JP2003265902A - Method for removing anionic metal complex - Google Patents
Method for removing anionic metal complexInfo
- Publication number
- JP2003265902A JP2003265902A JP2002074367A JP2002074367A JP2003265902A JP 2003265902 A JP2003265902 A JP 2003265902A JP 2002074367 A JP2002074367 A JP 2002074367A JP 2002074367 A JP2002074367 A JP 2002074367A JP 2003265902 A JP2003265902 A JP 2003265902A
- Authority
- JP
- Japan
- Prior art keywords
- metal complex
- exchange resin
- anion exchange
- anionic metal
- basic anion
- 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.)
- Granted
Links
- -1 anionic metal complex Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 57
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 5
- 239000011592 zinc chloride Substances 0.000 claims abstract description 5
- 229960001939 zinc chloride Drugs 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 30
- 239000011701 zinc Substances 0.000 description 27
- 239000007788 liquid Substances 0.000 description 20
- 238000003795 desorption Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002699 waste material Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 229920001429 chelating resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 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 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/07—Processes using organic exchangers in the weakly basic form
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、陰イオン性金属錯
体を含む溶液から陰イオン性金属錯体を除去する方法に
関する。TECHNICAL FIELD The present invention relates to a method for removing an anionic metal complex from a solution containing the anionic metal complex.
【０００２】[0002]
【従来の技術】イオン交換においては、溶液中の陽イオ
ンはカチオン交換樹脂に吸着され、陰イオンはアニオン
交換樹脂に吸着される。したがって、溶液中の金属陽イ
オンはカチオン交換樹脂に吸着される。ただし、金属陽
イオンは溶液中で陰イオン性金属錯体を形成することが
あり、したがってこの場合は、アニオン交換樹脂で陰イ
オン性金属錯体を吸着することにより溶液中の金属を除
去することが可能である。2. Description of the Related Art In ion exchange, cations in a solution are adsorbed by a cation exchange resin and anions are adsorbed by an anion exchange resin. Therefore, the metal cations in the solution are adsorbed on the cation exchange resin. However, metal cations may form anionic metal complexes in solution, so in this case it is possible to remove the metal in solution by adsorbing the anionic metal complex with an anion exchange resin. Is.
【０００３】上述のような溶液中の陰イオン性金属錯体
を除去する技術の具体例として、従来、強酸中に含まれ
る陰イオン性金属錯体を強塩基性アニオン交換樹脂を用
いて除去する技術がある。この技術は、例えば塩酸中に
含まれる鉄分を除去する場合に使用される。As a specific example of the technique for removing the anionic metal complex in the solution as described above, there is conventionally a technique for removing the anionic metal complex contained in a strong acid using a strongly basic anion exchange resin. is there. This technique is used, for example, when removing iron contained in hydrochloric acid.
【０００４】また、金属陽イオンには溶液中で陰イオン
性金属錯体を形成するものとしないものがある。そのた
め、上述した溶液中の陰イオン性金属錯体を強塩基性ア
ニオン交換樹脂を用いて除去する技術は、各種金属を含
む溶液から、陰イオン性金属錯体を形成する金属と、形
成しない金属とを分離する方法として用いられる。この
方法は、特定金属の定量分析や、鉄などの金属類の高純
度化にも使用される。In addition, there are metal cations which form an anionic metal complex in a solution and those which do not. Therefore, the technique of removing the anionic metal complex in the solution described above by using a strongly basic anion exchange resin, a solution containing various metals, a metal that forms an anionic metal complex, and a metal that does not form Used as a method of separation. This method is also used for quantitative analysis of specific metals and high purification of metals such as iron.
【０００５】[0005]
【発明が解決しようとする課題】前述したように、溶液
中の陰イオン性金属錯体を除去する方法として、従来、
陰イオン性金属錯体を強塩基性アニオン交換樹脂に吸着
させる方法があった。しかし、この方法は、強塩基性ア
ニオン交換樹脂は耐熱性が低いため高温の溶液を通液す
ることができない、強塩基性アニオン交換樹脂は通液後
における陰イオン性金属錯体の脱着性が悪いといった問
題を有するものであった。As described above, as a method for removing the anionic metal complex in the solution, the conventional method is as follows.
There has been a method of adsorbing an anionic metal complex on a strongly basic anion exchange resin. However, in this method, since the strongly basic anion exchange resin has low heat resistance, it is impossible to pass the solution at high temperature. The strongly basic anion exchange resin has poor desorption property of the anionic metal complex after passing the solution. There was such a problem.
【０００６】本発明は、前述した事情に鑑みてなされた
もので、溶液中の陰イオン性金属錯体をアニオン交換樹
脂を用いて除去する方法であって、アニオン交換樹脂に
高温の溶液を通液することができるとともに、アニオン
交換樹脂からの陰イオン性金属錯体の脱着性が良い陰イ
オン性金属錯体の除去方法を提供することを目的とす
る。The present invention has been made in view of the above circumstances, and is a method for removing an anionic metal complex in a solution by using an anion exchange resin, in which a high temperature solution is passed through the anion exchange resin. It is an object of the present invention to provide a method of removing an anionic metal complex which has good desorption property of the anionic metal complex from the anion exchange resin.
【０００７】[0007]
【課題を解決するための手段】本発明者は、前記課題を
解決すべく鋭意研究を重ねた結果、溶液中に含まれる陰
イオン性金属錯体の除去に弱塩基性アニオン交換樹脂を
用いた場合、強塩基性アニオン交換樹脂を用いる従来技
術と同様に陰イオン性金属錯体を除去することができる
上、弱塩基性アニオン交換樹脂は強塩基性アニオン交換
樹脂よりも耐熱性が高いため高温の溶液を通液すること
が可能になり、しかも通液後における陰イオン性金属錯
体の脱着性が向上することを見出した。As a result of intensive studies to solve the above problems, the present inventors have found that a weakly basic anion exchange resin is used to remove an anionic metal complex contained in a solution. , It is possible to remove the anionic metal complex in the same way as the conventional technique using a strongly basic anion exchange resin, and the weakly basic anion exchange resin has higher heat resistance than the strongly basic anion exchange resin, so that it is a high temperature solution. It has been found that it becomes possible to pass the liquid, and the desorption of the anionic metal complex is improved after passing the liquid.
【０００８】本発明は、上記知見に基づいてなされたも
ので、陰イオン性金属錯体を含有する溶液を弱塩基性ア
ニオン交換樹脂に接触させることを特徴とする陰イオン
性金属錯体の除去方法を提供する。The present invention has been made based on the above findings, and provides a method for removing an anionic metal complex, which comprises contacting a solution containing an anionic metal complex with a weakly basic anion exchange resin. provide.
【０００９】[0009]
【発明の実施の形態】以下、本発明につきさらに詳しく
説明する。本発明では、弱塩基性アニオン交換樹脂とし
て、スチレン−ジビニルベンゼン共重合体などのスチレ
ン系樹脂を樹脂母体とするもの（スチレン系弱塩基性ア
ニオン交換樹脂）、アクリル−ジビニルベンゼン共重合
体などのアクリル系樹脂を樹脂母体とするもの（アクリ
ル系弱塩基性アニオン交換樹脂）のいずれでも用いるこ
とができるが、スチレン系弱塩基性アニオン交換樹脂を
用いることがより好ましい。これは、スチレン系弱塩基
性アニオン交換樹脂はアクリル系弱塩基性アニオン交換
樹脂よりも耐熱性が高いからである。上記スチレン系弱
塩基性アニオン交換樹脂として、具体的にはロームアン
ドハース社製アンバーライト（登録商標、以下同じ）Ｉ
ＲＡ９６ＳＢ等が挙げられ、アクリル系弱塩基性アニオ
ン交換樹脂（ＷＡ）として、具体的にはアンバーライト
ＩＲＡ６７等が挙げられる。The present invention will be described in more detail below. In the present invention, as the weakly basic anion exchange resin, those having a styrene-based resin such as styrene-divinylbenzene copolymer as a resin matrix (styrene-based weakly basic anion exchange resin), acrylic-divinylbenzene copolymer, etc. Any of those having an acrylic resin as a resin matrix (acrylic weakly basic anion exchange resin) can be used, but it is more preferable to use a styrene weakly basic anion exchange resin. This is because the styrene weakly basic anion exchange resin has higher heat resistance than the acrylic weakly basic anion exchange resin. As the styrene-based weakly basic anion exchange resin, specifically, Amberlite (registered trademark, the same applies hereinafter) I manufactured by Rohm and Haas Co.
RA96SB and the like, and specific examples of the acrylic weakly basic anion exchange resin (WA) include Amberlite IRA67 and the like.
【００１０】また、本発明により除去する陰イオン性金
属錯体としては、例えば、塩化物イオン、フッ化物イオ
ン、硝酸イオン、燐酸イオン、シアンイオン等のアニオ
ン種と特定の金属とによって形成されたものを挙げるこ
とができるが、本発明はアニオン種が塩化物イオンであ
る陰イオン性金属錯体の除去に特に効果的に使用するこ
とができる。The anionic metal complex to be removed according to the present invention is, for example, one formed by an anion species such as chloride ion, fluoride ion, nitrate ion, phosphate ion, cyanide ion and a specific metal. The present invention can be used particularly effectively for the removal of anionic metal complexes whose anionic species is chloride ion.
【００１１】上述したアニオン種が塩化物イオンである
陰イオン性金属錯体の具体例としては、［ＺｎＣｌ4］
2-のような亜鉛−塩化物イオン錯体を挙げることがで
き、本発明は上記亜鉛−塩化物イオン錯体の除去に有効
に使用することができる。この場合、弱塩基性アニオン
交換樹脂に接触させる溶液中における亜鉛／塩化物イオ
ンのモル比は１０００／１以上、塩化物イオンの濃度は
０．３Ｎ以上とすることが適当であり、これにより溶液
中で亜鉛−塩化物イオン錯体を良好に形成させることが
できる。Specific examples of the above-mentioned anionic metal complex in which the anionic species is chloride ion include [ZnCl 4 ].
Examples thereof include zinc-chloride ion complexes such as 2- , and the present invention can be effectively used for removing the above zinc-chloride ion complexes. In this case, it is appropriate that the zinc / chloride ion molar ratio in the solution brought into contact with the weakly basic anion exchange resin is 1000/1 or more, and the chloride ion concentration is 0.3N or more. Among them, the zinc-chloride ion complex can be favorably formed.
【００１２】塩化物イオンと陰イオン性錯体を形成する
金属としては、上記亜鉛の他、Ｆｅ 2+、Ｐｄ2+、Ｃ
ｄ2+、Ａｇ+、Ｐｂ2+、Ｈｇ2+などが挙げられる。Form an anionic complex with chloride ion
As the metal, in addition to the above zinc, Fe 2+, Pd2+, C
d2+, Ag+, Pb2+, Hg2+And so on.
【００１３】本発明では、ｐＨが７以下の条件、特にｐ
Ｈが３以上７以下の条件で溶液を弱塩基性アニオン交換
樹脂に接触させることが好ましい。これにより、弱塩基
性アニオン交換樹脂によって陰イオン性金属錯体を効果
的に吸着することができる。In the present invention, pH is set to 7 or less, especially p
It is preferable to bring the solution into contact with the weakly basic anion exchange resin under the condition that H is 3 or more and 7 or less. Thereby, the anionic metal complex can be effectively adsorbed by the weakly basic anion exchange resin.
【００１４】また、本発明では、耐熱性の高い弱塩基性
アニオン交換樹脂を使用するため、温度が４０℃以上８
０℃以下の条件で溶液を弱塩基性アニオン交換樹脂に接
触させることができる。このように４０℃以上８０℃以
下という高温の溶液を通液する手段は、耐熱性の高いス
チレン系弱塩基性アニオン交換樹脂を使用する場合に特
に有効である。In the present invention, since a weakly basic anion exchange resin having high heat resistance is used, the temperature is 40 ° C. or higher and 8
The solution can be brought into contact with the weakly basic anion exchange resin under conditions of 0 ° C or lower. The means for passing a solution having a high temperature of 40 ° C. or higher and 80 ° C. or lower is particularly effective when using a styrene-based weakly basic anion exchange resin having high heat resistance.
【００１５】[0015]
【実施例】以下、実施例により本発明を具体的に示す
が、本発明は下記実施例に限定されるものではない。EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.
【００１６】（実施例１：食塩溶液中の亜鉛除去）スチ
レン系弱塩基性アニオン交換樹脂（アンバーライトＩＲ
Ａ９６ＳＢ）１．０Ｌを充填したカラムを用いて陰イオ
ン性金属錯体除去装置を作製した。上記弱塩基性アニオ
ン交換樹脂としては、予め塩酸を通薬してＣｌ形にした
ものを用いた。本実施例では、通液温度を室温として、
５％ＮａＣｌ溶液中のＺｎの除去を行った。原液のＺｎ
濃度は４００ｍｇ−Ｚｎ／Ｌ、ｐＨは３．７３であっ
た。上記カラムに原液を２Ｌ通液した。通液後に樹脂層
内に残った溶液を押し出すために、１Ｎ−ＨＣｌ溶液を
２Ｌ用いた。処理液中のＺｎ濃度を測定した結果を表１
に示す。Example 1 Removal of Zinc in Salt Solution Styrene-based weakly basic anion exchange resin (Amberlite IR)
An anionic metal complex removing device was produced using a column packed with 1.0 L of A96SB). As the above-mentioned weakly basic anion exchange resin, one which was previously passed through hydrochloric acid to be in the Cl form was used. In this embodiment, the liquid passing temperature is room temperature,
Removal of Zn in a 5% NaCl solution was performed. Undiluted Zn
The concentration was 400 mg-Zn / L and the pH was 3.73. 2 L of the stock solution was passed through the column. In order to extrude the solution remaining in the resin layer after passing the solution, 2 L of 1N-HCl solution was used. Table 1 shows the results of measuring the Zn concentration in the treatment liquid.
Shown in.
【００１７】（比較例１：食塩溶液中の亜鉛除去）強塩
基性アニオン交換樹脂（アンバーライトＩＲＡ４０２Ｂ
Ｌ）１．０Ｌを充填したカラムを用いて陰イオン性金属
錯体除去装置を作製した。上記強塩基性アニオン交換樹
脂としては、予め塩酸を通薬してＣｌ形にしたものを用
いた。その他の条件は実施例１と同様にして実験を行っ
た。処理液中のＺｎ濃度を測定した結果を表１に示す。Comparative Example 1: Removal of Zinc in Salt Solution Strongly Basic Anion Exchange Resin (Amberlite IRA402B)
L) An anionic metal complex removing apparatus was prepared using a column packed with 1.0 L. As the above-mentioned strongly basic anion exchange resin, one which had been previously passed through with hydrochloric acid to be in the Cl form was used. Other conditions were the same as in Example 1 for the experiment. Table 1 shows the results of measuring the Zn concentration in the treatment liquid.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１に示した結果より、弱塩基性アニオン
交換樹脂を用いる本発明（実施例１）によれば、強塩基
性アニオン交換樹脂を用いる従来技術（比較例１）と同
様に、陰イオン性金属錯体を除去できることが明らかに
なった。From the results shown in Table 1, according to the present invention (Example 1) using a weakly basic anion exchange resin, as in the prior art (Comparative Example 1) using a strongly basic anion exchange resin, anion It was revealed that the ionic metal complex can be removed.
【００２０】（実施例２：亜鉛の脱着除去）実施例１で
用いたカラムの弱塩基性アニオン交換樹脂からの亜鉛の
脱着を行った。脱着には純水を用いた。すなわち、上記
カラムに純水を通水することにより、弱塩基性アニオン
交換樹脂に吸着されている亜鉛の脱着を行った。脱着の
廃液を分析した結果として、純水の通水ＢＶ［通水Bed
Volume：水量（ｖ）／樹脂量（ｖ）］と廃液中の流出Ｚ
ｎ濃度との関係を表２および図１に示し、通水ＢＶと廃
液中の積算流出Ｚｎ濃度との関係を図１に示す。(Example 2: Desorption and removal of zinc) Desorption of zinc from the weakly basic anion exchange resin of the column used in Example 1 was carried out. Pure water was used for desorption. That is, pure water was passed through the column to desorb zinc adsorbed on the weakly basic anion exchange resin. As a result of analyzing the desorption waste liquid, pure water flow BV [water flow Bed
Volume: water amount (v) / resin amount (v)] and outflow Z in the waste liquid
Table 2 and FIG. 1 show the relationship with the n concentration, and FIG. 1 shows the relationship between the water flow BV and the cumulative outflow Zn concentration in the waste liquid.
【００２１】（比較例２：亜鉛の脱着除去）比較例１で
用いたカラムの強塩基性アニオン交換樹脂からの亜鉛の
脱着を行った。脱着には純水を用いた。脱着の廃液を分
析した結果を実施例２と同様に表２および図１に示す。(Comparative Example 2: Desorption and removal of zinc) Desorption of zinc from the strongly basic anion exchange resin of the column used in Comparative Example 1 was carried out. Pure water was used for desorption. The results of analysis of the desorption waste liquid are shown in Table 2 and FIG. 1 as in Example 2.
【００２２】[0022]
【表２】 [Table 2]
【００２３】表２および図１に示した結果より、弱塩基
性アニオン交換樹脂を用いる本発明（実施例２）では、
強塩基性アニオン交換樹脂を用いる従来技術（比較例
２）に比べ、アニオン交換樹脂からの陰イオン性金属錯
体の脱着性が良くなることが明らかになった。From the results shown in Table 2 and FIG. 1, in the present invention (Example 2) using a weakly basic anion exchange resin,
It was revealed that the desorption of the anionic metal complex from the anion exchange resin is improved as compared with the conventional technique using a strongly basic anion exchange resin (Comparative Example 2).
【００２４】（実施例３：高温での食塩溶液中の亜鉛除
去）スチレン系弱塩基性アニオン交換樹脂（アンバーラ
イトＩＲＡ９６ＳＢ）１．０Ｌを充填したカラムを用い
て陰イオン性金属錯体除去装置を作製した。上記弱塩基
性アニオン交換樹脂としては、予め塩酸を通薬してＣｌ
形にしたものを用いた。本実施例では、通液温度を５０
℃として、５％ＮａＣｌ溶液中のＺｎの除去を行った。
原液のＺｎ濃度は１６ｍｇ−Ｚｎ／Ｌ、ｐＨは４．７６
であった。上記カラムに原液を２Ｌ通液した。通液後に
樹脂層内に残った溶液を押し出すために、１Ｎ−ＨＣｌ
溶液を２Ｌ用いた。処理液中のＺｎ濃度を測定したとこ
ろ、亜鉛のリーク量は通液温度を室温とした実施例１と
同様に０．０５ｍｇ−Ｚｎ／Ｌ以下であった。(Example 3: Removal of zinc in salt solution at high temperature) An anionic metal complex removing apparatus was prepared using a column packed with 1.0 L of a styrene-based weakly basic anion exchange resin (Amberlite IRA96SB). did. As the weakly basic anion exchange resin, hydrochloric acid is previously passed through and Cl
The shape was used. In this embodiment, the liquid passing temperature is 50
At 5 ° C, Zn in the 5% NaCl solution was removed.
The stock solution has a Zn concentration of 16 mg-Zn / L and a pH of 4.76.
Met. 2 L of the stock solution was passed through the column. In order to push out the solution remaining in the resin layer after passing the liquid, 1N-HCl was added.
2 L of the solution was used. When the Zn concentration in the treatment liquid was measured, the leak amount of zinc was 0.05 mg-Zn / L or less as in Example 1 in which the liquid passing temperature was room temperature.
【００２５】また、通液温度を８０℃として同様の実験
を行った。処理液中のＺｎ濃度を測定したところ、亜鉛
のリーク量は通液温度を室温とした実施例１、通液温度
を５０℃とした実施例２と同様に０．０５ｍｇ−Ｚｎ／
Ｌ以下であった。A similar experiment was conducted with the liquid passing temperature set at 80 ° C. When the Zn concentration in the treatment liquid was measured, the amount of leakage of zinc was 0.05 mg-Zn /, as in Example 1 in which the liquid passing temperature was room temperature and in Example 2 in which the liquid passing temperature was 50 ° C.
It was below L.
【００２６】本実施例により、スチレン系弱塩基性アニ
オン交換樹脂は化学的に安定であるため、耐熱性が強塩
基性アニオン交換樹脂より高く、通液温度を８０℃にし
ても良好な陰イオン性金属錯体の除去性能を示すことが
確認された。According to this example, since the styrene-based weakly basic anion exchange resin is chemically stable, its heat resistance is higher than that of the strongly basic anion exchange resin, and a good anion is obtained even when the liquid passing temperature is 80 ° C. It was confirmed that the compound showed the removal performance of the metallic metal complex.
【００２７】[0027]
【発明の効果】本発明に係る陰イオン性金属錯体の除去
方法は、強塩基性アニオン交換樹脂を用いる従来技術と
同様に陰イオン性金属錯体を除去することができる上、
弱塩基性アニオン交換樹脂は強塩基性アニオン交換樹脂
よりも耐熱性が高いため高温の溶液を通液することが可
能になり、しかも通液後における陰イオン性金属錯体の
脱着性が向上する。INDUSTRIAL APPLICABILITY The method for removing an anionic metal complex according to the present invention is capable of removing an anionic metal complex in the same manner as in the prior art using a strongly basic anion exchange resin.
Since the weakly basic anion exchange resin has higher heat resistance than the strongly basic anion exchange resin, it becomes possible to pass the solution at a high temperature, and further, the desorption property of the anionic metal complex after passing the solution is improved.
【図１】実施例における通水ＢＶと廃液中の流出Ｚｎ濃
度との関係、および通水ＢＶと廃液中の積算流出Ｚｎ濃
度との関係を示すグラフである。FIG. 1 is a graph showing a relationship between a water flow BV and an outflow Zn concentration in a waste liquid and a relationship between a water flow BV and an integrated outflow Zn concentration in a waste liquid in an example.
Claims (6)
塩基性アニオン交換樹脂に接触させることを特徴とする
陰イオン性金属錯体の除去方法。1. A method for removing an anionic metal complex, which comprises contacting a solution containing the anionic metal complex with a weakly basic anion exchange resin.
樹脂を母体とすることを特徴とする請求項１に記載の陰
イオン性金属錯体の除去方法。2. The method for removing an anionic metal complex according to claim 1, wherein the weakly basic anion exchange resin has a styrene resin as a matrix.
オン種が塩化物イオンであることを特徴とする請求項１
または２に記載の陰イオン性金属錯体の除去方法。3. The anion species forming the anionic metal complex is chloride ion.
Alternatively, the method for removing an anionic metal complex according to item 2.
ン錯体であることを特徴とする請求項３に記載の陰イオ
ン性金属錯体の除去方法。4. The method for removing an anionic metal complex according to claim 3, wherein the anionic metal complex is a zinc-chloride ion complex.
体を含有する溶液を弱塩基性アニオン交換樹脂に接触さ
せることを特徴とする請求項１〜４のいずれか１項に記
載の陰イオン性金属錯体の除去方法。5. The anion according to claim 1, wherein the solution containing the anionic metal complex is brought into contact with the weakly basic anion exchange resin under the condition that the pH is 7 or less. Method for removing ionic metal complex.
イオン性金属錯体を含有する溶液を弱塩基性アニオン交
換樹脂に接触させることを特徴とする請求項１〜５のい
ずれか１項に記載の陰イオン性金属錯体の除去方法。6. The weak basic anion exchange resin is brought into contact with a solution containing an anionic metal complex under the condition of a temperature of 40 ° C. or higher and 80 ° C. or lower. The method for removing an anionic metal complex according to 1.
Priority Applications (3)
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|---|---|---|---|
| JP2002074367A JP4294253B2 (en) | 2002-03-18 | 2002-03-18 | Method for removing anionic metal complex |
| PCT/JP2003/001765 WO2003078330A1 (en) | 2002-03-18 | 2003-02-19 | Method of removing anionic metal complex |
| AU2003211490A AU2003211490A1 (en) | 2002-03-18 | 2003-02-19 | Method of removing anionic metal complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002074367A JP4294253B2 (en) | 2002-03-18 | 2002-03-18 | Method for removing anionic metal complex |
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| Publication Number | Publication Date |
|---|---|
| JP2003265902A true JP2003265902A (en) | 2003-09-24 |
| JP4294253B2 JP4294253B2 (en) | 2009-07-08 |
Family
ID=28035297
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|---|---|---|---|
| JP2002074367A Expired - Lifetime JP4294253B2 (en) | 2002-03-18 | 2002-03-18 | Method for removing anionic metal complex |
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| Country | Link |
|---|---|
| JP (1) | JP4294253B2 (en) |
| AU (1) | AU2003211490A1 (en) |
| WO (1) | WO2003078330A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005296892A (en) * | 2004-04-15 | 2005-10-27 | Japan Organo Co Ltd | Method for removing anionic metal complex |
| KR101247941B1 (en) * | 2005-03-31 | 2013-04-01 | 도아고세이가부시키가이샤 | Refining Method of Copper Chloride Etching Waste Fluid And Refined Copper Chloride Solution |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731593B (en) * | 2014-12-10 | 2021-03-09 | 陶氏环球技术有限公司 | Method for removing mercury from solution |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5481664A (en) * | 1977-12-10 | 1979-06-29 | Fuji Kasui Kogyo Kk | Method of treating waster water containing cyan |
| JPS588582A (en) * | 1981-07-07 | 1983-01-18 | Hitachi Plant Eng & Constr Co Ltd | Method for purifying fluorine-containing wastewater |
| JPS5864181A (en) * | 1981-10-15 | 1983-04-16 | Hitachi Plant Eng & Constr Co Ltd | Treatment of fluorine-containing waste water |
| DE3144974C2 (en) * | 1981-11-12 | 1986-01-09 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Process for the separation of actinide ions from aqueous, basic, carbonate-containing solutions |
| JPS58216775A (en) * | 1982-05-28 | 1983-12-16 | Kurita Water Ind Ltd | Ion exchange method for water containing heavy metals and chelating agents |
| JPH0354118A (en) * | 1989-07-24 | 1991-03-08 | Sumitomo Chem Co Ltd | Method for recovering rhenium |
| US5500125A (en) * | 1994-05-19 | 1996-03-19 | Eastman Kodak Company | Process for recycling photographic wash water |
| JPH09225203A (en) * | 1996-02-20 | 1997-09-02 | Chiyoda Corp | Adsorbent for metal-containing neutral complex and method for recovering metal-containing neutral complex from liquid |
-
2002
- 2002-03-18 JP JP2002074367A patent/JP4294253B2/en not_active Expired - Lifetime
-
2003
- 2003-02-19 WO PCT/JP2003/001765 patent/WO2003078330A1/en not_active Ceased
- 2003-02-19 AU AU2003211490A patent/AU2003211490A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005296892A (en) * | 2004-04-15 | 2005-10-27 | Japan Organo Co Ltd | Method for removing anionic metal complex |
| KR101247941B1 (en) * | 2005-03-31 | 2013-04-01 | 도아고세이가부시키가이샤 | Refining Method of Copper Chloride Etching Waste Fluid And Refined Copper Chloride Solution |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003211490A1 (en) | 2003-09-29 |
| WO2003078330A1 (en) | 2003-09-25 |
| JP4294253B2 (en) | 2009-07-08 |
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