JP2006281154A - Adsorbent for ionizable matter in aqueous solution - Google Patents
Adsorbent for ionizable matter in aqueous solution Download PDFInfo
- Publication number
- JP2006281154A JP2006281154A JP2005107312A JP2005107312A JP2006281154A JP 2006281154 A JP2006281154 A JP 2006281154A JP 2005107312 A JP2005107312 A JP 2005107312A JP 2005107312 A JP2005107312 A JP 2005107312A JP 2006281154 A JP2006281154 A JP 2006281154A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- amino acid
- layered double
- adsorbent
- double hydroxide
- 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
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Abstract
Description
本発明は、水溶液中の特定イオン性物質を層状複水酸化物で選択的に吸着する吸着剤に関するものである。 The present invention relates to an adsorbent that selectively adsorbs a specific ionic substance in an aqueous solution with a layered double hydroxide.
層状複水酸化物は、下記化学式(１)
［(Ｍ2+)1-x(Ｍ3+)x（ＯＨ）2］x+［Ａn- x/n・ｙＨ2Ｏ］x- ・・・(１)
（式(１)中、Ｍ2+は前記２価金属イオン、Ｍ3+は前記３価金属イオン、０＜ｘ＜１、Ａn-はｎ価の陰イオン、ｙＨ2Ｏは層間水）
であって、難燃化剤、安定剤、成型改質剤および保湿性改良剤などとして、樹脂に添加され、利用されてきた。
The layered double hydroxide has the following chemical formula (1)
[(M 2+ ) 1-x (M 3+ ) x (OH) 2 ] x + [A n− x / n · yH 2 O] x− (1)
(Formula (1) in, M 2+ is the divalent metal ion, M 3+ is a trivalent metal ion, 0 <x <1, A n- is an n-valent anion, yH 2 O is an interlayer water)
In addition, it has been added to a resin as a flame retardant, a stabilizer, a molding modifier, a moisture retention improver, and the like.
特許文献１には、樹脂用の配合剤として、層状複水酸化物の層間にアミノ酸をインターカレートさせたものが記載されている。
また、層状複水酸化物は、陰イオン交換能を有することから、有害物質の吸着剤として用いられている。 Further, the layered double hydroxide is used as an adsorbent for harmful substances because it has anion exchange ability.
特許文献２には、土壌中のフッ素及びホウ素を吸着固定化する方法として、層状複水酸化物を用いることが記載されている。
一方、人体や環境に悪影響を与える下記のような元素について厳しく規制が施されている。例えば、カドミウムは電池・メッキ・顔料等に使われており、鉱山排水・工場排水等のスラッジが廃棄された土壌等から河川等に混入する。イタイイタイ病の原因物質として知られている。水銀は温度計や歯科材料に使われており、有機水銀化合物は、水俣病の原因物質として知られている。セレンは半導体材料・薬剤・顔料等に使われており、自然水中に含まれることもあるが、その多くは鉱山排水・工場廃水等により混入する。鉛は鉛管・蓄電池・ハンダなどに使われ、工業製品中に添加物不純物として含まれており、環境中に広く分布している。ヒ素は合金・半導体材料として使われ、染料・製革・染料等の工場からの排水や農薬等が河川水中への汚染の原因となっている。六価クロムはクロム合金や皮なめしに使われており、工場排水等により混入し、検出されることがある。フッ素はフロンガス製造等に使われ、適量摂取は、虫歯の予防効果があるとされているが、高濃度で摂取した場合は斑状歯の症状が現れることがある。ホウ素は金属精錬時の脱酸剤、シリコン半導体のドーピング剤、原子炉の中性子吸着剤、医薬品、ガラス、ペイント、防腐剤、染料、顔料などに用いられる。亜鉛はトタン板・合金・乾電池等に使われ、高濃度に含まれると白濁の原因となる。鉄は鉱山排水・下水排水等からの混入や鉄管の使用で検出され、高濃度に含まれると異臭味や苦味を与える原因となる。銅は工場排水・農薬の混入や給水装置等に使われる銅管、真鍮器具等の溶出で検出され、高濃度であると洗濯物等を着色する原因となる。マンガンは合金・乾電池・ガラスなどに使われている。 On the other hand, the following elements that adversely affect the human body and the environment are strictly regulated. For example, cadmium is used in batteries, plating, pigments, etc., and sludge such as mine drainage and factory wastewater is mixed into rivers and the like from discarded soil. It is known as a causative agent of itai-itai disease. Mercury is used in thermometers and dental materials, and organic mercury compounds are known as a causative agent of Minamata disease. Selenium is used in semiconductor materials, chemicals, pigments, etc., and may be contained in natural water, but most of it is mixed with mine drainage and factory wastewater. Lead is used in lead pipes, storage batteries, solder, etc., and is contained as an additive impurity in industrial products, and is widely distributed in the environment. Arsenic is used as an alloy / semiconductor material, and wastewater from agricultural factories such as dyes, leather and dyes, and agricultural chemicals cause pollution in river water. Hexavalent chromium is used in chromium alloys and tanning, and it can be detected by mixing with factory wastewater. Fluorine is used in the production of chlorofluorocarbons, and taking an appropriate amount is said to have an effect of preventing tooth decay, but if taken at a high concentration, symptoms of patchy teeth may appear. Boron is used as a deoxidizer for metal refining, silicon semiconductor doping agents, neutron adsorbents for nuclear reactors, pharmaceuticals, glass, paints, preservatives, dyes and pigments. Zinc is used in tin plates, alloys, dry batteries, etc., and when it is contained in high concentrations, it causes white turbidity. Iron is detected by mixing from mine drainage, sewage drainage, etc., or by using iron pipes, and if it is contained in high concentrations, it can cause a strange odor or bitterness. Copper is detected by mixing industrial wastewater and agricultural chemicals, and elution from copper pipes and brass utensils used in water supply systems, etc., and if it is high in concentration, it causes coloring of laundry and the like. Manganese is used in alloys, batteries, and glass.
ところが、溶液中に存在するこれらの物質の回収は、イオン交換樹脂、水酸化物、硫酸バンドによる凝集沈澱法などにより行われているが、他の物質が存在すると効率よく回収が行えないという問題点があり、効果的な選択的吸着性を有した吸着剤が望まれている。 However, recovery of these substances present in the solution is carried out by an aggregation precipitation method using an ion exchange resin, a hydroxide, or a sulfuric acid band. However, when other substances are present, the recovery cannot be performed efficiently. Therefore, an adsorbent having effective selective adsorptivity is desired.
本発明は前記の課題を解決するためになされたもので、溶液中に存在する、人体や環境に悪影響を与える元素に対して、効果的な選択的吸着性を有する、安価な吸着剤を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems, and provides an inexpensive adsorbent having effective and selective adsorptivity to an element present in a solution that adversely affects the human body and the environment. The purpose is to do.
前記の目的を達成するためになされた請求項１に記載の発明は、水溶液中の特定イオン性物質を選択的に吸着する吸着剤であって、アミノ酸がインターカレートされた層状複水酸化物を有効成分とする吸着剤である。
In order to achieve the above object, the invention according to
請求項２に記載の発明は、該イオン性物質が、カドミウム、鉛、水銀、セレン、銅、亜鉛、クロム、鉄、マンガン、ニッケル、スズ、アンチモン、モリブデン、砒素、フッ素、ホウ素、臭素を含む化合物であることを特徴とする請求項１に記載の吸着剤である。
In the invention described in
請求項３に記載の発明は、該アミノ酸が、グリシン、アラニン、バリン、ロイシン、イソロイシン、フェニルアラニン、チロシン、ジヨードチロシン、チロキシン、セリン、トレオニン、メチオニン、システイン、シスチン、プロリン、ヒドロキシプロリン、トリプトファン、アスパラギン酸、グルタミン酸、リシン、ヒスチジン、アルギニンであることを特徴とする請求項１に記載の吸着剤である。
The invention according to
請求項４に記載の発明は、該アミノ酸が、重合体のアミノ酸であることを特徴とする請求項１に記載の吸着剤である。
The invention described in
請求項５に記載の発明は、アミノ酸がインターカレートされた前記層状複水酸化物の外層酸化物に、Ｌｉ＋、Ａｌ３＋、Ｃｒ３＋およびＦｅ３＋から選ばれる金属イオンと、Ｍｇ２＋、Ｚｎ２＋、Ｃａ２＋、Ｃｕ２＋、Ｚｒ２＋、Ｃｏ２＋、Ｎｉ２＋、Ｆｅ２＋およびＭｎ２＋から選ばれる金属イオンとの少なくとも一方を含むことを特徴とする請求項１に記載の吸着剤である。
The invention according to
アミノ酸をインターカレートした層状複水酸化物は、簡便に効率的かつ高純度で調製される。１価および／または３価の金属イオンを含有する水溶性塩を０．１〜９モル当量、２価の金属イオンを含有する水溶性塩および／または２価金属の酸化物を０．２５〜５０モル当量、アミノ酸を０．１〜９モル当量用いることが好ましい。 A layered double hydroxide intercalated with an amino acid is easily prepared efficiently and with high purity. 0.1 to 9 molar equivalents of a water-soluble salt containing a monovalent and / or trivalent metal ion, and 0.25 to 25% of a water-soluble salt and / or a divalent metal oxide containing a divalent metal ion. It is preferable to use 50 molar equivalents and 0.1-9 molar equivalents of amino acids.
本発明の吸着剤は、層状複水酸化物の層間にインターカレートしたアミノ酸の種類より、特定イオン性物質を選択的に吸着することができる。 The adsorbent of the present invention can selectively adsorb a specific ionic substance based on the type of amino acid intercalated between the layers of the layered double hydroxide.
本発明の吸着剤は、ｐＨを調整することにより、層間に吸着したイオン性物質を放出させることができるため、再利用することが可能である。 The adsorbent of the present invention can be reused because the ionic substance adsorbed between the layers can be released by adjusting the pH.
吸着方法は、まず、吸着剤をイオン性物質が含まれる水溶液に入れ、イオン性物質と接触させる。水溶液中では層間のアミノ酸を配位子とした、錯体反応により、回収したいイオン性物質が選択的に吸着される。次に、濾過をしてイオン性物質が吸着した層状複水酸化物を回収する。 In the adsorption method, first, an adsorbent is placed in an aqueous solution containing an ionic substance and brought into contact with the ionic substance. In an aqueous solution, an ionic substance to be recovered is selectively adsorbed by a complex reaction using an interlayer amino acid as a ligand. Next, the layered double hydroxide adsorbed with the ionic substance is collected by filtration.
層間のアミノ酸を配位子とした、錯体反応により、選択的に吸着するため、アミノ酸の種類により、選択的に吸着されるイオン性物質が異なる。 Since it is selectively adsorbed by a complex reaction using an interlayer amino acid as a ligand, the selectively adsorbed ionic substance varies depending on the type of amino acid.
カドミウム、水銀、銅の選択的吸着は、チオール基（−ＳＨ）又はヒドロキシル基（−ＯＨ）を有するアミノ酸をインターカレートした層状複水酸化物を用いる。 For selective adsorption of cadmium, mercury, and copper, a layered double hydroxide intercalated with an amino acid having a thiol group (—SH) or a hydroxyl group (—OH) is used.
亜鉛、鉄、鉛の選択的吸着は、アシル基（−Ｎ−）を有するアミノ酸をインターカレートした層状複水酸化物を用いる。 For selective adsorption of zinc, iron, and lead, a layered double hydroxide intercalated with an amino acid having an acyl group (—N—) is used.
ホウ素、フッ素、ヒ素、マンガン、クロムの選択的吸着は、イミド基（−ＮＨ−）又はアミジン基（−Ｃ＝ＮＨ）を有するアミノ酸をインターカレートした層状複水酸化物を用いる。 For selective adsorption of boron, fluorine, arsenic, manganese, and chromium, a layered double hydroxide intercalated with an amino acid having an imide group (—NH—) or an amidine group (—C═NH) is used.
また、吸着されるイオン性物質が複数の配位数をとる場合、配位数による立体配置が錯体形成に関係しているため、層間にインターカレートするアミノ酸を重合などして配位子の数を調整することで立体配置の違いによる選択的吸着が可能である。 In addition, when the adsorbed ionic substance has a plurality of coordination numbers, the configuration of the coordination number is related to the complex formation. By adjusting the number, it is possible to selectively adsorb by the difference in configuration.
さらに、吸着するイオン性物質が、両性物質であると、ｐＨが高い時は、陰イオン性となり吸着され、ｐＨが低い時は、陽イオン性となるため放出される。このことから、ｐＨを調整することにより、層間に吸着した両性物質を放出させて、吸着剤を再生し、再利用することが可能である。 Furthermore, when the ionic substance to be adsorbed is an amphoteric substance, it is anionic and adsorbed when the pH is high, and is released because it becomes cationic when the pH is low. From this, it is possible to regenerate and reuse the adsorbent by releasing the amphoteric substances adsorbed between the layers by adjusting the pH.
両性物質としては、例えば、亜鉛、カドミウム、ホウ素、アルミニウム、ガリウム、インジウム、ケイ素、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマスなどの酸化物が挙げられる。 Examples of the amphoteric substance include oxides such as zinc, cadmium, boron, aluminum, gallium, indium, silicon, germanium, tin, lead, arsenic, antimony, and bismuth.
以下、本発明の実施例を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
（実施例１ アルギニンをインターカレートしたMgAl系層状複水酸化物の合成）
アルギニン4.5g（0.026mol）をイオン交換水200gに溶解した。この時のpH値は8.98であった。次に硝酸マグネシウム6水和物9.9g(0.039mol)及び硝酸アルミニウム9水和物5.0g(0.013mol)を300gのイオン交換水に溶解し、混合金属水溶液を得た。アルギニン水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、アルギニン（NH2C=NHNH(CH2)3CH(NH2)CO2H）をインターカレートした層状複水酸化物を得た。
Example 1 Synthesis of MgAl-based layered double hydroxide intercalated with arginine
Arginine 4.5g (0.026mol) was dissolved in ion exchange water 200g. The pH value at this time was 8.98. Next, 9.9 g (0.039 mol) of magnesium nitrate hexahydrate and 5.0 g (0.013 mol) of aluminum nitrate nonahydrate were dissolved in 300 g of ion-exchanged water to obtain a mixed metal aqueous solution. The mixed metal aqueous solution was dropped into the arginine aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water, dried at room temperature, and layered double water intercalated with arginine (NH 2 C = NHNH (CH 2 ) 3 CH (NH 2 ) CO 2 H). An oxide was obtained.
（実施例２ アルギニンをインターカレートしたZnAl系層状複水酸化物の合成）
アルギニン4.5g（0.026mol）をイオン交換水200gに溶解した。この時のpH値は9.12であった。次に硝酸亜鉛6水和物9.9g(0.039mol)及び硝酸アルミニウム9水和物5.0g(0.013mol)を300gのイオン交換水に溶解し、混合金属水溶液を得た。アルギニン水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、アルギニンをインターカレートした層状複水酸化物を得た。
(Example 2 Synthesis of ZnAl-based layered double hydroxide intercalated with arginine)
Arginine 4.5g (0.026mol) was dissolved in ion exchange water 200g. The pH value at this time was 9.12. Next, 9.9 g (0.039 mol) of zinc nitrate hexahydrate and 5.0 g (0.013 mol) of aluminum nitrate nonahydrate were dissolved in 300 g of ion-exchanged water to obtain a mixed metal aqueous solution. The mixed metal aqueous solution was dropped into the arginine aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water and dried at room temperature to obtain a layered double hydroxide intercalated with arginine.
（比較例１ アラニンをインターカレートしたMgAl系層状複水酸化物の合成）
アラニン2.3g（0.026mol）をイオン交換水200gに溶解した。この時のpH値は7.23であった。次に硝酸マグネシウム6水和物9.9g(0.039mol)及び硝酸アルミニウム9水和物5.0g(0.013mol)を300gのイオン交換水に溶解し、混合金属水溶液を得た。アラニン水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、アラニン（CH3CH(NH2)CO2H）をインターカレートした層状複水酸化物を得た。
(Comparative Example 1 Synthesis of MgAl-based layered double hydroxide intercalated with alanine)
Alanine 2.3 g (0.026 mol) was dissolved in ion-exchanged water 200 g. The pH value at this time was 7.23. Next, 9.9 g (0.039 mol) of magnesium nitrate hexahydrate and 5.0 g (0.013 mol) of aluminum nitrate nonahydrate were dissolved in 300 g of ion-exchanged water to obtain a mixed metal aqueous solution. A mixed metal aqueous solution was dropped into an alanine aqueous solution while adjusting the pH value to be 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water and dried at room temperature to obtain a layered double hydroxide intercalated with alanine (CH 3 CH (NH 2 ) CO 2 H).
（比較例２ グルタミン酸をインターカレートしたMgAl系層状複水酸化物の合成）
グルタミン酸3.8g（0.026mol）を４９％NaOH4.2ｇ(0.05mol)を溶解したイオン交換水200gに溶解し、グルタミン酸ナトリウム水溶液を調製した。この時のpH値は10.83であった。次に硝酸マグネシウム6水和物9.9g(0.039mol)及び硝酸アルミニウム9水和物5.0g(0.013mol)を300gのイオン交換水に溶解し、混合金属水溶液を得た。グルタミン酸ナトリウム水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、グルタミン酸（HO2CCH2CH2CH(NH2)CO2H）をインターカレートした層状複水酸化物を得た。
(Comparative Example 2 Synthesis of MgAl-based layered double hydroxide intercalated with glutamic acid)
Glutamic acid (3.8 g, 0.026 mol) was dissolved in ion-exchanged water (200 g) in which 49% NaOH (4.2 g, 0.05 mol) was dissolved to prepare a sodium glutamate aqueous solution. The pH value at this time was 10.83. Next, 9.9 g (0.039 mol) of magnesium nitrate hexahydrate and 5.0 g (0.013 mol) of aluminum nitrate nonahydrate were dissolved in 300 g of ion-exchanged water to obtain a mixed metal aqueous solution. A mixed metal aqueous solution was dropped into a sodium glutamate aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water, dried at room temperature, and a layered double hydroxide intercalated with glutamic acid (HO 2 CCH 2 CH 2 CH (NH 2 ) CO 2 H) was obtained. It was.
（比較例３ ヒスチジンをインターカレートしたMgAl系層状複水酸化物の合成）
４９％NaOH2.1ｇ(0.026mol)を溶解したイオン交換水200gにリシン4.7g（0.026mol）を溶解し、リシン水溶液を調製した。この時のpH値は9.89であった。次に硝酸マグネシウム6水和物9.9g(0.039mol)及び硝酸アルミニウム9水和物5.0g(0.013mol)を300gのイオン交換水に溶解し、混合金属水溶液を得た。グルタミン酸ナトリウム水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、ヒスチジンをインターカレートした層状複水酸化物を得た。
(Comparative Example 3 Synthesis of MgAl-based layered double hydroxide intercalated with histidine)
4.7 g (0.026 mol) of lysine was dissolved in 200 g of ion-exchanged water in which 2.1 g (0.026 mol) of 49% NaOH was dissolved to prepare an aqueous lysine solution. The pH value at this time was 9.89. Next, 9.9 g (0.039 mol) of magnesium nitrate hexahydrate and 5.0 g (0.013 mol) of aluminum nitrate nonahydrate were dissolved in 300 g of ion-exchanged water to obtain a mixed metal aqueous solution. A mixed metal aqueous solution was dropped into a sodium glutamate aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water and dried at room temperature to obtain a layered double hydroxide intercalated with histidine.
（比較例４ 硝酸をインターカレートしたMgAl系層状複水酸化物の合成）
イオン交換水200gに硝酸ナトリウム2.2g（0.026mol）を溶解し、硝酸ナトリウム水溶液を調製した。この時のpH値は6.62であった。次に硝酸マグネシウム6水和物9.9g(0.039mol)及び硝酸アルミニウム9水和物5.0g(0.013mol)を300gのイオン交換水に溶解し、混合金属水溶液を得た。硝酸ナトリウム水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、硝酸をインターカレートした層状複水酸化物を得た。
(Comparative Example 4 Synthesis of MgAl-based layered double hydroxide intercalated with nitric acid)
Sodium nitrate 2.2 g (0.026 mol) was dissolved in ion-exchanged water 200 g to prepare an aqueous sodium nitrate solution. The pH value at this time was 6.62. Next, 9.9 g (0.039 mol) of magnesium nitrate hexahydrate and 5.0 g (0.013 mol) of aluminum nitrate nonahydrate were dissolved in 300 g of ion-exchanged water to obtain a mixed metal aqueous solution. A mixed metal aqueous solution was dropped into a sodium nitrate aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water, dried at room temperature, and a layered double hydroxide intercalated with nitric acid was obtained.
（比較例５ 硝酸をインターカレートしたZnAl系層状複水酸化物の合成）
イオン交換水200gに硝酸ナトリウム2.2g（0.026mol）を溶解し、硝酸ナトリウム水溶液を調製した。この時のpH値は6.70であった。次に硝酸亜鉛9.9g(0.039mol)及び硝酸アルミニウム9水和物5.0g(0.013mol)を300gのイオン交換水に溶解し、混合金属水溶液を得た。硝酸ナトリウム水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、硝酸をインターカレートした層状複水酸化物を得た。
(Comparative Example 5 Synthesis of ZnAl-based layered double hydroxide intercalated with nitric acid)
Sodium nitrate 2.2 g (0.026 mol) was dissolved in ion-exchanged water 200 g to prepare an aqueous sodium nitrate solution. The pH value at this time was 6.70. Next, zinc nitrate 9.9 g (0.039 mol) and aluminum nitrate nonahydrate 5.0 g (0.013 mol) were dissolved in 300 g of ion-exchanged water to obtain a mixed metal aqueous solution. A mixed metal aqueous solution was dropped into a sodium nitrate aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water, dried at room temperature, and a layered double hydroxide intercalated with nitric acid was obtained.
（比較例６ 層の構成成分がFe、Mg、Alからなる層状複水酸化物の合成）
イオン交換水200gに塩化ナトリウム1.5g（0.026mol）を溶解し、塩化ナトリウム水溶液を調製した。この時のpH値は6.30であった。次に塩化マグネシウム6水和物6.3g(0.031mol)及び塩化アルミニウム6水和物3.1g(0.013mol)及び塩化鉄6水和物1.2g(0.004mol)を300gのイオン交換水で溶解し、混合金属水溶液を得た。塩化ナトリウム水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、硝酸をインターカレートした層状複水酸化物を得た。
(Comparative Example 6 Synthesis of layered double hydroxide whose layer constituents are Fe, Mg, Al)
Sodium chloride (1.5 g, 0.026 mol) was dissolved in ion-exchanged water (200 g) to prepare an aqueous sodium chloride solution. The pH value at this time was 6.30. Next, 6.3 g (0.031 mol) of magnesium chloride hexahydrate, 3.1 g (0.013 mol) of aluminum chloride hexahydrate and 1.2 g (0.004 mol) of iron chloride hexahydrate were dissolved in 300 g of ion-exchanged water, A mixed metal aqueous solution was obtained. A mixed metal aqueous solution was dropped into a sodium chloride aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water, dried at room temperature, and a layered double hydroxide intercalated with nitric acid was obtained.
（比較例７ 層の構成成分がMg、Li、Alからなる層状複水酸化物の合成）
イオン交換水200gに塩化ナトリウム1.5g（0.026mol）を溶解し、塩化ナトリウム水溶液を調製した。次に塩化マグネシウム6水和物4.1g(0.02mol)及び塩化アルミニウム6水和物3.1g(0.013mol)及び塩化リチウム0.5g(0.013mol)を300gのイオン交換水で溶解し、混合金属水溶液を得た。塩化ナトリウム水溶液に、49%NaOH水溶液を用いてpH値8〜10になるように調整しながら混合金属水溶液を滴下していった。滴下終了後７５〜８０℃で加熱しながら24時間熟成した。得られた固体生成物をイオン交換水にて洗浄を行い、常温で乾燥し、硝酸をインターカレートした層状複水酸化物を得た。
(Comparative Example 7 Synthesis of layered double hydroxide whose layer constituents are Mg, Li, Al)
Sodium chloride (1.5 g, 0.026 mol) was dissolved in ion-exchanged water (200 g) to prepare an aqueous sodium chloride solution. Next, 4.1 g (0.02 mol) of magnesium chloride hexahydrate, 3.1 g (0.013 mol) of aluminum chloride hexahydrate and 0.5 g (0.013 mol) of lithium chloride were dissolved in 300 g of ion-exchanged water, and the mixed metal aqueous solution was dissolved. Obtained. A mixed metal aqueous solution was dropped into a sodium chloride aqueous solution while adjusting the pH value to 8 to 10 using a 49% NaOH aqueous solution. After completion of dropping, the mixture was aged for 24 hours while being heated at 75 to 80 ° C. The obtained solid product was washed with ion-exchanged water, dried at room temperature, and a layered double hydroxide intercalated with nitric acid was obtained.
実施例１〜２、比較例１〜７で得られた層状複水酸化物を用いて、ホウ素の吸着試験を行った。 Using the layered double hydroxides obtained in Examples 1 and 2 and Comparative Examples 1 to 7, a boron adsorption test was performed.
（ホウ酸水溶液吸着試験）
イオン交換水１０００ｍｌに、ホウ酸2.57g（0.04mol）を溶解し、４９％NaOH水溶液を用いてｐH８．３４に調製した。
(Boric acid aqueous solution adsorption test)
2.57 g (0.04 mol) of boric acid was dissolved in 1000 ml of ion-exchanged water, and the pH was adjusted to 8.34 using a 49% NaOH aqueous solution.
ホウ酸水溶液１００ｍｌ中に実施例１〜２、比較例１〜７で得られた固体をそれぞれ０．１ｇ入れ、２５℃で２時間、スタラーにて攪拌した。 0.1 g of each of the solids obtained in Examples 1 and 2 and Comparative Examples 1 to 7 was placed in 100 ml of an aqueous boric acid solution and stirred with a stirrer at 25 ° C. for 2 hours.
２時間後、固体と濾液に分離して、濾液中のホウ酸を定量することで吸着量を算出した。定量方法は滴定法に従った。濾液を１０ｍｌ計り採り、フェノールフタレインを数滴加え発色させる。次に、０．５N塩酸にて溶液を透明にした後、０．１N水酸化ナトリウム水溶液にてｐH７に調整して、グリセリン水溶液（グリセリン/交換水＝１．０の水溶液）を３０ｍｌ加えて、０．１N水酸化ナトリウム水溶液にて濾液中のホウ酸量を定量した。３回繰り返しその平均値を測定値とした。吸着試験結果を表１に示す。
After 2 hours, it was separated into a solid and a filtrate, and the amount of adsorption was calculated by quantifying boric acid in the filtrate. The determination method followed the titration method.
（混合処理液吸着試験）
イオン交換水１０００ｍｌに、ホウ酸0.25g(4.0×10-3mol)、フッ化ナトリウム0.17g(4.0×10-3mol)、燐酸ナトリウム１２水和物1.5g(4.0×10-3mol)を溶解し、１N塩酸４ｍｌ（4.0×10-3mol）を用いてｐH８．５１に調製した。
(Mixed liquid adsorption test)
Ion exchange water 1000 ml, boric acid 0.25g (4.0 × 10 -3 mol) , sodium fluoride 0.17g (4.0 × 10 -3 mol) , sodium phosphate dodecahydrate 1.5g (4.0 × 10 -3 mol) It was dissolved and adjusted to pH 8.51 using 4 ml (4.0 × 10 −3 mol) of 1N hydrochloric acid.
混合処理液１００ｍｌ中に実施例１及び実施例２をそれぞれ０．１ｇ入れ、２５℃で２時間、スタラーにて攪拌した。 0.1 g of Example 1 and Example 2 was put in 100 ml of the mixed processing solution, respectively, and stirred with a stirrer at 25 ° C. for 2 hours.
２時間後、固体と濾液に分離して、濾液中のホウ酸を定量することで吸着量を算出した。定量方法は滴定法に従った。濾液を１０ｍｌ計り採り、フェノールフタレインを数滴加え発色させる。次に、０．５N塩酸にて溶液を透明にした後、０．１N水酸化ナトリウム水溶液にてｐH７に調整して、グリセリン水溶液（グリセリン/交換水＝１．０の水溶液）を３０ｍｌ加えて、０．１N水酸化ナトリウム水溶液にて濾液中のホウ酸量を定量した。３回繰り返しその平均値を測定値とした。混合処理液を用いての吸着試験結果を行なった。結果を表１に示す。
After 2 hours, it was separated into a solid and a filtrate, and the amount of adsorption was calculated by quantifying boric acid in the filtrate. The determination method followed the titration method.
ホウ酸水溶液を用いた吸着試験の結果、実施例１〜２は層間にアミノ酸をインターカレートしていない比較例４〜５と比べ、高いホウ酸吸着を示した。また、実施例１〜２の結果と比較例１〜３の結果から、層間にインターカレートしているアミノ酸の種類によってホウ酸の吸着量が異なることが示された。 As a result of the adsorption test using an aqueous boric acid solution, Examples 1 and 2 showed higher boric acid adsorption than Comparative Examples 4 to 5 in which no amino acid was intercalated between layers. In addition, the results of Examples 1 and 2 and the results of Comparative Examples 1 to 3 indicate that the amount of boric acid adsorbed varies depending on the type of amino acid intercalated between layers.
混合処理液を用いた吸着試験の結果、実施例１及び実施例２は、層間交換容量に近いホウ酸吸着量を示した。この結果より、層間にインターカレートしているアルギニンが選択的ホウ酸吸着に関与していると推測できる。 As a result of the adsorption test using the mixed treatment liquid, Example 1 and Example 2 showed the boric acid adsorption amount close to the interlayer exchange capacity. From this result, it can be inferred that arginine intercalated between layers is involved in selective boric acid adsorption.
（結晶構造解析）
実施例１、実施例２及びホウ酸吸着前後の実施例１をＸ線回折に供した。Ｘ線回折は、Ｘ線回折装置を使用し、対陰極に銅（Cu Kα λ＝1.54Åとする。）を採用し、管電圧40kV,管電流100mA、スキャンスピード2.00°/minとした。そして、測定角度範囲２θ＝２〜６５°の範囲内でＸ線を照射し、回折図を得ると共に、ピークの先端から２θを求め、面間隔ｄをBraggの式（nλ=2dsinθ）に従い算出した。
(Crystal structure analysis)
Example 1, Example 2 and Example 1 before and after boric acid adsorption were subjected to X-ray diffraction. For X-ray diffraction, an X-ray diffractometer was used, copper (Cu Kα λ = 1.54 mm) was adopted as the counter cathode, the tube voltage was 40 kV, the tube current was 100 mA, and the scan speed was 2.00 ° / min. Then, X-rays are irradiated within the measurement angle range 2θ = 2 to 65 ° to obtain a diffractogram, and 2θ is obtained from the tip of the peak, and the surface interval d is calculated according to the Bragg equation (nλ = 2dsinθ). .
混合処理液で処理を施す前後での実施例１の結晶構造を確認した。ホウ酸吸着前の実施例１回折結果に格子定数c0=25.8Å、a0=3.04Åの六方晶系として指数付けすると（003）、（006）といった回折ピークが観測されることから実施例１はc軸方向に積層した層状構造を持つといえる。また、格子定数a0の値は一般的に報告されている値（3.0Å）と一致する。従って実施例１は層状複水酸化物様化合物であるといえる。基本面間隔の値（8.6Å）から層の厚み4.8Åを差し引いた値（3.8Å）から、層間にアルギニンがインターカレートしていると考えられる。実施例２においても同様な回折パターンを観測されたことから、実施例２も層間にアルギニンをインターカレートした層状複水酸化物であるといえる。 The crystal structure of Example 1 was confirmed before and after the treatment with the mixed treatment liquid. Example 1 before boric acid adsorption When diffraction results are indexed as hexagonal systems with lattice constants c 0 = 25.8Å and a 0 = 3.04Å, diffraction peaks such as (003) and (006) are observed. 1 can be said to have a layered structure laminated in the c-axis direction. In addition, the value of the lattice constant a 0 coincides with a generally reported value (3.0Å). Therefore, it can be said that Example 1 is a layered double hydroxide-like compound. It is considered that arginine is intercalated between the layers based on the value (3.8 mm) obtained by subtracting the layer thickness of 4.8 mm from the value of the basic spacing (8.6 mm). Since a similar diffraction pattern was observed also in Example 2, it can be said that Example 2 is also a layered double hydroxide in which arginine is intercalated between layers.
次に、ホウ酸吸着後の実施例１の結果からは、格子定数c0＝２８Åの相（B相と以下略記）と、格子定数c0=７．７Å（F相と以下略記）の相が観測された。F相は文献値からフッ素イオンをインターカレートした層状複水酸化物の格子定数と一致することから、フッ素イオンを層間にインターカレートした層状複水酸化物によるものであるといえる。次に、ホウ酸吸着後の実施例１を５０mlイオン交換水に投入して、０．１N塩酸によりｐHを３に調製して、２時間常温攪拌した後に、固体を分離し、処理液中のホウ酸を定量した結果、0.2mmolのホウ酸を観測した。 Next, from the results of Example 1 after boric acid adsorption, a phase of lattice constant c 0 = 28Å (B phase and abbreviated below) and a lattice constant c 0 = 7.7Å (F phase and abbreviated below) of phase. Was observed. Since the F phase is consistent with the lattice constant of the layered double hydroxide intercalated with fluorine ions from literature values, it can be said that it is due to the layered double hydroxide intercalated with fluorine ions between layers. Next, Example 1 after boric acid adsorption was put into 50 ml ion-exchanged water, pH was adjusted to 3 with 0.1N hydrochloric acid, stirred at room temperature for 2 hours, solids were separated, As a result of quantifying boric acid, 0.2 mmol of boric acid was observed.
この結果から、実施例１に吸着していたホウ酸がほぼ溶出していることがいえる。更に、この固体をXRDにより結晶構造解析をした結果、混合試験液で処理を施す前の実施例１が示す同一の格子定数c0=25.8Åの相が観測され、F相は若干残存していたが、B相は観測されなかった。この結果から、また、ｐHを調整することで層間に吸着したホウ酸が溶出することがわかった。また、実施例１が示す選択的ホウ酸吸着は他のアミノ酸に認められないアルギニンのアミジン基（RC（＝NH）NH2R）が関与していると考えられる。層間にインターカレートしているアルギニンのアミジン基にホウ酸が挟まれる様な形で層間に取り込まれているのではないかと推測される。 From this result, it can be said that boric acid adsorbed in Example 1 is almost eluted. Furthermore, as a result of crystal structure analysis of this solid by XRD, a phase having the same lattice constant c 0 = 25.8Å shown in Example 1 before being treated with the mixed test solution was observed, and the F phase remained slightly. However, phase B was not observed. From this result, it was also found that boric acid adsorbed between the layers was eluted by adjusting the pH. Moreover, it is considered that the selective boric acid adsorption shown in Example 1 involves the amidine group (RC (= NH) NH 2 R) of arginine that is not found in other amino acids. It is presumed that the boric acid is intercalated between the layers of arginine intercalated between the layers so that boric acid is sandwiched between the layers.
次に、実施例１を用いて処理時間に対するホウ酸吸着量と処理ｐHによるホウ酸吸着量について試験した。結果を図１、２に示す。 Next, the boric acid adsorption amount with respect to the treatment time and the boric acid adsorption amount by the treatment pH were tested using Example 1. The results are shown in FIGS.
図１からホウ酸の吸着量はホウ酸水溶液及び混合処理液において１時間でほぼ吸着量が平衡となっている。混合処理液における結果より、層間交換容量に近い値でホウ酸吸着量が平衡になっていることから、この結果においても層間に選択的にホウ酸が吸着していることが指示される。 From FIG. 1, the adsorption amount of boric acid is almost balanced in one hour in the boric acid aqueous solution and the mixed treatment liquid. Since the boric acid adsorption amount is balanced at a value close to the interlayer exchange capacity from the result in the mixed treatment liquid, it is indicated that boric acid is selectively adsorbed between the layers also in this result.
図２の結果よりホウ酸吸着の最適値は８付近であることがいえる。ｐHの値が８より小さく又は大きくなるに従い、ホウ酸吸着量の低下が認められる。これは、ホウ酸のイオン価数の違いによるホウ酸の構造形態の変化に伴うものであると考えられる。この結果から、ホウ酸の構造形態によって層間への選択的吸着は影響を受けると考えられる。 From the results of FIG. 2, it can be said that the optimum value of boric acid adsorption is around 8. As the pH value becomes smaller or larger than 8, a decrease in the boric acid adsorption amount is observed. This is considered to be accompanied by a change in the structural form of boric acid due to the difference in ionic valence of boric acid. From this result, it is considered that the selective adsorption between layers is influenced by the structural form of boric acid.
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| JP2003226681A (en) * | 2002-01-31 | 2003-08-12 | National Institute Of Advanced Industrial & Technology | Metal hydroxide and water layer |
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