JP7578982B2 - Method for purifying iron(II) chloride - Google Patents
Method for purifying iron(II) chloride Download PDFInfo
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- JP7578982B2 JP7578982B2 JP2021087215A JP2021087215A JP7578982B2 JP 7578982 B2 JP7578982 B2 JP 7578982B2 JP 2021087215 A JP2021087215 A JP 2021087215A JP 2021087215 A JP2021087215 A JP 2021087215A JP 7578982 B2 JP7578982 B2 JP 7578982B2
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 title claims description 127
- 229910021577 Iron(II) chloride Inorganic materials 0.000 title claims description 101
- 238000000034 method Methods 0.000 title claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 77
- 239000013078 crystal Substances 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 60
- 238000001816 cooling Methods 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 24
- 229910052791 calcium Inorganic materials 0.000 description 24
- 239000011575 calcium Substances 0.000 description 24
- 238000011084 recovery Methods 0.000 description 21
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、塩化鉄（ＩＩ）の高純度化方法に関する。 The present invention relates to a method for highly purifying iron(II) chloride.
プリント配線板やＩＣ、ＬＳＩ用のリードフレームなどは、塩化鉄（ＩＩＩ）を含むエッチング液で部分的に腐食処理することにより製造されている。
エッチング処理によって、エッチング液に含まれる塩化鉄（ＩＩＩ）が還元されて塩化鉄（ＩＩ）になり、塩化鉄（ＩＩＩ）の濃度が低下してエッチング効率が悪くなるので、定期的にエッチング液の交換が行われている。
Printed wiring boards, ICs, lead frames for LSIs, etc. are manufactured by partially etching them with an etching solution containing iron (III) chloride.
During the etching process, the iron (III) chloride contained in the etching solution is reduced to iron (II) chloride, which reduces the concentration of iron (III) chloride and reduces the etching efficiency, so the etching solution is periodically replaced.
特許文献１～２には、塩化第一鉄溶液と塩酸とを混合し、塩化第一鉄を析出させる、塩化第一鉄の精製方法が記載されている。 Patent documents 1 and 2 describe a method for purifying ferrous chloride in which a ferrous chloride solution is mixed with hydrochloric acid to precipitate ferrous chloride.
エッチング処理後の廃液であるエッチング廃液は銅成分、ニッケル成分を多量に含んでいる。そこで鉄粉を加えることでイオン化傾向の差により銅粉、ニッケル粉を液中から取り出す還元処理がなされている。還元後の塩化鉄（ＩＩ）は酸化処理され、塩化鉄（ＩＩＩ）となり、エッチング液として再びリサイクルされるが、プロセス上、余剰に塩化鉄（ＩＩ）を含む溶液が生成され、廃棄されているのが現状である。 Etching waste liquid, which is the waste liquid after the etching process, contains large amounts of copper and nickel components. Therefore, a reduction process is carried out in which iron powder is added to remove the copper and nickel powder from the liquid due to the difference in ionization tendency. After reduction, iron chloride (II) is oxidized to iron chloride (III) and recycled again as an etching liquid, but due to the process, a solution containing surplus iron chloride (II) is produced and discarded.
廃棄される塩化鉄（ＩＩ）を含む溶液を再利用することができれば、資源の有効利用の観点、及び廃棄物の減少による環境負荷の低減の観点から望ましい。
しかしながら、還元処理工程において銅成分、ニッケル成分が除去されても完全に除去されるわけではなく、また、鉄粉を加えても還元されない成分も種々液中には含まれる。塩化鉄（ＩＩ）を含む溶液中の不純物成分としては、典型元素であるカルシウムや亜鉛、遷移元素である銅、ニッケル、マンガン、コバルト等が挙げられる。これらの不純物が含まれる結果、塩化鉄（ＩＩ）の純度が低いため、様々な用途（例えば、リン酸鉄リチウムイオンバッテリーの正極材料や顔料の原料など）に再利用することが難しいという問題があった。
If it were possible to reuse a discarded solution containing iron (II) chloride, it would be desirable from the standpoint of effective utilization of resources and reduction of the environmental burden due to a reduction in waste.
However, even if the copper and nickel components are removed in the reduction process, they are not completely removed, and various liquids contain components that are not reduced even when iron powder is added. Impurity components in solutions containing iron (II) chloride include typical elements such as calcium and zinc, and transition elements such as copper, nickel, manganese, and cobalt. As a result of the inclusion of these impurities, the purity of iron (II) chloride is low, and there is a problem that it is difficult to reuse it for various applications (for example, a positive electrode material for lithium iron phosphate batteries and a raw material for pigments).
本発明の課題は、塩化鉄（ＩＩ）の純度を高くすることができ、かつ回収率に優れる塩化鉄（ＩＩ）の高純度化方法を提供することにある。 The object of the present invention is to provide a method for purifying iron(II) chloride that can increase the purity of iron(II) chloride and has an excellent recovery rate.
上記課題は下記手段により達成することができる。
（１）
塩化鉄（ＩＩ）を含む溶液と塩酸と混合し、混合液を得る工程（Ａ）と、
前記混合液を冷却し、塩化鉄（ＩＩ）４水和物の結晶を得る工程（Ｂ）とを含み、
前記混合液中のＦｅＣｌ
２
に対するＨＣｌのモル比であるＨＣｌ／ＦｅＣｌ
２
が１．０以上であり、
前記工程（Ｂ）の冷却を冷却速度０．０１℃／分～１℃／分で行い、
前記工程（Ａ）の前に、前記工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液を５５℃以上９５℃以下に加温する工程を含む、
塩化鉄（ＩＩ）の高純度化方法。
（２）
前記混合液中のＦｅＣｌ
２
に対するＨＣｌのモル比であるＨＣｌ／ＦｅＣｌ
２
が１．０以上３．０以下である、（１）に記載の塩化鉄（ＩＩ）の高純度化方法。
（３）
前記工程（Ｂ）の冷却を冷却速度０．０１℃／分～０．１℃／分で行う、（１）又は（２）に記載の塩化鉄（ＩＩ）の高純度化方法。
（４）
前記工程（Ａ）で用いられる前記塩化鉄（ＩＩ）を含む溶液が、エッチング廃液に由来する溶液である、（１）～（３）のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
（５）
前記工程（Ｂ）の後に、固液分離工程を含む、（１）～（４）のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
（６）
前記工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液は、塩化鉄（ＩＩ）を３０質量％以上４９質量％未満含有する、（１）～（５）のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
（７）
前記工程（Ｂ）の冷却を行う前の前記混合液の温度が５０℃以上である、（１）～（６）のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
本発明は、上記（１）～（７）に係るものであるが、本明細書には参考のためその他の事項についても記載した。
〔１〕
塩化鉄（ＩＩ）を含む溶液と塩酸と混合し、混合液を得る工程（Ａ）と、
前記混合液を冷却し、塩化鉄（ＩＩ）４水和物の結晶を得る工程（Ｂ）とを含み、
前記混合液中のＦｅＣｌ２に対するＨＣｌのモル比であるＨＣｌ／ＦｅＣｌ２が１．０以上であり、
前記工程（Ｂ）の冷却を冷却速度０．０１℃／分～１℃／分で行う、
塩化鉄（ＩＩ）の高純度化方法。
〔２〕
前記混合液中のＦｅＣｌ２に対するＨＣｌのモル比であるＨＣｌ／ＦｅＣｌ２が１．０以上３．０以下である、〔１〕に記載の塩化鉄（ＩＩ）の高純度化方法。
〔３〕
前記工程（Ｂ）の冷却を冷却速度０．０１℃／分～０．１℃／分で行う、〔１〕又は〔２〕に記載の塩化鉄（ＩＩ）の高純度化方法。
〔４〕
前記工程（Ａ）で用いられる前記塩化鉄（ＩＩ）を含む溶液が、エッチング廃液に由来する溶液である、〔１〕～〔３〕のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
〔５〕
前記工程（Ｂ）の後に、固液分離工程を含む、〔１〕～〔４〕のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
〔６〕
前記工程（Ａ）の前に、前記工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液を５５℃以上９５℃以下に加温する工程を含む、〔１〕～〔５〕のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
〔７〕
前記工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液は、塩化鉄（ＩＩ）を３０質量％以上４９質量％未満含有する、〔１〕～〔６〕のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
〔８〕
前記工程（Ｂ）の冷却を行う前の前記混合液の温度が５０℃以上である、〔１〕～〔７〕のいずれか１つに記載の塩化鉄（ＩＩ）の高純度化方法。
The above object can be achieved by the following means.
(1)
A step (A) of mixing a solution containing iron (II) chloride with hydrochloric acid to obtain a mixed solution;
and (B) cooling the mixture to obtain crystals of iron(II) chloride tetrahydrate,
The molar ratio of HCl to FeCl 2 in the mixed solution is 1.0 or more ;
The cooling in the step (B) is carried out at a cooling rate of 0.01° C./min to 1° C./min;
The method includes, prior to the step (A), a step of heating a solution containing iron (II) chloride used in the step (A) to a temperature of 55° C. or higher and 95° C. or lower.
A method for purifying iron(II) chloride.
(2)
The method for highly purifying iron (II) chloride according to (1), wherein the molar ratio of HCl to FeCl2 in the mixed solution, HCl/FeCl2 , is 1.0 or more and 3.0 or less.
(3)
The method for highly purifying iron(II) chloride according to (1) or (2), wherein the cooling in the step (B) is carried out at a cooling rate of 0.01° C./min to 0.1° C./min.
(4)
The method for increasing the purity of iron(II) chloride according to any one of (1) to (3), wherein the solution containing iron(II) chloride used in the step (A) is a solution derived from an etching waste liquid.
(5)
The method for increasing the purification rate of iron(II) chloride according to any one of (1) to (4), further comprising a solid-liquid separation step after the step (B).
(6)
The method for increasing the purity of iron(II) chloride according to any one of (1) to (5), wherein the solution containing iron(II) chloride used in the step (A) contains 30% by mass or more and less than 49% by mass of iron(II) chloride.
(7)
The method for highly purifying iron(II) chloride according to any one of (1) to (6), wherein the temperature of the mixture before the cooling in the step (B) is 50° C. or higher.
The present invention relates to the above items (1) to (7), but other items are also described in this specification for reference.
[1]
A step (A) of mixing a solution containing iron (II) chloride with hydrochloric acid to obtain a mixed solution;
and (B) cooling the mixture to obtain crystals of iron(II) chloride tetrahydrate,
The molar ratio of HCl to FeCl 2 in the mixed solution is 1.0 or more ;
The cooling in step (B) is carried out at a cooling rate of 0.01° C./min to 1° C./min.
A method for purifying iron(II) chloride.
[2]
The method for purifying iron (II) chloride according to [1], wherein the molar ratio of HCl to FeCl 2 in the mixed solution, HCl/FeCl 2, is 1.0 or more and 3.0 or less.
[3]
The method for highly purifying iron(II) chloride according to [1] or [2], wherein the cooling in the step (B) is carried out at a cooling rate of 0.01° C./min to 0.1° C./min.
[4]
The method for increasing the purity of iron(II) chloride according to any one of [1] to [3], wherein the solution containing iron(II) chloride used in the step (A) is a solution derived from an etching waste liquid.
[5]
The method for increasing the purification rate of iron(II) chloride according to any one of [1] to [4], further comprising a solid-liquid separation step after the step (B).
[6]
The method for increasing the purity of iron(II) chloride according to any one of [1] to [5], further comprising a step of heating a solution containing iron(II) chloride used in the step (A) to a temperature of 55° C. or higher and 95° C. or lower prior to the step (A).
[7]
The method for increasing the purity of iron(II) chloride according to any one of [1] to [6], wherein the solution containing iron(II) chloride used in the step (A) contains 30% by mass or more and less than 49% by mass of iron(II) chloride.
[8]
The method for increasing the purification rate of iron(II) chloride according to any one of [1] to [7], wherein the temperature of the mixture before the cooling in the step (B) is 50° C. or higher.
本発明によれば、塩化鉄（ＩＩ）の純度を高くすることができ、かつ回収率に優れる塩化鉄（ＩＩ）の高純度化方法を提供することにある。 The present invention provides a method for purifying iron(II) chloride that can increase the purity of iron(II) chloride and has an excellent recovery rate.
本発明の塩化鉄（ＩＩ）の高純度化方法は、
塩化鉄（ＩＩ）を含む溶液と塩酸と混合し、混合液を得る工程（Ａ）と、
前記混合液を冷却し、塩化鉄（ＩＩ）４水和物の結晶を得る工程（Ｂ）とを含み、
前記混合液中のＦｅＣｌ２に対するＨＣｌのモル比であるＨＣｌ／ＦｅＣｌ２が１．０以上であり、
前記工程（Ｂ）の冷却を冷却速度０．０１℃／分～１℃／分で行う、
塩化鉄（ＩＩ）の高純度化方法である。
The method for highly purifying iron(II) chloride of the present invention comprises the steps of:
A step (A) of mixing a solution containing iron (II) chloride with hydrochloric acid to obtain a mixed solution;
and (B) cooling the mixture to obtain crystals of iron(II) chloride tetrahydrate,
The molar ratio of HCl to FeCl 2 in the mixed solution is 1.0 or more ;
The cooling in step (B) is carried out at a cooling rate of 0.01° C./min to 1° C./min.
This is a method for highly purifying iron(II) chloride.
［工程（Ａ）］
工程（Ａ）は、塩化鉄（ＩＩ）を含む溶液と塩酸と混合し、混合液を得る工程である。
工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液は、塩化鉄（ＩＩ）を含む水溶液であることが好ましく、エッチング廃液に由来する溶液であることがより好ましい。エッチング廃液に由来する溶液とは、エッチング廃液又はエッチング廃液に対して何らかの処理（例えば酸化処理や還元処理）を行った後の溶液である。エッチング廃液に由来する溶液は通常は鉄以外の金属などの不純物を含有しており、本発明の方法を適用した際に本発明の効果が顕著に現れる。
工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液は、鉄以外の金属を含むものであることが好ましく、カルシウム、亜鉛、マンガン、コバルト、銅、ニッケルの少なくとも１種を含むものであることがより好ましく、カルシウム及びマンガンの少なくとも１種を含むことが更に好ましい。
工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液は、例えば、塩化鉄（ＩＩ）を１０～５０質量％、カルシウムを１００～３０００ｐｐｍ、マンガンを１００～３０００ｐｐｍ含むものであってもよい。「ｐｐｍ」は「ｐａｒｔｓ ｐｅｒ ｍｉｌｌｉｏｎ」の略であり、質量基準（「質量ｐｐｍ」）である。
[Step (A)]
Step (A) is a step of mixing a solution containing iron (II) chloride with hydrochloric acid to obtain a mixed solution.
The solution containing iron(II) chloride used in step (A) is preferably an aqueous solution containing iron(II) chloride, and more preferably a solution derived from etching waste liquid. The solution derived from etching waste liquid is a solution obtained by subjecting etching waste liquid or etching waste liquid to some treatment (e.g., oxidation treatment or reduction treatment). The solution derived from etching waste liquid usually contains impurities such as metals other than iron, and the effect of the present invention is remarkable when the method of the present invention is applied.
The solution containing iron(II) chloride used in step (A) preferably contains a metal other than iron, more preferably contains at least one of calcium, zinc, manganese, cobalt, copper, and nickel, and even more preferably contains at least one of calcium and manganese.
The solution containing iron(II) chloride used in step (A) may contain, for example, 10 to 50 mass% iron(II) chloride, 100 to 3000 ppm calcium, and 100 to 3000 ppm manganese. "ppm" is an abbreviation for "parts per million" and is based on mass ("ppm by mass").
工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液は、塩化鉄（ＩＩ）を３０質量％以上４９質量％未満含有することが好ましく、３０質量％以上４５質量％以下含有することがより好ましく、３０質量％以上４０質量％以下含有することが更に好ましく、３０質量％以上４０質量％未満含有することが特に好ましい。 The solution containing iron(II) chloride used in step (A) preferably contains 30% by mass or more and less than 49% by mass of iron(II) chloride, more preferably 30% by mass or more and less than 45% by mass, even more preferably 30% by mass or more and less than 40% by mass, and particularly preferably 30% by mass or more and less than 40% by mass.
工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液の塩化鉄（ＩＩ）の含有率が３０質量％以上であると、工程（Ｂ）で得られる結晶について、下記式で定義される回収率が高くなり好ましい。
回収率（％）＝１００×［得られた結晶の質量（ｇ）／｛用いた塩化鉄（ＩＩ）水溶液の質量（ｇ）＋用いた塩酸の質量（ｇ）｝］
When the iron(II) chloride content of the solution containing iron(II) chloride used in step (A) is 30 mass% or more, the recovery rate of the crystals obtained in step (B) is high as defined by the following formula, which is preferable.
Recovery rate (%) = 100 x [mass of crystals obtained (g) / {mass of aqueous iron(II) chloride solution used (g) + mass of hydrochloric acid used (g)}]
工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液の塩化鉄（ＩＩ）の含有率が４９質量％未満であると、工程（Ｂ）で得られる結晶の塩化鉄（ＩＩ）の純度が高くなり好ましい。 If the iron(II) chloride content of the solution containing iron(II) chloride used in step (A) is less than 49% by mass, the purity of the iron(II) chloride crystals obtained in step (B) will be high, which is preferable.
工程（Ａ）で、塩化鉄（ＩＩ）を含む溶液と塩酸と混合して得られた混合液の温度（工程（Ｂ）の冷却を行う前の混合液の温度）は特に限定されないが、５０℃以上であることが好ましく、６０℃以上であることがより好ましい。混合液の温度が上記範囲になるように、塩化鉄（ＩＩ）を含む溶液をあらかじめ加温させておくことが好ましい。これは、工程（Ｂ）で得られる結晶の純度を高くするためには、工程（Ｂ）で混合液を徐冷して、結晶をゆっくり析出させることが重要であるためである。また、工程（Ｂ）の冷却を行う前の混合液の温度は例えば７５℃未満とすることができる。
加温手段は特に限定されず、公知の加温手段を用いることができる。
例えば、塩化鉄（ＩＩ）を含む溶液を５５℃以上９５℃以下に加温することが好ましく、７５℃以上９５℃以下に加温することがより好ましく、８０℃以上９０℃以下に加温することが更に好ましい。
The temperature of the mixture obtained by mixing the solution containing iron (II) chloride and hydrochloric acid in step (A) (the temperature of the mixture before cooling in step (B)) is not particularly limited, but is preferably 50° C. or higher, more preferably 60° C. or higher. It is preferable to preheat the solution containing iron (II) chloride so that the temperature of the mixture is within the above range. This is because, in order to increase the purity of the crystals obtained in step (B), it is important to slowly cool the mixture in step (B) to slowly precipitate the crystals. In addition, the temperature of the mixture before cooling in step (B) can be, for example, less than 75° C.
The heating means is not particularly limited, and any known heating means can be used.
For example, the solution containing iron(II) chloride is preferably heated to 55°C or higher and 95°C or lower, more preferably 75°C or higher and 95°C or lower, and even more preferably 80°C or higher and 90°C or lower.
工程（Ａ）で用いられる塩酸の濃度は、３０質量％以上であることが好ましい。 The concentration of hydrochloric acid used in step (A) is preferably 30% by mass or more.
工程（Ａ）で得られる混合液中のＦｅＣｌ２に対するＨＣｌのモル比（ＨＣｌ／ＦｅＣｌ２）は１．０以上であり、１．０以上３．０以下であることが好ましい。 The molar ratio of HCl to FeCl 2 (HCl/FeCl 2 ) in the mixed liquid obtained in step (A) is 1.0 or more, and preferably 1.0 or more and 3.0 or less.
［工程（Ｂ）］
工程（Ｂ）は、工程（Ａ）で得られた混合液を冷却し、塩化鉄（ＩＩ）４水和物の結晶を得る工程である。
[Step (B)]
Step (B) is a step of cooling the mixed liquid obtained in step (A) to obtain crystals of iron(II) chloride tetrahydrate.
工程（Ｂ）を行うことで、通常は、塩化鉄（ＩＩ）４水和物の結晶と残液とのスラリーが得られる。塩化鉄（ＩＩ）を結晶化させることで、不純物を残液側に追い出すことができ、塩化鉄（ＩＩ）の純度を高くすることができる。 By carrying out step (B), a slurry of iron(II) chloride tetrahydrate crystals and residual liquid is usually obtained. By crystallizing iron(II) chloride, impurities can be expelled to the residual liquid, and the purity of iron(II) chloride can be increased.
工程（Ｂ）の冷却は、混合液の温度が５℃～３０℃になるまで行うことが好ましく、１０℃～２０℃になるまで行うことがより好ましい。冷却は公知の手段を用いて行うことができる。 The cooling in step (B) is preferably carried out until the temperature of the mixture reaches 5°C to 30°C, and more preferably 10°C to 20°C. Cooling can be carried out using known means.
工程（Ｂ）の冷却を冷却速度０．０１℃／分～１℃／分で行うことが好ましく、冷却速度０．０１℃／分～０．１℃／分で行うことがより好ましい。
工程（Ｂ）の冷却速度を上記範囲にすることで、得られる結晶中に不純物として存在する遷移元素（例えば、マンガン、コバルト、ニッケル等）の量を低減させることができ、塩化鉄（ＩＩ）の純度を高くすることができるため好ましい。
The cooling in step (B) is preferably carried out at a cooling rate of 0.01° C./min to 1° C./min, and more preferably at a cooling rate of 0.01° C./min to 0.1° C./min.
By setting the cooling rate in step (B) within the above range, the amount of transition elements (e.g., manganese, cobalt, nickel, etc.) present as impurities in the obtained crystals can be reduced, and the purity of iron(II) chloride can be increased, which is preferable.
［その他の工程］
本発明の塩化鉄（ＩＩ）の高純度化方法は、前述の工程（Ａ）と工程（Ｂ）に加え、更にその他の工程を含むことができる。
その他の工程は特に限定されないが、本発明の塩化鉄（ＩＩ）の高純度化方法は、工程（Ｂ）の後に固液分離工程を含むことが好ましい。
固液分離工程は、工程（Ｂ）を経て得られた結晶と残液を分離する工程である。固液分離は公知の手段（例えば、遠心分離機や濾過機）を用いて行うことができる。
[Other steps]
The method for highly purifying iron (II) chloride of the present invention can further include other steps in addition to the above-mentioned steps (A) and (B).
The other steps are not particularly limited, but the method for highly purifying iron(II) chloride of the present invention preferably includes a solid-liquid separation step after step (B).
The solid-liquid separation step is a step of separating the crystals obtained through step (B) from the residual liquid. The solid-liquid separation can be carried out by using a known means (e.g., a centrifuge or a filter).
また、本発明の塩化鉄（ＩＩ）の高純度化方法は、工程（Ａ）の前に、工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液を加温する工程を含むことができる。
工程（Ａ）で、塩化鉄（ＩＩ）を含む溶液と塩酸と混合して得られた混合液の温度（工程（Ｂ）の冷却を行う前の混合液の温度）が５０℃以上になるように、塩化鉄（ＩＩ）を含む溶液を加温することが好ましく、６０℃以上になるように、塩化鉄（ＩＩ）を含む溶液を加温することがより好ましい。また、工程（Ｂ）の冷却を行う前の混合液の温度を例えば７５℃未満になるように加温することができる。
例えば、塩化鉄（ＩＩ）を含む溶液を７５℃以上９５℃以下に加温することが好ましく、８０℃以上９０℃以下に加温することがより好ましい。
Furthermore, the method for highly purifying iron (II) chloride of the present invention may include, prior to step (A), a step of heating the solution containing iron (II) chloride to be used in step (A).
In step (A), the solution containing iron(II) chloride is preferably heated so that the temperature of the mixed solution obtained by mixing the solution containing iron(II) chloride with hydrochloric acid (the temperature of the mixed solution before cooling in step (B)) becomes 50° C. or higher, and more preferably the solution containing iron(II) chloride is heated so that the temperature becomes 60° C. or higher. In addition, the mixed solution before cooling in step (B) can be heated, for example, to less than 75° C.
For example, the solution containing iron(II) chloride is preferably heated to 75° C. or higher and 95° C. or lower, and more preferably to 80° C. or higher and 90° C. or lower.
以下、本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
実施例及び比較例で使用した塩化鉄（ＩＩ）水溶液Ａ～Ｆは、下記表１に示す成分を表１に示す含有量で含む塩化鉄（ＩＩ）水溶液である。 The iron(II) chloride aqueous solutions A to F used in the examples and comparative examples are iron(II) chloride aqueous solutions containing the components shown in Table 1 below in the amounts shown in Table 1.
（実施例１）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ａ１００ｇと３５質量％塩酸５０ｇをビーカーに入れ、６０℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比１．５０）。混合液をプログラム冷却装置（水槽中の温度をプログラム制御できる装置）に入れ、０．０５℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。カルシウム及びマンガンの除去率が高いと、相対的に塩化鉄（ＩＩ）の純度が高くなるため、高純度化の効果が優れる。
Example 1
100g of aqueous iron (II) chloride solution A heated to 80°C and 50g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 60°C (HCl/FeCl 2 molar ratio 1.50). The mixed solution was placed in a program cooling device (a device capable of programmatically controlling the temperature in a water bath) and cooled at a rate of 0.05°C/min until it reached 20°C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). The content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate are shown in Table 3. When the removal rate of calcium and manganese is high, the purity of iron (II) chloride is relatively high, and therefore the effect of high purification is excellent.
回収率（％）＝１００×［得られた結晶の質量（ｇ）／｛用いた塩化鉄（ＩＩ）水溶液の質量（ｇ）＋用いた塩酸の質量（ｇ）｝］ Recovery rate (%) = 100 x [mass of crystals obtained (g) / {mass of iron(II) chloride solution used (g) + mass of hydrochloric acid used (g)}]
除去率（％）＝１００×［（用いた塩化鉄（ＩＩ）水溶液中の不純物量（ｐｐｍ）－結晶溶解後の不純物量（ｐｐｍ）（※））／用いた塩化鉄（ＩＩ）水溶液中の不純物量（ｐｐｍ）］
※用いた塩化鉄（ＩＩ）水溶液のＦｅ濃度になるよう結晶を溶解、希釈させた際の不純物量
Removal rate (%) = 100 x [(amount of impurities (ppm) in the iron (II) chloride aqueous solution used) - amount of impurities (ppm) after dissolving the crystals (*)) / amount of impurities (ppm) in the iron (II) chloride aqueous solution used]
* The amount of impurities when the crystals were dissolved and diluted to match the Fe concentration of the iron (II) chloride solution used
（実施例２）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ａ１００ｇと３５質量％塩酸９９ｇをビーカーに入れ、５２℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比３．００）。混合液をプログラム冷却装置に入れ、０．０１℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
Example 2
100 g of aqueous iron (II) chloride solution A heated to 80° C. and 99 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 52° C. (HCl/FeCl 2 molar ratio 3.00). The mixed solution was placed in a program cooling device and cooled at a rate of 0.01° C./min until it reached 20° C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（実施例３）
５５℃に加温された塩化鉄（ＩＩ）水溶液Ｂ１００ｇと３５質量％塩酸３８ｇをビーカーに入れ、６２℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比１．５０）。混合液をプログラム冷却装置に入れ、０．０５℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
Example 3
100 g of aqueous iron (II) chloride solution B heated to 55° C. and 38 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 62° C. (HCl/FeCl 2 molar ratio 1.50). The mixed solution was placed in a program cooling device and cooled at a rate of 0.05° C./min until it reached 20° C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（実施例４）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ｂ１００ｇと３５質量％塩酸７４ｇをビーカーに入れ、５１℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比３．００）。混合液をプログラム冷却装置に入れ、０．０１℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
Example 4
100 g of aqueous iron (II) chloride solution B heated to 80° C. and 74 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 51° C. (HCl/FeCl 2 molar ratio 3.00). The mixed solution was placed in a program cooling device and cooled at a rate of 0.01° C./min until it reached 20° C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（実施例５）
９５℃に加温された塩化鉄（ＩＩ）水溶液Ｃ１００ｇと３５％塩酸１１０ｇをビーカーに入れ、５４℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比３．００）。混合液をプログラム冷却装置に入れ、０．１℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
Example 5
100 g of aqueous iron (II) chloride solution C heated to 95°C and 110 g of 35% hydrochloric acid were placed in a beaker to obtain a mixed solution at 54°C (HCl/FeCl 2 molar ratio 3.00). The mixed solution was placed in a programmable cooling device and cooled at a rate of 0.1°C/min until it reached 20°C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). The content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate are shown in Table 3.
（実施例６）
９０℃に加温された塩化鉄（ＩＩ）水溶液Ｃ１００ｇと３５質量％塩酸３７ｇをビーカーに入れ、７０℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比１．００）。混合液をプログラム冷却装置に入れ、０．０１℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
Example 6
100 g of aqueous iron (II) chloride solution C heated to 90 ° C and 37 g of 35 mass% hydrochloric acid were placed in a beaker to obtain a mixed solution at 70 ° C (HCl / FeCl 2 molar ratio 1.00). The mixed solution was placed in a program cooling device and cooled at a rate of 0.01 ° C / min until it reached 20 ° C. After cooling, the obtained slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). The content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate are shown in Table 3.
（実施例７）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ａ１００ｇと３５質量％塩酸５０ｇをビーカーに入れ、６２℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比１．５０）。混合液をプログラム冷却装置に入れ、１℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
(Example 7)
100 g of aqueous iron (II) chloride solution A heated to 80° C. and 50 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 62° C. (HCl/FeCl 2 molar ratio 1.50). The mixed solution was placed in a program cooling device and cooled at a rate of 1° C./min until it reached 20° C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（実施例８）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ｆ１００ｇと３５質量％塩酸５０ｇをビーカーに入れ、６０℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比１．５０）。混合液をプログラム冷却装置（水槽中の温度をプログラム制御できる装置）に入れ、０．０５℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
(Example 8)
100 g of aqueous iron (II) chloride solution F heated to 80 ° C. and 50 g of 35 mass% hydrochloric acid were placed in a beaker to obtain a mixed solution at 60 ° C. (HCl / FeCl 2 molar ratio 1.50). The mixed solution was placed in a program cooling device (a device that can programmatically control the temperature in a water tank) and cooled at a rate of 0.05 ° C. / min until it reached 20 ° C. After cooling, the obtained slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（比較例１）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ａ１００ｇと３５質量％塩酸５０ｇをビーカーに入れ、６２℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比１．５０）。混合液を恒温槽に入れ、３℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
(Comparative Example 1)
100 g of aqueous iron (II) chloride solution A heated to 80° C. and 50 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 62° C. (HCl/FeCl 2 molar ratio 1.50). The mixed solution was placed in a thermostatic bath and cooled at a rate of 3° C./min until it reached 20° C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（比較例２）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ａ１００ｇと３５質量％塩酸２０ｇをビーカーに入れ、７１℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比０．２０）。混合液をプログラム冷却装置に入れ、０．０５℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
(Comparative Example 2)
100 g of aqueous iron (II) chloride solution A heated to 80° C. and 20 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 71° C. (HCl/FeCl 2 molar ratio 0.20). The mixed solution was placed in a program cooling device and cooled at a rate of 0.05° C./min until it reached 20° C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（比較例３）
９０℃に加温された塩化鉄（ＩＩ）水溶液Ｄ１００ｇと３５質量％塩酸５０ｇをビーカーに入れ、６９℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比０．２１）。混合液を恒温槽に入れ、３℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
(Comparative Example 3)
100 g of aqueous iron (II) chloride solution D heated to 90 ° C. and 50 g of 35 mass% hydrochloric acid were placed in a beaker to obtain a mixed solution at 69 ° C. (HCl / FeCl 2 molar ratio 0.21). The mixed solution was placed in a thermostatic bath and cooled at a rate of 3 ° C. / min until it reached 20 ° C. After cooling, the obtained slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（比較例４）
５０℃に加温された塩化鉄（ＩＩ）水溶液Ｅ１００ｇと３５質量％塩酸１５ｇをビーカーに入れ、４５℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比０．９０）。混合液を恒温槽に入れ、３℃／分の速度で２０℃に達するまで冷却を行った。しかしながら結晶は得られなかった。
(Comparative Example 4)
100 g of aqueous iron (II) chloride solution E heated to 50° C. and 15 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 45° C. (HCl/FeCl 2 molar ratio: 0.90). The mixed solution was placed in a thermostatic bath and cooled at a rate of 3° C./min until it reached 20° C. However, no crystals were obtained.
（比較例５）
５０℃に加温された塩化鉄（ＩＩ）水溶液Ｅ１００ｇと３５質量％塩酸６５ｇをビーカーに入れ、４０℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比４．００）。混合液を恒温槽に入れ、３℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
(Comparative Example 5)
100g of aqueous iron(II) chloride solution E heated to 50°C and 65g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 40°C (HCl/FeCl 2 molar ratio 4.00). The mixed solution was placed in a thermostatic bath and cooled at a rate of 3°C/min until it reached 20°C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron(II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
（比較例６）
８０℃に加温された塩化鉄（ＩＩ）水溶液Ａ１００ｇと３５質量％塩酸５０ｇをビーカーに入れ、６２℃の混合液とした（ＨＣｌ／ＦｅＣｌ２モル比１．５０）。混合液をプログラム冷却装置に入れ、０．００５℃／分の速度で２０℃に達するまで冷却を行った。冷却後、得られたスラリーを遠心分離機にかけて結晶（塩化鉄（ＩＩ）４水和物の結晶）を回収した。得られた結晶中の各成分の含有率、カルシウム及びマンガンの除去率、並びに回収率を表３に示す。
(Comparative Example 6)
100 g of aqueous iron (II) chloride solution A heated to 80° C. and 50 g of 35% by mass hydrochloric acid were placed in a beaker to obtain a mixed solution at 62° C. (HCl/FeCl 2 molar ratio 1.50). The mixed solution was placed in a program cooling device and cooled at a rate of 0.005° C./min until it reached 20° C. After cooling, the resulting slurry was centrifuged to recover crystals (crystals of iron (II) chloride tetrahydrate). Table 3 shows the content of each component in the obtained crystals, the removal rate of calcium and manganese, and the recovery rate.
実施例１～８、比較例１～６のＨＣｌ／ＦｅＣｌ２モル比と冷却速度を下記表２にまとめた。 The HCl/FeCl 2 molar ratios and cooling rates for Examples 1 to 8 and Comparative Examples 1 to 6 are summarized in Table 2 below.
実施例１～８は、回収率が高く、かつカルシウムとマンガンの除去率が高いため、塩化鉄（ＩＩ）の高純度化の効果が高かった。比較例１は結晶中のマンガンの除去率が低く、塩化鉄（ＩＩ）の純度が低かった。比較例２は結晶中のカルシウムの除去率が低く、塩化鉄（ＩＩ）の純度が低かった。比較例３は結晶中のカルシウムとマンガンの除去率が低く、塩化鉄（ＩＩ）の純度が低かった。比較例５は結晶中のカルシウムとマンガンの除去率が高いが、これは使用した塩化鉄（ＩＩ）水溶液中のカルシウムとマンガンの含有率が低かったためである。比較例５の回収率は低く、残液量も多くなるため実用に適したものではなかった。また、比較例６は冷却速度を実施例よりも遅くしたものであるが、回収率や、カルシウムとマンガンの除去率については実施例の結果以上の効果が得られないものであり、冷却に時間がかかってしまうため非効率的であった。
In Examples 1 to 8, the recovery rate was high, and the removal rates of calcium and manganese were high, so the effect of purifying iron chloride (II) was high. In Comparative Example 1, the removal rate of manganese in the crystals was low, and the purity of iron chloride (II) was low. In Comparative Example 2, the removal rate of calcium in the crystals was low, and the purity of iron chloride (II) was low. In Comparative Example 3, the removal rate of calcium and manganese in the crystals was low, and the purity of iron chloride (II) was low. In Comparative Example 5, the removal rate of calcium and manganese in the crystals was high, but this was because the contents of calcium and manganese in the aqueous iron chloride (II) solution used were low. In Comparative Example 5, the recovery rate was low and the amount of residual liquid was large, so it was not suitable for practical use. In Comparative Example 6, the cooling rate was slower than in the Examples, but the recovery rate and the removal rate of calcium and manganese were not more effective than those in the Examples, and it was inefficient because it took a long time to cool.
Claims (7)
前記混合液を冷却し、塩化鉄（ＩＩ）４水和物の結晶を得る工程（Ｂ）とを含み、
前記混合液中のＦｅＣｌ２に対するＨＣｌのモル比であるＨＣｌ／ＦｅＣｌ２が１．０以上であり、
前記工程（Ｂ）の冷却を冷却速度０．０１℃／分～１℃／分で行い、
前記工程（Ａ）の前に、前記工程（Ａ）で用いられる塩化鉄（ＩＩ）を含む溶液を５５℃以上９５℃以下に加温する工程を含む、
塩化鉄（ＩＩ）の高純度化方法。 A step (A) of mixing a solution containing iron (II) chloride with hydrochloric acid to obtain a mixed solution;
and (B) cooling the mixture to obtain crystals of iron(II) chloride tetrahydrate,
The molar ratio of HCl to FeCl 2 in the mixed solution is 1.0 or more ;
The cooling in the step (B) is carried out at a cooling rate of 0.01° C./min to 1° C./min;
The method includes, prior to the step (A), a step of heating a solution containing iron (II) chloride used in the step (A) to a temperature of 55° C. or higher and 95° C. or lower.
A method for purifying iron(II) chloride.
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