JP5572887B2 - Magnesium concentration adjusting agent for molten aluminum alloy and magnesium concentration adjusting method using the same - Google Patents
Magnesium concentration adjusting agent for molten aluminum alloy and magnesium concentration adjusting method using the same Download PDFInfo
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- 239000011777 magnesium Substances 0.000 title claims description 96
- 229910052749 magnesium Inorganic materials 0.000 title claims description 78
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 77
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 57
- 239000003795 chemical substances by application Substances 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 17
- 239000000843 powder Substances 0.000 claims description 136
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 111
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 100
- 235000011164 potassium chloride Nutrition 0.000 claims description 55
- 239000001103 potassium chloride Substances 0.000 claims description 55
- 239000011780 sodium chloride Substances 0.000 claims description 50
- 150000003839 salts Chemical class 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 238000007716 flux method Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 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 1
- 230000002427 irreversible effect Effects 0.000 claims 1
- SKFYTVYMYJCRET-UHFFFAOYSA-J potassium;tetrafluoroalumanuide Chemical compound [F-].[F-].[F-].[F-].[Al+3].[K+] SKFYTVYMYJCRET-UHFFFAOYSA-J 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000002184 metal Substances 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 32
- 230000000694 effects Effects 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 16
- 230000001603 reducing effect Effects 0.000 description 12
- 238000010298 pulverizing process Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910020549 KCl—NaCl Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
- Y02W30/84—Recycling of batteries or fuel cells
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- Manufacture And Refinement Of Metals (AREA)
- Primary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Description
本発明は、アルミニウムのスクラップを溶解した溶湯中のＭｇを低減して高純度化するためのマグネシウム濃度調整剤及びそれを用いたアルミニウム合金溶湯のマグネシウム濃度調整方法に関する。 The present invention relates to a magnesium concentration adjusting agent for reducing Mg in a molten metal in which aluminum scrap is melted to achieve high purity, and a magnesium concentration adjusting method for an aluminum alloy molten metal using the same.
従来から、アルミニウムはそのスクラップを再溶解して再生地金にリサイクルされている。しかし、スクラップを再溶解したアルミニウム溶湯中には、多くの非金属介在物や合金元素が不純物として混入していることから、通常、新地金に比べて品質が著しく劣っている。
そこで、アルミニウムをリサイクルする際に、アルミニウム又はアルミニウム合金スクラップ溶湯から合金元素又は不純物を除去する高純度化処理も行われているが、高純度化処理には、有害な塩素ガスの使用や高価なフラックスの使用又は複雑な装置及び工程を必要とするなど、環境面、コスト面の問題があり、実用化の障害となっている。
Conventionally, aluminum is recycled into recycled metal by remelting the scrap. However, since many non-metallic inclusions and alloy elements are mixed as impurities in the molten aluminum obtained by remelting scrap, the quality is usually significantly inferior to that of new metal.
Therefore, when aluminum is recycled, high purity treatment is also performed to remove alloy elements or impurities from aluminum or aluminum alloy scrap molten metal. There are environmental and cost problems such as the use of flux or complicated equipment and processes, which are obstacles to practical use.
ところで、アルミニウムのリサイクルは、回収したアルミニウムスクラップを溶解、希釈によりある合金成分濃度域まで調節したグレードの低い合金（ベースメタル）を、主に自動車部品(ホイール)等の製造に用いられるダイカスト用合金ＡＤＣ１２の原料として使用される場合が多い。二次合金の代表格であるダイカスト用ＪＩＳＡＤＣ１２合金は、その組成規格においてマグネシウム濃度が０．３％以下に限定されている。このため、マグネシウム濃度が比較的高いアルミニウム缶由来のスクラップは再利用し難くなっている。 By the way, aluminum recycling is a die-casting alloy mainly used for manufacturing automobile parts (wheels), etc., with a low-grade alloy (base metal) adjusted to a certain alloy component concentration range by melting and diluting the recovered aluminum scrap. Often used as a raw material for ADC12. JIS ADC12 alloy for die casting, which is a typical secondary alloy, has a magnesium concentration limited to 0.3% or less in the composition standard. For this reason, it is difficult to reuse scraps derived from aluminum cans having a relatively high magnesium concentration.
アルミニウム溶湯中のマグネシウム濃度の微調整には、通称「脱Ｍｇ剤」が用いられているが、市販の脱Ｍｇ剤は高価であるために、容易に使用できないのが現状である。
そこで、アルミニウム溶湯中のマグネシウム濃度を低減するための手法が各種提案されている。
例えば特許文献１には、アルミニウム又はアルミニウム合金スクラップを溶融し、当該溶湯に使用済みの乾電池を焙焼及び粉砕して得られた粉末状のアルミニウム回収用材料を添加し、アルミニウム回収用材料に合金元素又は不純物を反応又は吸着させ、これらを分離してアルミニウムに含まれる合金元素又は不純物を除去し、純度を高めてアルミニウムを回収することが記載されている。
For fine adjustment of the magnesium concentration in the molten aluminum, a so-called “de-Mg agent” is used, but since a commercially available de-Mg agent is expensive, it cannot be used easily.
Therefore, various methods for reducing the magnesium concentration in the molten aluminum have been proposed.
For example, in Patent Document 1, powdered aluminum recovery material obtained by melting aluminum or aluminum alloy scrap, roasting and pulverizing a used dry battery in the molten metal is added, and alloy is added to the aluminum recovery material. It describes that elements or impurities are reacted or adsorbed, and these are separated to remove alloy elements or impurities contained in aluminum, thereby improving the purity and recovering aluminum.
特許文献１に記載の方法によると、使用済みの乾電池を焙焼した後これを粉砕して得られた粉末である電池滓に、電解液由来のＫＣｌ等の塩化物が適度（Ｃｌ濃度に換算して１〜１０ｗｔ％）に含まれる場合には、適量の電池滓をアルミニウム合金溶湯に添加することにより、Ｍｇ等の合金元素又は不純物を吸着・除去する効果が著しく高まるとされている。 According to the method described in Patent Document 1, chlorides such as KCl derived from the electrolytic solution are moderately (converted to Cl concentration) in the battery bowl, which is a powder obtained by baking a used dry battery and then pulverizing it. 1 to 10 wt%), it is said that the effect of adsorbing and removing alloy elements or impurities such as Mg is remarkably enhanced by adding an appropriate amount of the battery case to the molten aluminum alloy.
一方、近年マンガン電池の使用割合が低下しアルカリ電池の使用割合が増加しているため、電池滓に含まれる塩化物含有量は低下する傾向にあり、現状はＣｌ換算で約１ｗｔ％に過ぎないことが明らかとなっている。このため、電池滓をそのままアルミニウム合金溶湯中に添加するにしても、多量に添加しないことには十分なＭｇ除去効果を得ることが難しい状況にある。 On the other hand, since the usage rate of manganese batteries has decreased in recent years and the usage rate of alkaline batteries has increased, the chloride content contained in battery cells tends to decrease, and the current situation is only about 1 wt% in terms of Cl. It has become clear. For this reason, even if the battery cage is added to the molten aluminum alloy as it is, it is difficult to obtain a sufficient Mg removal effect without adding a large amount.
本発明は、このような課題を解決するために案出されたものであり、使用済みの乾電池を焙焼した後これを粉砕して得られた粉末である電池滓に対して、さらに数種類の混合塩粉末を適量添加することにより、経済的で且つアルミニウム合金溶湯中に含まれるＭｇの除去効果の高い、経済的なマグネシウム濃度調整剤を見出し、それを用いることによりアルミニウムを効率的にリサイクルする方法を提供することを目的とするものである。 The present invention has been devised in order to solve such a problem, and further several types of battery shells, which are powders obtained by baking a used dry battery and then pulverizing it, are used. By adding an appropriate amount of mixed salt powder, an economical magnesium concentration regulator that is economical and has a high effect of removing Mg contained in the molten aluminum alloy is found, and aluminum is efficiently recycled by using it. It is intended to provide a method.
本発明のアルミニウム合金溶湯用マグネシウム濃度調整剤は、その目的を達成するため、アルミニウム合金溶湯中に含有されるマグネシウムを除去してアルミニウム合金溶湯中のマグネシウム濃度を調整する粉末であって、使用済みの乾電池を焙焼した後これを粉砕して得られた粉末である電池滓１００質量部に対して、少なくとも塩化ナトリウム粉末と塩化カリウム粉末とを含む混合塩粉末を１〜３０質量部添加した粉末であることを特徴とする。 The magnesium concentration adjusting agent for molten aluminum alloy of the present invention is a powder that removes magnesium contained in the molten aluminum alloy and adjusts the magnesium concentration in the molten aluminum alloy in order to achieve the object, and has been used. A powder obtained by adding 1 to 30 parts by mass of a mixed salt powder containing at least a sodium chloride powder and a potassium chloride powder to 100 parts by mass of a battery basket which is a powder obtained by baking a dry battery of It is characterized by being.
前記混合塩粉末は、塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率が２０〜７０質量％であることが好ましい。
前記混合塩粉末は、塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率が３０〜８０質量％であることが好ましい。
そして、前記混合塩粉末は、塩化ナトリウム粉末２０〜７０質量％、塩化カリウム粉末３０〜８０質量％を含み、残部が不可避的不純物からなる粉末であることが好ましい。
In the mixed salt powder, the ratio of the sodium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder is preferably 20 to 70% by mass.
In the mixed salt powder, the ratio of the potassium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder is preferably 30 to 80% by mass.
And it is preferable that the said mixed salt powder is a powder which contains sodium chloride powder 20-70 mass% and potassium chloride powder 30-80 mass%, and the remainder consists of an unavoidable impurity.
また、本発明のアルミニウム合金溶湯中のマグネシウム濃度調整方法は、上記アルミニウム合金溶湯用マグネシウム濃度調整剤を、アルミニウム合金溶湯１００質量部に対して０．５〜２０質量部添加することを特徴とする。
このマグネシウム濃度調整剤の添加により、アルミニウム合金溶湯中のマグネシウム濃度を低減させることができる。
前記マグネシウム濃度調整剤の添加は、投げ込み法、押し込み法及びインジェクションフラックス法いずれの方法であってもよいが、インジェクションフラックス法によって行うことが好ましい。
Moreover, the magnesium concentration adjustment method in the aluminum alloy molten metal of this invention adds 0.5-20 mass parts of said magnesium concentration regulator for aluminum alloy molten metals with respect to 100 mass parts of molten aluminum alloys. .
By adding this magnesium concentration adjusting agent, the magnesium concentration in the molten aluminum alloy can be reduced.
The magnesium concentration adjusting agent may be added by any of a casting method, an indentation method, and an injection flux method, but is preferably performed by an injection flux method.
本発明方法によれば、使用済みの乾電池を焙焼した後これを粉砕して得られた粉末である電池滓に対して、さらに数種類の混合塩粉末を適量添加するのみで、アルミニウム合金溶湯中に含まれるＭｇを効率よく低減することができるアルミニウム合金溶湯用マグネシウム濃度調整剤が経済的に調製できる。
そして、本発明のマグネシウム濃度調整剤を用いることにより、アルミニウムスクラップリサイクル材の品質を大幅に向上できることが可能となり、アルミニウム材料のリサイクル化を大きく進展させることができる。また、今まで十分なリサイクルが行なわれていなかった使用済みの乾電池の有効利用を図ることができる。
According to the method of the present invention, it is only necessary to add an appropriate amount of several kinds of mixed salt powder to the battery shell, which is a powder obtained by baking a used dry battery and then pulverizing it. A magnesium concentration adjusting agent for molten aluminum alloy that can efficiently reduce Mg contained in can be economically prepared.
And by using the magnesium concentration regulator of this invention, it becomes possible to improve the quality of an aluminum scrap recycled material significantly, and can recycle aluminum material greatly. Further, it is possible to effectively use a used dry battery that has not been sufficiently recycled until now.
本発明者等は、使用済みの乾電池を焙焼した後これを粉砕して得られた粉末である電池滓をアルミニウム合金溶湯に添加することによりアルミニウム合金溶湯中に含まれるＭｇをより効率的に低減する技術について、鋭意検討を重ねてきた。
その過程で、電池滓中のＣｌ濃度を高くすることが有効であることがわかった。そしてそのＣｌ分を、塩化ナトリウムの粉末及び塩化カリウムの粉末を適正比率で混合した混合塩粉末の添加により増量することが有効であることがわかり、本発明に到達した。
以下に、その詳細を説明する。
The inventors of the present invention more efficiently add Mg contained in the molten aluminum alloy by adding a battery rod, which is a powder obtained by roasting a used dry battery and then pulverizing it, to the molten aluminum alloy. We have intensively studied about the technology to reduce.
In the process, it was found effective to increase the Cl concentration in the battery case. It has been found that it is effective to increase the Cl content by adding a mixed salt powder in which sodium chloride powder and potassium chloride powder are mixed at an appropriate ratio, and the present invention has been achieved.
The details will be described below.
電池滓は、マンガン電池、アルカリ電池などの使用済み乾電池を焙焼炉（ロータリーキルン）により大気中８００℃で焙焼し、粉砕後に電池表皮に用いられる鉄などの有価金属、または古い電池や輸入した電池に含まれる有害金属を除去した後の粉末である。
電池滓は、黒色の粉末であり、電子顕微鏡による観察の結果、通常は５μｍ程度の微粉末であることが確認されている。電池滓の組成例を表１に示す。なお、分析は蛍光Ｘ線分析法及びＸ線回折法を併用し、これら分析法から得られる各元素の蛍光Ｘ線強度データ、Ｘ線回折強度プロファイルを基に専用ソフトを用いて電池滓の組成を計算した。これにより電池滓は亜鉛酸化物（ＺｎＯ）とマンガン酸化物（ＭｎＯ２）を主成分とする数種類の酸化物から構成されていることがわかる。
Batteries were used to burn used dry batteries such as manganese batteries and alkaline batteries in a roasting furnace (rotary kiln) at 800 ° C in the atmosphere, and after pulverization, valuable metals such as iron used for the battery skin, or old batteries or imported It is a powder after removing harmful metals contained in the battery.
The battery case is a black powder, and as a result of observation with an electron microscope, it has been confirmed that it is usually a fine powder of about 5 μm. Table 1 shows an example of the composition of the battery case. The analysis uses both fluorescent X-ray analysis and X-ray diffraction, and the composition of the battery case using dedicated software based on the fluorescent X-ray intensity data and X-ray diffraction intensity profile of each element obtained from these analysis methods Was calculated. Thereby, it can be seen that the battery case is composed of several kinds of oxides mainly composed of zinc oxide (ZnO) and manganese oxide (MnO 2 ).
乾電池の成分は、本願発明のアルミニウム合金溶湯用マグネシウム濃度調整剤の主成分となるものであるが、亜鉛酸化物（ＺｎＯ）とマンガン酸化物（ＭｎＯ２）以外にマンガン電池には電解液としてＮＨ４Ｃｌ、アルカリ電池には電解液としてＫＯＨ、Ｃ、Ｆｅ２Ｏ３、ＳｉＯ２等を含有する。マンガン電池に含まれるＮＨ４Ｃｌ及びアルカリ電池に含まれるＫＯＨは、焙焼により多くはＫＣｌを形成し電池滓に残存することになる。
電解液由来のＫＣｌ等の塩化物が適度（Ｃｌ濃度に換算して１〜１０ｗｔ％）に含まれる場合には、適量の電池滓をアルミニウム合金溶湯に添加することにより、電池滓に残存するＫＣｌが電池滓とアルミニウム溶湯との濡れ性を改善するとともに、ＫＣｌと溶湯中のＭｇが発熱反応してＭｇＣｌ２を生成するため、溶湯中のマグネシウム濃度を低減させることができるのである。
The component of the dry battery is a main component of the magnesium concentration adjusting agent for molten aluminum alloy of the present invention. In addition to zinc oxide (ZnO) and manganese oxide (MnO 2 ), the manganese battery has NH as an electrolyte. The 4Cl, alkaline battery contains KOH, C, Fe 2 O 3 , SiO 2 or the like as an electrolytic solution. NH 4 Cl contained in the manganese battery and KOH contained in the alkaline battery mostly form KCl by roasting and remain in the battery case.
When chloride such as KCl derived from the electrolyte is moderately contained (1 to 10 wt% in terms of Cl concentration), an appropriate amount of battery shell is added to the molten aluminum alloy to leave KCl remaining in the battery shell. However, it improves the wettability between the battery case and the molten aluminum, and KCl and Mg in the molten metal undergo an exothermic reaction to produce MgCl 2 , so that the magnesium concentration in the molten metal can be reduced.
しかしながら、近年マンガン電池の使用割合が低下しアルカリ電池の使用割合が増加しているため、電池滓に含まれる塩化物含有量は低下する傾向にあり、現状はＣｌ換算で約１ｗｔ％に過ぎないことが明らかとなっている。このため、電池滓をそのままアルミニウム合金溶湯中に添加するにしても、多量に添加しないことには十分なＭｇ除去効果を得ることが難しい状況にある。
そこで、電池滓に対して、塩化ナトリウム粉末と塩化カリウム粉末とを含む混合塩粉末を加えて、塩化物量を増量したものである。
However, since the usage rate of manganese batteries has decreased in recent years and the usage rate of alkaline batteries has increased, the chloride content contained in the battery cell tends to decrease, and the current situation is only about 1 wt% in terms of Cl. It has become clear. For this reason, even if the battery cage is added to the molten aluminum alloy as it is, it is difficult to obtain a sufficient Mg removal effect without adding a large amount.
Therefore, the amount of chloride is increased by adding a mixed salt powder containing sodium chloride powder and potassium chloride powder to the battery case.
〔電池滓１００質量部に対して、少なくとも塩化ナトリウム粉末と塩化カリウム粉末とを含む混合塩粉末を１〜３０質量部添加〕
塩化ナトリウム（ＮａＣｌ）粉末も塩化カリウム（ＫＣｌ）粉末も、アルミニウム合金溶湯の脱滓処理用のフラックスとして、広く用いられている。電池滓に新たに混合されたこれら塩化物は、電池滓とアルミニウム溶湯との濡れ性を改善するため、電池滓由来の塩化物よるマグネシウム濃度低減効果をさらに高めることができる。特に塩化ナトリウムと塩化カリウムとの混合フラックスにすると、共晶融解するために溶融温度が低くなり、電池滓とアルミニウム溶湯との濡れ性を改善する効果が高くなる。
[1 to 30 parts by mass of mixed salt powder containing at least sodium chloride powder and potassium chloride powder with respect to 100 parts by mass of battery case]
Both sodium chloride (NaCl) powder and potassium chloride (KCl) powder are widely used as fluxes for the deaeration treatment of molten aluminum alloys. Since these chlorides newly mixed in the battery case improve the wettability between the battery case and the molten aluminum, the effect of reducing the magnesium concentration by the chloride derived from the battery case can be further enhanced. In particular, when a mixed flux of sodium chloride and potassium chloride is used, eutectic melting lowers the melting temperature, and the effect of improving the wettability between the battery shell and the molten aluminum increases.
この効果は塩化ナトリウムと塩化カリウムとの質量比が４：６の場合に最も高くなる。
電池滓に新たに加えられた混合塩粉末中の塩化物自身がアルミニウム合金溶湯中に含まれるマグネシウムと反応してＭｇＣｌ２を生成するため、マグネシウム濃度調整剤のマグネシウム濃度低減効果をより一層高めることができる。
This effect is highest when the mass ratio of sodium chloride to potassium chloride is 4: 6.
Since chloride in the mixed salt powder newly added to the battery shell reacts with magnesium contained in the molten aluminum alloy to produce MgCl 2 , the magnesium concentration regulator can further enhance the magnesium concentration reduction effect. Can do.
電池滓１００質量部に対して前記混合塩粉末を１〜３０質量部の範囲で添加することが好ましい。前記混合塩粉末の添加割合が１質量部未満であると、電池滓とアルミニウム溶湯との濡れ性を改善する効果、マグネシウム濃度低減効果を改善する効果を発揮することができない。前記混合塩粉末の添加割合が３０質量部を超えると、マグネシウム濃度調整剤の原料コストが増加し、電池滓を再利用するという目的を達成することが困難となる。
より好ましい前記混合塩粉末の添加割合は、電池滓１００質量部に対して３〜２０質量部の範囲である。さらに好ましい前記混合塩粉末の添加割合は、電池滓１００質量部に対して５〜１５質量部の範囲である。
The mixed salt powder is preferably added in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the battery case. When the addition ratio of the mixed salt powder is less than 1 part by mass, the effect of improving the wettability between the battery case and the molten aluminum and the effect of improving the magnesium concentration reducing effect cannot be exhibited. When the addition ratio of the mixed salt powder exceeds 30 parts by mass, the raw material cost of the magnesium concentration adjusting agent increases, and it becomes difficult to achieve the purpose of reusing the battery case.
The addition ratio of the mixed salt powder is more preferably in the range of 3 to 20 parts by mass with respect to 100 parts by mass of the battery case. The addition ratio of the mixed salt powder is more preferably in the range of 5 to 15 parts by mass with respect to 100 parts by mass of the battery case.
〔塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率が２０〜７０質量％〕
さらに、本願発明において、前記混合塩粉末は、塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率が２０〜７０質量％の範囲であることが好ましい。
塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率が２０質量％未満であると、電池滓とアルミニウム溶湯との濡れ性を改善する効果、マグネシウム濃度低減効果を改善する効果が十分ではない。塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率が７０質量％を超えると、電池滓とアルミニウム溶湯との濡れ性を改善する効果、マグネシウム濃度低減効果を改善する効果が十分ではない。
より好ましい塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率は３０〜６０質量％の範囲である。さらに好ましい塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率は３０〜５０質量％の範囲である。
[The ratio of sodium chloride powder to the total mass of sodium chloride powder and potassium chloride powder is 20 to 70% by mass]
Furthermore, in this invention, it is preferable that the ratio of sodium chloride powder with respect to the total mass of sodium chloride powder and potassium chloride powder is 20-70 mass% in the said mixed salt powder.
When the ratio of the sodium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder is less than 20% by mass, the effect of improving the wettability between the battery case and the molten aluminum and the effect of reducing the magnesium concentration are sufficient. is not. If the ratio of the sodium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder exceeds 70% by mass, the effect of improving the wettability between the battery case and the molten aluminum and the effect of reducing the magnesium concentration are not sufficient. Absent.
A more preferable ratio of the sodium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder is in the range of 30 to 60% by mass. Furthermore, the ratio of the sodium chloride powder with respect to the total mass of sodium chloride powder and potassium chloride powder is in the range of 30 to 50% by mass.
〔塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率が３０〜８０質量％〕
さらに、本願発明において、前記混合塩粉末は、塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率が３０〜８０質量％の範囲であることが好ましい。
塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率が３０質量％未満であると、電池滓とアルミニウム溶湯との濡れ性を改善する効果、マグネシウム濃度低減効果を改善する効果が十分ではない。塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率が８０質量％を超えると、電池滓とアルミニウム溶湯との濡れ性を改善する効果、マグネシウム濃度低減効果を改善する効果が十分ではない。
[The ratio of potassium chloride powder to the total mass of sodium chloride powder and potassium chloride powder is 30 to 80% by mass]
Furthermore, in this invention, it is preferable that the ratio of the potassium chloride powder with respect to the total mass of sodium chloride powder and potassium chloride powder is 30-80 mass% in the said mixed salt powder.
When the ratio of the potassium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder is less than 30% by mass, the effect of improving the wettability between the battery case and the molten aluminum and the effect of reducing the magnesium concentration are sufficient. is not. If the ratio of the potassium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder exceeds 80% by mass, the effect of improving the wettability between the battery case and the molten aluminum and the effect of reducing the magnesium concentration are not sufficient. Absent.
より好ましい塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率は４０〜７０質量％の範囲である。さらに好ましい塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率は５０〜７０質量％の範囲である。
前記混合塩粉末には、塩化ナトリウム粉末２０〜７０質量％、塩化カリウム粉末３０〜８０質量％の他に、不可避的な不純物を含んでいてもよい。
この不可避的不純物とは、塩化ナトリウム粉末及び塩化カリウム粉末を製造、精製する際に不可避的に混入する水分、酸化物、硫酸塩などである。
A more preferable ratio of the potassium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder is in the range of 40 to 70% by mass. Furthermore, the ratio of the potassium chloride powder with respect to the total mass of a preferable sodium chloride powder and potassium chloride powder is the range of 50-70 mass%.
The mixed salt powder may contain inevitable impurities in addition to
The inevitable impurities are water, oxides, sulfates and the like which are inevitably mixed when sodium chloride powder and potassium chloride powder are produced and purified.
なお、混合塩粉末には、ＮａＣｌ、ＫＣｌの粉末以外に、アルミニウム合金溶湯とマグネシウム濃度調整剤との反応性を高めるＫＡｌＦ３、ＡｌＦ３、Ｋ２ＳＯ４、Ｎａ２ＳＯ４、Ｎａ２ＣＯ３等の粉末を積極的に含ませていてもよい。特にインジェクションフラックス法により、Ａｒ、Ｎ２などの不活性ガスとともにマグネシウム濃度調整剤をアルミニウム合金溶湯中に混入・分散させてもよい。
前記混合塩粉末中におけるＫＡｌＦ３、ＡｌＦ３、Ｋ２ＳＯ４、Ｎａ２ＳＯ４、Ｎａ２ＣＯ３等の粉末の混合比率は２０質量％以下であることが好ましい。より好ましくは１０質量％以下である。さらに好ましくは５質量％以下である。
In addition to NaCl and KCl powders, the mixed salt powder includes KAlF 3 , AlF 3 , K 2 SO 4 , Na 2 SO 4 , and Na 2 CO 3 that increase the reactivity between the molten aluminum alloy and the magnesium concentration adjusting agent. Etc. may be positively included. In particular, a magnesium concentration adjusting agent may be mixed and dispersed in the molten aluminum alloy together with an inert gas such as Ar and N 2 by an injection flux method.
The mixing ratio of powders such as KAlF 3 , AlF 3 , K 2 SO 4 , Na 2 SO 4 and Na 2 CO 3 in the mixed salt powder is preferably 20% by mass or less. More preferably, it is 10 mass% or less. More preferably, it is 5 mass% or less.
次に、マグネシウム濃度調整剤を用いてアルミニウム合金溶湯のマグネシウム濃度を低減させる方法について説明する。
上記のアルミニウム合金溶湯用マグネシウム濃度調整剤を、アルミニウム合金溶湯１００質量部に対して、０．５〜２０質量部添加し、何らの手段で当該マグネシウム濃度調整剤を溶湯中に分散させることにより、マグネシウム濃度調整剤中の塩化物等の成分とアルミニウム合金溶湯中のＭｇとが反応して、ＭｇＣｌ２なる反応生成物を形成してアルミニウム合金から分離される。
Next, a method for reducing the magnesium concentration of the molten aluminum alloy using a magnesium concentration adjusting agent will be described.
By adding 0.5 to 20 parts by mass of the magnesium concentration adjusting agent for molten aluminum alloy to 100 parts by mass of the molten aluminum alloy, and dispersing the magnesium concentration adjusting agent in the molten metal by any means, Components such as chloride in the magnesium concentration adjusting agent react with Mg in the molten aluminum alloy to form a reaction product of MgCl 2 to be separated from the aluminum alloy.
アルミニウム溶湯の対する上記マグネシウム濃度調整剤の適切な添加量は次の通りである。
〔アルミニウム合金溶湯用マグネシウム濃度調整剤を、アルミニウム合金溶湯１００質量部に対して、０．５〜２０質量部添加〕
アルミニウム合金溶湯用マグネシウム濃度調整剤を、アルミニウム合金溶湯１００質量部に対して、０.５〜２０質量部の範囲で添加することが好ましい。アルミニウム合金溶湯へのマグネシウム濃度調整剤の添加量が０.５質量部未満であると、マグネシウム濃度低減効果が発揮されない。アルミニウム合金溶湯へのマグネシウム濃度調整剤の添加量が２０質量部を超えると、添加方法にもよるが、アルミニウム合金溶湯中への電池滓中のいわゆる骨材（亜鉛酸化物（ＺｎＯ）とマンガン酸化物（ＭｎＯ２）を主成分とする数種類の酸化物）の混入量が多くなって、インゴット、鋳物製品等の品質劣化を招くおそれがある。
より好ましいアルミニウム合金溶湯へのマグネシウム濃度調整剤の添加量は１〜１５質量部の範囲である。さらに好ましいアルミニウム合金溶湯へのマグネシウム濃度調整剤の添加量は２〜１０質量部の範囲である。
Appropriate amounts of the magnesium concentration adjusting agent added to the molten aluminum are as follows.
[Addition of 0.5 to 20 parts by mass of magnesium concentration regulator for molten aluminum alloy to 100 parts by mass of molten aluminum alloy]
It is preferable to add the magnesium concentration adjusting agent for molten aluminum alloy in a range of 0.5 to 20 parts by mass with respect to 100 parts by mass of the molten aluminum alloy. If the amount of the magnesium concentration adjusting agent added to the molten aluminum alloy is less than 0.5 parts by mass, the effect of reducing the magnesium concentration is not exhibited. When the amount of the magnesium concentration modifier added to the molten aluminum alloy exceeds 20 parts by mass, depending on the addition method, so-called aggregates (zinc oxide (ZnO) and manganese oxidation in the battery shell into the molten aluminum alloy) The amount of mixed materials (several types of oxides mainly composed of MnO 2 ) increases, which may cause quality deterioration of ingots, cast products, and the like.
The addition amount of the magnesium concentration adjusting agent to the molten aluminum alloy is more preferably in the range of 1 to 15 parts by mass. Furthermore, the addition amount of the magnesium concentration adjusting agent to the preferable aluminum alloy molten metal is in the range of 2 to 10 parts by mass.
続いて、適切な添加方法について説明する。
〔インジェクションフラックス法によって添加〕
アルミニウム合金溶湯用マグネシウム濃度調整剤は、アルミニウム合金溶湯の湯面から上方添加してもよいし、適量をアルミニウム箔に包んでフォスフォライザーを使用して押し込み添加してもよい。しかしながら、マグネシウム濃度調整剤を溶湯中に迅速に分散させるためには、インジェクションフラックス法として、ランスを使用し、Ａｒ、Ｎ２などの不活性ガスとともに溶湯中に吹き込むことが好ましい。回転脱ガス装置を使用し、マグネシウム濃度調整剤を溶湯中に吹き込み分散させてもよい。
Subsequently, an appropriate addition method will be described.
[Add by injection flux method]
The magnesium concentration adjusting agent for molten aluminum alloy may be added upward from the surface of the molten aluminum alloy, or an appropriate amount may be wrapped in aluminum foil and pushed in using a phosphorizer. However, in order to rapidly disperse the magnesium concentration adjusting agent in the molten metal, it is preferable to use a lance as an injection flux method and blow it into the molten metal together with an inert gas such as Ar and N 2 . A rotary degassing device may be used to blow and disperse the magnesium concentration adjusting agent into the molten metal.
マグネシウム濃度調整剤を添加する際のアルミニウム合金溶湯の保持温度は、７２０〜８６０℃の範囲が好ましい。溶湯温度７２０℃未満であると、マグネシウム濃度調整剤中の塩化物等の成分とアルミニウム溶湯中のＭｇとの反応が進まず、マグネシウム濃度低減効果が低下する。溶湯温度８６０℃を超えると、マグネシウム濃度調整剤中の塩化物等の成分が坩堝や溶解・保持炉の内壁ブロックの劣化を促進する。より好ましい溶湯保持温度は、７４０〜８４０℃の範囲内である。さらに好ましくは、７６０〜８２０℃の範囲内である。 The retention temperature of the molten aluminum alloy when adding the magnesium concentration adjusting agent is preferably in the range of 720 to 860 ° C. When the molten metal temperature is lower than 720 ° C., the reaction between components such as chloride in the magnesium concentration adjusting agent and Mg in the molten aluminum does not proceed, and the magnesium concentration reducing effect decreases. When the molten metal temperature exceeds 860 ° C., components such as chloride in the magnesium concentration adjusting agent promote deterioration of the crucible and the inner wall block of the melting / holding furnace. A more preferable molten metal holding temperature is in the range of 740 to 840 ° C. More preferably, it exists in the range of 760-820 degreeC.
電池滓として、マンガン電池、アルカリ電池などの使用済み乾電池を焙焼炉（ロータリーキルン）により大気中８００℃で焙焼し、粉砕後に電池表皮に用いられる鉄などの有価金属、または古い電池や輸入した電池に含まれる有害金属を除去した後の粉末を用いた。
用いた電池滓は、黒色の粉末であり、電子顕微鏡による観察の結果、通常は５μｍ程度の微粉末であり、その成分組成を表２に示す。なお、分析は蛍光Ｘ線分析法で行った。電池滓には、分析値を超えるＣ（炭素）及びＯ（酸素）が含まれていると考えられるが、蛍光Ｘ線分析法では、いわゆる軽元素を正確に半定量分析することができない。
この電池滓に、ＫＣｌとＮａＣｌを種々の比率で混合した混合塩を加えてマグネシウム濃度調整剤とした。なお、用いた塩化ナトリウムの平均粒径（Ｄ５０）は、２００μｍ程度であった。塩化カリウム粉末の平均粒径（Ｄ５０）は、２００μｍ程度であった。
Used batteries such as manganese batteries and alkaline batteries were roasted at 800 ° C. in the atmosphere in a roasting furnace (rotary kiln), and valuable metals such as iron used for the battery skin after pulverization, or old batteries or imported The powder after removing harmful metals contained in the battery was used.
The battery case used was a black powder, and as a result of observation with an electron microscope, it was usually a fine powder of about 5 μm. The analysis was performed by fluorescent X-ray analysis. Although it is considered that the battery case contains C (carbon) and O (oxygen) exceeding the analytical value, the so-called light element cannot be accurately semi-quantitatively analyzed by the fluorescent X-ray analysis method.
A mixed salt in which KCl and NaCl were mixed at various ratios was added to this battery case to obtain a magnesium concentration adjusting agent. The average particle size of sodium chloride was used (D 50) was about 200 [mu] m. The average particle diameter (D 50 ) of the potassium chloride powder was about 200 μm.
実施例１：（予備試験、最適な塩化物割合の検討）
電池滓１００質量部に対し、ＫＣｌ：ＮａＣｌを１：１としたＫＣｌ−ＮａＣｌ混合塩を０質量部（添加なし）、５質量部、１０質量部、1５質量部添加した、４種類のマグネシウム濃度調整剤を各５００ｇ調製した。
次に、離型剤を塗布した黒鉛坩堝（４個）にそれぞれ表３に示す成分組成を有するＪＩＳＡＤＣ１２アルミニウム合金地金を１０ｋｇずつ装入配置し、黒鉛坩堝を電気炉内に挿入して７８０℃で溶解・保持し、さらにＭｇインゴットをフォスフォライザーにて各坩堝のＪＩＳＡＤＣ１２アルミニウム合金溶湯にそれぞれ３５ｇずつ添加した。
なお、表３に示すＪＩＳＡＤＣ１２アルミニウム合金の成分組成は、地金出荷時の分析値である。したがって、Ｍｇインゴット添加後のＪＩＳＡＤＣ１２アルミニウム合金溶湯中のＭｇ濃度は０.６４質量％となっている。
Example 1: (Preliminary test, examination of optimum chloride ratio)
Four types of magnesium concentrations with 0 parts by mass of KCl-NaCl mixed salt (KCl: NaCl 1: 1), 5 parts by mass, 10 parts by mass, and 15 parts by mass added to 100 parts by mass of the battery case 500 g of the adjusting agent was prepared for each.
Next, 10 kg each of JIS ADC12 aluminum alloy ingots having the composition shown in Table 3 were placed in the graphite crucible (4 pieces) coated with the release agent, and the graphite crucible was inserted into an electric furnace at 780 ° C. Then, 35 g of Mg ingot was added to each crucible JISADC12 aluminum alloy melt with a phosphorizer.
In addition, the component composition of JISADC12 aluminum alloy shown in Table 3 is an analysis value at the time of metal shipping. Therefore, the Mg concentration in the JISADC12 aluminum alloy molten metal after the addition of the Mg ingot is 0.64% by mass.
このＭｇ添加ＪＩＳＡＤＣ１２アルミニウム合金溶湯（４ロット）に対して、上記４種類のマグネシウム濃度調整剤をそれぞれ５００ｇずつフォスフォライザーにて押し込み添加した。
マグネシウム濃度調整剤の添加直後に１分間の攪拌を行い、７８０℃で３０分間溶湯を保持した。湯面の除滓を行った後、スプーンにて各溶湯を採取し、ディスクサンプルを分析用試料採取鋳型に鋳造した。鋳型から取り出したディスクサンプルは空冷後、旋盤を用いて表面を約２ｍｍ切削し、蛍光Ｘ線分析装置を用いてマグネシウム濃度を測定した。
To the Mg-added JIS ADC12 aluminum alloy melt (4 lots), 500 g of each of the above four kinds of magnesium concentration adjusting agents was pushed in and added with a phosphorizer.
Immediately after the addition of the magnesium concentration regulator, stirring was performed for 1 minute, and the molten metal was held at 780 ° C. for 30 minutes. After removing the molten metal surface, each molten metal was collected with a spoon, and a disk sample was cast into a sample collection mold for analysis. The disk sample taken out from the mold was air-cooled, and the surface was cut by about 2 mm using a lathe, and the magnesium concentration was measured using a fluorescent X-ray analyzer.
結果を図１に示す。
電池滓１００質量部に上記混合塩５質量部を添加した場合、十分なＭｇ低減効果を示さなかったが、電池滓１００質量部に上記混合塩１０質量部を添加した場合、高いＭｇ低減効果を示した。しかし、電池滓１００質量部に上記混合塩１５質量部を添加した場合、Ｍｇ低減効果は電池滓１００質量部に上記混合塩１０質量部を添加した場合に比べて、ほとんど変わらない。したがって、マグネシウム濃度調整剤としては、電池滓１００質量部に対する上記混合塩添加量が１０質量部であるものが最適であると判断した。
The results are shown in FIG.
When 5 parts by mass of the mixed salt was added to 100 parts by mass of the battery case, the Mg reduction effect was not sufficiently exhibited. However, when 10 parts by mass of the mixed salt was added to 100 parts by mass of the battery case, a high Mg reduction effect was obtained. Indicated. However, when 15 parts by mass of the mixed salt is added to 100 parts by mass of the battery case, the Mg reduction effect is almost the same as when 10 parts by mass of the mixed salt is added to 100 parts by mass of the battery case. Therefore, the magnesium concentration adjusting agent was determined to be optimal when the amount of the mixed salt added was 10 parts by mass with respect to 100 parts by mass of the battery case.
実施例２：
次に、電池滓に新たに加える塩化物の添加量を、電池滓１００質量部に対して１０質量部に固定し、塩化ナトリウム粉末、塩化カリウム粉末の混合塩粉末の混合比率を変化させて電池滓に混合し、これらの塩化物混合電池滓からなるマグネシウム濃度調整剤をＪＩＳＡＣ７Ａ合金溶湯１００質量部に対して５質量部添加して、マグネシウム濃度の低減効果に及ぼす塩化ナトリウム粉末と塩化カリウム粉末との混合比率の影響について調査した。
なお、試験に使用したＪＩＳＡＣ７Ａ合金の成分組成を表４に示す。
Example 2:
Next, the amount of chloride newly added to the battery case is fixed to 10 parts by mass with respect to 100 parts by mass of the battery case, and the mixing ratio of the mixed salt powder of sodium chloride powder and potassium chloride powder is changed. 5 parts by mass of a magnesium concentration regulator composed of these chloride mixed battery tanks is added to 100 parts by mass of JISAC7A alloy molten metal, and sodium chloride powder and potassium chloride powder have an effect on the magnesium concentration reducing effect. The effect of the mixing ratio was investigated.
In addition, Table 4 shows the component composition of the JISAC7A alloy used in the test.
上記電池滓５.０ｇ（６ロット分）に対して、塩化ナトリウム粉末と塩化カリウム粉末を塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化カリウム粉末の比率が０，２０，４０，６０，８０，１００質量％になるように混合した塩化物粉末０.５ｇを添加した塩化物混合電池滓からなる６種類のマグネシウム濃度調整剤を調製した。
次に、１００ｇ（６ロット分）のＪＩＳＡＣ７Ａ合金地金を切り出し、離型剤を塗布した黒鉛坩堝内に挿入・配置して、黒鉛坩堝を電気炉内に挿入し、ＪＩＳＡＣ７Ａ合金地金を大気中７８０℃で溶解した。次にそれぞれのＪＩＳＡＣ７Ａ合金溶湯（６ロット分）に対して、上記６種類の塩化物添加電池滓からなるマグネシウム濃度調整剤を５.０ｇずつ湯面上方から添加した。
電池滓の添加直後に１分間の攪拌を行い、７８０℃で３０分間溶湯を保持した。湯面の除滓を行った後、スプーンにて各溶湯を採取し、ディスクサンプルを分析用試料採取鋳型に鋳造した。鋳型から取り出したディスクサンプルは空冷後、旋盤を用いて表面を約２ｍｍ切削し、蛍光Ｘ線分析装置を用いてマグネシウム濃度を測定した。
The ratio of the potassium chloride powder to the total mass of the sodium chloride powder and the potassium chloride powder with respect to 5.0 g (for 6 lots) of the battery is 0, 20, 40, 60, 80. , 6 types of magnesium concentration regulators were prepared, which consisted of a chloride-mixed battery tank to which 0.5 g of chloride powder mixed to 100 mass% was added.
Next, 100 g (6 lots) of JISAC7A alloy ingot was cut out, inserted and placed in a graphite crucible coated with a release agent, the graphite crucible was inserted in an electric furnace, and JISAC7A alloy ingot was placed in the atmosphere. Dissolved at 780 ° C. Next, to each JISAC7A alloy molten metal (for 6 lots), 5.0 g of a magnesium concentration adjusting agent composed of the above six types of chloride-added battery tanks was added from above the molten metal surface.
Immediately after the addition of the battery cage, stirring was performed for 1 minute, and the molten metal was held at 780 ° C. for 30 minutes. After removing the molten metal surface, each molten metal was collected with a spoon, and a disk sample was cast into a sample collection mold for analysis. The disk sample taken out from the mold was air-cooled, and the surface was cut by about 2 mm using a lathe, and the magnesium concentration was measured using a fluorescent X-ray analyzer.
電池滓に添加した塩化物中の塩化ナトリウム比率（塩化カリウム比率）に従って、ディスクサンプルのマグネシウム濃度をプロットしたものが図２である。
塩化ナトリウム粉末と塩化カリウム粉末との合計質量に対する塩化ナトリウム粉末の比率が２０〜７０質量％の範囲で、塩化カリウム粉末の比率では８０〜３０質量％の範囲で、確実にマグネシウム濃度が低減できていることがわかる。好ましくは、塩化ナトリウム粉末の比率が３０〜６０質量％の範囲、塩化カリウム粉末の比率では７０〜４０質量％の範囲であることがわかる。
FIG. 2 is a plot of the magnesium concentration of the disk sample according to the sodium chloride ratio (potassium chloride ratio) in the chloride added to the battery case.
When the ratio of sodium chloride powder to the total mass of sodium chloride powder and potassium chloride powder is in the range of 20 to 70% by mass, and the ratio of potassium chloride powder is in the range of 80 to 30% by mass, the magnesium concentration can be reliably reduced. I understand that. Preferably, the ratio of sodium chloride powder is in the range of 30 to 60% by mass, and the ratio of potassium chloride powder is in the range of 70 to 40% by mass.
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