JPH06227813A - Noble metallic ion collector and its production - Google Patents
Noble metallic ion collector and its productionInfo
- Publication number
- JPH06227813A JPH06227813A JP28701192A JP28701192A JPH06227813A JP H06227813 A JPH06227813 A JP H06227813A JP 28701192 A JP28701192 A JP 28701192A JP 28701192 A JP28701192 A JP 28701192A JP H06227813 A JPH06227813 A JP H06227813A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- glucosamine
- derivative
- pyridine ring
- chemical formula
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は貴金属イオン捕集材及び
その製法、貴金属の回収法に関するものであり、更に詳
しく述べると塩酸酸性の水溶液から希薄濃度の貴金属イ
オン、特に金、パラジウム(II)及び白金(IV)を効率よく
回収出来る貴金属イオンの捕集剤である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a noble metal ion scavenger, a method for producing the same, and a noble metal recovery method. More specifically, the present invention relates to a noble metal ion in a dilute concentration, particularly gold or palladium (II) It is also a scavenger of precious metal ions that can efficiently collect platinum (IV).
【０００２】[0002]
【従来の技術】水溶液からの貴金属イオンの分離・回収
法としては、油溶性の捕集剤を溶解した有機溶媒と液−
液接触させる溶媒抽出法及び、イオン交換樹脂や活性炭
などを用いて固−液接触させる吸着法があり、特に後者
は希薄溶液の処理に適している。また、現在まで選択性
の高いキレート樹脂の開発が活発に進められ、多くのキ
レート樹脂が市販されている。しかしながら、これらの
キレート樹脂は比較的高価であるが、特定の貴金属イオ
ンに対する選択性はそれほど高くないものが多かった。2. Description of the Related Art As a method for separating and recovering precious metal ions from an aqueous solution, an organic solvent and a liquid in which an oil-soluble scavenger is dissolved are used.
There are a solvent extraction method in which a liquid is contacted and an adsorption method in which a solid-liquid contact is performed using an ion exchange resin or activated carbon, and the latter is particularly suitable for treating a dilute solution. Further, until now, chelate resins with high selectivity have been actively developed, and many chelate resins are commercially available. However, although these chelate resins are relatively expensive, many of them are not so selective with respect to a specific noble metal ion.
【０００３】[0003]
【発明が解決しようとする課題】水産加工場ではエビ、
カニ等甲殻類の殻が大量に発生し、現在は産業廃棄物と
して処理されている。これらの殻にはカルシウム、天然
多糖類であるキチン及びタンパク質がほぼ等量づつ含ま
れている。キチンをアルカリ水溶液中で加熱するとアミ
ノ基を含み反応性に富むキトサンが得られるため、多く
の分野で有効利用の研究が進められている。[Problems to be solved by the invention] Shrimp,
A large amount of crustacean shells such as crabs have been generated and are now treated as industrial waste. These shells contain approximately equal amounts of calcium, natural polysaccharide chitin and protein. When chitin is heated in an alkaline aqueous solution, chitosan containing an amino group and having a high reactivity can be obtained. Therefore, researches on effective utilization of the chitin have been advanced in many fields.
【０００４】ここではキトサンのアミノ基にキレート形
成能を有する官能基の導入について研究し、貴金属捕集
剤を開発しようとするものである。Here, the introduction of a functional group having a chelate-forming ability into the amino group of chitosan is studied to develop a noble metal scavenger.
【０００５】[0005]
【課題を解決するための手段】本発明者等は先にキトサ
ンが特定の金属イオンに対して高い選択性を有し、且つ
飽和吸着量も相当大きいことを見出して発表した[ Che
m,Lett. p.1281(1988)]。これは天然多糖類キトサンの
持つ、(1) 高い親水性、(2) 柔軟性に富んだ骨格構造及
び、(3) 多くの活性アミノ基の存在、によるものと考え
られる。[Means for Solving the Problems] The present inventors have previously announced that chitosan has a high selectivity with respect to a specific metal ion and has a large saturated adsorption amount [Che.
m, Lett. p. 1281 (1988)]. It is considered that this is due to (1) high hydrophilicity, (2) flexible skeletal structure, and (3) the presence of many active amino groups, which the natural polysaccharide chitosan has.
【０００６】しかし、キトサンを構成するグルコサミン
のアミノ基に直接キレート性官能基を導入すると、貴金
属の吸着が起こる酸性領域ではキトサンが溶解するた
め、貴金属イオンの回収が出来ない。この問題を解決す
るためキトサン分子間の架橋構造の形成とキレート形成
能を有する官能基の導入について研究した結果、本発明
に到達した。However, if a chelating functional group is directly introduced into the amino group of glucosamine constituting chitosan, the chitosan is dissolved in an acidic region where the adsorption of the noble metal occurs, so that the noble metal ion cannot be recovered. In order to solve this problem, the present invention has been achieved as a result of research on formation of a crosslinked structure between chitosan molecules and introduction of a functional group having a chelate forming ability.
【０００７】すなわち、キトサン分子間に架橋せしめた
構造を有するポリマーにおいて、キトサンを構成するグ
ルコサミン (2-アミノ-D- グルコース) として、化学式
３に示すピリジン環を含むグルコサミン誘導体及び／ま
たは化学式４に示すチオフェン環を含むグルコサミン誘
導体を含むポリマーである貴金属イオン捕集剤である。That is, in a polymer having a structure in which chitosan molecules are crosslinked, a glucosamine derivative containing a pyridine ring shown in Chemical Formula 3 and / or a chemical formula 4 is used as glucosamine (2-amino-D-glucose) constituting chitosan. It is a noble metal ion scavenger which is a polymer containing a glucosamine derivative containing a thiophene ring.
【０００８】[0008]
【化３】 [Chemical 3]
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】また、キトサンをピリジン環またはチオフ
ェン環を含むアルデヒド誘導体と反応せしめて、キトサ
ンを構成するグルコサミンのアミノ基にシッフ塩基を形
成させた後、架橋剤を加えてキトサン分子間の架橋を行
い、四水素化ホウ素ナトリウムによってシッフ塩基を還
元することにより、キトサン分子間に架橋構造を有し且
つグルコサミンのアミノ基にピリジン環またはチオフェ
ン環を導入した、化学式３及び／または化学式４に示す
グルコサミン誘導体を含むポリマーである貴金属イオン
捕集剤の製法及び、貴金属イオンの回収方法である。Further, chitosan is reacted with an aldehyde derivative containing a pyridine ring or a thiophene ring to form a Schiff base at the amino group of glucosamine constituting chitosan, and then a cross-linking agent is added to cross-link chitosan molecules. , A glucosamine derivative represented by Chemical Formula 3 and / or Chemical Formula 4 having a cross-linking structure between chitosan molecules and introducing a pyridine ring or a thiophene ring into the amino group of glucosamine by reducing a Schiff base with sodium tetraborohydride A method for producing a noble metal ion scavenger, which is a polymer containing, and a method for recovering noble metal ions.
【００１１】以下本発明について詳しく説明する。The present invention will be described in detail below.
【００１２】前記の様にキトサンは、市販のキレート樹
脂にはみられない優れた金属イオン吸着特性を有し、か
つ出発原料がバイオマス産業の廃棄物であるため、安価
に得られる利点がある。しかし、貴金属または重金属イ
オンの吸着が起こるのは、酸性ではあるが、比較的pHが
高い領域であるため、pHが極めて低い酸侵出液などを処
理する場合には、アルカリを加えてpH調整をしなければ
ならないという難点があった。この問題を解決するため
多くのキトサン誘導体が合成され、金属イオンの吸着性
が検討された。しかし、金属イオンの効果的な捕集を目
的としてキレート形成能を有する官能基を導入すると、
キトサン誘導体が酸性溶液に溶解する問題が発生した。[0012] As described above, chitosan has excellent metal ion adsorption properties not found in commercially available chelating resins, and has a merit that it can be obtained at a low cost because the starting material is waste from the biomass industry. However, the adsorption of noble metal or heavy metal ions occurs in the relatively high pH region although it is acidic, so when treating an acid leachate with an extremely low pH, add an alkali to adjust the pH. There was a difficulty that I had to In order to solve this problem, many chitosan derivatives have been synthesized and their adsorption of metal ions was investigated. However, when a functional group having a chelate-forming ability is introduced for the purpose of effectively collecting metal ions,
There was a problem that the chitosan derivative was dissolved in the acidic solution.
【００１３】そこで官能基を導入したキトサン誘導体を
架橋して、酸性溶液に不溶な樹脂にすることが試みられ
たが、その架橋反応によって官能基がつぶされるため交
換容量が大幅に低下する問題が生じた。Therefore, it has been attempted to crosslink a chitosan derivative having a functional group introduced thereinto to make a resin insoluble in an acidic solution, but the crosslinking reaction crushes the functional group, resulting in a large decrease in the exchange capacity. occured.
【００１４】本発明者等はこの問題を解決するため、先
ずキトサンを構成するグルコサミンのアミノ基を、ピリ
ジン環またはチオフェン環を含むアルデヒド誘導体と反
応させ、シッフ塩基を形成させてアミノ基を保護してか
ら、エピクロロヒドリンによりキトサン分子間の架橋を
行い、次に四水素化ホウ素ナトリウムでシッフ塩基を還
元することにより、キレート形成能を有する官能基であ
るピリジン環、またはチオフェン環を有する架橋ポリマ
ーを合成する方法によってこの問題を解決した。In order to solve this problem, the present inventors first react the amino group of glucosamine constituting chitosan with an aldehyde derivative containing a pyridine ring or a thiophene ring to form a Schiff base to protect the amino group. After that, cross-linking between chitosan molecules with epichlorohydrin, and then reducing the Schiff base with sodium tetraborohydride, cross-linking with a pyridine ring or thiophene ring, which is a functional group capable of forming a chelate. This problem was solved by the method of polymer synthesis.
【００１５】すなわち、分子骨格が架橋構造を有するた
め、貴金属イオンの吸着に適した酸性溶液中で溶解する
ことがなく、且つキレート形成能を有する官能基が結合
されているキレート樹脂である。That is, since the molecular skeleton has a crosslinked structure, it is a chelate resin to which a functional group capable of forming a chelate is bonded without being dissolved in an acidic solution suitable for adsorption of noble metal ions.
【００１６】本発明の貴金属イオン捕集剤であるポリマ
ーの骨格は、キトサンの分子間に架橋結合が形成されて
いる構造となっている必要がある。キトサン分子間を架
橋する化学成分は特に限定しない。例えば、架橋反応に
おける反応性が高く安定した架橋結合を形成するエピク
ロロヒドリン等が好ましい。The skeleton of the polymer which is the noble metal ion scavenger of the present invention must have a structure in which cross-linking bonds are formed between chitosan molecules. The chemical component that crosslinks the chitosan molecules is not particularly limited. For example, epichlorohydrin or the like, which forms a stable cross-link with high reactivity in the cross-linking reaction, is preferable.
【００１７】キトサンは中性溶液中では溶解しないが、
塩酸その他酸性溶液中では酸がグルコサミン中に含まれ
るアミノ基と塩を作って溶解する。しかし、本発明のポ
リマーは前述の様に架橋構造を有するため、耐酸性のみ
ならず耐アルカリ性も高くキレート樹脂のベースとして
適している。Chitosan does not dissolve in neutral solution,
In hydrochloric acid and other acidic solutions, acid forms a salt with the amino groups contained in glucosamine and dissolves. However, since the polymer of the present invention has a crosslinked structure as described above, it has high acid resistance as well as alkali resistance and is suitable as a base for a chelate resin.
【００１８】また、本発明の貴金属イオン捕集剤のポリ
マーに含まれるピリジン環またはチオフェン環は、キト
サンを構成するグルコサミン (2-アミノ-D- グルコー
ス) のアミノ基に結合している。キトサンに含まれるア
ミノ基の中ピリジン環またはチオフェン環が結合してい
る比率は特に限定しないが、アミノ基の中約90％または
それ以上にピリジン環またはチオフェン環が結合してい
るポリマーが好ましい。本発明の貴金属捕集剤ポリマー
分子に含まれるキレート形成能を有する官能基は、ピリ
ジン環のみまたはチオフェン環のみでもよく、或いはこ
の両者が含まれていてもよい。The pyridine ring or thiophene ring contained in the polymer of the noble metal ion scavenger of the present invention is bonded to the amino group of glucosamine (2-amino-D-glucose) constituting chitosan. The ratio of the pyridine ring or thiophene ring bonded to the amino group contained in chitosan is not particularly limited, but a polymer in which the pyridine ring or thiophene ring is bonded to about 90% or more of the amino groups is preferable. The chelate-forming functional group contained in the noble metal scavenger polymer molecule of the present invention may be a pyridine ring alone or a thiophene ring alone, or may contain both of them.
【００１９】本発明の貴金属イオン捕集剤を調製するに
は先に述べた様に、先ずキトサンを構成するグルコサミ
ンのアミノ基を保護するため、ピリジン環またはチオフ
ェン環を含むアルデヒド誘導体との反応によって、シッ
フ塩基を形成させた後、エピクロロヒドリンによりキト
サン分子間の架橋を行い、次に四水素化ホウ素ナトリウ
ムでシッフ塩基を還元することにより、グルコサミンの
アミノ基にキレート形成能を有する官能基であるピリジ
ン環、またはチオフェン環が結合した架橋結合を有する
キトサン誘導体が得られる。To prepare the noble metal ion scavenger of the present invention, as described above, first, in order to protect the amino group of glucosamine constituting chitosan, it is reacted with an aldehyde derivative containing a pyridine ring or a thiophene ring. After forming a Schiff base, cross-linking between chitosan molecules with epichlorohydrin, and then reducing the Schiff base with sodium tetraborohydride, a functional group capable of forming a chelate at the amino group of glucosamine. A chitosan derivative having a cross-linking bond with a pyridine ring or a thiophene ring is obtained.
【００２０】本発明において捕集の対象となる貴金属イ
オンの種類は特に限定しないが、キトサン誘導体ポリマ
ーのピリジン環を有するグルコサミンを含む捕集剤も、
チオフェン環を含む捕集剤も、酸性溶液の中比較的pHが
高い領域において貴金属イオン特に金、パラジウム(I
I)、白金(IV)等のイオンに対して高い吸着性を示す。ピ
リジン環を有する捕集剤は水銀イオンにも吸着性を有す
るが、ロジウム、銅、ニッケル等の重金属イオンの吸着
性は低い。また、チオフェン環を有する捕集剤は金、白
金、パラジウムには高い吸着性を示すが、それ以外の金
属イオンの吸着性は低い。また、両者とも特に塩酸酸性
溶液中において高い吸着性を示す。The kind of the noble metal ion to be collected in the present invention is not particularly limited, but the collecting agent containing glucosamine having a pyridine ring of the chitosan derivative polymer is also included.
The scavenger containing a thiophene ring is also used for precious metal ions, especially gold and palladium (I
It has high adsorption properties for ions such as I) and platinum (IV). The pyridine ring-containing scavenger also has an adsorbability for mercury ions, but has a low adsorbability for heavy metal ions such as rhodium, copper, and nickel. Further, the scavenger having a thiophene ring has high adsorptivity for gold, platinum and palladium, but has low adsorptivity for other metal ions. Further, both of them show high adsorptivity especially in an acidic solution of hydrochloric acid.
【００２１】以下、実施例を挙げて本発明を更に具体的
に説明する。Hereinafter, the present invention will be described more specifically with reference to examples.
【００２２】[0022]
（実施例１）キトサン16g を２％の酢酸水溶液に溶解
し、メタノールで希釈した後、窒素還流下でピリジン−
２−アルデヒドを滴下し、室温で24時間攪拌した後、一
夜放置した。中間体として得られたシッフ塩基を濾別
後、ジメチルスルホキシドで膨潤させエピクロロヒドリ
ン中で24時間ゆっくりと攪拌した。これを濾別後、0.1N
水酸化ナトリウム溶液に入れ、80℃で24時間攪拌し架橋
反応を行った。次に水を溶媒として四水素化ホウ素ナト
リウムを加えてシッフ塩基を還元した。(Example 1) 16 g of chitosan was dissolved in a 2% aqueous acetic acid solution, diluted with methanol, and then pyridine was added under nitrogen reflux.
2-aldehyde was added dropwise, the mixture was stirred at room temperature for 24 hours, and then left overnight. The Schiff base obtained as an intermediate was filtered off, swollen with dimethyl sulfoxide and slowly stirred in epichlorohydrin for 24 hours. After filtering this off, 0.1N
The mixture was placed in a sodium hydroxide solution and stirred at 80 ° C. for 24 hours to carry out a crosslinking reaction. Next, using water as a solvent, sodium borohydride was added to reduce the Schiff base.
【００２３】この結果、キトサン分子間に架橋構造を有
し、キトサンを構成するグルコサミンとして、化学式３
に示すピリジン環を含むグルコサミン誘導体を含むポリ
マーが得られた。As a result, glucosamine having a cross-linking structure between chitosan molecules and constituting chitosan is represented by the chemical formula 3
A polymer containing the glucosamine derivative containing the pyridine ring shown in was obtained.
【００２４】前記で得られたポリマー約0.1gと、濃度５
×10-3mol/dm3 の金属イオンを含む塩酸溶液15mlを、振
り混ぜて混合し平衡吸着量を測定した。各種金属イオン
の吸着率と塩酸濃度との関係を図１に示す。About 0.1 g of the polymer obtained above and a concentration of 5
15 ml of a hydrochloric acid solution containing × 10 −3 mol / dm 3 of metal ions was shaken and mixed to measure the equilibrium adsorption amount. The relationship between the adsorption rate of various metal ions and the concentration of hydrochloric acid is shown in FIG.
【００２５】（比較例１）大賀氏等が発表した方法に従
って[ Bull.Chem.Soc.Jpn,. 60,444(1987)] 、銅イオン
をキトサンのアミノ基の保護基として用い、エピクロロ
ヒドリンによってキトサン分子間の架橋を行い、酸に不
溶な架橋キトサン樹脂を合成した。架橋キトサン樹脂と
ピリジン環を導入したキトサン誘導体の金属イオン吸着
性を比較するため、架橋キトサン樹脂を用いて塩酸溶液
からパラジウムの吸着試験を行った。その結果を図１の
曲線９に示す。(Comparative Example 1) According to the method published by Oga et al. [Bull.Chem.Soc.Jpn, 60,444 (1987)], copper ion was used as a protecting group for the amino group of chitosan, and epichlorohydrin was used. Cross-linking between chitosan molecules was carried out to synthesize an acid-insoluble cross-linked chitosan resin. In order to compare the metal ion adsorption properties of the crosslinked chitosan resin and the chitosan derivative having a pyridine ring introduced, the adsorption test of palladium was carried out from the hydrochloric acid solution using the crosslinked chitosan resin. The result is shown by the curve 9 in FIG.
【００２６】図１に示した結果より、実施例１で得られ
たグルコサミンとして化学式３に示したグルコサミン誘
導体を含むキトサンの架橋ポリマーは、架橋キトサン樹
脂より高い塩酸濃度においても尚、パラジウムおよび白
金に対して高い吸着性を有することが認められる。From the results shown in FIG. 1, the crosslinked polymer of chitosan containing the glucosamine derivative represented by the chemical formula 3 as glucosamine obtained in Example 1 was converted to palladium and platinum even at higher hydrochloric acid concentration than the crosslinked chitosan resin. It is recognized that it has a high adsorptivity.
【００２７】（実施例２）実施例１および比較例に示し
た方法で合成した、ピリジン環を導入したキトサン誘導
体及び架橋キトサンを用いて、0.01M の塩酸溶液中で種
々な濃度のパラジウム溶液からパラジウムの吸着試験を
行った。(Example 2) Using a chitosan derivative having a pyridine ring introduced and a crosslinked chitosan synthesized by the methods shown in Example 1 and Comparative Example, a palladium solution having various concentrations was prepared in a 0.01 M hydrochloric acid solution. A palladium adsorption test was conducted.
【００２８】その結果を図２に示す。The results are shown in FIG.
【００２９】図２に示したパラジウムの吸着量は吸着剤
乾燥量当たりの吸着パラジウムのモル数で、水溶液中の
パラジウム濃度が増加するにつれて吸着量は増加した。
更に水相中のパラジウム濃度が増加すると吸着量はほぼ
一定値に達し、パラジウムイオンの飽和吸着量、あるい
は最大交換量を示している。The amount of adsorbed palladium shown in FIG. 2 is the number of moles of adsorbed palladium per dry amount of the adsorbent, and the adsorbed amount increased as the concentration of palladium in the aqueous solution increased.
When the palladium concentration in the aqueous phase further increases, the adsorption amount reaches a substantially constant value, which indicates the saturated adsorption amount of palladium ions or the maximum exchange amount.
【００３０】これらの比較によって、実施例１で得られ
たピリジン環を導入した架橋キトサン誘導体のパラジウ
ムの飽和吸着量は、架橋キトサン樹脂より著しく高いこ
とが分かる。From these comparisons, it is found that the saturated adsorption amount of palladium of the crosslinked chitosan derivative having the pyridine ring introduced therein obtained in Example 1 is significantly higher than that of the crosslinked chitosan resin.
【００３１】（実施例３）キトサン16g を２％の酢酸水
溶液に溶解し、メタノールで希釈した後、窒素還流下で
チオフェン−２−アルデヒドを滴下し、室温で24時間攪
拌した後、一夜放置した。中間体として得られたシッフ
塩基を濾別後、ジメチルスルホキシドで膨潤させエピク
ロロヒドリン中で24時間ゆっくりと攪拌した。これを濾
別後、0.1N水酸化ナトリウム溶液に入れ、80℃で24時間
攪拌し架橋反応を行った。次に水を溶媒として水素化ホ
ウ素ナトリウムを加えてシッフ塩基を還元した。(Example 3) 16 g of chitosan was dissolved in a 2% aqueous acetic acid solution, diluted with methanol, thiophene-2-aldehyde was added dropwise under nitrogen reflux, and the mixture was stirred at room temperature for 24 hours and then left overnight. . The Schiff base obtained as an intermediate was filtered off, swollen with dimethyl sulfoxide and slowly stirred in epichlorohydrin for 24 hours. After filtering this off, it was placed in a 0.1N sodium hydroxide solution and stirred at 80 ° C. for 24 hours to carry out a crosslinking reaction. Next, using water as a solvent, sodium borohydride was added to reduce the Schiff base.
【００３２】この結果、キトサン分子間に架橋構造を有
し、キトサンを構成するグルコサミンとして、化学式４
に示すチオフェン環を含むグルコサミン誘導体を含むポ
リマーが得られた。As a result, glucosamine having a cross-linking structure between chitosan molecules and constituting chitosan is represented by the chemical formula 4
A polymer containing a glucosamine derivative containing a thiophene ring shown in was obtained.
【００３３】前記で得られたポリマー約0.1gと濃度５×
10-3mol/dm3 の金属イオンを含む塩酸溶液15mlを振り混
ぜて混合し平衡吸着量を測定した。各種金属イオンの吸
着率と塩酸濃度との関係を図３に示す。このポリマーは
金、白金及びパラジウムには高い吸着性を示すが、ロジ
ウム、水銀、カドミウム、銅、ニッケル、亜鉛、マンガ
ンは全く吸着されなかった。About 0.1 g of the polymer obtained above and a concentration of 5 ×
15 ml of a hydrochloric acid solution containing 10 −3 mol / dm 3 of metal ions was shaken and mixed to measure the equilibrium adsorption amount. The relationship between the adsorption rate of various metal ions and the concentration of hydrochloric acid is shown in FIG. This polymer showed high adsorptivity for gold, platinum and palladium, but rhodium, mercury, cadmium, copper, nickel, zinc and manganese were not adsorbed at all.
【００３４】（実施例４）実施例３および比較例に示し
た方法で合成した、化学式４に示すチオフェン環を含む
グルコサミン誘導体を含むポリマー及び、架橋キトサン
樹脂を用いて種々の濃度のパラジウムを含む0.01M の塩
酸溶液からパラジウムの吸着試験を行った。Example 4 A polymer containing the glucosamine derivative having a thiophene ring represented by the chemical formula 4 synthesized by the method shown in Example 3 and the comparative example, and a cross-linked chitosan resin were used to contain various concentrations of palladium. An adsorption test of palladium was carried out from a 0.01 M hydrochloric acid solution.
【００３５】その結果を図４に示す。The results are shown in FIG.
【００３６】図４に示したパラジウムの吸着量は吸着剤
乾燥量当たりの吸着パラジウムのモル数で、水溶液中の
パラジウム濃度が増加すると共に吸着量は増加した。更
に水相中のパラジウム濃度が増加すると吸着量はほぼ一
定値に達し、これがパラジウムイオンの飽和吸着量、あ
るいは最大交換量を示している。The amount of adsorbed palladium shown in FIG. 4 is the number of moles of adsorbed palladium per dry amount of the adsorbent, and the adsorbed amount increased as the concentration of palladium in the aqueous solution increased. When the palladium concentration in the aqueous phase further increases, the adsorption amount reaches a substantially constant value, which indicates the saturated adsorption amount or maximum exchange amount of palladium ions.
【００３７】これらの試験結果の比較によって、実施例
３で得られたチオフェン環を導入した架橋キトサン誘導
体のパラジウムの飽和吸着量は、架橋キトサン樹脂より
著しく高いことが分かる。Comparison of these test results shows that the saturated adsorption amount of palladium of the crosslinked chitosan derivative having a thiophene ring introduced therein obtained in Example 3 is significantly higher than that of the crosslinked chitosan resin.
【００３８】[0038]
【発明の効果】本発明の貴金属捕集剤は、水産加工業の
廃棄物であるキチンから得られたもので、架橋構造を有
するキトサン分子に、キレート形成能を有するピリジン
環或いはチオフェン環を結合させたものである。特に
金、白金、パラジウム等の貴金属イオンに対して高い吸
着性を示し、これらの貴金属の回収に有効な捕集剤であ
る。Industrial Applicability The precious metal scavenger of the present invention is obtained from chitin, which is a waste product of the marine product processing industry, and a chitosan molecule having a crosslinked structure is bound with a pyridine ring or a thiophene ring having a chelate-forming ability. It was made. In particular, it shows a high adsorptivity for precious metal ions such as gold, platinum, and palladium, and is an effective scavenger for recovering these precious metals.
【図１】貴金属イオン捕集剤として化学式３に示したグ
ルコサミン誘導体を含む本発明の捕集剤及び架橋キトサ
ン樹脂を使用した場合の、水溶液中の塩酸濃度と金属イ
オンの吸着率の関係を示す。FIG. 1 shows the relationship between the concentration of hydrochloric acid in an aqueous solution and the adsorption rate of metal ions when the scavenger of the present invention containing the glucosamine derivative represented by Chemical Formula 3 and the crosslinked chitosan resin are used as the noble metal ion scavenger. .
１ 本発明の捕集剤−白金 ２ 〃 〃 −パラジウム ３ 〃 〃 −ロジウム ４ 〃 〃 −金 ５ 〃 〃 −水銀 ６ 〃 〃 −カドミウム ７ 〃 〃 −銅 ８ 〃 〃 −ニッケル ９ 架橋キトサン樹脂−パラジウム 1 Scavenger of the present invention-platinum 2 〃 〃-palladium 3 〃 〃-rhodium 4 〃 〃-gold 5 〃 〃-mercury 6 〃 〃-cadmium 7 〃 〃-copper 8 〃 sodium 〃 〃
【図２】貴金属イオン捕集剤として、化学式３及び化学
式４に示したグルコサミン誘導体を含む本発明の捕集剤
を使用した場合の、塩酸水溶液中のパラジウム濃度とパ
ラジウムイオンの吸着量の関係を示す。FIG. 2 shows the relationship between the palladium concentration in a hydrochloric acid aqueous solution and the amount of adsorbed palladium ions when the scavenger of the present invention containing the glucosamine derivative represented by the chemical formulas 3 and 4 is used as the noble metal ion scavenger. Show.
10 化学式３に示したグルコサミン誘導体を含む本発明
の捕集剤 11 架橋キトサン樹脂10 Collection Agent of the Present Invention Containing Glucosamine Derivative Shown in Chemical Formula 11 11 Crosslinked Chitosan Resin
【図３】貴金属イオン捕集剤として化学式４に示したグ
ルコサミン誘導体を含む本発明の捕集剤を使用した場合
の、水溶液の塩酸濃度と金属イオンの吸着率の関係を示
す。FIG. 3 shows the relationship between the concentration of hydrochloric acid in an aqueous solution and the adsorption rate of metal ions when the scavenger of the present invention containing the glucosamine derivative represented by Chemical Formula 4 is used as the noble metal ion scavenger.
12 白金 13 パラジウム 14 金 12 platinum 13 palladium 14 gold
【図４】貴金属イオン捕集剤として架橋キトサン樹脂と
化学式４に示したグルコサミン誘導体を含む本発明の捕
集剤を使用した場合の、塩酸水溶液中のパラジウム濃度
とパラジウムイオン吸着量の関係を示す。FIG. 4 shows the relationship between the palladium concentration in a hydrochloric acid aqueous solution and the amount of adsorbed palladium ions when a scavenger of the present invention containing a crosslinked chitosan resin and a glucosamine derivative represented by Chemical Formula 4 is used as a noble metal ion scavenger. .
15 化学式４に示したグルコサミン誘導体を含む本発明
の捕集剤 16 架橋キトサン樹脂15 Collection Agent of the Present Invention Containing Glucosamine Derivative Shown in Chemical Formula 4 16 Crosslinked Chitosan Resin
Claims (3)
するポリマーにおいて、キトサンを構成するグルコサミ
ン (2-アミノ-D- グルコース) として、化学式１に示す
ピリジン環を含むグルコサミン誘導体及び／または化学
式２に示すチオフェン環を含むグルコサミン誘導体を含
むポリマーである貴金属イオン捕集剤。 【化１】 【化２】 1. In a polymer having a structure in which chitosan molecules are crosslinked, a glucosamine derivative containing a pyridine ring shown in Chemical Formula 1 and / or a chemical formula 2 is used as glucosamine (2-amino-D-glucose) constituting chitosan. A noble metal ion scavenger which is a polymer containing a glucosamine derivative containing a thiophene ring. [Chemical 1] [Chemical 2]
環を含むアルデヒド誘導体と反応せしめて、キトサンを
構成するグルコサミンのアミノ基にシッフ塩基を形成さ
せた後、架橋剤を加えてキトサン分子間の架橋を行い、
四水素化ホウ素ナトリウムによってシッフ塩基を還元す
ることにより、キトサン分子間に架橋構造を有し且つグ
ルコサミンのアミノ基にピリジン環またはチオフェン環
を導入した、化学式１及び／または化学式２に示すグル
コサミン誘導体を含むポリマーである貴金属イオン捕集
剤の製法。2. Chitosan is reacted with an aldehyde derivative containing a pyridine ring or a thiophene ring to form a Schiff base at the amino group of glucosamine forming chitosan, and then a cross-linking agent is added to cross-link the chitosan molecules. ,
A glucosamine derivative represented by Chemical Formula 1 and / or Chemical Formula 2 having a bridge structure between chitosan molecules and having a pyridine ring or a thiophene ring introduced into the amino group of glucosamine by reducing a Schiff base with sodium tetraborohydride A method for producing a noble metal ion scavenger that is a polymer containing.
子間に架橋せしめた構造を有し、キトサンを構成するグ
ルコサミン (2-アミノ-D- グルコース) として、化学式
１に示すピリジン環を含むグルコサミン誘導体及び／ま
たは化学式２に示すチオフェン環を含む、グルコサミン
誘導体を含むポリマーを使用することを特徴とする貴金
属イオン回収法。3. A glucosamine having a pyridine ring represented by the chemical formula 1 as glucosamine (2-amino-D-glucose) having a structure in which chitosan molecules are crosslinked as an adsorbent in an acidic solution and constituting chitosan. A method for recovering noble metal ions, which comprises using a polymer containing a glucosamine derivative, which comprises a derivative and / or a thiophene ring represented by Chemical Formula 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28701192A JP3236363B2 (en) | 1992-09-30 | 1992-09-30 | Noble metal ion scavenger and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28701192A JP3236363B2 (en) | 1992-09-30 | 1992-09-30 | Noble metal ion scavenger and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06227813A true JPH06227813A (en) | 1994-08-16 |
| JP3236363B2 JP3236363B2 (en) | 2001-12-10 |
Family
ID=17711877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28701192A Expired - Fee Related JP3236363B2 (en) | 1992-09-30 | 1992-09-30 | Noble metal ion scavenger and its production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3236363B2 (en) |
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| JP2007224333A (en) * | 2006-02-21 | 2007-09-06 | Miyazaki Tlo:Kk | Method of selectively collecting metal with the use of cross-linked chitosan |
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