JP2021147632A - Flux for refining aluminum - Google Patents
Flux for refining aluminum Download PDFInfo
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- JP2021147632A JP2021147632A JP2020046240A JP2020046240A JP2021147632A JP 2021147632 A JP2021147632 A JP 2021147632A JP 2020046240 A JP2020046240 A JP 2020046240A JP 2020046240 A JP2020046240 A JP 2020046240A JP 2021147632 A JP2021147632 A JP 2021147632A
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- 230000004907 flux Effects 0.000 title claims abstract description 78
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 60
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000007670 refining Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 239000000126 substance Substances 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 230000005484 gravity Effects 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 6
- 239000008262 pumice Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 25
- 239000011777 magnesium Substances 0.000 description 36
- 239000002893 slag Substances 0.000 description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、アルミニウム（合金も含む）溶湯中のＭｇを除去するために用いられるアルミニウム精錬用フラックスに関する。 The present invention relates to an aluminum refining flux used for removing Mg in molten aluminum (including alloys).
アルミニウム合金の鋳造ラインにおいて、脱ガス、脱介在物、脱不純物、品質改良などを目的とした溶湯処理が行われる。
Ｍｇはアルミニウム合金の機械的強度を向上させる有効な合金元素である一方、Ｓｉを多量に含む鋳物、ダイカスト用合金においては靭性を低下させ、また、自然時効におけるＭｇ２Ｓｉの析出による容積膨張のため、例えば、ＪＩＳ ＡＤＣ １０、１２においては共に０．３％以下のようにＭｇの許容量は低く制限されている。回収アルミニウムくずなどのスクラップ中のＭｇ含有量は年々増加傾向にあり、アルミニウムの溶解精製における脱Ｍｇ処理の必要性が高まりつつある。
In the aluminum alloy casting line, molten metal treatment is performed for the purpose of degassing, decontamination, decontamination, quality improvement, and the like.
While Mg is an effective alloying element that improves the mechanical strength of aluminum alloys, it reduces toughness in castings and die casting alloys that contain a large amount of Si, and also causes volume expansion due to precipitation of Mg 2 Si during natural aging. Therefore, for example, in JIS ADCs 10 and 12, the allowable amount of Mg is limited to 0.3% or less in both cases. The Mg content in scraps such as recovered aluminum scrap is increasing year by year, and the need for deMg treatment in the dissolution and purification of aluminum is increasing.
フラックスを用いて溶湯処理を行うと溶湯表面に酸化物等の不純物からなる滓（ドロス）が浮いてくる。浮いてきた滓を除去することにより、アルミニウム溶湯の精錬が行われる。ＭｇとＡｌはフッ化物の生成熱に著しい差があることから、脱Ｍｇ用のフラックスとしては、フッ化物を主成分とするもの、例えば、カリ氷晶石とＡｌＦ３の混合物などのフッ化物を含むものが知られている。しかし、フッ化物を含むフラックスを使用した場合、滓にフッ化物が濃縮し、近年の環境規制の高まりから滓を再利用することが難しくなり、滓中のフッ素物含有量を低減することが要求されるようになってきた。このため、フッ化物を含まないフラックスが検討されており、特許文献１にはハロゲンを含まないフラックスが、特許文献２にはフッ素含有化合物を含まないフラックスが開示されている。
特許文献３には、アルミニウム合金の溶湯にシラスを添加し、マグネシウム化合物を含む反応生成物を除去する方法が記載されている。しかしながら、特許文献３に記載の方法は、反応性が低く、シラスを大量に、かつ繰り返し添加する必要があるため、脱Ｍｇ効率が低い。
When the molten metal is treated with flux, slag (dross) made of impurities such as oxides floats on the surface of the molten metal. By removing the floating slag, the molten aluminum is smelted. Since there is a significant difference in the heat of formation of fluoride between Mg and Al, as the flux for deMg, a fluoride containing fluoride as a main component, for example, a fluoride such as a mixture of potassium cryolite and AlF 3 is used. Those that include are known. However, when a flux containing fluoride is used, fluoride is concentrated in the slag, and it becomes difficult to reuse the slag due to the recent increase in environmental regulations, and it is required to reduce the fluorine content in the slag. It has come to be done. Therefore, a flux containing no fluoride has been studied, and Patent Document 1 discloses a flux containing no halogen, and Patent Document 2 discloses a flux containing no fluorine-containing compound.
Patent Document 3 describes a method of adding shirasu to a molten aluminum alloy to remove a reaction product containing a magnesium compound. However, the method described in Patent Document 3 has low reactivity and requires a large amount of shirasu to be added repeatedly, so that the Mg removal efficiency is low.
本発明は、フッ化物を含まない脱Ｍｇ効果のあるアルミニウム精錬用フラックスを提供することを目的とする。 An object of the present invention is to provide a flux for aluminum refining that does not contain fluoride and has a deMg effect.
本発明者らは、種々の研究を行った結果、塩化物と、比重が小さく、かつアルミニウムの溶湯に対して不溶性を有する物質とを組み合わせることにより、フッ化物を含まずとも、フッ化物を含む従来のアルミニウム精錬用フラックスと同等以上の脱Ｍｇ効果を得ることができることを見出し、本発明を完成するに至った。 As a result of various studies, the present inventors have conducted various studies, and by combining chloride and a substance having a small specific gravity and being insoluble in molten aluminum, fluoride is contained even if it is not contained. We have found that it is possible to obtain a de-Mg effect equal to or higher than that of a conventional flux for aluminum refining, and have completed the present invention.
即ち、本発明は、塩化物と、比重が２．６未満であり、かつアルミニウムの溶湯に対して不溶性を有する物質とを含み、フッ化物を含まないことを特徴とするアルミニウム精錬用フラックスである。 That is, the present invention is an aluminum refining flux characterized by containing chloride and a substance having a specific gravity of less than 2.6 and being insoluble in molten aluminum and not containing fluoride. ..
本発明の一態様によれば、比重が２．６未満であり、かつアルミニウムの溶湯に対して不溶性を有する物質が、炭素材料、酸化ケイ素質材料又はこれらの混合物であることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the substance having a specific gravity of less than 2.6 and being insoluble in molten aluminum is a carbon material, a silicon oxide material, or a mixture thereof. The above aluminum refining flux is provided.
本発明の一態様によれば、塩化物の含有量が２０〜７０ｍａｓｓ％であり、炭素材料、酸化ケイ素質材料又はこれらの混合物の含有量が１０〜７０ｍａｓｓ％であることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the content of chloride is 20 to 70 mass%, and the content of carbon material, silicon oxide material or a mixture thereof is 10 to 70 mass%. Aluminum refining flux is provided.
本発明の一態様によれば、塩化物がアルカリ金属の塩化物であることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the above-mentioned flux for aluminum refining is provided, wherein the chloride is an alkali metal chloride.
本発明の一態様によれば、塩化物が、ＮａＣｌ、ＫＣｌ又はこれらの混合物であることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, there is provided the above-mentioned flux for aluminum refining, wherein the chloride is NaCl, KCl or a mixture thereof.
本発明の一態様によれば、炭素材料がコークスであることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the above-mentioned flux for aluminum refining is provided, wherein the carbon material is coke.
本発明の一態様によれば、酸化ケイ素質材料が軽石であることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the above-mentioned flux for aluminum refining is provided, wherein the silicon oxide material is pumice.
本発明の一態様によれば、発熱助剤をさらに含むことを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, there is provided the above-mentioned flux for aluminum refining, which further comprises a heat-generating auxiliary agent.
本発明の一態様によれば、発熱助剤の含有量が１〜１５ｍａｓｓ％であることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the above-mentioned flux for aluminum refining is provided, wherein the content of the exothermic aid is 1 to 15 mass%.
本発明の一態様によれば、発熱助剤が金属硫酸塩、炭酸塩、硝酸塩のいずれか１以上であることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the above-mentioned aluminum refining flux is provided, wherein the exothermic aid is at least one of a metal sulfate, a carbonate, and a nitrate.
本発明の一態様によれば、金属硫酸塩が、硫酸カリウム、硫酸ナトリウム、硫酸アルミニウム、硫酸マグネシウムのうち少なくとも一つであることを特徴とする、上記のアルミニウム精錬用フラックスが提供される。 According to one aspect of the present invention, the above-mentioned aluminum refining flux is provided, wherein the metal sulfate is at least one of potassium sulfate, sodium sulfate, aluminum sulfate, and magnesium sulfate.
本発明は、フッ化物を含まない、脱Ｍｇ効果のあるアルミニウム精錬用フラックスを提供することができる。 The present invention can provide a flux for aluminum refining that does not contain fluoride and has a deMg effect.
以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。なお、以下の説明において、「Ａ〜Ｂ」は、「Ａ以上かつＢ以下」を意味する。 Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired. In the following description, "A to B" means "A or more and B or less".
本実施形態に係るアルミニウム精錬用フラックスは、塩化物と、比重が２．６未満であり、かつアルミニウムの溶湯に対して不溶性を有する物質（以下、小比重不溶性物質ともいう）とをとして含み、フッ化物を含まない。フッ化物を含まないことにより、滓にはフッ素が含まれない又は滓に含まれるフッ素の含有量を低減することができる。
小比重不溶性物質は、Ｍｇをその表面に濃化し，溶湯表面と溶湯中とを浮上、浸漬を繰り返すことにより、大気中の酸素によりＭｇが酸化され、ＭｇＯとしてＭｇを溶湯から滓に除去する効果を有する。塩化物は、小比重不溶性物質とアルミニウム溶湯との濡れ性を向上させる効果を有し、アルミニウム溶湯上に浮いてしまう比重の小さい小比重不溶性物質が溶湯表面と溶湯中とを浮上、浸漬を繰り返すことを促進し、ひいては脱Ｍｇ効果を向上させる。
塩化物と小比重不溶性物質との相乗効果により、フッ化物を含まずとも、フッ化物を含む従来のアルミニウム精錬用フラックスと同等以上の脱Ｍｇ効果を奏する。
本実施形態に係るアルミニウム精錬用フラックスにおいては、塩化物と小比重不溶性物質とが主成分、即ち、フラックス中を占める割合が最も高い成分として含まれることが好ましい。
The flux for aluminum refining according to the present embodiment contains chloride and a substance having a specific gravity of less than 2.6 and being insoluble in molten aluminum (hereinafter, also referred to as a small specific gravity insoluble substance). Contains no fluoride. By not containing fluoride, the slag does not contain fluorine or the content of fluorine contained in the slag can be reduced.
The small specific density insoluble substance has the effect of concentrating Mg on its surface, floating the surface of the molten metal and the inside of the molten metal, and repeating immersion, so that Mg is oxidized by oxygen in the atmosphere and Mg is removed from the molten metal as MgO. Has. Chloride has the effect of improving the wettability between the small specific density insoluble substance and the molten aluminum, and the small specific density insoluble substance with a small specific density that floats on the molten aluminum floats on the surface of the molten metal and in the molten aluminum, and is repeatedly immersed. This promotes the fact that the Mg removal effect is improved.
Due to the synergistic effect of chloride and the small specific density insoluble substance, even if it does not contain fluoride, it exhibits a Mg removal effect equal to or higher than that of the conventional flux for aluminum refining containing fluoride.
In the aluminum refining flux according to the present embodiment, it is preferable that chloride and a small specific gravity insoluble substance are contained as the main components, that is, the components having the highest proportion in the flux.
本実施形態に係るアルミニウム精錬用フラックスにおいて、比重が２．６未満であり、かつアルミニウムの溶湯に対して不溶性を有する物質（小比重不溶性物質）は、炭素材料、酸化ケイ素質材料又はこれらの混合物であることが好ましい。
炭素材料としては、コークス、木炭、竹炭、炭素繊維屑、黒鉛、石炭など炭素を主成分とする炭素材料であることが好ましく、特に好ましくはコークスである。
本明細書において、「酸化ケイ素質材料」とは、酸化ケイ素（ＳｉＯ２）等を主成分とする物質で意味する。酸化ケイ素質材料としては、軽石、珪石、珪砂、珪藻土などが好ましく、特に好ましくは軽石である。
小比重不溶性物質は表面積の大きい粉末状であることが好ましく、溶湯表面と溶湯中とを浮上、浸漬を繰り返すことによるＭｇの酸化の効果のためには、粒径が１０〜３００μｍであることが好ましく、特に好ましくは５０〜１５０μｍである。
In the aluminum refining flux according to the present embodiment, the substance having a specific gravity of less than 2.6 and being insoluble in the molten aluminum (small specific gravity insoluble substance) is a carbon material, a silicon oxide material, or a mixture thereof. Is preferable.
The carbon material is preferably a carbon material containing carbon as a main component, such as coke, charcoal, bamboo charcoal, carbon fiber waste, graphite, and coal, and particularly preferably coke.
In the present specification, the "silicon oxide material" means a substance containing silicon oxide (SiO 2 ) or the like as a main component. As the silicon oxide material, pumice stone, silica stone, silica sand, diatomaceous earth and the like are preferable, and pumice stone is particularly preferable.
The small specific density insoluble substance is preferably in the form of a powder having a large surface area, and the particle size is preferably 10 to 300 μm for the effect of oxidation of Mg by floating the surface of the molten metal and the inside of the molten metal and repeating immersion. It is preferably, particularly preferably 50 to 150 μm.
本実施形態に係るアルミニウム精錬用フラックスにおいて、塩化物の含有量が好ましくは２０〜７０ｍａｓｓ％、より好ましくは２５〜６０ｍａｓｓ％、さらに好ましくは３０〜５５ｍａｓｓ％、特に好ましくは３０〜５０ｍａｓｓ％であり、小比重不溶性物質の含有量が好ましくは１０〜７０ｍａｓｓ％、より好ましくは２０〜６０ｍａｓｓ％、さらに好ましくは２５〜５５ｍａｓｓ％、特に好ましくは３０〜５０ｍａｓｓ％である。上記範囲の含有量の塩化物及び小比重不溶性物質を含むことにより、塩化物と小比重不溶性物質とを含み、その相乗効果により脱Ｍｇ効果を奏する。 In the flux for aluminum refining according to the present embodiment, the chloride content is preferably 20 to 70 mass%, more preferably 25 to 60 mass%, further preferably 30 to 55 mass%, and particularly preferably 30 to 50 mass%. The content of the small specific gravity insoluble substance is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, further preferably 25 to 55 mass%, and particularly preferably 30 to 50 mass%. By containing chloride and a small specific gravity insoluble substance in the above range, a chloride and a small specific gravity insoluble substance are contained, and the synergistic effect thereof exerts a deMg effect.
本実施形態に係るアルミニウム精錬用フラックスに含まれる塩化物としては、アルカリ金属の塩化物であることが好ましく、特に好ましくは、ＮａＣｌ、ＫＣｌ又はこれらの混合物である。 The chloride contained in the aluminum refining flux according to the present embodiment is preferably an alkali metal chloride, and particularly preferably NaCl, KCl or a mixture thereof.
本実施形態に係るアルミニウム精錬用フラックスは、発熱助剤をさらに含んでいてもよい。発熱助剤は、フラックスを発熱させ、発生するアルミニウムドロスをドライ化する効果を有し、また、酸化剤としてＭｇの酸化を促進し、脱Ｍｇ効果を向上させる効果を有する。しかし、発熱助剤の含有量が多すぎる場合、アルミニウム溶湯の酸化ロスを引き起こす可能性がある。
発熱助剤をさらに含む場合、発熱助剤の含有量は１〜１５ｍａｓｓ％であることが好ましく、より好ましくは２〜１４ｍａｓｓ％、さらに好ましくは４〜１３ｍａｓｓ％、更により好ましくは６〜１２ｍａｓｓ％である。
発熱助剤は、特に限定されず、一般にフラックスにおける発熱助剤として知られている、炭酸塩、硫酸塩、硝酸塩などを用いることができるが、好ましくは金属硫酸塩、炭酸塩、硝酸塩のいずれか１以上、より好ましくは金属硫酸塩である。特に好ましい金属硫酸塩としては、硫酸カリウム、硫酸ナトリウム、硫酸アルミニウム、硫酸マグネシウムであり、これらのうちの少なくとも一つを発熱助剤として含むことが好ましい。
The aluminum refining flux according to the present embodiment may further contain a heat generating aid. The heat-generating auxiliary has the effect of generating heat of flux and drying the generated aluminum dross, and also has the effect of promoting the oxidation of Mg as an oxidizing agent and improving the effect of removing Mg. However, if the content of the exothermic aid is too high, it may cause an oxidation loss of the molten aluminum.
When the exothermic aid is further contained, the content of the exothermic aid is preferably 1 to 15 mass%, more preferably 2 to 14 mass%, further preferably 4 to 13 mass%, still more preferably 6 to 12 mass%. be.
The heat-generating auxiliary agent is not particularly limited, and carbonates, sulfates, nitrates and the like, which are generally known as heat-generating auxiliary agents in flux, can be used, but any one of metal sulfates, carbonates and nitrates is preferable. 1 or more, more preferably metal sulfate. Particularly preferable metal sulfates are potassium sulfate, sodium sulfate, aluminum sulfate, and magnesium sulfate, and it is preferable to include at least one of these as a heat generating aid.
本実施形態に係るアルミニウム精錬用フラックスは、塩化物と小比重不溶性物質とを所望の含有量となるように秤量し、混合することにより製造される。発熱助剤と含む場合も同様に、所望の含有量となるように秤量し、混合することにより製造される。 The aluminum refining flux according to the present embodiment is produced by weighing and mixing chloride and a small specific gravity insoluble substance so as to have a desired content. Similarly, when it is contained with a heat-generating auxiliary agent, it is produced by weighing and mixing so as to have a desired content.
本実施形態に係るアルミニウム精錬用フラックスのアルミニウム溶湯への添加方法は、特に限定されず、従来公知の脱Ｍｇ用のフラックスと同様に、溶湯表面に散布した後に攪拌を行っても、不活性ガスと共にフラックスを溶湯に吹き込むフラックスインジェクション法を用いてもよい。 The method for adding the flux for aluminum refining according to the present embodiment to the molten aluminum is not particularly limited, and the inert gas may be agitated after being sprayed on the surface of the molten metal in the same manner as the conventionally known flux for removing Mg. You may also use the flux injection method in which the flux is blown into the molten metal.
以下に本発明の実施例を示す。本発明の内容はこれらの実施例により限定して解釈されるものではない。 Examples of the present invention are shown below. The content of the present invention is not construed as being limited by these examples.
表１に示される割合を有するように塩化物と小比重不溶性物質とを秤量、混合し、実施例１−２３及び比較例１−４に係るフラックスを製造した。なお、比較例１は、市販の脱Ｍｇ用フラックス〔ＫＫ０３１−Ｍ：日軽エムシーアルミ株式会社製〕であり、カリ氷晶石（Ｋ３ＡｌＦ６）とＡｌＦ３の混合物を主成分とし、炭素材料や酸化ケイ素質材料を含まないフラックスである。 Chloride and a small specific gravity insoluble substance were weighed and mixed so as to have the ratios shown in Table 1, and the fluxes according to Examples 1-23 and Comparative Examples 1-4 were produced. Comparative Example 1 is a commercially available flux for de-Mg [KK031-M: manufactured by Nikkei MC Aluminum Co., Ltd.], which contains a mixture of potassium cryolite (K 3 AlF 6 ) and AlF 3 as a main component and carbon. It is a flux that does not contain materials or silicon oxide materials.
坩堝〔フェニックス坩堝（３０番）、日本ルツボ（株）製〕にてアルミニウム合金（ＡＤＣ１２）を７ｋｇ溶解し、金属Ｍｇを添加して溶湯中のＭｇが約０．４ｍａｓｓ％になるように調製した。
溶湯の温度を７８０℃に調整し、溶湯量に対して約１〜２ｍａｓｓ％となるよう秤量した実施例１−２２及び比較例１−４に係る各フラックスを添加し、ホスフォライザーを用いて、３分間押し込み攪拌を行った。その後、各フラックスの添加から、３．５分後及び３３分後の溶湯を採取し、固体発光分析にて溶湯中のＭｇの組成を分析した。
また、溶湯中のＭｇが約０．４ｍａｓｓ％の５ｔの溶湯に対し、実施例２３に係る各フラックスを添加し、２０分間撹拌を行った。各フラックスの添加から、１０分後及び２０分後の溶湯を採取し、固体発光分析にて溶湯中のＭｇの組成を分析した。
7 kg of aluminum alloy (ADC12) was dissolved in a crucible [Phoenix crucible (No. 30), manufactured by Nippon Crucible Co., Ltd.], and metal Mg was added to prepare the Mg in the molten metal to be about 0.4 mass%. ..
The temperature of the molten metal was adjusted to 780 ° C., and each flux according to Example 1-22 and Comparative Example 1-4 weighed so as to be about 1 to 2 mass% with respect to the amount of the molten metal was added, and a phosphorizer was used. The mixture was pushed in for 3 minutes and stirred. Then, after 3.5 minutes and 33 minutes from the addition of each flux, the molten metal was collected, and the composition of Mg in the molten metal was analyzed by solid-state luminescence analysis.
Further, each flux according to Example 23 was added to a 5t molten metal containing about 0.4 mass% of Mg in the molten metal, and the mixture was stirred for 20 minutes. The molten metal 10 minutes and 20 minutes after the addition of each flux was collected, and the composition of Mg in the molten metal was analyzed by solid-state luminescence analysis.
表１、２に示されるように、実施例に係るフラックスは、比較例に係る市販の脱Ｍｇ用フラックスと同等以上の脱Ｍｇ効果を有している。即ち、本願発明のフラックスは、フッ化物を含まずとも、フッ化物を含む従来のアルミニウム精錬用フラックスと同等以上の脱Ｍｇ効果を有しており、フッ化物を含まないことにより、滓にフッ素が含まれない又は滓に含まれるフッ素の含有量を低減することができることが分かる。塩化物であるＮａＣｌ及びＫＣｌと小比重不溶性物質である炭素材料（本実施例においてはコークス）、又は酸化ケイ素質材料（本実施例においては軽石）又はこれらの混合物とを含む実施例に係るフラックスは、比較例に係るフラックスと同等以上の脱Ｍｇ効果を有している、即ち、主成分である塩化物と小比重不溶性物質との相乗効果により、脱Ｍｇ効果が向上することが分かる。さらに、驚くべきことに、実施例５、６に係るフラックスは、酸化剤としてＭｇの酸化を促進し、脱Ｍｇ効果を向上させる発熱助剤を含まずとも、高い脱Ｍｇ効果を有する。 As shown in Tables 1 and 2, the flux according to the example has an effect of removing Mg equal to or higher than that of the commercially available flux for removing Mg according to the comparative example. That is, the flux of the present invention has a deMg effect equal to or higher than that of the conventional flux for aluminum refining containing fluoride even if it does not contain fluoride, and since it does not contain fluoride, fluorine is contained in the slag. It can be seen that the content of fluorine that is not contained or is contained in the slag can be reduced. Flux according to an example containing NaCl and KCl as chlorides and a carbon material (coke in this example) or a silicon oxide material (pumice in this example) or a mixture thereof which are insoluble substances with a small specific density. Has an effect of removing Mg equal to or higher than that of the flux according to the comparative example, that is, it can be seen that the effect of removing Mg is improved by the synergistic effect of the chloride as the main component and the small specific density insoluble substance. Further, surprisingly, the flux according to Examples 5 and 6 has a high Mg removal effect even if it does not contain a heat generating aid that promotes the oxidation of Mg as an oxidizing agent and improves the Mg removal effect.
表３に示されるように、実施例に係るフラックスは、発熱助剤として金属硫酸塩であるＮａ２ＳＯ４を含む場合、炭酸塩であるＮａ２ＣＯ３を含む場合、硝酸塩であるＮａＮＯ３を含む場合のいずれの場合も、同様に高い脱Ｍｇ効果を有することが分かる。即ち、実施例に係るフラックスは、発熱助剤の種類を問わず、高い脱Ｍｇ効果を有することが分かる。
表４に示されるように、実施例に係るフラックスは、工業規模である５ｔの溶湯に対しても７ｋｇの溶湯の場合と同様に脱Ｍｇ効果を奏することが分かる。即ち、実施例に係るフラックスは、実際に工業規模のアルミニウムの溶解精製において、脱Ｍｇ処理のためのフラックスとして優れた性能を有することが分かる。
As shown in Table 3, the flux according to the example contains Na 2 SO 4 which is a metal sulfate as a heat generating aid, and Na NO 3 which is a nitrate when it contains Na 2 CO 3 which is a carbonate. It can be seen that in any case of inclusion, the effect of removing Mg is similarly high. That is, it can be seen that the flux according to the embodiment has a high Mg removal effect regardless of the type of heat generating aid.
As shown in Table 4, it can be seen that the flux according to the example exerts a Mg removal effect on an industrial scale 5 ton molten metal as in the case of a 7 kg molten metal. That is, it can be seen that the flux according to the example actually has excellent performance as a flux for the deMg treatment in the dissolution and purification of aluminum on an industrial scale.
表５は、実施例１、１８、１９及び比較例１に係るフラックスを用いた溶湯処理後の滓の蛍光Ｘ線分析の結果である。実施例１、１８、１９に係るフラックスを用いた溶湯処理後の滓からは溶湯由来のＭｇが検出された。比較例１に係るフラックスは、フッ素を含む市販の脱Ｍｇ用フラックスであるため、溶湯処理後の滓にはフッ素が濃縮されているが、実施例１、１８、１９に係るフラックスはフッ素を含まないため、溶湯処理後の滓からはフッ素は検出されなかった。
表６は、実施例１に係るフラックスを用いた溶湯処理後の滓のＸ線回析の結果である。滓から多量成分としてＭｇＯが検出され、ＭｇがＭｇＯとして溶湯から除去されたことが確認された。
Table 5 shows the results of fluorescent X-ray analysis of the slag after the molten metal treatment using the flux according to Examples 1, 18, 19 and Comparative Example 1. Mg derived from the molten metal was detected in the slag after the molten metal treatment using the flux according to Examples 1, 18 and 19. Since the flux according to Comparative Example 1 is a commercially available flux for removing Mg containing fluorine, fluorine is concentrated in the slag after the molten metal treatment, but the flux according to Examples 1, 18 and 19 contains fluorine. No fluorine was detected in the slag after the molten metal treatment.
Table 6 shows the results of X-ray diffraction of the slag after the molten metal treatment using the flux according to Example 1. MgO was detected as a large amount of component in the slag, and it was confirmed that Mg was removed from the molten metal as MgO.
図１は、実施例１に係るフラックスを用いた溶湯処理後の滓の走査型電子顕微鏡（ＳＥＭ）の反射電子組成像である。図１に示されるように、コークス表面にＭｇＯの濃化が確認され、表６に示されるＸ線回析の結果とも一致している。この結果から、主成分である塩化物と小比重不溶性物質との組み合わせ及びその相乗効果による脱Ｍｇ効果について確認された。 FIG. 1 is a reflected electron composition image of a slag scanning electron microscope (SEM) after a molten metal treatment using the flux according to Example 1. As shown in FIG. 1, the concentration of MgO was confirmed on the surface of the coke, which is consistent with the result of X-ray diffraction shown in Table 6. From this result, it was confirmed that the combination of the main component chloride and the small specific density insoluble substance and the synergistic effect of the de-Mg effect.
Claims (11)
比重が２．６未満であり、かつアルミニウムの溶湯に対して不溶性を有する物質とを含み、
フッ化物を含まないことを特徴とする、アルミニウム精錬用フラックス。 Chloride and
Contains substances with a specific density of less than 2.6 and insoluble in molten aluminum.
A flux for aluminum refining, which is characterized by being free of fluoride.
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| JPS6442532A (en) * | 1987-08-07 | 1989-02-14 | Toyo Denka Kogyo Kk | Method for regenerating aluminum alloy |
| JP2010275620A (en) * | 2009-06-01 | 2010-12-09 | Kagoshima Univ | Method for removing magnesium |
| JP2011168830A (en) * | 2010-02-18 | 2011-09-01 | Hokkaido Research Organization | Magnesium concentration adjusting agent for aluminum alloy molten metal and magnesium concentration adjustment method using the same |
| JP2017122257A (en) * | 2016-01-06 | 2017-07-13 | 東洋電化工業株式会社 | Magnesium removing agent and magnesium removing method |
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| JPS6442532A (en) * | 1987-08-07 | 1989-02-14 | Toyo Denka Kogyo Kk | Method for regenerating aluminum alloy |
| JP2010275620A (en) * | 2009-06-01 | 2010-12-09 | Kagoshima Univ | Method for removing magnesium |
| JP2011168830A (en) * | 2010-02-18 | 2011-09-01 | Hokkaido Research Organization | Magnesium concentration adjusting agent for aluminum alloy molten metal and magnesium concentration adjustment method using the same |
| JP2017122257A (en) * | 2016-01-06 | 2017-07-13 | 東洋電化工業株式会社 | Magnesium removing agent and magnesium removing method |
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