JP2005296811A - Method for metal ion separation - Google Patents
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- JP2005296811A JP2005296811A JP2004116973A JP2004116973A JP2005296811A JP 2005296811 A JP2005296811 A JP 2005296811A JP 2004116973 A JP2004116973 A JP 2004116973A JP 2004116973 A JP2004116973 A JP 2004116973A JP 2005296811 A JP2005296811 A JP 2005296811A
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000926 separation method Methods 0.000 title claims abstract description 20
- 239000002689 soil Substances 0.000 claims abstract description 30
- 239000012074 organic phase Substances 0.000 claims abstract description 18
- 239000008346 aqueous phase Substances 0.000 claims abstract description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 15
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002576 ketones Chemical class 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 19
- 238000000975 co-precipitation Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 15
- 238000000638 solvent extraction Methods 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 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
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Processing Of Solid Wastes (AREA)
- Physical Water Treatments (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
この出願の発明は金属イオンの分離方法に関するものである。さらに詳しくは、この出願の発明は、産業上の重要資源であるとともに、環境への影響も大きい各種の重金属の回収、再利用をも可能とする、溶媒抽出、さらには共沈殿法による効率的な金属イオンの分離方法に関するものである。 The invention of this application relates to a method for separating metal ions. More specifically, the invention of this application is an important resource in the industry, and also enables recovery and reuse of various heavy metals that have a large impact on the environment, and is efficient by solvent extraction and further by a coprecipitation method. The present invention relates to a method for separating metal ions.
金属の分離回収法には、溶媒抽出法およびイオン交換樹脂などの吸着剤を利用する固相抽出法、そして共沈殿法が一般に知られている。これら方法のうち、固相抽出法（たとえば特許文献１を参照）は微量成分の分離・濃縮、そして連続的な抽出が可能である反面、大変にコストがかかり、樹脂の再生が必要であるという問題がある。このため、より簡便な手段として低コストで重金属等を分離する方法として溶媒抽出法（たとえば特許文献２を参照）や共沈法の採用が考慮される。しかしながら、溶媒抽出法の場合には、定量的な分離条件の設定が可能であるが、一般的に抽出化学種が限られるという問題があり、また共沈法の場合には濾過が困難であって、連続的に多量の対象物を扱うことが難しいという問題がある。 Generally known methods for separating and recovering metals include a solvent extraction method, a solid phase extraction method using an adsorbent such as an ion exchange resin, and a coprecipitation method. Among these methods, the solid-phase extraction method (see, for example, Patent Document 1) can separate / concentrate trace components and continuously extract them, but it is very expensive and requires regeneration of the resin. There's a problem. For this reason, the adoption of a solvent extraction method (see, for example, Patent Document 2) or a coprecipitation method is considered as a simpler means for separating heavy metals and the like at low cost. However, in the case of the solvent extraction method, quantitative separation conditions can be set. However, in general, there is a problem that the extraction chemical species is limited, and in the case of the coprecipitation method, filtration is difficult. Therefore, there is a problem that it is difficult to handle a large amount of objects continuously.
そして、溶媒抽出法の場合にも、通常、分離する金属イオンは溶液の状態にしておく必要があり、溶液のｐＨは金属イオンの水酸化物沈殿が生成しない領域に設定しておかなければならない。特に、金属イオンと弱酸との錯形成反応を利用する分離法の場合、高ｐＨ領域では金属イオンは水酸化物の沈殿を形成し弱酸と反応しにくくなるため、通常は水酸化物の沈殿が生成しない弱酸性領域で分離を行うのが普通である。しかしながら、この場合、弱酸の錯形成能力は酸性領域では小さいため、分離の効率は悪い。以上のように、従来の金属イオンの抽出分離法では、水酸化物沈殿の生成しない条件で分離を行う必要があり、そのため、分離効率が悪くなる問題があった。 Also in the case of the solvent extraction method, the metal ions to be separated usually need to be in a solution state, and the pH of the solution must be set in a region where no metal ion hydroxide precipitate is generated. . In particular, in the case of a separation method that uses a complex-forming reaction between a metal ion and a weak acid, the metal ion forms a hydroxide precipitate and hardly reacts with a weak acid in a high pH region. It is usual to perform the separation in a weakly acidic region that does not form. However, in this case, the ability of complexing weak acids is small in the acidic region, so the separation efficiency is poor. As described above, the conventional extraction and separation method for metal ions needs to perform the separation under conditions that do not generate hydroxide precipitates, and thus has a problem of poor separation efficiency.
このことから、溶媒抽出においては、水酸化物の沈殿が生成されるような条件であっても金属イオンを定量的に抽出することのできる方法の確立が望まれていた。 From this, in the solvent extraction, it has been desired to establish a method capable of quantitatively extracting metal ions even under conditions where a hydroxide precipitate is generated.
また、さらには、溶媒抽出法における抽出化学種の制約の問題を解消することも望まれていた。 Furthermore, it has also been desired to eliminate the problem of restriction of extraction chemical species in the solvent extraction method.
重金属等の分離にとっての大きな課題の一つとして、河川や湖沼、あるいは排水中からの分離回収とともに、土壌中からの簡便で効率的な回収のための手段の実現が望まれており、この観点からも溶媒抽出等による手法の更なる発展が求められていた。
そこで、この出願の発明は、以上の背景から、溶媒抽出法の特徴を生かしつつ、水酸化物の沈殿が生成されるような条件であっても金属イオンを確実に抽出することができ、また、多くの金属イオンの分離をも可能とし、しかも水中からだけではなく、土壌中からの重金属の回収を可能とすることのできる新しい金属イオンの分離方法を提供することを課題としている。 In view of the above, the invention of this application can extract metal ions reliably even under conditions where a precipitate of hydroxide is generated while taking advantage of the characteristics of the solvent extraction method. It is an object of the present invention to provide a new method for separating metal ions that enables separation of many metal ions and enables recovery of heavy metals not only from water but also from soil.
この出願は、上記の課題を解決するものとして以下の発明を提供する。
〔１〕金属イオン含有の水相に、水中では金属水酸化物沈殿が生成するｐＨ値以上で、ジアルキルリン酸を溶解した非水溶性のケトンの溶液を有機相として混合し、金属イオンを有機相に抽出分離することを特徴とする金属イオンの分離方法。
〔２〕金属水酸化物沈殿を含有する水相に有機相を混合して抽出分離することを特徴とする上記の金属イオンの分離方法。
〔３〕金属イオン含有の水相に、水中で金属水酸化物の沈殿を生成するマトリックス金属のイオンの水溶液を添加し、金属イオンの少くとも一部をマトリックス金属の水酸化物沈殿に共沈により取込み、次いで有機相を混合して抽出分離することを特徴とする金属イオンの分離方法。
〔４〕金属含有の土壌に、水中で金属水酸化物の沈殿を生成するマトリックス金属のイオンの水溶液とジアルキルリン酸を溶解した非水溶性のケトンの溶液を加え、マトリックス金属の水酸化物沈殿が生成するｐＨ値以上として土壌中の金属イオンを有機相に抽出分離することを特徴とする土壌中の金属の分離方法。
〔５〕金属イオンの還元剤を水溶液に含有させることを特徴とする上記いずれかの分離方法。
This application provides the following invention to solve the above-mentioned problems.
[1] A water-insoluble ketone solution in which dialkyl phosphoric acid is dissolved is mixed with an aqueous phase containing metal ions at a pH value or higher at which a metal hydroxide precipitate is generated in water, and the metal ions are organically mixed. A method for separating metal ions, characterized by extracting and separating into phases.
[2] The method for separating metal ions as described above, wherein an organic phase is mixed with an aqueous phase containing a metal hydroxide precipitate and extracted and separated.
[3] An aqueous solution of matrix metal ions that forms a metal hydroxide precipitate in water is added to the aqueous phase containing metal ions, and at least some of the metal ions are co-precipitated into the matrix metal hydroxide precipitate. A method for separating metal ions, wherein the organic phase is mixed and extracted and separated.
[4] To the metal-containing soil, an aqueous solution of a matrix metal ion that forms a metal hydroxide precipitate in water and a water-insoluble ketone solution in which dialkyl phosphoric acid is dissolved are added to the matrix metal hydroxide precipitate. A method for separating metal in soil, wherein the metal ion in soil is extracted and separated into an organic phase at a pH value higher than the pH value.
[5] The separation method according to any one of the above, wherein a reducing agent for metal ions is contained in the aqueous solution.
上記のとおりのこの出願の第１および第２の発明によれば、従来のような分離効率が悪い酸性領域での抽出を行うことなしに、水酸化物の沈殿が生成する条件下であっても優れた分離効率で重金属イオン等の抽出分離が可能とされる。また、第３から第５の発明によれば、マトリックス金属を用いることによって他種金属イオンの共沈抽出が可能とされ、複数種の金属イオンであっても極めて効率的な分離が可能とされる。 According to the first and second inventions of this application as described above, under conditions where hydroxide precipitates are formed without performing extraction in an acidic region with poor separation efficiency as in the prior art. In addition, it is possible to extract and separate heavy metal ions and the like with excellent separation efficiency. Further, according to the third to fifth inventions, coprecipitation extraction of other types of metal ions is possible by using a matrix metal, and extremely efficient separation is possible even with a plurality of types of metal ions. The
土壌中に含有されている重金属等の抽出分離も可能とされる。 Extraction and separation of heavy metals contained in the soil is also possible.
以上のように、この出願の発明によって、重金属による環境汚染の解消と、これら金属の資源としての再利用への道が大きく前進することになる。 As described above, the invention of this application greatly advances the path to environmental pollution caused by heavy metals and the reuse of these metals as resources.
この出願の発明が抽出分離の対象とする金属イオンは、いわゆる重金属イオンとしてその回収除去が課題とされているものをはじめ、各種のものであってよい。これらの金属は水中においてイオンとして存在し得る形態であればよい。 The metal ions to be extracted and separated by the invention of this application may be various types, including those for which recovery and removal is a problem as so-called heavy metal ions. These metals may be in any form that can exist as ions in water.
抽出のための有機相におけるジアルキルリン酸としては、次式で表わされる各種のものであってよい。 The dialkyl phosphoric acid in the organic phase for extraction may be various types represented by the following formula.
Ｒ1およびＲ2のアルキル基としては、特に限定されることはないが、炭素数４以上、さらには６〜１２の範囲のものが好適に考慮される。分枝状鎖であることも好適に考慮される。
The alkyl group of R 1 and R 2, There is no particular limitation, 4 or more carbon atoms, more is in the range of 6 to 12 is preferably considered. A branched chain is also preferably considered.
そして、このようなジアルキルリン酸は、非水溶性のケトンに溶解されているものとする。この場合のケトンとしては、次式で表わされる各種のものであってよい。 And such a dialkyl phosphoric acid shall be melt | dissolved in the water-insoluble ketone. The ketone in this case may be various types represented by the following formula.
これらＲ3およびＲ4のアルキル基としては、炭素数１〜６程度のものが好適に考慮される。
As these alkyl groups of R 3 and R 4 , those having about 1 to 6 carbon atoms are preferably considered.
そしてこの出願の発明においては、金属イオン含有の水相に上記のジアルキルリン酸を溶解したケトン溶液を有機相として混合するが、その際に、通常、水中においては金属イオンの水酸化物沈殿を生成してしまうｐＨ値以上とする。このようなｐＨ値の調整は、アルカリ水溶液の添加、さらには酸水溶液の添加によって適宜に行うことができる。 In the invention of this application, a ketone solution in which the above dialkyl phosphoric acid is dissolved is mixed as an organic phase in a metal ion-containing aqueous phase. At this time, normally, hydroxide precipitation of metal ions is performed in water. Above the pH value that would be generated. Such adjustment of the pH value can be appropriately performed by adding an aqueous alkali solution, and further by adding an aqueous acid solution.
また、このような条件下での金属イオンの有機相への抽出分離を特徴とするこの出願の発明では、抽出分離の対象とする金属イオンからの水酸化物の沈殿を水相に含有していてもよい。このことは、この出願の発明の大変に大きな特徴である。金属イオンの水酸化物沈殿そのものが有機相に抽出されるからである。このようなことは、これまでの溶媒抽出法によっては実現されなかったことである。 In the invention of this application, which is characterized by extraction and separation of metal ions into an organic phase under such conditions, the aqueous phase contains a precipitate of hydroxide from the metal ions to be extracted and separated. May be. This is a very important feature of the invention of this application. This is because the metal ion hydroxide precipitate itself is extracted into the organic phase. This is not realized by the conventional solvent extraction method.
そして、この出願の第３および第４の発明においては、全く新しい「共沈抽出法」と呼ぶことのできる方法を提案し、さらにこの方法の適用を土壌中の金属の抽出除去にまで拡大することを可能としている。 And in the 3rd and 4th invention of this application, the method which can be called a completely new "coprecipitation extraction method" is proposed, and also the application of this method is extended to the extraction removal of the metal in soil. Making it possible.
上記の共沈抽出法においては、他の金属種のイオンの抽出のためのマトリックス金属を用い、水中で金属水酸化物沈殿を生成するこのマトリックス金属の水酸化物との共沈として分離対象の金属を有機相へ抽出して分離する。この場合にも抽出条件は上記の第１および第２の発明と同様の有機相の使用と、ｐＨ条件の採用が重要となる。 In the coprecipitation extraction method described above, the matrix metal is used for extraction of ions of other metal species, and is separated as the coprecipitation with this matrix metal hydroxide that forms a metal hydroxide precipitate in water. The metal is extracted into the organic phase and separated. In this case as well, it is important to use the same organic phase as in the first and second inventions and to adopt pH conditions as extraction conditions.
そして上記の共沈抽出法では、マトリックス金属としては、水酸化物沈殿を生成しやすい各種の金属を用いることができる。取扱い、入手しやすさ、コスト等の観点からは、その好適な代表的なものとして鉄（III)を例示することができる。またその他としては、アルミニウム（III)、ランタン（III)、ガリウム（III)、インジウム（III)、ベリリウム（II)等が例示される。 And in said coprecipitation extraction method, the various metals which are easy to produce | generate hydroxide precipitation can be used as a matrix metal. From the viewpoint of handling, availability, cost and the like, iron (III) can be exemplified as a suitable representative one. Other examples include aluminum (III), lanthanum (III), gallium (III), indium (III), and beryllium (II).
また、マトリックス金属の水酸化物に共沈として取込まれる金属イオンは、水中においては陽イオンの形態にあることが好適である。たとえば六価クロム：Ｃｒ(VI)を分離対象とする場合、このものは水中においてＣｒＯ4 2-，あるいはＣｒ2Ｏ7 2-の陰イオンの形態にあるため共沈によって取込むことは必ずしも容易ではない。このような場合には、水溶液に還元剤を存在させて三価クロムのように還元してやると共沈による分離が容易となる。そしてこの還元剤を存在させる場合には、マトリックス金属としてはその水酸化物沈殿が阻害されないものとすることが必要となる。 Moreover, it is preferable that the metal ion taken as a coprecipitation in the hydroxide of the matrix metal is in the form of a cation in water. For example, when hexavalent chromium: Cr (VI) is to be separated, it is in the form of CrO 4 2- or Cr 2 O 7 2- anion in water, so it is not always easy to incorporate it by coprecipitation. is not. In such a case, if a reducing agent is present in the aqueous solution and reduced like trivalent chromium, separation by coprecipitation becomes easy. When this reducing agent is present, it is necessary that the matrix metal does not inhibit the hydroxide precipitation.
そこで以下に実施例を示し、さらに詳しく説明する。もちろん以下の例によって発明が限定されることはない。 Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.
＜実施例１＞
０．１Ｍの鉄を含む水溶液（２０ｍｌ）にアルカリ（ＮａＯＨ）を添加し、水酸化物の沈殿を形成させる（０．１Ｍ鉄(III) の抽出ではｐＨを２以上にすると沈殿する）。この溶液に１Ｍのリン酸ジ（２−エチルヘキシル）（Ｄ２ＥＨＰＡ）を含む４−メチル−２−ペンタノン（ＭＩＢＫ）溶液２０ｍｌを加えて激しく攪拌する。
<Example 1>
Alkali (NaOH) is added to an aqueous solution (20 ml) containing 0.1 M iron to form a hydroxide precipitate (in the extraction of 0.1 M iron (III), it precipitates at a pH of 2 or more). To this solution, 20 ml of 4-methyl-2-pentanone (MIBK) solution containing 1M di (2-ethylhexyl) phosphate (D2EHPA) is added and stirred vigorously.
上記の操作後、溶液を静置分相し、水相を分取する。この水相中の金属濃度（〔Ｍ〕ｗ〕とする）を原子吸光光度計またはＩＣＰ発光分光光度計により測定する。金属の分配比Ｄは抽出前の水相の金属濃度（〔Ｍ〕ｉ）、および〔Ｍ〕ｗの値から以下の式を用いて計算される。 After the above operation, the solution is subjected to stationary phase separation to separate the aqueous phase. The metal concentration (referred to as [M] w) in this aqueous phase is measured with an atomic absorption photometer or an ICP emission spectrophotometer. The metal distribution ratio D is calculated using the following equation from the metal concentration ([M] i) of the aqueous phase before extraction and the value of [M] w.
Ｄ＝（〔Ｍ〕ｉ−〔Ｍ〕ｗ）／（〔Ｍ〕ｗ）
この鉄(III) の抽出では、水酸化物の沈殿はｐＨ２以上で生成するが、ｐＨの増加に伴ってｌｏｇＤの値は増大し、ｐＨ３以上では、水相の鉄濃度は原子吸光光度計の検出限界以下となる。この場合の分配比は１００万以上と推定される。
D = ([M] i- [M] w) / ([M] w)
In this extraction of iron (III), hydroxide precipitates are generated at pH 2 or higher, but the log D value increases with increasing pH, and at pH 3 or higher, the iron concentration in the aqueous phase is determined by an atomic absorption photometer. Below the detection limit. In this case, the distribution ratio is estimated to be 1 million or more.
同様にして、アルミニウム(III) 、ランタン(III) 、コバルト(II)、ベリリウム(II)についての抽出を行った。優れた抽出結果が同様にして確認された。 Similarly, extraction of aluminum (III), lanthanum (III), cobalt (II), and beryllium (II) was performed. Excellent extraction results were confirmed as well.
また、リン酸ジ（２−エチルヘキシル）に代えてリン酸ジ（ブチル）を用いて上記の鉄イオンの抽出を行った。 Further, the above iron ions were extracted using di (butyl) phosphate instead of di (2-ethylhexyl) phosphate.
同様にして優れた抽出結果が得られた。 Similarly, excellent extraction results were obtained.
さらに、抽出溶剤としてのＭＩＢＫに代えてジイソプロピルケトンを用いて上記の鉄イオンの抽出を行った。ＭＩＢＫの場合に比べて効率は若干低かったが、鉄イオンの抽出が良好に行われた。
＜実施例２＞
図１に示した重金属除去のための共沈殿抽出フローシステムでポンプＰ１のＳから１×１０-4Ｍのこれらの金属および０．１Ｍの鉄を含む水溶液を、Ｒ１から１ＭのＤ２ＥＨＰＡ−ＭＩＢＫ溶液を送液した。次にこの流れの中にポンプＰ２のＲ２から１Ｍの水酸化ナトリウム溶液を送液し、抽出コイルＥＣで抽出した。溶出液を静置分相後、水相中の金属濃度を原子吸光光度法により測定し、あわせてｐＨも測定した。
Further, the above iron ions were extracted using diisopropyl ketone instead of MIBK as the extraction solvent. Although the efficiency was slightly lower than in the case of MIBK, iron ions were extracted well.
<Example 2>
In the coprecipitation extraction flow system for heavy metal removal shown in FIG. 1, an aqueous solution containing 1 × 10 −4 M of these metals and 0.1 M of iron from S of pump P1 is used as an R2 to 1M D2EHPA-MIBK solution. Was fed. Next, a 1M sodium hydroxide solution was fed from the R2 of the pump P2 into this flow and extracted with the extraction coil EC. After the stationary eluate was phase-separated, the metal concentration in the aqueous phase was measured by atomic absorption spectrometry, and the pH was also measured.
図２には、銅および亜鉛の場合の抽出除去率に対するｐＨの影響を示した。ｐＨの上昇に伴い鉄の水酸化物沈殿が生成し、重金属が沈殿に取り込まれ、除去率が増加していくことが確認された。またｐＨ４付近になると、銅および亜鉛の除去率はほぼ１００％となり、定量的な抽出が可能であった。 FIG. 2 shows the effect of pH on the extraction removal rate in the case of copper and zinc. It was confirmed that as the pH increased, iron hydroxide precipitates were generated, heavy metals were incorporated into the precipitates, and the removal rate increased. When the pH was around 4, the removal rate of copper and zinc was almost 100%, and quantitative extraction was possible.
図３は、カドミウムおよび鉛の場合について示したものである。カドミウム、鉛においても同様にｐＨ４で定量的に除去できることがわかった。
＜実施例３＞
六価クロムについて実施例２と同様の抽出を行った。六価クロムの抽出除去率は約８０％であった。そこで、より一層除去率を向上させるために、鉄溶液に代えて還元剤（１．０×１０-2Ｍ塩酸ヒドロキシルアミン）とアルミニウム(III) の水溶液を用いた。
FIG. 3 shows the case of cadmium and lead. It was also found that cadmium and lead can be removed quantitatively at pH 4 as well.
<Example 3>
Hexavalent chromium was extracted in the same manner as in Example 2. The extraction removal rate of hexavalent chromium was about 80%. Therefore, in order to further improve the removal rate, an aqueous solution of a reducing agent (1.0 × 10 −2 M hydroxylamine hydrochloride) and aluminum (III) was used in place of the iron solution.
その結果、六価クロムは定量的に抽出分離された。このことは、六価クロムが三価クロムに還元されたことに起因していると考えられる。
＜実施例４＞
重金属で汚染された土壌試料を以下のように調製した。図４に示したように、採取した土壌を風乾した後、２ｍｍの篩にかけ、篩を通過したもの２ｋｇを用意し、これに、１×１０-3Ｍのカドミウム、コバルト、銅、マンガン、ニッケル、鉛、亜鉛の７種類の金属を含む溶液１０Ｌを加え２４時間攪拌した。その後、この土壌をろ過し、風乾させ本実験の土壌試料とした。
As a result, hexavalent chromium was quantitatively extracted and separated. This is considered to be due to the reduction of hexavalent chromium to trivalent chromium.
<Example 4>
A soil sample contaminated with heavy metals was prepared as follows. As shown in FIG. 4, the collected soil was air-dried, passed through a 2 mm sieve, and 2 kg passed through the sieve, and 1 × 10 −3 M cadmium, cobalt, copper, manganese, nickel Then, 10 L of a solution containing 7 kinds of metals such as lead and zinc was added and stirred for 24 hours. Then, this soil was filtered and air-dried to obtain a soil sample for this experiment.
調製した土壌の重金属含有量を調べるため、この土壌試料６ｇに１Ｍ塩酸２００ｍｌを加え、２時間攪拌した後、孔径０．４５μｍのメンブランフィルターで濾過し、そのろ液の重金属濃度を原子吸光光度計で測定した。この操作は、環境省告示第１９号にある重金属の土壌含有量測定法にのっとったものである。 In order to examine the heavy metal content of the prepared soil, 200 ml of 1M hydrochloric acid was added to 6 g of this soil sample, stirred for 2 hours, filtered through a membrane filter having a pore size of 0.45 μm, and the heavy metal concentration of the filtrate was measured by an atomic absorption photometer. Measured with This operation is in accordance with the heavy metal soil content measurement method described in Ministry of the Environment Notification No. 19.
表１には重金属含有量の分析結果を示した。数値は原子吸光光度計によって検出されたろ液中の金属濃度をもとに計算した、土壌試料１ｇあたりの重金属量を示している。土壌汚染対策法では、カドミウムと鉛の土壌含有量基準が設定されているが、試料土壌ではカドミウムは基準値の３倍量、鉛は基準値の６倍量が含まれている。 Table 1 shows the analysis results of the heavy metal content. The numerical value indicates the amount of heavy metal per 1 g of soil sample calculated based on the metal concentration in the filtrate detected by an atomic absorption photometer. In the Soil Contamination Countermeasures Law, cadmium and lead soil content standards are set, but sample soil contains cadmium three times the standard value and lead six times the standard value.
土壌試料に残った重金属量を測定するため、土壌を取り出し、風乾した後、この６ｇに、１Ｍ塩酸２００ｍｌを加え２時間攪拌した。その後、０．４５μｍのメンブランフィルターで濾過し、ろ液中の金属濃度を原子吸光光度計で測定した。 In order to measure the amount of heavy metal remaining in the soil sample, the soil was taken out and air-dried, and then 200 ml of 1M hydrochloric acid was added to 6 g, and the mixture was stirred for 2 hours. Then, it filtered with the 0.45 micrometer membrane filter, and measured the metal concentration in a filtrate with the atomic absorption photometer.
表２には結果を示した。左より、土壌試料１ｇ当りの重金属含有量、除去後の重金属含有量、これから計算される重金属の除去率を示している。このように、何れの重金属においても除去率は９５％以上となり、土壌からの重金属の除去が行なえることが確認された。カドミウムと鉛においても、除去後の含有量は基準値以下となり、汚染土壌の浄化技術として十分活用可能である。
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