JP2006222105A - Process for producing filler containing ferrite, electromagnetic wave heating material, electromagnetic wave shielding material - Google Patents
Process for producing filler containing ferrite, electromagnetic wave heating material, electromagnetic wave shielding material Download PDFInfo
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- JP2006222105A JP2006222105A JP2005031178A JP2005031178A JP2006222105A JP 2006222105 A JP2006222105 A JP 2006222105A JP 2005031178 A JP2005031178 A JP 2005031178A JP 2005031178 A JP2005031178 A JP 2005031178A JP 2006222105 A JP2006222105 A JP 2006222105A
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000010438 heat treatment Methods 0.000 title claims abstract description 22
- 239000000945 filler Substances 0.000 title claims abstract description 14
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title description 11
- 239000002893 slag Substances 0.000 claims abstract description 122
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000008187 granular material Substances 0.000 claims abstract description 42
- 230000003647 oxidation Effects 0.000 claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 38
- 239000000428 dust Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 239000004567 concrete Substances 0.000 abstract description 3
- 239000005060 rubber Substances 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 2
- -1 pottery Substances 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000005484 gravity Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000010405 reoxidation reaction Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Compositions Of Macromolecular Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
Description
本発明は電磁波加熱材料や電磁波遮蔽材料として有用なフェライト含有充填材の製造方法に関するものである。 The present invention relates to a method for producing a ferrite-containing filler useful as an electromagnetic wave heating material or an electromagnetic wave shielding material.
例えば電磁波加熱材料や電磁波遮蔽材料としては合成樹脂、ゴム、アスファルト、コンクリート、陶磁器等に金属粉を混合するか、金属網や金属薄膜挿入あるいは埋設あるいは貼着したものが提供されている（例えば特許文献１〜５参照）。 For example, as electromagnetic wave heating materials and electromagnetic wave shielding materials, synthetic resin, rubber, asphalt, concrete, ceramics, etc. are mixed with metal powder, or a metal net or metal thin film is inserted, embedded or stuck (for example, patents). Reference 1-5).
しかし金属粉、金属網あるいは金属薄膜は非常に高価であるし、また腐食され易く、更に金属網や金属薄膜は機械的強度が小さく破損し易いと云う問題点がある。 However, the metal powder, the metal net or the metal thin film is very expensive and easily corroded, and the metal net and the metal thin film have a problem that they have a low mechanical strength and are easily damaged.
本発明は上記従来の課題を解決するための手段として、鉄を含有するスラグ粒状体または破砕物を酸素富化状態で加熱攪拌した後急冷処理することを特徴とするフェライト含有充填材の製造方法を提供するものである。
該鉄を含有するスラグ粒状体または破砕物は、電気炉酸化スラグまたは銅スラグまたは電気炉ダスト処理スラグであることが望ましい。上記フェライト含有充填材は例えば電磁波加熱材料や電磁波遮蔽材料として使用される。
As a means for solving the above-mentioned conventional problems, the present invention is a method for producing a ferrite-containing filler characterized in that iron-containing slag granules or crushed materials are heated and stirred in an oxygen-enriched state and then rapidly cooled. Is to provide.
The iron-containing slag granule or crushed material is preferably electric furnace oxidation slag, copper slag, or electric furnace dust treatment slag. The ferrite-containing filler is used as, for example, an electromagnetic heating material or an electromagnetic shielding material.
〔作用〕
鉄を含有するスラグ粒状体または破砕物を酸素富化状態で加熱すると、スラグ粒状体に含まれるＦｅＯがＦｅ2Ｏ3やＦｅ3Ｏ4に酸化され、フェライト含有率が高められ、電磁波加熱性や電磁波遮蔽性が向上する。フェライトは耐化学性を有するので腐食されにくゝ、耐久性のある電磁波加熱材料や電磁波遮蔽材料になる。
該鉄を含有するスラグ粒状体または破砕物として、電気炉酸化スラグまたは銅スラグまたは電気炉ダスト処理スラグを選択すると、上記気炉酸化スラグ、銅スラグあるいは電気炉ダスト処理スラグは産業廃棄物であり、安価な電磁波加熱材料や電磁波遮蔽材料が提供出来る。
[Action]
When iron-containing slag granules or crushed materials are heated in an oxygen-enriched state, FeO contained in the slag granules is oxidized to Fe 2 O 3 and Fe 3 O 4 , and the ferrite content is increased, and electromagnetic wave heating properties And electromagnetic wave shielding properties are improved. Since ferrite has chemical resistance, it is difficult to be corroded and becomes a durable electromagnetic heating material or electromagnetic shielding material.
When electric furnace oxidation slag, copper slag, or electric furnace dust treatment slag is selected as the iron-containing slag granule or crushed material, the above-mentioned furnace oxidation slag, copper slag or electric furnace dust treatment slag is an industrial waste. An inexpensive electromagnetic heating material or electromagnetic shielding material can be provided.
〔効果〕
本発明においては、安価でかつ耐久性がある電磁波加熱材料や電磁波遮蔽材料として有用なフェライト含有充填材が得られる。
〔effect〕
In the present invention, a ferrite-containing filler useful as an electromagnetic heating material or electromagnetic shielding material that is inexpensive and durable can be obtained.
本発明を以下に詳細に説明する。
〔鉄を含有するスラグ〕
本発明において、鉄を含有するスラグとは、主としてＦｅＯ、Ｆｅ2Ｏ3、Ｆｅ3Ｏ4等の鉄酸化物を含有するスラグであり、例えば電気炉酸化スラグ、銅スラグ、電気炉ダスト処理スラグ等が例示される。
The present invention is described in detail below.
[Slag containing iron]
In the present invention, the iron-containing slag is a slag mainly containing iron oxide such as FeO, Fe 2 O 3 , Fe 3 O 4 , for example, electric furnace oxidation slag, copper slag, electric furnace dust treatment slag. Etc. are exemplified.
電気炉酸化スラグは、通常ＣａＯ１０〜２６質量％、ＳｉＯ2 ８〜２２質量％、ＭｎＯ４〜７質量％、ＭｇＯ２〜８質量％、ＦｅＯ１３〜３２質量％、Ｆｅ2Ｏ3９〜４５質量％、Ａｌ2Ｏ3４〜１６質量％、Ｃｒ2Ｏ3１〜４質量％程度含み、更に微量成分としてＢａＯ０．０５〜０．２０質量％、ＴｉＯ2 ０．２５〜０．７０質量％、Ｐ2Ｏ5０．１５〜０．５０質量％、Ｓ０．００５〜０．０８５質量％程度含み、安定な鉱物組成を得るためのＦｅを２０〜４５質量％程度含むものであり、天然骨材成分に含まれる粘土、有機不純物、塩分を全く含まず、不安定な遊離石灰、遊離マグネシアあるいは鉱物も殆ど含まない。該電気炉酸化スラグは粒状物または破砕物として提供される。
銅スラグは銅精錬工程で得られるスラグであり、通常ＣａＯ１〜１０質量％、ＳｉＯ2２５〜４０質量％、ＦｅはＦｅＯ換算１５〜５５質量％程度含み、上記電気炉酸化スラグと同様天然骨材に含まれる粘土、有機不純物、塩分は全く含まない。
電気炉ダストは電気炉による製鋼過程において発生する集塵ダストであり、該ダストを加熱溶融することによって亜鉛、カドミウム、鉛等の有害物質を蒸発除去され、電気炉ダスト処理スラグになる。該ダスト処理スラグは、通常ＣａＯ５〜２０質量％、ＦｅはＦｅＯ換算３５〜５５質量％程度含み、上記電気炉酸化スラグと同様天然骨材に含まれる粘土、有機不純物、塩分は全く含まない。
上記銅スラグ、電気炉ダスト処理スラグも上記電気炉酸化スラグと同様に粒状物または破砕物として提供される。
The electric furnace oxidation slag is usually
Copper slag is a slag obtained in the copper refining process, and usually contains
Electric furnace dust is dust collection dust generated in the steelmaking process by an electric furnace. By heating and melting the dust, harmful substances such as zinc, cadmium and lead are removed by evaporation to form electric furnace dust treatment slag. The dust-treated slag usually contains about 5 to 20% by mass of CaO and about 35 to 55% by mass of Fe in terms of FeO, and does not contain clay, organic impurities, and salt contained in the natural aggregate in the same manner as the electric furnace oxidation slag.
The copper slag and the electric furnace dust treatment slag are also provided as granular materials or crushed materials in the same manner as the electric furnace oxidation slag.
〔電気炉酸化スラグ粒化法〕
上記電気炉酸化スラグを粒化して粒状物を製造するには、該電気炉酸化スラグの溶融物を高速回転する羽根付きドラムに注入し、該溶融物を該羽根付きドラムによって破砕粒状化し、粒状化した該溶融物を水ミスト雰囲気中で急冷処理する方法が採られる。該羽根付きドラムは複数個配置して複数段の破砕粒状化を行なってもよい。
このようにして得られる電気炉酸化スラグの粒状物は、再酸化が促進されるので、Ｆｅ2Ｏ3系の鉱物およびＦｅ3Ｏ4系の鉱物（マグネタイト）を多く含み、かつ急冷により、極微細な粒状物になるため、電磁波吸収性が非常に良好なものとなる。また通常５ｍｍ以下の粒径を有し、粒径２．５ｍｍ以下のものは略球状であり、比重は３．３〜４．１の範囲にあり、表面にはひび割れ等の欠陥はなく、微細な凹凸を有しまた中空構造のものからなるかまたは中空構造のものを含んでいる。
[Electric furnace oxidation slag granulation method]
In order to granulate the electric furnace oxidation slag, a granular material is produced by injecting a melt of the electric furnace oxidation slag into a bladed drum rotating at high speed, and crushing and granulating the melt with the bladed drum. A method of quenching the melted melt in a water mist atmosphere is employed. A plurality of bladed drums may be arranged to perform a plurality of stages of crushing and granulating.
Since the granular material of the electric furnace oxidation slag obtained in this manner promotes reoxidation, it contains a large amount of Fe 2 O 3 -based minerals and Fe 3 O 4 -based minerals (magnetite), and by quenching, Since it becomes a fine granular material, electromagnetic wave absorptivity becomes very good. In addition, usually those having a particle size of 5 mm or less, those having a particle size of 2.5 mm or less are substantially spherical, the specific gravity is in the range of 3.3 to 4.1, and there are no defects such as cracks on the surface, and fine And have a hollow structure or a hollow structure.
〔電気炉酸化スラグ破砕法〕
上記電気炉酸化スラグ破砕物を製造するには、上記電気炉酸化スラグを溶融状態で耐熱容器中に所定の厚みに流し出し、上から水をかけることによって急冷改質処理が施される。この場合、耐熱容器中のスラグ溶融物の厚さが小さすぎると、水をかける前に自然冷却（徐冷）によって硬化し易くなり、所望の硬度が得られなくなるおそれがあり、また厚さが大きくなり過ぎると、水をかけた場合に水が急激に水蒸気となり、水蒸気爆発の危険がある。望ましいスラグ溶融物の厚さは８０ｍｍ〜１２０ｍｍである。
[Electric furnace oxidation slag crushing method]
In order to manufacture the electric furnace oxidized slag crushed material, the electric furnace oxidized slag is poured into a heat-resistant container in a molten state to a predetermined thickness, and subjected to rapid cooling reforming by pouring water from above. In this case, if the thickness of the slag melt in the heat-resistant container is too small, it tends to harden by natural cooling (slow cooling) before applying water, and the desired hardness may not be obtained. If it becomes too large, when water is applied, the water suddenly becomes water vapor and there is a danger of water vapor explosion. A desirable slag melt thickness is 80 mm to 120 mm.
水をかける場合には耐熱容器中のスラグ溶融物のスラグ溶融物の表面に水が溜まらないようにすることが望ましく、水をかける量が多過ぎてスラグ溶融物の表面に水が溜まって水の蒸発潜熱による急冷効果が期待出来なくなる。
上記水をかける量は、スラグ溶融物１トン当たり毎秒２００〜４００リットル程度が望ましい。
上記急冷によってスラグ溶融物は急速に硬化するが、この際自己破砕によって容器中のスラグ溶融物の厚さ程度の径を有するスラグ原塊が得られる。
When water is applied, it is desirable to prevent water from accumulating on the surface of the slag melt in the heat-resistant container. Too much water is applied and water accumulates on the surface of the slag melt. The rapid cooling effect due to the latent heat of vaporization cannot be expected.
The amount of water applied is preferably about 200 to 400 liters per second per ton of slag melt.
The slag melt is rapidly cured by the rapid cooling, and at this time, a slag ingot having a diameter of about the thickness of the slag melt in the container is obtained by self-crushing.
該スラグ原塊は粗砕機で粗砕され、更に細砕機で細砕される。上記粉砕によって、スラグ塊はスラグ成分のマトリクスと鉱物相との境界で破断し、表面に微細な凹凸が形成される。所望なれば上記破砕物は粗篩機等によって粗分級され、更に細砕機等によって細分級して５〜２５ｍｍ望ましくは５〜２０ｍｍの粗骨材、粒径５〜１３ｍｍ望ましくは５〜１０ｍｍの粗骨材、および５ｍｍ以下の細骨材に分ける。 The slag bulk is crushed by a pulverizer and further pulverized by a pulverizer. By the pulverization, the slag lump is broken at the boundary between the slag component matrix and the mineral phase, and fine irregularities are formed on the surface. If desired, the crushed material is coarsely classified by a coarse sieving machine, etc., and further subdivided by a fine pulverizer or the like to give coarse aggregate of 5 to 25 mm, preferably 5 to 20 mm, and a coarse particle size of 5 to 13 mm, preferably 5 to 10 mm. Divide into aggregates and fine aggregates of 5mm or less.
上記粗砕および細砕はスラグ原塊が水で濡れたまゝで行ってもよいし、またスラグ原塊を乾燥して粗砕以後の工程を行ってもよいし、あるいはスラグ原塊を粗砕した後に乾燥して細砕以後の工程を行ってもよい。また上記分級工程において、篩を通過しない残分は破砕工程に戻されることが望ましい。
このようにして得られる破砕物は徐冷スラグに較べ、再酸化が促進されるので、Ｆｅ2Ｏ3系の鉱物を多く含み、かつ急冷により、微細な粒状物になるため、電磁波吸収性が非常に良好なものとなり、その比重は水砕品と同様３．３〜４．１の範囲にある。
The above crushing and pulverization may be carried out while the slag block is wet with water, or the slag block may be dried and subjected to the steps after crushing, or the slag block may be crushed. Then, it may be dried to carry out the steps after grinding. Moreover, in the said classification process, it is desirable to return the residue which does not pass a sieve to a crushing process.
Since the crushed material obtained in this way promotes reoxidation as compared with slow-cooled slag, it contains a large amount of Fe 2 O 3 mineral and becomes a fine granular material by rapid cooling. It becomes very good, and its specific gravity is in the range of 3.3 to 4.1 like the granulated product.
〔改質電気炉酸化スラグ〕
更に本発明にあっては、電気炉酸化スラグに電磁波吸収性を向上させるための添加物を添加してもよい。
上記電磁波吸収性を向上させるための添加物としては、Ｆｅ，Ｂａ，Ｃｏ，Ｎｉ，Ｃｒ，Ｃｕ，Ｍｎ，Ｓｒ，Ｚｎ等の金属あるいはこれら金属を含む合金あるいはこれらの金属の酸化物、水酸化物、塩化物、硫酸塩等の加熱により酸化物を与える化合物およびシリカ粉、ケイ砂、ケイ石の粉末、水ガラス、ケイ藻土、ドロマイト、シリカヒューム、高炉スラグ、フライアッシュ、シラスバルーン、パーライト等のケイ酸含有物質がある。望ましい添加物としては鉄スクラップ、スケール、ＢａＯ屑、硫酸バリウムを含む重晶石等がある。
上記添加物は前記粒化法あるいは破砕法において、電気炉酸化スラグ溶融物に添加されるかあるいは電気炉酸化スラグに混合されて共に溶融される。上記溶融は通常電気溶解炉で行われるが、この時溶融物に空気または酸素を吹込み強制酸化処理を施す。上記強制酸化処理は特にＦｅＯ比率が高い破砕法によるスラグに対して有効であり、上記強制酸化処理によってＦｅ2Ｏ3やＦｅ3Ｏ4の含有率を高めて電磁波吸収性を向上せしめることが出来る。
該改質電気炉酸化スラグも粒状物または破砕物として提供される。
[Reformed electric furnace oxidation slag]
Furthermore, in this invention, you may add the additive for improving electromagnetic wave absorptivity to an electric furnace oxidation slag.
Examples of the additive for improving the electromagnetic wave absorption include metals such as Fe, Ba, Co, Ni, Cr, Cu, Mn, Sr, and Zn, alloys containing these metals, oxides of these metals, and hydroxylation. Compounds that give oxides when heated, such as chlorides, chlorides, sulfates, etc., silica powder, silica sand, silica powder, water glass, diatomaceous earth, dolomite, silica fume, blast furnace slag, fly ash, shirasu balloon, perlite There are silicic acid-containing substances such as Desirable additives include iron scrap, scale, BaO scrap, barite containing barium sulfate, and the like.
In the granulation method or crushing method, the additive is added to the electric furnace oxidation slag melt or mixed with the electric furnace oxidation slag and melted together. The melting is usually carried out in an electric melting furnace. At this time, air or oxygen is blown into the melt and subjected to forced oxidation treatment. The forced oxidation treatment is particularly effective for slag by a crushing method with a high FeO ratio, and the content of Fe 2 O 3 and Fe 3 O 4 can be increased by the forced oxidation treatment to improve electromagnetic wave absorption. .
The reformed electric furnace oxidation slag is also provided as a granular or crushed material.
銅スラグは上記電気炉酸化スラグと同様に、上記銅スラグの溶融物を急冷処理して粒化あるいは破砕して分級する。電気炉ダスト処理スラグは前記したようにダストを溶融して有害物質を蒸発除去後、該溶融物を急冷処理して粒化あるいは破砕して分級する。
上記電気炉酸化スラグと同様に、上記銅スラグおよび電気炉ダスト処理スラグには上記電磁波吸収性を向上させるための添加物が添加されてもよいし、また強制酸化処理が行なわれてもよい。
上記銅スラグ粒状物および電気炉ダスト処理スラグ粒状物は上記電気炉酸化スラグ粒状物と同様に通常５ｍｍ以下の粒径を有し、粒径２．５ｍｍ以下のものは略球状であり、比重は銅スラグ粒状物で３．２〜３．７、電気炉ダスト処理スラグで３．５〜４．５の範囲にあり、表面にはひび割れ等の欠陥はなく、微細な凹凸を有し、また中空構造のものからなるかまたは中空構造のものを含んでいる。
Similar to the electric furnace oxidation slag, the copper slag is classified by granulating or crushing the melt of the copper slag by rapid cooling. As described above, the electric furnace dust treatment slag is obtained by melting dust and evaporating and removing harmful substances, and then rapidly cooling the melt to granulate or crush and classify the melt.
Similarly to the electric furnace oxidation slag, the copper slag and the electric furnace dust treatment slag may be added with an additive for improving the electromagnetic wave absorption, or may be subjected to forced oxidation treatment.
The copper slag granule and the electric furnace dust-treated slag granule have a particle size of usually 5 mm or less like the electric furnace oxidation slag granule, and those having a particle size of 2.5 mm or less are substantially spherical, and the specific gravity is Copper slag granular material is in the range of 3.2 to 3.7, electric furnace dust treatment slag is in the range of 3.5 to 4.5, the surface has no defects such as cracks, has fine irregularities, and is hollow It consists of a structure or includes a hollow structure.
〔加熱処理〕
上記鉄を含有するスラグは酸素富化状態で加熱攪拌される。上記加熱攪拌は通常ＬＰＧ等の燃料を使用したロータリーキルン内で行なわれる。加熱温度は通常７００℃〜１１００℃程度の範囲に設定される。上記加熱攪拌によってスラグに含まれるＦｅＯがＦｅ2Ｏ3やＦｅ3Ｏ4に酸化され、フェライト含有率が高くなり、電磁波加熱性や電磁波遮蔽性が向上する。
[Heat treatment]
The iron-containing slag is heated and stirred in an oxygen-enriched state. The heating and stirring is usually performed in a rotary kiln using a fuel such as LPG. The heating temperature is usually set in a range of about 700 ° C to 1100 ° C. FeO contained in the slag is oxidized to Fe 2 O 3 or Fe 3 O 4 by the heating and stirring, and the ferrite content is increased, so that the electromagnetic wave heating property and the electromagnetic wave shielding property are improved.
以下に本発明を具体的に説明するための実施例を示す。 Examples for specifically explaining the present invention are shown below.
〔実施例１〕（電気炉酸化スラグ粒状物の製造）
図１に本発明の電気炉酸化スラグ粒状物（以下スラグ粒状物と略す）８を製造する装置を示す。
即ち１５００℃前後の電気炉酸化スラグ溶融物１は電気溶解炉から取鍋２に移され、該取鍋２からシューター３に移し、該シューター３から高速回転する羽根付きドラム４，５に注入する。該製鋼スラグ溶融物１は該羽根付きドラム４，５によって細破砕されて粒状化し、該電気炉酸化スラグ溶融物の粒化物１Ａは急冷チャンバー６内にスプレー装置７からスプレーされる水ミストによって急冷される。そしてこのようにして得られたスラグ粒状物８は備蓄容器９内に備蓄される。
該スラグ粒状物８は略球状の中空体であり、表面にはひび割れ等の欠陥はなく、微細な凹凸が有り、高硬度（モース硬さでマトリックスが６程度、鉱物相が８程度であった。）を有し耐摩耗性に優れており、真比重は３．８４、絶乾比重は３．５２、耐火度は１１００℃で、電磁波吸収性、透磁性、誘電性、耐酸性、耐アルカリ性等にも優れている。
該スラグ粒状物８の粒度分布を図２に示す。
[Example 1] (Manufacture of electric furnace oxidation slag granular material)
FIG. 1 shows an apparatus for producing an electric furnace oxidation slag granular material (hereinafter abbreviated as slag granular material) 8 of the present invention.
That is, the electric furnace
The slag granular material 8 is a substantially spherical hollow body, has no defects such as cracks on the surface, has fine irregularities, and has high hardness (Mohs hardness is about 6 matrix and mineral phase is about 8). )) And has excellent wear resistance, true specific gravity of 3.84, absolute dry specific gravity of 3.52, fire resistance of 1100 ° C., electromagnetic wave absorption, magnetic permeability, dielectric property, acid resistance, alkali resistance Etc. are also excellent.
The particle size distribution of the slag granular material 8 is shown in FIG.
〔実施例２〕（電気炉酸化スラグ破砕物の製造）
実施例１において電気溶解炉から取鍋２に移された上記スラグ溶融物は約１３５０℃に加熱されているが、取鍋２から耐熱容器（皿型鋼鉄製）に約１００ｍｍの厚さに流し出され、直ちにスラグ溶融物１トン当たり毎秒３００リットル、スプレーにより散水する。
[Example 2] (Production of electric furnace oxidized slag crushed material)
In the first embodiment, the slag melt transferred from the electric melting furnace to the ladle 2 is heated to about 1350 ° C., but is poured from the ladle 2 into a heat-resistant container (made of dish-shaped steel) to a thickness of about 100 mm. Immediately spray 300 liters per second per ton of slag melt by spraying.
このようにして約１００ｍｍ径のスラグ原塊が得られ、該スラグ原塊のモース硬さはマトリクスで６、鉱物相で８であった。該スラグ原塊は粗砕機で粗砕され、乾燥機で乾燥後細砕機で細砕される。細砕されたスラグ原塊は次いで粗篩機で粗分級され、更に細篩機で細分級されて、５〜２０ｍｍ粒径の粗骨材または５〜１３ｍｍ粒径の粗骨材、５ｍｍ以下の細骨材に分けられる。 In this way, a slag bulk having a diameter of about 100 mm was obtained, and the Mohs hardness of the slag bulk was 6 in the matrix and 8 in the mineral phase. The slag bulk is crushed with a crusher, dried with a drier and then pulverized with a crusher. The crushed slag ingot is then coarsely classified by a coarse sieve machine, and further finely classified by a fine sieve machine to obtain a coarse aggregate having a particle size of 5 to 20 mm or a coarse aggregate having a particle size of 5 to 13 mm, and a particle size of 5 mm or less. Divided into fine aggregates.
〔実施例３〕（銅スラグ、電気炉ダスト処理スラグ粒状物の製造）
銅スラグおよび電気炉ダスト処理スラグ粒状物は、電気炉酸化スラグと同様図１に示す装置によって製造される。銅スラグまたは電気炉ダストはあらかじめ図３に示すような電気溶解炉１０中で溶融され、ランス管１２から圧縮空気を吹精して強制酸化処理を行ない、電気炉ダストの場合には同時に有害物質を蒸発除去され、上記強制酸化処理を施された銅スラグまたは電気炉ダスト処理スラグ溶融物は１４００℃前後の温度であり、該電気溶解炉１０から取鍋２に移され、以後実施例１と同様な方法によって粒化される。
得られた銅スラグ粒状物または電気炉ダスト処理スラグ粒状物は略球状の中空体であり、表面にはひび割れ等の欠陥はなく、微細な凹凸があり、高硬度（モース硬さでマトリックスが６程度、鉱物相が８程度であった）を有し、耐摩耗性に優れており、耐火度は１１００℃程度であって、比重は銅スラグ粒状物で３．５０、電気炉ダスト処理スラグ粒状物で４．１であり、電磁波吸収性、透磁性、誘電性、耐酸性、耐アルカリ性に優れている。上記銅スラグ粒状物および電気炉ダスト処理スラグ粒状物の粒度分布は図２に示す電気炉酸化スラグ粒状物の粒度分布と略同様である。
[Example 3] (Copper slag, manufacture of electric furnace dust treatment slag granules)
Copper slag and electric furnace dust treatment slag granules are produced by the apparatus shown in FIG. 1 in the same manner as electric furnace oxidation slag. Copper slag or electric furnace dust is previously melted in an
The obtained copper slag granule or electric furnace dust-treated slag granule is a substantially spherical hollow body, has no defects such as cracks on the surface, has fine irregularities, and has a high hardness (Mohs hardness of 6 matrix). Grade, mineral phase was about 8), excellent wear resistance, fire resistance of about 1100 ° C, specific gravity of copper slag granules 3.50, electric furnace dust treatment slag granules It is 4.1 and is excellent in electromagnetic wave absorption, magnetic permeability, dielectric properties, acid resistance, and alkali resistance. The particle size distribution of the copper slag granules and the electric furnace dust-treated slag granules is substantially the same as the particle size distribution of the electric furnace oxidation slag granules shown in FIG.
〔実施例４〕（加熱攪拌処理）
実施例１、実施例３において製造した電気炉酸化スラグ粒状物、銅スラグ粒状物、電気炉ダスト粒状物の主要化学成分を表１に示す。
[Example 4] (heating and stirring treatment)
Table 1 shows the main chemical components of the electric furnace oxidation slag granule, copper slag granule, and electric furnace dust granule produced in Example 1 and Example 3.
上記スラグ粒状物の種々の粒度の試料をＬＰＧを燃料とするロータリーキルン内に投入して酸素富化状態で所定温度に加熱し攪拌しその後ロータリーキルンから排出したスラグ粒状物を例えば撒水または水槽中に投入することによって急冷する。上記加熱攪拌によるＦｅ2Ｏ3＋Ｆｅ3Ｏ4含有率の変化を表２に示す。 Samples of various particle sizes of the above slag particles are put into a rotary kiln using LPG as fuel, heated to a predetermined temperature in an oxygen-enriched state, stirred, and then discharged from the rotary kiln into, for example, brine or a water tank. To cool quickly. Table 2 shows the change in the content of Fe 2 O 3 + Fe 3 O 4 by the heating and stirring.
表２に示すように、いずれの材料も加熱攪拌処理によって経時的にＦｅ2Ｏ3＋Ｆｅ3Ｏ4の含有率が増大するが、粒度が小さい試料の方がＦｅ2Ｏ3＋Ｆｅ3Ｏ4含有率の増大が顕著になる。 As shown in Table 2, the content of Fe 2 O 3 + Fe 3 O 4 increases with time by heating and stirring treatment, but samples with smaller particle sizes contain Fe 2 O 3 + Fe 3 O 4. The increase in rate becomes significant.
本発明では、電磁波加熱性あるいは電磁波遮蔽性に富むフェライト含有充填材が極めて安価に提供出来、該充填材はプラスチック、ゴム、コンクリート、陶磁器、セラミック等に添加されて優れた電磁波加熱材や電磁波遮蔽材を提供する。 In the present invention, a ferrite-containing filler rich in electromagnetic wave heating property or electromagnetic wave shielding property can be provided at a very low cost. The filler is added to plastic, rubber, concrete, ceramics, ceramics, etc. Providing materials.
１ 電気炉酸化スラグ溶融物
８ 電気炉スラグ粒状物
1 Electric furnace oxidation slag melt 8 Electric furnace slag granular material
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016075213A1 (en) * | 2014-11-13 | 2016-05-19 | Ce-Sys Engineering Gmbh | Building material for shielding against electromagnetic waves, method for producing the same and use thereof |
| CN108690557A (en) * | 2018-07-09 | 2018-10-23 | 兰州理工大学 | A kind of method and absorbing material preparing absorbing material using lead cadmia |
| CN108753252A (en) * | 2018-07-09 | 2018-11-06 | 兰州理工大学 | A kind of method and absorbing material preparing absorbing material using copper ashes |
| CN108822796A (en) * | 2018-07-09 | 2018-11-16 | 兰州理工大学 | A kind of method and absorbing material preparing absorbing material using nickel slag |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016075213A1 (en) * | 2014-11-13 | 2016-05-19 | Ce-Sys Engineering Gmbh | Building material for shielding against electromagnetic waves, method for producing the same and use thereof |
| DE102014017049A1 (en) | 2014-11-13 | 2016-05-19 | Ce-Sys Engineering Gmbh | Building material for shielding electromagnetic waves by absorption, process for its preparation and its use |
| CN108690557A (en) * | 2018-07-09 | 2018-10-23 | 兰州理工大学 | A kind of method and absorbing material preparing absorbing material using lead cadmia |
| CN108753252A (en) * | 2018-07-09 | 2018-11-06 | 兰州理工大学 | A kind of method and absorbing material preparing absorbing material using copper ashes |
| CN108822796A (en) * | 2018-07-09 | 2018-11-16 | 兰州理工大学 | A kind of method and absorbing material preparing absorbing material using nickel slag |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |