と
なる。The desulfurization agent of the present invention is characterized by C, which is the main component of the acetylene generation slag.
CaO obtained by firing a (OH)2 becomes the main desulfurization agent.
溶銑の脱硫反応においてＣａＯの活性度をくらべると、
溶銑中でアセチレン発生滓から分解生成したＣａＯが一
番良好であると考えられる。しかしながら、溶銑中に添
加されるＣａＯの単位量当シで比較すると、アセチレン
発生滓はＣａ （ＯＨ）２で換算して、アセチレン発生
滓焼成物の約１．３倍量ｔ−Ｖし、しかも分解吸熱を伴
うことから、溶銑温度が降下し、アセチレン発生滓をそ
のまま添加しても脱硫効果が向上しないのである。Comparing the activity of CaO in the desulfurization reaction of hot metal,
It is thought that CaO produced by decomposition from acetylene generation slag in hot metal is the best. However, when comparing the unit amount of CaO added to hot metal, the amount of acetylene generated slag is approximately 1.3 times the amount t-V of the fired acetylene generated slag in terms of Ca (OH)2, and Since decomposition endotherms are involved, the hot metal temperature drops, and the desulfurization effect does not improve even if the acetylene generation slag is added as it is.
次に、アセチレン発生滓焼成物は融点が高く、滓化しに
くいので滓化促進剤が配合される。滓化促進剤の配合方
法により、単純混合物と焼成混合物がある。Next, since the acetylene-generating slag fired product has a high melting point and is difficult to form into a slag, a slag-forming accelerator is added. There are simple mixtures and fired mixtures depending on the method of blending the sludge accelerator.
アセチレン発生滓焼成物に蛍石全単純に混合しｆｃ場合
、粒度偏析などによる均一性に欠け、滓化性に劣り、脱
硫効果が充分でない。When all the fluorite is simply mixed into the acetylene-generating slag fired product, it lacks uniformity due to particle size segregation, has poor slag forming properties, and does not have a sufficient desulfurization effect.
次に、アセチレン発生滓焼成物に蛍石を混合焼成した場
合、単純混合にくらべて滓化性は向上するが、蛍石がＣ
ａＯ粒子の表面部分のみで共融状態となり、ＣａＯの脱
硫反応が表面部分でしか進行しないことになる。Next, when fluorite is mixed and fired with the acetylene-generating slag fired product, the slag forming property is improved compared to simple mixing, but the fluorite
A eutectic state occurs only at the surface portion of the aO particles, and the desulfurization reaction of CaO proceeds only at the surface portion.
以上で述べたように、アセチレン発生滓に蛍石を単純混
合した場合、アセチレン発生滓を焼成してから蛍石を単
純混合あふいは焼成混合した場合のいずれにおいても脱
硫効果が充分ではない。As described above, the desulfurization effect is not sufficient in either cases where fluorite is simply mixed with the acetylene generation slag, when the acetylene generation slag is fired and then fluorite is simply mixed, or when it is fired and mixed.
本発明は、アセチレン発生滓に蛍石を混合造粒してから
焼成した脱硫剤である。アセチレン発生滓は、高温下で
生成したカルシウムカーバイドを経て発生したＣａ（Ｏ
Ｈ）２であるから、微細な結晶構造を有している。した
がって、焼成により分解生成したＣａＯ粒子も他のＣａ
Ｏ源にくらべて微細であることが特徴である。微細なＣ
ａＯ粒子と蛍石の共融反応も均一に進行することから、
滓化促進剤としての配合量が他にくらべて少なくてすむ
。The present invention is a desulfurization agent prepared by mixing and granulating fluorite into acetylene generation slag and then firing the mixture. The acetylene generation slag is composed of Ca(O) generated through calcium carbide generated under high temperature.
H) Since it is 2, it has a fine crystal structure. Therefore, the CaO particles decomposed and produced by calcination also contain other CaO particles.
It is characterized by being finer than O sources. fine C
Since the eutectic reaction between aO particles and fluorite also proceeds uniformly,
The amount of sludge accelerator required is smaller than other types.
次に、造粒焼成すると造粒しない焼成物にくらべて多孔
性に優れている。Ｃａ （ＯＨ）２が分解してＨ２Ｏが
揮散するとぎ、造粒物内に多数の孔を残している。造粒
しない場合は、揮散が自由で孔も少なく、さらに粉砕整
粒することにより多孔性が失われる。造粒焼成物が多孔
性であるから、粒状物であっても溶銑との接触面積が拡
大することになり、脱硫反応が粒内においても期待され
、粉末にくらべて著しい脱硫効果を発揮するものと考え
られる。Next, when granulated and fired, the porosity is superior to that of a fired product that is not granulated. As Ca(OH)2 decomposes and H2O evaporates, it leaves a large number of pores within the granules. When not granulated, volatilization is free and there are few pores, and porosity is lost by further pulverization and granulation. Since the granulated and fired product is porous, the contact area with the hot metal increases even though it is a granular material, and desulfurization reactions are expected to occur even within the grains, and it exhibits a remarkable desulfurization effect compared to powder. it is conceivable that.
本発明による脱硫剤を製造するには、アセチレン発生滓
にアルカリ土類金属７ツ化物を、焼成後０．５〜５ｘｊ
ｉ％になるように配合し、パン形造粒機、プレングー形
造粒機等で概ねサイズ０．３〜５龍に造粒する。In order to produce the desulfurization agent according to the present invention, an alkaline earth metal heptadide is added to the acetylene generation slag in an amount of 0.5 to 5xj after calcination.
i%, and granulated into approximately 0.3-5.
次に造粒品をロータリー・キルン、トンネルキルン、シ
リコニット炉等に装入し、温度６００°Ｃ〜８００°Ｃ
で焼成する。Next, the granulated product is charged into a rotary kiln, tunnel kiln, silicone kiln, etc. and heated to a temperature of 600°C to 800°C.
Fire it with
造粒焼成物は、サイズ０．３ｍｍ下及び５嘗鳳上ｔｌ−
篩別して除く。インジェクション法で用いる場合は０．
６〜１龍に整粒する。The granulated and fired product is 0.3 mm in size and 5 years old in size.
Remove by sieving. 0 when used in the injection method.
Sort the grain into 6 to 1 pieces.
以下、本発明を実施例、比較例をあげて説明する。 The present invention will be described below with reference to Examples and Comparative Examples.
アセチレン発生環（Ｃａ（ＯＨ）２．純度９０重量％）
に、焼成物のＣａＦ２成分が表で示す割合になるように
、螢石（中国産、 ＣａＦ２純度８純度８俤粒を行い、
１〜５１１１１ＩＯ造粒物を得た。この造粒物をロータ
リー・中ルンへ装入し、６００〜７００℃の温度で焼成
し、焼成物（１〜■）を得た。Acetylene generating ring (Ca(OH)2. Purity 90% by weight)
Then, 8 grains of fluorite (produced in China, CaF2 purity 8 purity) were added so that the CaF2 component of the fired product was in the proportion shown in the table.
1 to 51111IO granules were obtained. This granulated product was charged into a rotary medium run and fired at a temperature of 600 to 700°C to obtain fired products (1 to ■).
次いでこの焼成物を篩分し、１〜３ｓｍの粒状脱硫剤と
なった。比較例として、消石灰（市販品０５Ｌ（ＯＨ）
、純度９５重量％）と螢石との焼成物（■）、焼成物（
１）と螢石の混合物、生石灰（ ＣａＯ純度９５１量％
）と螢石の混合物を１４整した。Next, this fired product was sieved to obtain a granular desulfurizing agent with a size of 1 to 3 sm. As a comparative example, slaked lime (commercial product 05L (OH)
, purity 95% by weight) and fluorite (■), fired product (
1) and a mixture of fluorite, quicklime (CaO purity 951% by weight)
) and fluorite were mixed together.
表の実験−１〜９で示す脱硫剤を黒鉛ルツボ内で高周波
誘導浴解した溶銑に対し、１．０１１［％添加し、窒素
がスで５分間攪拌処理した。Desulfurization agents shown in Experiments 1 to 9 in the table were added in an amount of 1.011% to hot metal melted in a high-frequency induction bath in a graphite crucible, and stirred for 5 minutes in a nitrogen gas atmosphere.
その結果ｔ′表に示す。尚溶銑中の［Ｓ）分析は、硫黄
分析機器Ｉｎ−３２ｆｆｉ（レコ゛社製）によった。The results are shown in table t'. [S] in the hot metal was analyzed using a sulfur analyzer In-32ffi (manufactured by Record Co., Ltd.).
本発明のアセチレン発生環とアルカリ土類金属フッ化物
とを造粒焼成して得られ大溶銑用脱硫剤は、脱硫性能を
向上することが出来るので、高品質の溶銑を得るために
使用できる。The desulfurizing agent for large hot metal obtained by granulating and firing the acetylene generating ring and alkaline earth metal fluoride of the present invention can improve the desulfurization performance, so it can be used to obtain high quality hot metal.
Claims (1)
焼成物であつて、アルカリ土類金属フッ化物を０．５〜
５重量％含有してなることを特徴とする溶銑用脱硫剤。A granulated and fired product of acetylene generation slag and an alkaline earth metal fluoride, the alkaline earth metal fluoride being contained in an amount of 0.5 to
A desulfurizing agent for hot metal characterized by containing 5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104757A JPH02285018A (en) | 1989-04-26 | 1989-04-26 | Desulfurizing agent for molten pig iron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104757A JPH02285018A (en) | 1989-04-26 | 1989-04-26 | Desulfurizing agent for molten pig iron |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02285018A true JPH02285018A (en) | 1990-11-22 |
Family
ID=14389362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1104757A Pending JPH02285018A (en) | 1989-04-26 | 1989-04-26 | Desulfurizing agent for molten pig iron |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02285018A (en) |
-
1989
- 1989-04-26 JP JP1104757A patent/JPH02285018A/en active Pending
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