JPH02124721A - Production of chromium chloride - Google Patents
Production of chromium chlorideInfo
- Publication number
- JPH02124721A JPH02124721A JP27576188A JP27576188A JPH02124721A JP H02124721 A JPH02124721 A JP H02124721A JP 27576188 A JP27576188 A JP 27576188A JP 27576188 A JP27576188 A JP 27576188A JP H02124721 A JPH02124721 A JP H02124721A
- Authority
- JP
- Japan
- Prior art keywords
- chromium chloride
- iron ions
- solution
- extraction
- trialkylphosphine oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021555 Chromium Chloride Inorganic materials 0.000 title claims abstract description 45
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052742 iron Inorganic materials 0.000 claims abstract description 55
- -1 iron ions Chemical class 0.000 claims abstract description 48
- 238000000605 extraction Methods 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 7
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910000604 Ferrochrome Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 4
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical group CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/04—Chromium halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、塩化クロムの製造法に関し、更に詳しくは鉄
イオンを実質的に含有しない高純度塩化クロム水溶液の
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing chromium chloride, and more particularly to a method for producing a high-purity aqueous chromium chloride solution containing substantially no iron ions.
〔従来の技術］
従来、塩化クロムの製造方法としてはクロム鉱石をアル
カリ酸化焙焼して得た重クロム酸ソーダ溶液に硫酸を加
え、有機物で還元して硫酸クロム溶液とし、これに苛性
ソーダまたはソーダ灰を加えて水酸化クロムまたは炭酸
クロムの沈澱を造り、濾過、水洗した後、塩酸を加えて
溶解する方法が採用されていた。[Prior art] Conventionally, chromium chloride was produced by adding sulfuric acid to a sodium dichromate solution obtained by roasting chromium ore with alkali oxidation, reducing it with an organic substance to obtain a chromium sulfate solution, and adding caustic soda or soda to this solution. The method used was to add ash to form a precipitate of chromium hydroxide or chromium carbonate, filter it, wash it with water, and then add hydrochloric acid to dissolve it.
また、クロム鉱石を炭酸還元剤を用いて電気炉で還元し
て得た高炭素フエロクロムを硫酸で抽出処理し、この溶
液を電気分解して金属クロムとし、金属クロムに塩酸を
加えて塩化クロムを製造する方法、あるいはクロム鉱石
を炭素還元剤を用いて電気炉で還元して得た高炭素フエ
ロクロムを塩酸に溶解し、この溶解抽出液にアミンまた
はメチルイソブチレン等の有機溶媒と接触させて抽出液
中の鉄分を抽出分離して塩化クロムを製造する方法も知
られている（特開昭６２−７８１１７号公報）。In addition, high carbon ferrochrome obtained by reducing chromium ore in an electric furnace using a carbonic acid reducing agent is extracted with sulfuric acid, this solution is electrolyzed to produce metallic chromium, and hydrochloric acid is added to metallic chromium to produce chromium chloride. Alternatively, high carbon ferrochrome obtained by reducing chromium ore in an electric furnace using a carbon reducing agent is dissolved in hydrochloric acid, and this dissolved extract is brought into contact with an organic solvent such as amine or methyl isobutylene to produce an extract. A method for producing chromium chloride by extracting and separating the iron content is also known (Japanese Patent Application Laid-open No. 78117/1983).
これら従来法のうち、水酸化クロムまたは炭酸クロムを
塩酸で溶解する方法は、硫酸クロムに苛性ソーダまたは
ソーダ灰を加えて得た水酸化クロム沈澱または炭酸クロ
ム沈澱の水洗が大変難しく、水酸化クロムまたは炭酸ク
ロム中のナトリウムまたは硫酸塩等の不純物を除くこと
ができず、高純度の塩化クロムｉ８ ？＆が得られにく
い。Among these conventional methods, the method of dissolving chromium hydroxide or chromium carbonate with hydrochloric acid is very difficult to wash the chromium hydroxide precipitate or chromium carbonate precipitate obtained by adding caustic soda or soda ash to chromium sulfate. Impurities such as sodium or sulfate in chromium carbonate cannot be removed, resulting in high purity chromium chloride i8? & is difficult to obtain.
また、裔炭素フェロクロムを硫酸で処理する方法は、分
離する際には鉄台を物の処理量は多くなり、無害化処理
など多大の費用を要する欠点がある。In addition, the method of treating ferrochrome ferrochrome with sulfuric acid has the disadvantage that a large amount of iron pedestals must be processed during separation, and a large amount of cost is required for detoxification treatment.
また、高炭素フエロクロムを硫酸で処理し、ＭＩＢＫで
鉄分を抽出する方法は、この抽出剤のみでは、鉄分をは
じめ他の不純金属イオンの除去が不充分なため、更に陽
イオン交換樹脂で処理することを必要としている。In addition, in the method of treating high carbon ferrochrome with sulfuric acid and extracting iron with MIBK, this extractant alone is insufficient to remove iron and other impurity metal ions, so it must be further treated with a cation exchange resin. I need that.
このようなことから、本出願人は先に、クロム酸？８液
に塩酸及びクロム酸と反応して完全に炭酸ガスと水に分
解しうる有機還元剤とを反応させる方法により高純度塩
化クロムの製造を開発した（特願昭６２−３３３６４７
号）。Based on this, the applicant first decided to use chromic acid? Developed the production of high-purity chromium chloride by reacting 8 liquids with hydrochloric acid and chromic acid and an organic reducing agent that can be completely decomposed into carbon dioxide gas and water (Patent Application No. 62-333647)
issue).
しかし、この方法も、主として原料のクロム酸液の純度
に左右されることから、原料やその後の工程において混
入した鉄イオンの除去法については解決されない。However, this method also mainly depends on the purity of the raw chromic acid solution, and therefore does not solve the problem of removing iron ions mixed into the raw material or in subsequent steps.
近時、塩化クロム溶液がレドックス・フロー形電池の負
極液として注目されているが、その用途に適用する塩化
クロム溶液にあっては、特に鉄イオンの存在は電池の使
用効率を著しく低下させるために実質的に避けなければ
ならない。Recently, chromium chloride solutions have been attracting attention as negative electrode fluids for redox flow batteries, but the presence of iron ions in chromium chloride solutions used for this purpose, in particular, significantly reduces battery usage efficiency. must be substantially avoided.
本発明は、これらの欠点を解消し、不純物特に鉄イオン
が極めて少ない高純度塩化クロム溶液の工業的な製造法
を提供することを目的とする。The object of the present invention is to eliminate these drawbacks and provide an industrial method for producing a high purity chromium chloride solution containing extremely few impurities, particularly iron ions.
上記の目的を達成するための本発明による塩化クロムの
製造法は、不純物として鉄イオンを含む粗製塩化クロム
溶液にトリアルキルホスフィンオキサイド含を液を接触
して粗製塩化クロム溶液から鉄イオンを抽出分離し、次
いでこのトリアルキルホスフィンオキサイド含有液を逆
抽出して鉄イオンを除去し、これを循環使用することを
構成上の特徴とするものである。To achieve the above object, the method for producing chromium chloride according to the present invention involves contacting a crude chromium chloride solution containing iron ions as impurities with a solution containing trialkylphosphine oxide to extract and separate iron ions from the crude chromium chloride solution. The structure is characterized in that the trialkylphosphine oxide-containing liquid is then back-extracted to remove iron ions and recycled.
以下、本発明について説明する。The present invention will be explained below.
本発明に適用できる粗製塩化クロムは、鉄イオンを含有
するものであれば、特にその製造履歴は問わない。The production history of the crude chromium chloride that can be applied to the present invention is not particularly limited as long as it contains iron ions.
例えば、無水クロム酸を出発原料として、これを塩酸の
存在下で有機還元して調製するもの４．フェロクロムを
出発原料としてこれを塩酸溶解するもの、あるいは水酸
化クロムと塩酸との反応により調製するもの等が挙げら
れ、不純物として鉄イオンを含有しているものである。For example, those prepared by using chromic anhydride as a starting material and organically reducing it in the presence of hydrochloric acid4. Examples include those that use ferrochrome as a starting material and dissolve it in hydrochloric acid, or those that are prepared by reacting chromium hydroxide with hydrochloric acid, and contain iron ions as impurities.
この鉄イオンは、多くの場合Ｆｅ”’ として存在する
か、Ｆｅ”にあたっては後述する抽出操作に際し、予め
無水クロム酸や過酸化水素等で酸化処理を施し、完全に
Ｆｅ゛’にしておくことが必要である。In many cases, this iron ion exists as Fe"', or in the case of Fe", it must be oxidized with chromic anhydride, hydrogen peroxide, etc. in advance to completely convert it into Fe" during the extraction operation described later. is necessary.
本発明は、このような粗製塩化クロム溶液から鉄イオン
を抽出分離するための抽出剤として、トリアルキルホス
フィンオキサイド含有液を用いることが、その特徴の１
つとなっている。One of the features of the present invention is that a trialkylphosphine oxide-containing liquid is used as an extractant for extracting and separating iron ions from such a crude chromium chloride solution.
It is one.
トリアルキルホスフィンオキサイド（Ｒ，ＰＯ）は、水
又は酸性水溶液において実質的に不溶性のものでなけれ
ばならず、多くの場合、Ｒが炭素数６〜１２のアルキル
基をもつ、トリアルキルホスフィンオキサイドが適当で
ある。The trialkylphosphine oxide (R,PO) must be substantially insoluble in water or an acidic aqueous solution, and in many cases, the trialkylphosphine oxide (R,PO) in which R has an alkyl group having 6 to 12 carbon atoms is used. Appropriate.
この理由は、炭素数が６未満のアルキル基をもつものに
あっては、臭気や水への溶解度があって不適であり、又
逆に炭素数１２を越えるものにあっては、工業的に産業
上の都合から余り有利でないことによる。本発明では、
特にトリオクチルホスフィンオキサイド（（Ｃｍ Ｈ−
７＞ｓＰｏ、以下「ＴＯＰＯ，という〕が有利に用いら
れる。The reason for this is that those with an alkyl group having less than 6 carbon atoms are unsuitable due to their odor and water solubility, while those with more than 12 carbon atoms are not suitable for industrial use. This is because it is not very advantageous from an industrial standpoint. In the present invention,
Especially trioctylphosphine oxide ((Cm H-
7>sPo, hereinafter referred to as "TOPO", is advantageously used.
同様に、抽出溶媒も実質的に水又は酸性水溶液に不溶性
の有機溶媒であることが必要で、Ｒ３ＰＯを）容解し、
かつ不活性のものであれば特に限定はない。Similarly, the extraction solvent must also be an organic solvent that is substantially insoluble in water or acidic aqueous solution, and that dissolves R3PO);
There is no particular limitation as long as it is inert.
このような溶媒としては、例えばケロシン、シクロヘキ
サン及び四塩化炭素等が挙げられる。Examples of such solvents include kerosene, cyclohexane, and carbon tetrachloride.
従って、本発明においてトリアルキルホスフィンオキサ
イド含有液というのは、を機溶媒にトリアルキルホスフ
ィンオキサイドをン容解して均−ｌ夜とした抽出剤のこ
とをいう。Therefore, in the present invention, the trialkylphosphine oxide-containing liquid refers to an extractant in which trialkylphosphine oxide is dissolved in a solvent and allowed to stand overnight.
かかる抽出剤を用いて粗製塩化クロム溶液から銖イオン
を抽出分離するプロセスは、次のとおりである。The process of extracting and separating the ion from the crude chromium chloride solution using such an extractant is as follows.
即ち、抽出剤の使用量は、溶存する鉄イオンの星に対し
Ｒ，ＰＯとして１．５倍モル以上であり、特に１．６０
〜３．０倍モルが好適である。That is, the amount of extractant used is at least 1.5 times the mole of R and PO relative to the dissolved iron ion star, especially 1.60
~3.0 times the molar amount is suitable.
この理由は、１．５′＊倍モル未溝にあたっては、鉄イ
オンの抽出率が著しく低下するからであり、又上限は特
に限定されないが、経済的理由と同時に３倍モルを越え
ると、抽出率が飽和するか若干低減する傾向にあるから
、実質的には３倍モルが上限となる。The reason for this is that the extraction rate of iron ions decreases significantly when the 1.5'* molar concentration is not reached, and although there is no particular upper limit, for economic reasons and when the iron ion extraction rate exceeds 3 times the molar amount, the Since the ratio tends to be saturated or slightly reduced, the practical upper limit is 3 times the mole.
なお、粗製塩化クロム溶液と本発明に係る抽出剤との接
触における容量比は、分離操作を考慮して所望のか１合
が設定できるが、多くの場合ｌ：１を中心にしてその前
後の割合がとられる。Note that the volume ratio of the crude chromium chloride solution and the extractant according to the present invention in contact with each other can be set at a desired value of 1/1 in consideration of the separation operation, but in many cases, the ratio around 1:1 is used. is taken.
次に、抽出に際しては粗製塩化クロムの理ＸＱ ｐＩｔ
が０．１以下、好ましくは０以上であることが必要であ
る。Next, during extraction, the method of crude chromium chloride XQ pIt
is 0.1 or less, preferably 0 or more.
この理由は、０．１を越える高いｐＨにあっては、抽出
率が著しく低下するとともに、Ｆｅ”” とＣｒ゛゛の
選択的分離が不完全となる傾向となるからである。The reason for this is that at a high pH exceeding 0.1, the extraction rate decreases markedly and the selective separation of Fe'' and Cr'' tends to be incomplete.
なお、本発明において理論ｐＨというのは、粗製塩化ク
ロム溶液中の水素イオン濃度を解離度１００％として計
算して求めた値をいう。In the present invention, the theoretical pH refers to a value calculated by assuming that the hydrogen ion concentration in the crude chromium chloride solution is 100% of the degree of dissociation.
従って、ｉｆｆ製塩化クロム溶液のｐＨが高い場合には
、必ず塩酸を添加して低いｐＨ溶液に調製しておくこと
が好ましいが、もっとも抽出操作の際にｐＨ調整をして
もよい。Therefore, if the pH of the iff chromium chloride solution is high, it is preferable to always add hydrochloric acid to prepare a low pH solution, but the pH may be adjusted during the extraction operation.
なお、両液の接触混合方法は特に限定はなく、常温にて
少なくとも１０分以上充分に混合することにより行えば
よい。The method of contact mixing of both liquids is not particularly limited, and may be carried out by sufficiently mixing at room temperature for at least 10 minutes.
上記抽出操作は比較的短時間で完了し、また抽出後の水
相と有機相との分相も良好であるから、効果的に鉄イオ
ンを抽出分離できる。The above extraction operation can be completed in a relatively short time, and the phase separation between the aqueous phase and the organic phase after extraction is also good, so iron ions can be extracted and separated effectively.
更に、抽出後の塩化クロム溶液中の存機物の混入も実質
的にない。Furthermore, there is substantially no contamination of existing substances in the chromium chloride solution after extraction.
次いで、上記により抽出分離した鉄イオン含有のトリア
ルキルホスフィンオキサイド含有液は、所望の水溶液で
前記と同様の抽出条件にて接触混合することにより水相
に鉄イオンを移行せしめ、いわゆる逆抽出（ｓｔｒｉｐ
ｐｉｎｇ）される。Next, the iron ion-containing trialkylphosphine oxide-containing liquid extracted and separated in the above manner is contact-mixed with a desired aqueous solution under the same extraction conditions as above to transfer the iron ions to the aqueous phase, resulting in so-called back extraction (strip).
ping).
逆抽出の方法は、希塩酸水溶液又は、Ｆｅ”’をＦｅ”
に転換しうる還元剤含有の水／８液にて接触混合するこ
とにより行われる。The back extraction method uses dilute hydrochloric acid aqueous solution or
This is carried out by contact mixing with water/8 liquid containing a reducing agent that can be converted into .
前者においては、塩酸濃度が低いほど逆抽出ｒは高くな
り、逆抽出率の観点からでは水のみでもよいが、反面分
層が不安定となって分離が不完全となることから、Ｏ，
ＩＮ以下の塩酸水溶液であるのがよい。In the former case, the lower the hydrochloric acid concentration, the higher the back extraction r, and from the viewpoint of the back extraction rate, water alone may be used, but on the other hand, the separation becomes unstable and the separation becomes incomplete, so O,
It is preferable to use an aqueous hydrochloric acid solution below IN.
また、この鉄イオンの逆抽出率は先の抽出率に比べて低
いので数段の抽出操作が必要であり、３段以上好ましく
は５段程度を採用することが望ましい。Furthermore, since the back extraction rate of this iron ion is lower than the previous extraction rate, several stages of extraction operations are required, and it is desirable to employ three or more stages, preferably about five stages.
後者においては、例えばンユウ酸の如きぶ元剤水溶液が
よく、これによってＦ ｅ ”’がＦｅ”に還元される
と速やかに水相へ移行するので、はぼ完全に逆抽出が達
成できる。In the latter case, an aqueous solution of a base agent such as sulfuric acid is preferable, and when Fe'' is reduced to Fe, it is quickly transferred to the aqueous phase, so that almost complete back extraction can be achieved.
この場合還元剤の使用量は、前記還元に要する理論量以
上であれば特に限定はなく、経済的に設定すればよい。In this case, the amount of the reducing agent to be used is not particularly limited as long as it is at least the theoretical amount required for the reduction, and may be set economically.
従って、効率の点から後者の方が有利であるが、いずれ
の方法を採用するかは経済的観点から決定すればよい。Therefore, the latter method is more advantageous in terms of efficiency, but which method to adopt may be determined from an economical point of view.
かくして、鉄イオンを逆抽出して再生されたトリアルキ
ルホスフィンオキサイド含有液は、再び粗製塩化クロム
溶液の抽出剤として循環使用する。The trialkylphosphine oxide-containing liquid thus regenerated by back-extracting iron ions is recycled and used again as an extractant for the crude chromium chloride solution.
この再生抽出剤中には一定レベルで鉄イオンを含有する
ことになるが、その使用において実質的に支障となるこ
とはない。This regenerated extractant will contain iron ions at a certain level, but this will not substantially interfere with its use.
鉄イオンを含有する粗製塩化クロム溶液に、トリアルキ
ルホスフィンオキサイド含有液と混合することにより、
鉄イオン（Ｆｅ”’）を選択的に有機層に移行せしめて
抽出分離する。By mixing a crude chromium chloride solution containing iron ions with a solution containing trialkylphosphine oxide,
Iron ions (Fe"') are selectively transferred to the organic layer and extracted and separated.
次に、鉄イオンを含有する抽出後のトリアルキルホスフ
ィンオキサイド含有液と希塩酸水溶液あるいはシュウ酸
の如き還元剤水溶液とを混合して鉄イオンを水層に移行
せしめて逆抽出することにより、トリアルキルホスフィ
ンオキサイド含有液が再生される。Next, the trialkylphosphine oxide-containing solution containing iron ions after extraction is mixed with a dilute hydrochloric acid aqueous solution or a reducing agent aqueous solution such as oxalic acid to transfer the iron ions to the aqueous layer and back-extract the trialkylphosphine oxide. The phosphine oxide-containing liquid is regenerated.
この再生抽出剤を循環使用する機構を介して鉄イオン含
有の粗製塩化クロム溶液から鉄イオンが効率的に除去さ
れ、高純度塩化クロム溶液を得ることが可能となる。Iron ions are efficiently removed from the iron ion-containing crude chromium chloride solution through this mechanism of circulating the regenerated extractant, making it possible to obtain a highly pure chromium chloride solution.
以下、本発明を実施例に基づいて説明する。 Hereinafter, the present invention will be explained based on examples.
実施例１〜９
第１表に示す鉄イオン（Ｆｅ””）を含むＣｒとして６
１１ｔ％の各種塩化クロム溶液（理論ｐｌ＝−０，６８
〜−０，６９） ５００−と２０ｗｔ／ｖｏ１％のＴＯ
ＰＯ含有ケロシン溶液の抽出剤５００ｍ１とを常温にし
て１５分間振とうした後、１５分間静置したところよく
分層したので水層と有機層とを分離した０分離後の各塩
化クロム溶液中のＦｅ””イオン濃度を測定したところ
、第１表に示す結果が得られた。Examples 1 to 9 6 as Cr containing iron ions (Fe"") shown in Table 1
11t% various chromium chloride solutions (theoretical pl=-0,68
~-0,69) 500- and 20wt/vo1% TO
After shaking 500 ml of PO-containing kerosene solution extractant at room temperature for 15 minutes and allowing it to stand for 15 minutes, the layers separated well, so the aqueous layer and the organic layer were separated. When the Fe"" ion concentration was measured, the results shown in Table 1 were obtained.
第１表
次いで、鉄イオン抽出後のそれぞれの有機層に０．０２
５Ｎ−ＨＣｊＩ！溶液を同量添加して、上記と同じ条件
にて鉄イオンの逆抽出を行ったところ、第２表の結果が
得られた。Table 1 Then, 0.02
5N-HCjI! When the same amount of the solution was added and back extraction of iron ions was performed under the same conditions as above, the results shown in Table 2 were obtained.
第２表
更に、上記で抽出回数３に係る再生抽出剤（Ｎα９）を
用いて再び粗製塩化クロム溶液（魔９）より鉄イオンの
抽出分離を１０回繰り返し行ったところ、第３表の結果
が得られた。Table 2 Furthermore, when we repeated the extraction and separation of iron ions from the crude chromium chloride solution (Magic 9) 10 times using the regenerated extractant (Nα9) according to the extraction number 3 above, the results shown in Table 3 were obtained. Obtained.
なお、Ｆｅの分析はＩＣＰＣ光発光法った。Note that Fe was analyzed by ICPC photoluminescence method.
第３表
実施例１Ｏ
先の実施例と同様に粗製塩化クロム溶液がらＴＯＰＯ含
有抽出剤により除鉄した０次いで、鉄イオン含有抽出剤
１００ｄに鉄イオンの含有量に対し、３倍モルを含有す
るシュウ酸水溶液ｆｏｏｄと常温にて１５分間振とうし
た後１５分間静置して鉄イオンの逆抽出を行った。シュ
ウ酸水溶液の鉄の分析から結果を第４表に示す。Table 3 Example 1O Iron was removed from the crude chromium chloride solution using a TOPO-containing extractant in the same manner as in the previous example. Next, 100d of the iron ion-containing extractant contained 3 times the mole of iron ions. After shaking with oxalic acid aqueous solution food at room temperature for 15 minutes, the mixture was allowed to stand for 15 minutes to perform back extraction of iron ions. Table 4 shows the results from the analysis of iron in the oxalic acid aqueous solution.
第４表
以上の結果から判るように、シュウ酸水溶液の逆抽出で
はゾ完全にＴＯＰＯ抽出剤が再生され、これをよりｈａ
実に循環使用することが明らかとなった。As can be seen from the results in Table 4, the TOPO extractant is completely regenerated by back extraction with an oxalic acid aqueous solution, and this can be
It has become clear that they are actually used repeatedly.
本発明による方法によれば、鉄イオンを含有する粗製塩
化クロム溶液から選択的に除鉄された高純度塩化クロム
が工業的に有利に製造できる。According to the method of the present invention, high purity chromium chloride from which iron has been selectively removed from a crude chromium chloride solution containing iron ions can be industrially advantageously produced.
鉄イオンの抽出剤として使用するトリアルキルホフィン
オキサイドは効果的に再生され、これを循環使用するこ
とができる。The trialkylphophine oxide used as an extractant for iron ions is effectively regenerated and can be recycled.
本発明に係る方法は、そのままレドックス・フロー形電
池の負極液の再生方法として適用できると共に、
該電池用の塩化クロム電解液としても適用できる。The method according to the present invention can be applied as it is as a method for regenerating the negative electrode liquid of a redox flow type battery, and can also be applied as a chromium chloride electrolyte for the battery.
Claims (1)
トリアルキルホスフィンオキサイド含有液を接触して粗
製塩化クロム溶液から鉄イオンを抽出分離し、次いでこ
のトリアルキルホスフィンオキサイド含有液を逆抽出し
て、鉄イオンを除去し、これを循環使用することを特徴
とする塩化クロムの製造法。 ２、トリアルキルホスフィンオキサイドは、トリオクチ
ルホスフィンオキサイドである請求項１記載の塩化クロ
ムの製造法。 ３、トリアルキルホスフィンオキサイドは、鉄イオン量
の１．５倍モル以上の使用である請求項１又は２記載の
塩化クロムの製造法。 ４、トリアルキルホスフィンオキサイド含有液による粗
製塩化クロム溶液から鉄イオンの抽出分離は、該クロム
溶液の理論ｐＨが０．１以下である請求項１、２又は３
記載の塩化クロム溶液の製造法。 ５、鉄イオン抽出後のトリアルキルホスフィンオキサイ
ドの逆抽出は希塩酸で行う請求項１記載の塩化クロムの
製造法。 ６、鉄イオン抽出後のトリアルキルホスフィンオキサイ
ドの逆抽出はシュウ酸水溶液で行う請求項１記載の塩化
クロムの製造法。[Claims] 1. A solution containing trialkylphosphine oxide is brought into contact with a crude chromium chloride solution containing iron ions as impurities to extract and separate iron ions from the crude chromium chloride solution, and then this solution containing trialkylphosphine oxide is extracted and separated from the crude chromium chloride solution. A method for producing chromium chloride, which is characterized by removing iron ions through back extraction and recycling the iron ions. 2. The method for producing chromium chloride according to claim 1, wherein the trialkylphosphine oxide is trioctylphosphine oxide. 3. The method for producing chromium chloride according to claim 1 or 2, wherein the trialkylphosphine oxide is used in an amount of at least 1.5 times the amount of iron ions by mole. 4. The extraction and separation of iron ions from a crude chromium chloride solution using a trialkylphosphine oxide-containing solution is carried out in accordance with Claims 1, 2, or 3, wherein the theoretical pH of the chromium solution is 0.1 or less.
Method for producing the described chromium chloride solution. 5. The method for producing chromium chloride according to claim 1, wherein the back extraction of trialkylphosphine oxide after iron ion extraction is performed with dilute hydrochloric acid. 6. The method for producing chromium chloride according to claim 1, wherein the back extraction of the trialkylphosphine oxide after the iron ion extraction is carried out using an oxalic acid aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27576188A JPH02124721A (en) | 1988-10-31 | 1988-10-31 | Production of chromium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27576188A JPH02124721A (en) | 1988-10-31 | 1988-10-31 | Production of chromium chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02124721A true JPH02124721A (en) | 1990-05-14 |
Family
ID=17560025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27576188A Pending JPH02124721A (en) | 1988-10-31 | 1988-10-31 | Production of chromium chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02124721A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030086631A (en) * | 2002-05-06 | 2003-11-12 | 현대자동차주식회사 | A fuel filler door opening and shutting structure of Rotation sliding type |
| KR20030087117A (en) * | 2002-05-06 | 2003-11-13 | 현대자동차주식회사 | Open and close structure of a new type fuel filler door incorporating roller system |
| WO2005056478A1 (en) * | 2003-12-10 | 2005-06-23 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| JP2005194167A (en) * | 2003-12-10 | 2005-07-21 | Nippon Chem Ind Co Ltd | Chromium chloride aqueous solution and its manufacturing method |
| JPWO2008136223A1 (en) * | 2007-04-27 | 2010-07-29 | 日本化学工業株式会社 | Chromium hydroxide, production method thereof, trivalent chromium-containing liquid using the same, and chromium plating method |
| CN103130280A (en) * | 2013-03-25 | 2013-06-05 | 国药集团化学试剂有限公司 | Method for improving quality of industrial chromic chloride |
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|---|---|---|---|---|
| JPS5111093A (en) * | 1974-07-19 | 1976-01-28 | Tetsukosha Kk | Kuromumetsuki suratsujikara jukaseibuno kaishusuru hoho |
| JPS532437A (en) * | 1976-06-28 | 1978-01-11 | Sumitomo Chem Co Ltd | Decomposition of m-(2-hydroxy-2-propyl)cumenehydroperoxide |
| JPS5499079A (en) * | 1978-09-16 | 1979-08-04 | Morio Watanabe | Method of recovering waste acid by using organic solvent |
| JPS57113807A (en) * | 1980-05-08 | 1982-07-15 | Canada Cyanamid | Method of extracting solvent for removing iron (iii) from aqueous solution |
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1988
- 1988-10-31 JP JP27576188A patent/JPH02124721A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5111093A (en) * | 1974-07-19 | 1976-01-28 | Tetsukosha Kk | Kuromumetsuki suratsujikara jukaseibuno kaishusuru hoho |
| JPS532437A (en) * | 1976-06-28 | 1978-01-11 | Sumitomo Chem Co Ltd | Decomposition of m-(2-hydroxy-2-propyl)cumenehydroperoxide |
| JPS5499079A (en) * | 1978-09-16 | 1979-08-04 | Morio Watanabe | Method of recovering waste acid by using organic solvent |
| JPS57113807A (en) * | 1980-05-08 | 1982-07-15 | Canada Cyanamid | Method of extracting solvent for removing iron (iii) from aqueous solution |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030086631A (en) * | 2002-05-06 | 2003-11-12 | 현대자동차주식회사 | A fuel filler door opening and shutting structure of Rotation sliding type |
| KR20030087117A (en) * | 2002-05-06 | 2003-11-13 | 현대자동차주식회사 | Open and close structure of a new type fuel filler door incorporating roller system |
| WO2005056478A1 (en) * | 2003-12-10 | 2005-06-23 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| JP2005194167A (en) * | 2003-12-10 | 2005-07-21 | Nippon Chem Ind Co Ltd | Chromium chloride aqueous solution and its manufacturing method |
| US7641721B2 (en) | 2003-12-10 | 2010-01-05 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| US8083842B2 (en) | 2003-12-10 | 2011-12-27 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| JPWO2008136223A1 (en) * | 2007-04-27 | 2010-07-29 | 日本化学工業株式会社 | Chromium hydroxide, production method thereof, trivalent chromium-containing liquid using the same, and chromium plating method |
| JP4576456B2 (en) * | 2007-04-27 | 2010-11-10 | 日本化学工業株式会社 | Chromium hydroxide, production method thereof, trivalent chromium-containing liquid using the same, and chromium plating method |
| CN103130280A (en) * | 2013-03-25 | 2013-06-05 | 国药集团化学试剂有限公司 | Method for improving quality of industrial chromic chloride |
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