JP5845644B2 - Boron adsorbent and method for producing the same - Google Patents

Boron adsorbent and method for producing the same Download PDF

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JP5845644B2
JP5845644B2 JP2011131777A JP2011131777A JP5845644B2 JP 5845644 B2 JP5845644 B2 JP 5845644B2 JP 2011131777 A JP2011131777 A JP 2011131777A JP 2011131777 A JP2011131777 A JP 2011131777A JP 5845644 B2 JP5845644 B2 JP 5845644B2
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信一 笠井
信一 笠井
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本発明は、ホウ素吸着剤及びその製造方法に関する。   The present invention relates to a boron adsorbent and a method for producing the same.

従来のホウ素吸着剤としては、スチレン−ジビニルベンゼンからなる架橋型共重合体にN−メチル−D−グルカミノ基を導入したグルカミン型樹脂や、水酸化セリウムを主原料とするものが知られている。   As a conventional boron adsorbent, a glucamine type resin in which an N-methyl-D-glucamino group is introduced into a cross-linked copolymer composed of styrene-divinylbenzene, and a material mainly composed of cerium hydroxide are known. .

しかし、グルカミン型樹脂は、疎水性である上に吸着速度が遅く、実用的なホウ素吸着性能を有するものではなかった。一方、水酸化セリウムは吸着容量が大きいものの、セリウムが希土類であるため、製造コストが高く、安定供給が困難であるという問題があった。このため、いずれも普及するには至らなかった。   However, the glucamine type resin is hydrophobic and has a slow adsorption rate, and has no practical boron adsorption performance. On the other hand, although cerium hydroxide has a large adsorption capacity, cerium is a rare earth, so that there are problems in that the production cost is high and stable supply is difficult. For this reason, none of them has become widespread.

このほか、活性炭へ陰イオン吸着剤を担持させた陰イオン吸着剤(特許文献1、2)などが開示されているが、ホウ素イオンの吸着性能を向上させたものではなかった。   In addition, although an anion adsorbent (Patent Documents 1 and 2) in which an anion adsorbent is supported on activated carbon has been disclosed, the adsorption performance of boron ions has not been improved.

特開2004−91276号公報JP 2004-91276 A 特開平7−743号公報Japanese Patent Laid-Open No. 7-743 特開2008−29985号公報JP 2008-29985 A 特開2009−178682号公報JP 2009-178682 A 特開2009−173535号公報JP 2009-173535 A

そこで、本発明は、吸着性能が高く安価に製造できる、新規のホウ素吸着剤及びその製造方法を提供することを目的とする。   Therefore, an object of the present invention is to provide a novel boron adsorbent having high adsorption performance and capable of being produced at low cost, and a method for producing the same.

本発明者は、上記発明を解決するために、ハイドロタルサイトに着目した。ハイドロタルサイト微粒子は、イオン交換反応により、無機アニオン及び有機アニオンを素早く吸着することが知られている。しかし、ハイドロタルサイトのイオン交換容量は、水酸化セリウムを主原料としたホウ素吸着剤には及ばないという問題があった。そこで、鋭意検討した結果、活性炭の微細孔内にAl,Si,Mgからなるハイドロタルサイト様物質を担持させることにより、ホウ素イオンの吸着性能が飛躍的に向上した吸着剤が得られることを見出し、本発明に想到した。   The present inventors paid attention to hydrotalcite in order to solve the above-mentioned invention. Hydrotalcite fine particles are known to quickly adsorb inorganic anions and organic anions by an ion exchange reaction. However, the ion exchange capacity of hydrotalcite has a problem that it does not reach that of a boron adsorbent mainly composed of cerium hydroxide. Thus, as a result of intensive studies, it was found that an adsorbent with drastically improved boron ion adsorption performance can be obtained by supporting a hydrotalcite-like substance composed of Al, Si, and Mg in the fine pores of activated carbon. The present invention has been conceived.

すなわち、本発明の請求項1記載のホウ素吸着剤の製造方法は、Si 2x Mg 1−x Al (OH) ・(A n− x−ny ・(B z− ・mH Oの組成式を有するハイドロタルサイト様物質(ここで、式中xは0.1<x<0.4の正数であり、A n− 、B z− はそれぞれ異なった価数の陰イオンであり、yは正数であり、mは0.1<m<1の正数である)が活性炭に担持されてなるホウ素吸着剤の製造方法であって、ケイ酸塩、アルミニウム塩、マグネシウム塩を溶解させた水溶液と活性炭とを混合して混合溶液を調製する混合工程と、この混合工程で調製された混合溶液のpHを10〜11に調整するpH調整工程と、このpH調製工程でpHが調整された混合溶液から固形分を分離する分離工程と、この分離工程で分離された固形分を乾燥させる乾燥工程とを備えたことを特徴とする That is, the manufacturing method of the boron adsorbent according to claim 1 of the present invention, Si 2x Mg 1-x Al x (OH) 2 · (A n-) x-ny · (B z-) y · mH 2 O (Wherein x is a positive number of 0.1 <x <0.4, and A n− and B z− are anions having different valences, respectively). And y is a positive number, and m is a positive number of 0.1 <m <1). A mixing step of preparing a mixed solution by mixing an aqueous solution in which activated carbon and activated carbon are mixed , a pH adjusting step of adjusting the pH of the mixed solution prepared in this mixing step to 10 to 11, and a pH in this pH adjusting step A separation step of separating the solid content from the mixed solution adjusted, and the separation step And a drying step for drying the solid content separated in (1) .

本発明のホウ素吸着剤は、Si 2x Mg 1−x Al (OH) ・(A n− x−ny ・(B z− ・mH Oの組成式を有するハイドロタルサイト様物質(ここで、式中xは0.1<x<0.4の正数であり、A n− 、B z− はそれぞれ異なった価数の陰イオンであり、yは正数であり、mは0.1<m<1の正数である)が活性炭に担持されてなることを特徴とする。 The boron adsorbent of the present invention is a hydrotalcite-like substance having a composition formula of Si 2x Mg 1-x Al x (OH) 2. (A n− ) x-ny · (B z− ) y · mH 2 O (Wherein x is a positive number of 0.1 <x <0.4, A n− and B z− are anions having different valences, y is a positive number, m Is a positive number of 0.1 <m <1) and is supported on activated carbon .

本発明のホウ素吸着剤及びその製造方法によれば、ホウ素イオンの吸着容量の大きいホウ素吸着剤を安価に提供することができる。   According to the boron adsorbent and the method for producing the same of the present invention, a boron adsorbent having a large boron ion adsorption capacity can be provided at low cost.

実施例1で得られたホウ素吸着剤のSEM写真である。2 is a SEM photograph of the boron adsorbent obtained in Example 1. 活性炭のSEM写真である。It is a SEM photograph of activated carbon. 実施例2のホウ素吸着実験の結果を示すグラフである。6 is a graph showing the results of a boron adsorption experiment of Example 2.

本発明のホウ素吸着剤の製造方法は、ケイ酸塩、アルミニウム塩、マグネシウム塩を溶解させた水溶液と活性炭とを混合して混合溶液を調製する混合工程と、この混合工程で調製された混合溶液のpHを調整するpH調整工程と、このpH調製工程でpHが調整された混合溶液から固形分を分離する分離工程と、この分離工程で分離された固形分を乾燥させる乾燥工程とを備えたものである。   The method for producing a boron adsorbent of the present invention comprises a mixing step of preparing a mixed solution by mixing an aqueous solution in which silicate, aluminum salt, and magnesium salt are dissolved and activated carbon, and a mixed solution prepared in this mixing step A pH adjustment step for adjusting the pH of the solid, a separation step for separating the solid content from the mixed solution whose pH was adjusted in the pH adjustment step, and a drying step for drying the solid content separated in the separation step Is.

はじめに、混合工程において、ケイ酸塩、アルミニウム塩、マグネシウム塩を溶解させた水溶液と活性炭とを混合して混合溶液を調製する。ここで、ケイ酸塩としては、ケイ酸ナトリウムなどを用いることができ、ケイ酸ナトリウムとしては、水ガラスなどを用いることができる。また、アルミニウム塩としては塩化アルミニウムなど、マグネシウム塩としては塩化マグネシウムなどを用いることができる。   First, in the mixing step, an aqueous solution in which silicate, aluminum salt, and magnesium salt are dissolved and activated carbon are mixed to prepare a mixed solution. Here, sodium silicate or the like can be used as the silicate, and water glass or the like can be used as the sodium silicate. Further, aluminum chloride or the like can be used as the aluminum salt, and magnesium chloride or the like can be used as the magnesium salt.

つぎに、pH調整工程において、混合工程で調製された混合溶液のpHを調整する。pHの調整は、アルカリ性水溶液を添加することにより行なわれ、アルカリ性水溶液としては、水酸化ナトリウム水溶液などを用いることができる。アルカリ性水溶液を添加していくと、混合溶液のpHが10〜11の範囲内で安定するので、そこで添加を終了する。また、アルカリ性水溶液を添加すると、混合溶液に沈殿物による懸濁が生じる。その後、好ましくは、40〜60℃において10〜20時間の熟成を行なう。   Next, in the pH adjustment step, the pH of the mixed solution prepared in the mixing step is adjusted. Adjustment of pH is performed by adding alkaline aqueous solution, and sodium hydroxide aqueous solution etc. can be used as alkaline aqueous solution. As the alkaline aqueous solution is added, the pH of the mixed solution is stabilized within the range of 10 to 11, and the addition is terminated there. Moreover, when alkaline aqueous solution is added, suspension by a precipitate will arise in a mixed solution. Thereafter, aging is preferably performed at 40 to 60 ° C. for 10 to 20 hours.

そして、分離工程において、pH調製工程でpHが調整された混合溶液から固形分、すなわち、活性炭と、pH調整工程において生じた沈殿物を分離する。なお、活性炭は濾過分離後に水で洗浄し、沈殿物は遠心分離後に水で洗浄する。沈殿物の洗浄は、上澄みを除いた後に水を加えて攪拌し、遠心分離を行うことにより行うことができる。沈殿物の洗浄は複数回行うのが好ましい。   In the separation step, the solid content, that is, activated carbon, and the precipitate generated in the pH adjustment step are separated from the mixed solution whose pH is adjusted in the pH adjustment step. In addition, activated carbon is washed with water after separation by filtration, and the precipitate is washed with water after centrifugation. The precipitate can be washed by removing the supernatant, adding water, stirring, and centrifuging. It is preferable to wash the precipitate a plurality of times.

最後に、乾燥工程において、分離工程で分離された固形分を乾燥させる。乾燥時の温度は、好ましくは40〜60℃とする。   Finally, in the drying step, the solid content separated in the separation step is dried. The temperature during drying is preferably 40 to 60 ° C.

以上の工程により、本発明のホウ素吸着剤が得られる。   The boron adsorbent of the present invention is obtained through the above steps.

本発明のホウ素吸着剤は、活性炭の孔内に、アルミニウム、マグネシウム、ケイ素を構成元素として含むハイドロタルサイト様物質が担持された構造を有し、ホウ素イオンの吸着容量が極めて大きい。本発明のホウ素吸着剤は、ハイドロタルサイト様物質にケイ素を含んでいることにより、ハイドロタルサイト様物質のアモルファス化が促進され、その結果、イオン移動度が増加してホウ素の吸着効果が向上しているものと考えられ、さらに、このハイドロタルサイト様物質が活性炭に担持されることにより、吸着効果がさらに向上している。   The boron adsorbent of the present invention has a structure in which a hydrotalcite-like substance containing aluminum, magnesium and silicon as constituent elements is supported in the pores of activated carbon, and the adsorption capacity of boron ions is extremely large. The boron adsorbent of the present invention contains silicon in the hydrotalcite-like substance, which promotes the amorphization of the hydrotalcite-like substance, resulting in increased ion mobility and improved boron adsorption effect. Further, the adsorption effect is further improved by supporting the hydrotalcite-like substance on activated carbon.

また、本発明のホウ素吸着剤は、安価な材料を用いて、安価に製造することができる。また、有害な材料を用いていないので人体に対する安全性が高い。さらに、本発明のホウ素吸着剤は、熱処理によりイオンの脱着を行うだけで再生可能である。   Moreover, the boron adsorbent of the present invention can be manufactured at low cost using an inexpensive material. In addition, since no harmful materials are used, safety to the human body is high. Furthermore, the boron adsorbent of the present invention can be regenerated only by desorption of ions by heat treatment.

なお、本発明のホウ素吸着剤において、活性炭に担持されるハイドロタルサイト様物質は、Si2xMg1−xAl(OH)・(An−x−ny・(Bz−・mHOの組成式を有する。ここで、式中xは0.1<x<0.4の正数であり、An−、Bz−はそれぞれ異なった価数の陰イオンであり、yは正数であり、mは0.1<m<1の正数である。 In the boron adsorbent of the present invention, the hydrotalcite-like substance supported on activated carbon is Si 2x Mg 1-x Al x (OH) 2 · (A n− ) x-ny · (B z− ) y · mH having 2 O in the composition formula. Here, in the formula, x is a positive number of 0.1 <x <0.4, A n− and B z− are anions having different valences, y is a positive number, and m is It is a positive number of 0.1 <m <1.

以下、本発明のホウ素吸着剤とその製造方法について、具体的な実施例に基づいて説明する。なお、本発明は以下の実施形態に限定されるものではなく、本発明の思想を逸脱しない範囲で種々の変形実施が可能である。   Hereinafter, the boron adsorbent of the present invention and the production method thereof will be described based on specific examples. Note that the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit of the present invention.

[ホウ素吸着剤の調製]
蒸留水 100mLに3号水ガラス 3.42gを溶解させ、活性炭 5.0gを加えて30分間攪拌した。つぎに、AlCl(無水物) 1.333gとMgCl 6.664gを加えて溶解させ、2時間攪拌した。そして、5.0MのNaOH溶液を加えると懸濁を生じた。pHメーターでpHを確認しながらNaOH溶液の添加を続け、pHが10.5で安定するようになったところで添加を終了した。さらに、マグネチックスターラーで30分間攪拌を続け、攪拌を終えた後、50℃の恒温槽に入れて15時間の熟成を行った。
[Preparation of boron adsorbent]
3.42 g of No. 3 water glass was dissolved in 100 mL of distilled water, 5.0 g of activated carbon was added, and the mixture was stirred for 30 minutes. Next, 1.333 g of AlCl 3 (anhydride) and 6.664 g of MgCl 2 were added and dissolved, followed by stirring for 2 hours. Then, a 5.0 M NaOH solution was added resulting in suspension. The addition of the NaOH solution was continued while confirming the pH with a pH meter, and the addition was terminated when the pH became stable at 10.5. Further, stirring was continued for 30 minutes with a magnetic stirrer, and after stirring, the mixture was placed in a thermostatic bath at 50 ° C. and aged for 15 hours.

その後、蒸留水で固形分の洗浄を4回繰り返した。なお、洗浄は、上澄みを除いた後、蒸留水を加えて攪拌し、遠心分離を行うことにより行った。洗浄後、固形分を50℃で24時間乾燥させた。乾燥した固形分を乳鉢・乳棒により粉砕し、ホウ素吸着剤を得た。   Thereafter, washing of the solid content with distilled water was repeated four times. Washing was performed by removing the supernatant, adding distilled water, stirring, and centrifuging. After washing, the solid content was dried at 50 ° C. for 24 hours. The dried solid was pulverized with a mortar and pestle to obtain a boron adsorbent.

得られたホウ素吸着剤のSEM写真を図1に示す。また、比較のために活性炭のSEM写真を図2に示す。得られたホウ素吸着剤では、活性炭の孔内にハイドロタルサイト様物質が詰まっていることが確認された。   An SEM photograph of the obtained boron adsorbent is shown in FIG. For comparison, an SEM photograph of activated carbon is shown in FIG. In the obtained boron adsorbent, it was confirmed that hydrotalcite-like substances were clogged in the pores of the activated carbon.

[ホウ素吸着実験]
実施例1で調製したホウ素吸着剤 1gを50ppm−Bのホウ素溶液 25mLに添加し、24時間攪拌した。その後、溶液を5種C濾紙によって濾過し、濾液のホウ素イオン濃度をアゾメチンH法によって測定した。処理後の残存ホウ素イオン濃度とホウ素吸着剤の添加量から、吸着剤単位量あたりの吸着容量を求めた。
[Boron adsorption experiment]
1 g of the boron adsorbent prepared in Example 1 was added to 25 mL of a 50 ppm-B boron solution and stirred for 24 hours. Thereafter, the solution was filtered through 5 types C filter paper, and the boron ion concentration of the filtrate was measured by the azomethine H method. The adsorption capacity per adsorbent unit amount was determined from the residual boron ion concentration after treatment and the amount of boron adsorbent added.

また、比較例として、実施例1のホウ素吸着剤と組成が同じになるように活性炭とハイドロタルサイト様物質を単に混合したもの、市販品の水酸化セリウムを用いて、上記と同様に吸着容量を求めた。   In addition, as a comparative example, the activated carbon and the hydrotalcite-like substance are simply mixed so that the composition is the same as that of the boron adsorbent of Example 1, and commercially available cerium hydroxide is used. Asked.

その結果を表1及び図3に示す。実施例1のホウ素吸着剤は、活性炭とハイドロタルサイト様物質を単に混合したものよりも吸着容量が大きく、市販の水酸化セリウムと同等以上のホウ素吸着性能を有することが確認された。   The results are shown in Table 1 and FIG. It was confirmed that the boron adsorbent of Example 1 has a larger adsorption capacity than that obtained by simply mixing activated carbon and a hydrotalcite-like substance, and has a boron adsorption performance equivalent to or higher than that of commercially available cerium hydroxide.

Claims (2)

Si 2x Mg 1−x Al (OH) ・(A n− x−ny ・(B z− ・mH Oの組成式を有するハイドロタルサイト様物質(ここで、式中xは0.1<x<0.4の正数であり、A n− 、B z− はそれぞれ異なった価数の陰イオンであり、yは正数であり、mは0.1<m<1の正数である)が活性炭に担持されてなるホウ素吸着剤の製造方法であって、ケイ酸塩、アルミニウム塩、マグネシウム塩を溶解させた水溶液と活性炭とを混合して混合溶液を調製する混合工程と、この混合工程で調製された混合溶液のpHを10〜11に調整するpH調整工程と、このpH調製工程でpHが調整された混合溶液から固形分を分離する分離工程と、この分離工程で分離された固形分を乾燥させる乾燥工程とを備えたことを特徴とするホウ素吸着剤の製造方法。 Hydrotalcite-like substance having a composition formula of Si 2x Mg 1-x Al x (OH) 2. (A n− ) x-ny · (B z− ) y · mH 2 O (where x is 0.1 <x <0.4, A n− and B z− are anions having different valences, y is a positive number, and m is 0.1 <m <1. Is a method for producing a boron adsorbent supported on activated carbon, in which an aqueous solution in which silicate, aluminum salt and magnesium salt are dissolved and activated carbon are mixed to prepare a mixed solution A pH adjustment step for adjusting the pH of the mixed solution prepared in this mixing step to 10 to 11, a separation step for separating solids from the mixed solution adjusted in pH in this pH adjustment step, and this separation A drying process for drying the solid content separated in the process Method for producing a boron adsorbent. Si 2x Mg 1−x Al (OH) ・(A n− x−ny ・(B z− ・mH Oの組成式を有するハイドロタルサイト様物質(ここで、式中xは0.1<x<0.4の正数であり、A n− 、B z− はそれぞれ異なった価数の陰イオンであり、yは正数であり、mは0.1<m<1の正数である)が活性炭に担持されてなることを特徴とするホウ素吸着剤。 Hydrotalcite-like substance having a composition formula of Si 2x Mg 1-x Al x (OH) 2. (A n− ) x-ny · (B z− ) y · mH 2 O (where x is 0.1 <x <0.4, A n− and B z− are anions having different valences, y is a positive number, and m is 0.1 <m <1. Boron adsorbent characterized by being supported on activated carbon .
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