JP6301814B2 - Method for separating aluminum from acidic solution containing aluminum, and method for producing lithium / aluminum composite hydroxide - Google Patents
Method for separating aluminum from acidic solution containing aluminum, and method for producing lithium / aluminum composite hydroxide Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 133
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 133
- 239000003929 acidic solution Substances 0.000 title claims description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 46
- 229910052744 lithium Inorganic materials 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 24
- 239000002131 composite material Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 238000001914 filtration Methods 0.000 claims description 37
- 238000006386 neutralization reaction Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 8
- 230000003472 neutralizing effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229910010199 LiAl Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Removal Of Specific Substances (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、アルミニウム含有酸性溶液からのアルミニウム分離方法、リチウム・アルミニウム系複合水酸化物に関する。 The present invention relates to a method for separating aluminum from an aluminum-containing acidic solution and a lithium / aluminum-based composite hydroxide.
鉱山で発生する排水、アルミニウムの表面処理、或いは有価金属回収処理において発生する各種排水に含有されるアルミニウムを分離回収するための方法が知られている。 There are known methods for separating and recovering aluminum contained in various wastewaters generated in wastewater generated in mines, surface treatment of aluminum, or valuable metal recovery processing.
例えば、特開２０１０−２２２１５９号公報では、アルミニウム又はアルミニウム合金からなるアルミニウム材の表面処理工程で生じた水酸化アルミニウムを含む水酸化アルミニウム含有酸性溶液から結晶性水酸化アルミニウムを回収する方法が記載されている。 For example, Japanese Patent Application Laid-Open No. 2010-222159 describes a method for recovering crystalline aluminum hydroxide from an aluminum hydroxide-containing acidic solution containing aluminum hydroxide generated in the surface treatment step of an aluminum material made of aluminum or an aluminum alloy. ing.
特開２０１１−２０６７５７号公報では、アルミニウム、マグネシウム及びマンガンを含有する硫酸酸性排水を中和して脱アルミニウム後液と水酸化アルミニウム澱物とに分離する方法が記載されている。 Japanese Patent Application Laid-Open No. 2011-206757 describes a method of neutralizing sulfuric acid wastewater containing aluminum, magnesium and manganese and separating it into a solution after dealumination and an aluminum hydroxide starch.
特許文献１及び２のいずれの方法も、アルミニウム含有酸性溶液から中和により水酸化アルミニウムの沈殿を生じさせる方法を提案しているが、このような水酸化アルミニウムの沈殿を生じさせる従来法では、中和処理により生じるゲル状の水酸化アルミニウム沈殿が濾過性を悪化させ、処理効率を低下させてしまう場合がある。 Both methods of Patent Documents 1 and 2 have proposed a method of causing precipitation of aluminum hydroxide by neutralization from an aluminum-containing acidic solution. However, in the conventional method of causing precipitation of such aluminum hydroxide, The gelled aluminum hydroxide precipitate produced by the neutralization treatment may deteriorate filterability and reduce the treatment efficiency.
更に、分離したアルミニウムをその後有効利用する可能性を考慮すると、分離したアルミニウムを、ゲル状の水酸化アルミニウムとして回収するのではなく、例えば他用途への利用などに適した取り扱い容易な別形態のアルミニウム化合物にする必要性が求められる場合もある。 Furthermore, considering the possibility of effective use of the separated aluminum thereafter, the separated aluminum is not recovered as gelled aluminum hydroxide, but is another form that is easy to handle and suitable for use in other applications, for example. There may be a need to use aluminum compounds.
上記課題を鑑み、本発明は、アルミニウム含有酸性溶液の中和処理によって得られる中和処理物を濾過する際の濾過性を向上させることができ、且つ分離したアルミニウムを他用途への利用に適した取り扱い容易な形態にすることが可能なアルミニウム含有酸性溶液からのアルミニウム分離方法及びリチウム・アルミニウム系複合水酸化物を提供する。 In view of the above problems, the present invention can improve the filterability when filtering a neutralized product obtained by neutralizing an aluminum-containing acidic solution, and is suitable for use of separated aluminum for other purposes. The present invention provides a method for separating aluminum from an aluminum-containing acidic solution and a lithium-aluminum-based composite hydroxide that can be easily handled.
本発明者は鋭意検討を重ねた結果、アルミニウム含有酸性溶液にリチウム源を添加してアルミニウム含有酸性溶液中のリチウムに対するアルミニウムのモル比（Ａｌ／Ｌｉ比）を１．１以下になるように調整し、これにアルカリを加えて中和処理し、アルミニウム含有酸性溶液中のアルミニウムをリチウム・アルミニウム系複合水酸化物として沈殿させることで、その後の固液分離時の濾過性が向上することを見いだした。 As a result of intensive studies, the inventors have added a lithium source to the aluminum-containing acidic solution and adjusted the molar ratio of aluminum to lithium (Al / Li ratio) in the aluminum-containing acidic solution to be 1.1 or less. Then, it was found that the filterability during the subsequent solid-liquid separation was improved by adding alkali to this and neutralizing it to precipitate the aluminum in the aluminum-containing acidic solution as lithium-aluminum composite hydroxide. It was.
以上の知見を基礎として完成した本発明は一側面において、アルミニウム含有酸性溶液にリチウム源を添加して、アルミニウム含有酸性溶液中のリチウムに対するアルミニウムのモル比（Ａｌ／Ｌｉ比）を１．１以下になるように調整し、アルミニウム含有酸性溶液にアルカリを加えて中和処理することにより、リチウム・アルミニウム系複合水酸化物の沈殿を生じさせ、その後固液分離することにより、リチウム・アルミニウム系複合水酸化物を含む濾過残渣とリチウムを含む濾過後液とに分離することを含むアルミニウム含有酸性溶液からのアルミニウム分離方法が提供される。 The present invention completed on the basis of the above knowledge, in one aspect, a lithium source is added to the aluminum-containing acidic solution, and the molar ratio of aluminum to lithium (Al / Li ratio) in the aluminum-containing acidic solution is 1.1 or less. Lithium / aluminum-based composite is prepared by adding lithium to the aluminum-containing acidic solution and neutralizing it by causing precipitation of lithium-aluminum-based composite hydroxide, followed by solid-liquid separation. There is provided a method for separating aluminum from an aluminum-containing acidic solution comprising separating into a filtration residue containing hydroxide and a post-filtration solution containing lithium.
本発明に係るアルミニウム含有酸性溶液からのアルミニウム分離方法は一実施態様において、濾過残渣中のリチウムに対するアルミニウムのモル比（Ａｌ／Ｌｉ比）が３．５未満となるように中和処理を行うことを含む。 In one embodiment of the method for separating aluminum from an aluminum-containing acidic solution according to the present invention, the neutralization treatment is performed so that the molar ratio of aluminum to lithium (Al / Li ratio) in the filtration residue is less than 3.5. including.
本発明に係るアルミニウム含有酸性溶液からのアルミニウム分離方法は別の一実施態様において、濾過後液が、２．０ｇ／Ｌ以上のリチウムを含むように中和処理を行うことを含む。 In another embodiment, the method for separating aluminum from an aluminum-containing acidic solution according to the present invention includes performing a neutralization treatment so that the liquid after filtration contains 2.0 g / L or more of lithium.
本発明に係るアルミニウム含有酸性溶液からのアルミニウム分離方法は更に別の一実施態様において、中和処理が、アルミニウム含有酸性溶液を３０〜９０℃に加温することを含む。 In another embodiment, the method for separating aluminum from an aluminum-containing acidic solution according to the present invention includes heating the aluminum-containing acidic solution to 30 to 90 ° C.
本発明に係るアルミニウム含有酸性溶液からのアルミニウム分離方法は更に別の一実施態様において、アルカリが水酸化物である。 In another embodiment of the method for separating aluminum from an aluminum-containing acidic solution according to the present invention, the alkali is a hydroxide.
本発明に係るアルミニウム含有酸性溶液からのアルミニウム分離方法は更に別の一実施態様において、アルカリが水酸化ナトリウムである。 In another embodiment of the method for separating aluminum from an aluminum-containing acidic solution according to the present invention, the alkali is sodium hydroxide.
本発明は別の一側面において、上記アルミニウム含有酸性溶液からのアルミニウム分離方法により得られたリチウム・アルミニウム系複合水酸化物が提供される。 In another aspect of the present invention, there is provided a lithium / aluminum composite hydroxide obtained by the method for separating aluminum from the aluminum-containing acidic solution.
本発明によれば、アルミニウム含有酸性溶液の中和処理によって得られる中和処理物を濾過する際の濾過性を向上させることができ、且つ分離したアルミニウムを他用途への利用に適した取り扱い容易な形態にすることが可能なアルミニウム含有酸性溶液からのアルミニウム分離方法及びリチウム・アルミニウム系複合水酸化物が提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the filterability at the time of filtering the neutralization processed material obtained by the neutralization process of an aluminum containing acidic solution can be improved, and the separated aluminum is easy to handle suitable for utilization to other uses. It is possible to provide a method for separating aluminum from an aluminum-containing acidic solution and a lithium / aluminum-based composite hydroxide that can be formed into a different form.
以下、図面を参照しながら本発明について説明する。本発明の実施の形態に係るアルミニウム含有酸性溶液とは、アルミニウムを含有する酸性溶液であればよい。具体的には、以下に制限されるものではないが、アルミニウム材の表面処理工程で生じるアルミニウム含有酸性廃水、鉱山重金属含有酸性排水、有価金属回収工程などで生じるアルミニウム含有硫酸酸性溶液などがあげられる。これらアルミニウム含有酸性溶液のｐＨは１．５〜３．５に調整されていることが好ましい。 Hereinafter, the present invention will be described with reference to the drawings. The aluminum-containing acidic solution according to the embodiment of the present invention may be an acidic solution containing aluminum. Specific examples include, but are not limited to, aluminum-containing acidic wastewater generated in the surface treatment process of aluminum materials, mine heavy metal-containing acidic waste water, aluminum-containing sulfuric acid acidic solution generated in valuable metal recovery processes, and the like. . The pH of these aluminum-containing acidic solutions is preferably adjusted to 1.5 to 3.5.
（１）Ａｌ／Ｌｉ比の調整
アルミニウム含有酸性溶液からアルミニウムを効果的且つ効率的に除去するとともに、固液分離時の濾過性を向上させるためには、アルミニウム含有酸性溶液中に存在するリチウム濃度を一定以上に制御することが好ましい。即ち、アルミニウム含有酸性溶液中にリチウム源を添加して、リチウムに対するアルミニウムのモル比（Ａｌ／Ｌｉ比）を１．１以下に、より好ましくは１．０以下に、更に好ましくは０．９以下となるように調製する。
(1) Adjustment of Al / Li ratio In order to effectively and efficiently remove aluminum from an aluminum-containing acidic solution and improve the filterability during solid-liquid separation, the concentration of lithium present in the aluminum-containing acidic solution Is preferably controlled to a certain level or more. That is, a lithium source is added to an aluminum-containing acidic solution, and the molar ratio of aluminum to lithium (Al / Li ratio) is 1.1 or less, more preferably 1.0 or less, and still more preferably 0.9 or less. Prepare so that.
後述する中和工程においてリチウム・アルミニウム系複合水酸化物を形成させる目的からすると、アルミニウム濃度に対してリチウム濃度が高くても特に問題とならないことから、アルミニウム含有酸性溶液中のＡｌ／Ｌｉ比は、０を超えるモル比とすることができる。これにより、アルミニウムの除去率を高く維持できるとともに、後述する中和処理におけるアルミニウムの沈殿形態が結晶性のある粒子となり、その後の濾過処理における濾過性が向上する。 For the purpose of forming a lithium / aluminum-based composite hydroxide in the neutralization step to be described later, there is no particular problem even if the lithium concentration is higher than the aluminum concentration, so the Al / Li ratio in the aluminum-containing acidic solution is , And a molar ratio exceeding zero. Thereby, while being able to maintain the removal rate of aluminum high, the precipitation form of the aluminum in the neutralization process mentioned later becomes a particle | grain with crystallinity, and the filterability in subsequent filtration process improves.
添加するリチウム源としては、炭酸リチウム、水酸化リチウムなどのリチウム化合物、これらを水に溶解させたリチウム水溶液などを利用することができる。 As a lithium source to be added, lithium compounds such as lithium carbonate and lithium hydroxide, a lithium aqueous solution in which these are dissolved in water, and the like can be used.
なお、アルミニウム含有酸性溶液中にＡｌ／Ｌｉ比が１．１以下となる程度にリチウムが予め存在する場合には、上記調整工程においてリチウムを積極的に添加しない場合もあるが、このような態様も、本発明に含み得るものとする。 In addition, when lithium is previously present in the aluminum-containing acidic solution so that the Al / Li ratio is 1.1 or less, lithium may not be positively added in the adjustment step. Can also be included in the present invention.
リチウム源を添加してアルミニウム含有酸性溶液中のＡｌ／Ｌｉ比を調整するタイミングは特に限定されない。例えば、後述する中和工程の途中にアルミニウムを含む沈殿物が生じるｐＨ領域でリチウム源を添加しても構わない。 The timing for adjusting the Al / Li ratio in the aluminum-containing acidic solution by adding a lithium source is not particularly limited. For example, the lithium source may be added in a pH range where a precipitate containing aluminum is generated during the neutralization step described later.
（２）中和工程
中和工程では、アルミニウム含有酸性溶液に中和剤を添加し、ｐＨを所定の範囲に調整することにより、アルミニウム含有酸性溶液中にリチウム・アルミニウム系複合水酸化物の沈殿を生じさせる。
(2) Neutralization step In the neutralization step, a neutralizing agent is added to the aluminum-containing acidic solution, and the pH is adjusted to a predetermined range, thereby precipitating lithium / aluminum composite hydroxide in the aluminum-containing acidic solution. Give rise to
中和剤としては、ナトリウム塩（ＮａＨＣＯ3、Ｎａ2ＣＯ3）やカリウム塩（ＫＨＣＯ3、Ｋ2ＣＯ3）等のアルカリ性の炭酸水素塩又は炭酸塩、或いは水酸化ナトリウム、水酸化カリウムなどのアルカリが利用可能である。 Examples of neutralizers include alkaline hydrogen carbonates or carbonates such as sodium salts (NaHCO 3 , Na 2 CO 3 ) and potassium salts (KHCO 3 , K 2 CO 3 ), sodium hydroxide, potassium hydroxide, and the like. Alkali is available.
上記アルカリの中でも特に、水酸化物を用いることが好ましい。水酸化物としては、水酸化ナトリウム、水酸化カリウム等を利用することが好ましい。この中でも、水酸化ナトリウムを使用することが特に好ましい。炭酸ナトリウムや炭酸水素ナトリウム等を使用した場合、中和により液量が増加するために処理量が増加して処理時間が長くなる場合があるが、中和剤として水酸化ナトリウムを用いることにより、炭酸ナトリウムや炭酸水素ナトリウム等を使用する場合に比べて中和に必要な薬液の量を低減することができるため、処理効率を向上させることができる。 Among the alkalis, it is particularly preferable to use a hydroxide. As the hydroxide, sodium hydroxide, potassium hydroxide or the like is preferably used. Among these, it is particularly preferable to use sodium hydroxide. When sodium carbonate or sodium hydrogen carbonate is used, the amount of liquid increases due to neutralization, so the treatment amount may increase and the treatment time may become longer, but by using sodium hydroxide as a neutralizing agent, Since the amount of the chemical solution required for neutralization can be reduced as compared with the case where sodium carbonate, sodium hydrogen carbonate, or the like is used, the processing efficiency can be improved.
中和工程では、中和剤の添加によりアルミニウム含有酸性溶液のｐＨを３．０〜７．５の範囲に調整する。ｐＨが３．０未満の場合には、アルミニウム含有酸性溶液中にアルミニウムの沈殿が生じず、アルミニウムの分離除去ができない場合がある。ｐＨが７．５より高い場合には、アルミニウム含有酸性溶液に例えばニッケルなどの他金属が存在する場合にはその他金属の析出が始まって析出物が多くなるため、後述する濾過工程における濾過時間が長期化し、残渣の取り扱いが困難になる。 In the neutralization step, the pH of the aluminum-containing acidic solution is adjusted to a range of 3.0 to 7.5 by adding a neutralizing agent. When pH is less than 3.0, precipitation of aluminum does not occur in the aluminum-containing acidic solution, and aluminum may not be separated and removed. When the pH is higher than 7.5, when other metals such as nickel are present in the aluminum-containing acidic solution, precipitation of other metals starts and the amount of precipitates increases. Prolonged and difficult to handle residue.
中和終了時のアルミニウム含有酸性溶液のｐＨは、４．０〜６．０がより好ましく、更に好ましくは５．０〜６．０である。中和工程では、アルミニウム含有酸性溶液を３０〜９０℃、より好ましくは５０〜８５℃で一定温度に加温しながら行うことが好ましい。 The pH of the aluminum-containing acidic solution at the end of neutralization is more preferably 4.0 to 6.0, still more preferably 5.0 to 6.0. In the neutralization step, the aluminum-containing acidic solution is preferably heated at a constant temperature of 30 to 90 ° C, more preferably 50 to 85 ° C.
中和工程では、アルミニウム含有酸性溶液を攪拌しながら行う。攪拌は添加するアルカリとアルミニウム含有酸性溶液とを十分混合するようにすることが好ましい。具体的には、アルミニウム含有酸性溶液を攪拌機により１００〜１０００ｒｐｍ、より具体的には２００〜５００ｒｐｍ程度で攪拌することが好ましい。攪拌速度が１００ｒｐｍよりも遅い場合、混合が十分でないということがある。攪拌速度が１０００ｒｐｍを超えると、液が飛散しロスが増える場合がある。 In the neutralization step, the aluminum-containing acidic solution is stirred. Stirring is preferably performed by sufficiently mixing the alkali to be added and the aluminum-containing acidic solution. Specifically, it is preferable to stir the aluminum-containing acidic solution with a stirrer at 100 to 1000 rpm, more specifically about 200 to 500 rpm. If the stirring speed is slower than 100 rpm, mixing may not be sufficient. If the stirring speed exceeds 1000 rpm, the liquid may scatter and loss may increase.
（３）濾過工程
濾過工程では、中和工程で得られたスラリー状の中和処理液を濾過することにより、中和処理液中に沈殿したリチウム・アルミニウム系複合水酸化物を含む濾過残渣と、濾過後液とに分離する。本実施形態では、上述した酸浸出工程において、リチウムに対するアルミニウムのモル比（Ａｌ／Ｌｉ比）が１．１以下となるような、リチウムが比較的過剰となるようなアルミニウム含有酸性溶液を処理している。このアルミニウム含有酸性溶液を用いることにより、２．０ｇ／Ｌ以上、より具体的には２．４ｇ／Ｌ以上のリチウムを含む濾過後液が得られるとともに、リチウムに対するアルミニウムのモル比（Ａｌ／Ｌｉ比）が３．５未満の濾過残渣が得られる。
(3) Filtration step In the filtration step, by filtering the slurry-like neutralization treatment liquid obtained in the neutralization step, a filtration residue containing lithium / aluminum composite hydroxide precipitated in the neutralization treatment solution; Then, it is separated into a liquid after filtration. In the present embodiment, in the acid leaching step described above, an aluminum-containing acidic solution in which lithium is relatively excessive is treated such that the molar ratio of aluminum to lithium (Al / Li ratio) is 1.1 or less. ing. By using this aluminum-containing acidic solution, a post-filtration liquid containing lithium of 2.0 g / L or more, more specifically 2.4 g / L or more is obtained, and the molar ratio of aluminum to lithium (Al / Li A filtration residue with a ratio) of less than 3.5 is obtained.
濾過残渣中のリチウムに対するアルミニウムのモル比（Ａｌ／Ｌｉ比）の下限値は特に制限されないが、リチウム・アルミニウム系複合水酸化物（［ＬｉＡｌ2（ＯＨ）6］+［Ｘ1/n n-・ｙＨ2Ｏ］- 、Ｘ1/n n-は層間の陰イオン）をより多く形成させて濾過性を向上させる目的を考慮すると、化学量論比から、その下限値は２程度である。また、濾過残渣中のＡｌ／Ｌｉ比は中和処理を終了するｐＨによって多少上下するが、ｐＨ３．０〜７．５で中和処理を終了する場合、残渣中のＡｌ／Ｌｉ比が３．５未満、より好ましくは３．４以下であれば濾過性が良好となる。 The lower limit of the molar ratio of aluminum to lithium (Al / Li ratio) in the filtration residue is not particularly limited, but lithium-aluminum composite hydroxide ([LiAl 2 (OH) 6 ] + [X 1 / n n− In consideration of the purpose of improving filterability by forming more anions (yH 2 O] − and X 1 / n n− ), the lower limit is about 2 from the stoichiometric ratio. Moreover, although the Al / Li ratio in the filtration residue slightly increases or decreases depending on the pH at which the neutralization treatment is finished, when the neutralization treatment is finished at pH 3.0 to 7.5, the Al / Li ratio in the residue is 3. If it is less than 5, more preferably 3.4 or less, the filterability will be good.
アルミニウム含有酸性溶液に浸出したアルミニウムは、［ＬｉＡｌ2（ＯＨ）6］+［Ｘ1/n n-・ｙＨ2Ｏ］-に加えて、Ａｌ（ＯＨ）3、ＬｉＡｌＯ2、ＬｉＡｌ2（ＯＨ）7等の沈殿物も含まれる。濾過工程は、中和工程と同様に加温しながら行ってもよいが、本実施形態では、加温せずに常温で行っても短時間で濾過処理を行うことができる。処理効率を鑑みれば、濾過工程は加温せずに行うことが好ましい。本実施形態に係る中和処理液は、中和工程の後に一定時間（数時間〜数日程度）中和処理液を加温せずに保持した後で濾過したとしても、十分良好な濾過性が得られる。 Aluminum leached in an aluminum-containing acidic solution is added to [LiAl 2 (OH) 6 ] + [X 1 / n n− · yH 2 O] − , Al (OH) 3 , LiAlO 2 , LiAl 2 (OH) 7 precipitates are also included. The filtration step may be performed while heating in the same manner as the neutralization step, but in the present embodiment, the filtration process can be performed in a short time even when performed at room temperature without heating. In view of processing efficiency, it is preferable to perform the filtration step without heating. The neutralization treatment liquid according to the present embodiment has sufficiently good filterability even if the neutralization treatment liquid is filtered for a certain period of time (several hours to several days) without being heated. Is obtained.
本実施形態に係るアルミニウム分離方法によれば、アルミニウム含有酸性溶液のＡｌ／Ｌｉ比を調整することにより、リチウムがアルミニウム含有酸性溶液中に一定濃度以上存在する条件下で、中和処理を実施し、且つ中和処理液中に一定濃度以上リチウムが残存するような条件で中和処理を終了させて、上述の濾過処理を行う。これにより、従来の中和処理で発生するＡｌ（ＯＨ）3等のゲル状の沈殿物が少なく、粉末に近い形態の沈殿物が得られるため、濾過に必要な時間が短時間化され、濾過性を向上できる。 According to the aluminum separation method according to the present embodiment, the neutralization treatment is performed under the condition that lithium is present in a certain concentration or more in the aluminum-containing acidic solution by adjusting the Al / Li ratio of the aluminum-containing acidic solution. In addition, the above-described filtration treatment is performed by terminating the neutralization treatment under conditions such that lithium remains in a certain concentration or more in the neutralization treatment solution. As a result, gel-like precipitates such as Al (OH) 3 generated in the conventional neutralization treatment are few, and precipitates in a form close to powder are obtained, so the time required for filtration is shortened and filtration is performed. Can be improved.
分離除去後のアルミニウム沈殿物は、ゲル状ではなく粉状であるため、濾過残渣の取り扱いが容易である。この濾過残渣を、自然乾燥するか、或いは例えば６０〜８０℃で加熱して水分を除去する（加熱乾燥）ことによって、白色粉状のリチウム・アルミニウム系複合水酸化物粉末が得られる。 Since the aluminum precipitate after separation and removal is in the form of a powder rather than a gel, it is easy to handle the filtration residue. The filtered residue is naturally dried or, for example, heated at 60 to 80 ° C. to remove moisture (heat drying), whereby white powdery lithium aluminum composite hydroxide powder is obtained.
このリチウム・アルミニウム系複合水酸化物をＳＥＭで観察した結果、図１に示すように、直径１〜２μｍ程度の薄片状を有する結晶の集合体が得られていることがわかる。以下に制限されるものではないが、この複合酸化物を容器に入れて保存することも可能であるし、例えば、リンなどを吸着させるための陰イオン吸着材等の他用途に利用することも可能であると考えられる。或いは、この複合化合物をその他の廃水処理プロセス中に利用する場合も考えられる。いずれにしても本実施形態によれば、資源の有効利用の観点からより効率的なアルミニウム含有酸性溶液からのアルミニウム分離方法が提供できる。 As a result of observing this lithium-aluminum-based composite hydroxide with an SEM, it can be seen that an aggregate of crystals having a flake shape with a diameter of about 1 to 2 μm is obtained as shown in FIG. Although not limited to the following, it is possible to store this composite oxide in a container, and for example, it can be used for other applications such as an anion adsorbent for adsorbing phosphorus and the like. It is considered possible. Alternatively, the composite compound may be used during other wastewater treatment processes. In any case, according to this embodiment, a more efficient method for separating aluminum from an aluminum-containing acidic solution can be provided from the viewpoint of effective use of resources.
以下に本発明の実施例を比較例と共に示すがこれらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。 EXAMPLES Examples of the present invention are shown below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
アルミニウム含有酸性溶液にリチウムを添加して、Ａｌ／Ｌｉ比が０．６〜２．２のアルミニウム含有酸性溶液（LotNo.１〜LotNo.６）を用意した。各アルミニウム含有酸性溶液のリチウム組成とアルミニウム含有酸性溶液のｐＨを表１に示す。このアルミニウム含有酸性溶液を８０℃に加温して、３００ｒｐｍで攪拌しながら、濃度２００ｇ／ＬのＮａＯＨ溶液を中和剤として添加し、アルミニウム含有酸性溶液のｐＨが５．０になった時点で中和処理を終了させ、中和処理液を得た。この中和処理液を濾過し、濾過後液と濾過残渣とに分離した。濾過後液の組成を表２に、残渣の組成を表３に示す。 Lithium was added to the aluminum-containing acidic solution to prepare an aluminum-containing acidic solution (Lot No. 1 to Lot No. 6) having an Al / Li ratio of 0.6 to 2.2. Table 1 shows the lithium composition of each aluminum-containing acidic solution and the pH of the aluminum-containing acidic solution. When this aluminum-containing acidic solution is heated to 80 ° C. and stirred at 300 rpm, a 200 g / L NaOH solution is added as a neutralizing agent, and when the pH of the aluminum-containing acidic solution reaches 5.0. The neutralization treatment was terminated, and a neutralization treatment solution was obtained. This neutralization treatment liquid was filtered, and separated into a post-filtration liquid and a filtration residue. Table 2 shows the composition of the liquid after filtration, and Table 3 shows the composition of the residue.
各サンプルに対する濾過特性を評価した。結果を表４に示す。 The filtration characteristics for each sample were evaluated. The results are shown in Table 4.
表１〜４に示すように、濾過残渣LotNo.３、４、６は、単位時間・単位面積あたりの濾過量が１００Ｌを超えており、他濾過残渣に比べて極めて短時間で濾過処理を行うことができた。 As shown in Tables 1 to 4, the filtration residue Lot No. 3, 4, 6 has a filtration amount per unit time / unit area of more than 100 L, and performs filtration in an extremely short time compared to other filtration residues. I was able to.
更に、LotNo.２とLotNo.４で得られた濾過残渣をそれぞれ６０℃で加熱して水分を蒸発乾固させたところいずれも白色粉状の処理物が得られた。更に、濾過残渣LotNo.２と、LotNo.４に対して、走査型電子顕微鏡（ＳＥＭ）で確認した結果を図１及び図２に示す。 Furthermore, when the filtration residue obtained by Lot No. 2 and Lot No. 4 was each heated at 60 degreeC and the water | moisture content was evaporated to dryness, all processed material of white powder form was obtained. Furthermore, the result confirmed with the scanning electron microscope (SEM) with respect to the filtration residue LotNo.2 and LotNo.4 is shown in FIG.1 and FIG.2.
LotNo.４では、直径１〜２μｍ程度の薄片状を有する結晶の集合体がみられたが、LotNo.２では、直径１μｍ未満の粒塊状の結晶の集合体がみられた。濾過残渣LotNo.２及びLotNo.４に対しＸ線回折解析（ＸＲＤ）で観察したところ、LotNo.４では、リチウム・アルミニウム系複合水酸化物（［ＬｉＡｌ2（ＯＨ）6］+［Ｘ1/n n-・ｙＨ2Ｏ］-、Ｘ1/n n-は層間の陰イオン）が生成されていることが分かったが、サンプルLotNo.２ではリチウム・アルミニウム系複合酸化物の生成はみられなかった。 In Lot No. 4, an aggregate of crystals having a flake shape having a diameter of about 1 to 2 μm was observed, but in Lot No. 2, an aggregate of crystal aggregates having a diameter of less than 1 μm was observed. When the filtration residues Lot No. 2 and Lot No. 4 were observed by X-ray diffraction analysis (XRD), in the case of Lot No. 4, lithium-aluminum composite hydroxide ([LiAl 2 (OH) 6 ] + [X 1 / n n− · yH 2 O] − , X 1 / n n− is an anion between the layers), but in the sample Lot No. 2, the formation of lithium / aluminum complex oxide was observed. There wasn't.
Claims (9)
を含むアルミニウム含有酸性溶液からのアルミニウム分離方法。 A lithium source is added to the aluminum-containing acidic solution, the molar ratio of aluminum to lithium (Al / Li ratio) in the aluminum-containing acidic solution is adjusted to 1.1 or less, and neutralization is performed by adding an alkali. Thus, precipitation of lithium / aluminum composite hydroxide is caused, followed by solid-liquid separation, whereby separation into a filtration residue containing lithium / aluminum composite hydroxide and a post-filtration liquid containing lithium is possible. A method for separating aluminum from an aluminum-containing acidic solution.
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