JP4547528B2 - Nitrate ion selective adsorbent, production method thereof, nitrate ion removal method and nitrate ion recovery method using the same - Google Patents
Nitrate ion selective adsorbent, production method thereof, nitrate ion removal method and nitrate ion recovery method using the same Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims description 52
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000011084 recovery Methods 0.000 title description 2
- -1 nitrate ions Chemical class 0.000 claims description 51
- 229910002651 NO3 Inorganic materials 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- 150000002500 ions Chemical class 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 26
- 150000001450 anions Chemical class 0.000 claims description 17
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 15
- 150000004692 metal hydroxides Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 35
- 238000001179 sorption measurement Methods 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 125000005271 tributylamino group Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005571 anion exchange chromatography Methods 0.000 description 1
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、硝酸イオン含有溶液、例えば河川、湖沼、海水、上下水等の汚染源から、特に富栄養化の原因となる硝酸イオンを効率よく除去するための新規な吸着剤、該吸着剤の製造方法、および該吸着剤を用いて硝酸イオンを効率的に除去或いは回収する方法に関する。 The present invention relates to a novel adsorbent for efficiently removing nitrate ions that cause eutrophication from a source of nitrate ion-containing solution such as rivers, lakes, seawater, and water and sewage, and the production of the adsorbent. The present invention relates to a method and a method for efficiently removing or recovering nitrate ions using the adsorbent.
硝酸性窒素は、吸着をしたり、沈殿物を作らないため、通常の化学的処理法が適用しにくく、除去が困難である。また、水環境では他の陰イオンが共存するため、一般に広く利用されているイオン交換法では硝酸イオンの除去率は低下するという問題がある。 Since nitrate nitrogen does not adsorb or form precipitates, it is difficult to apply ordinary chemical treatment methods and it is difficult to remove nitrate nitrogen. In addition, since other anions coexist in an aqueous environment, there is a problem that the removal rate of nitrate ions is lowered in the ion exchange method that is generally widely used.
これまで硝酸イオン含有溶液から硝酸イオンを選択的に除去できる適当な吸着剤はなく、黒鉛−硝酸化合物（特許文献１参照）、トリブチルアミノ基を有するイオン交換樹脂（特許文献２参照）、二級アミン置換基および三級アミン置換基を有する樹脂（特許文献３参照）、リン酸エステル基とアミノ基を有する共重合体（特許文献４参照）などが知られている。黒鉛−硝酸化合物は、吸着量が小さく欠点があり、トリブチルアミノ基を有するイオン交換樹脂は、硝酸イオンに対する選択性は高いが、樹脂の再生が困難であった。二級アミン置換基および三級アミン置換基を有する樹脂およびリン酸エステル基とアミノ基を有する共重合体は、硝酸イオンに対する選択吸着性が十分ではなく、他の陰イオンが大量に共存する溶液中では吸着量が不十分であった。
本発明の目的は、硝酸イオン含有溶液、中でも他の陰イオンの共存する硝酸イオン含有溶液において、高い硝酸イオン選択吸着性を有する吸着剤を提供することである。 An object of the present invention, nitrate ion-containing solutions, in nitrate ion-containing solution Of these co-existing anions is to provide adsorbents that have a high nitrate ion selective adsorptivity.
本発明者らは、上記した目的を達成すべく鋭意研究を重ねた結果、所定の組成で所定の面間隔を有する複合金属水酸化物およびその水熱処理物が高い硝酸イオン選択吸着性を有することを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that a composite metal hydroxide having a predetermined composition and a predetermined interplanar spacing and its hydrothermally treated product have high nitrate ion selective adsorption. As a result, the present invention has been completed.
すなわち、本発明は、下記に示すとおりの硝酸イオン選択的吸着剤、その製造方法、それを用いた硝酸イオン除去方法および硝酸イオン回収方法を提供するものである。
項１． 下記一般式（１）：
Ｍ2+ 1-xＭ3+ x（ＯＨ）2［Ａn-］x/n・ｍＨ2Ｏ （１）
（式中、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンであり、Ａn-はｎ価の陰イオンからなる。ｘは０．２０≦ｘ≦０．２５を満たす数である。）で表され、面間隔（００３）が８．０５〜８．１５Åの複合金属水酸化物およびその水熱処理物からなる群より選択される少なくとも１種を有効成分とする硝酸イオン選択的吸着剤。
項２． ＭｇおよびＺｎからなる群より選択される少なくとも１種の２価金属の水溶性化合物と、ＡｌおよびＦｅからなる群より選択される少なくとも１種の３価金属の水溶性化合物とを、該３価金属の水溶性化合物に対する該２価金属の水溶性化合物のモル比が３．０〜４．０となるように混合した溶液と、アルカリまたはその溶液とを混合して反応させ、下記一般式（１）：
Ｍ2+ 1-xＭ3+ x（ＯＨ）2［Ａn-］x/n・ｍＨ2Ｏ （１）
（式中、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンであり、Ａn-はｎ価の陰イオンからなる。ｘは０．２０≦ｘ≦０．２５を満たす数である。）で表され、面間隔（００３）が８．０５〜８．１５Åの複合金属水酸化物を沈殿させ、この沈殿を分離することを特徴とする硝酸イオン選択的吸着剤の製造方法。
項３． ＭｇおよびＺｎからなる群より選択される少なくとも１種の２価金属の水溶性化合物と、ＡｌおよびＦｅからなる群より選択される少なくとも１種の３価金属の水溶性化合物とを、該３価金属の水溶性化合物に対する該２価金属の水溶性化合物のモル比が３．０〜４．０となるように混合した溶液と、アルカリまたはその溶液とを混合して反応させ、下記一般式（１）：
Ｍ2+ 1-xＭ3+ x（ＯＨ）2［Ａn-］x/n・ｍＨ2Ｏ （１）
（式中、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンであり、Ａn-はｎ価の陰イオンからなる。ｘは０．２０≦ｘ≦０．２５を満たす数である。）で表され、面間隔（００３）が８．０５〜８．１５Åの複合金属水酸化物を沈殿させ、次いで水熱処理することを特徴とする選択的硝酸イオン吸着剤の製造方法。
項４． 項１に記載の硝酸イオン選択的吸着剤を硝酸イオン含有溶液に添加し、硝酸イオンを選択的に吸着させた後に、固液分離することを特徴とする硝酸イオン除去方法。
項５． 項１に記載の硝酸イオン選択的吸着剤を硝酸イオン含有溶液に添加し、硝酸イオンを選択的に吸着させ、次いで硝酸イオンの吸着された吸着剤を分離し、１００〜５００℃の温度で加熱処理した後に、塩化物イオンを含む溶液に接触させることを特徴とする硝酸イオン脱着および吸着剤再生方法。
項６． 項１に記載の硝酸イオン選択的吸着剤を硝酸イオン含有溶液に添加し、硝酸イオンを選択的に吸着させ、次いで、硝酸イオンの吸着された吸着剤を、脱着剤を含む溶液に接触させて硝酸イオンを脱着させて回収することを特徴とする硝酸イオン回収方法。
That is, the present invention provides a nitrate ion selective adsorbent as shown below, a production method thereof, a nitrate ion removal method and a nitrate ion recovery method using the same.
Item 1. The following general formula (1):
M 2+ 1-x M 3+ x (OH) 2 [A n− ] x / n · mH 2 O (1)
( Wherein M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and M 3+ is at least one type selected from the group consisting of Al ions and Fe ions) A n− is made of an n-valent anion. X is a number satisfying 0.20 ≦ x ≦ 0.25.) And the surface spacing (003) is 8. A nitrate ion selective adsorbent comprising as an active ingredient at least one selected from the group consisting of a mixed metal hydroxide of 05 to 8.15 kg and a hydrothermally treated product thereof.
Item 2. A trivalent metal water-soluble compound selected from the group consisting of Mg and Zn, and at least one trivalent metal water-soluble compound selected from the group consisting of Al and Fe. A solution mixed so that the molar ratio of the water-soluble compound of the divalent metal to the water-soluble compound of the metal is 3.0 to 4.0 is mixed with an alkali or a solution thereof to be reacted, and the following general formula ( 1):
M 2+ 1-x M 3+ x (OH) 2 [A n− ] x / n · mH 2 O (1)
( Wherein M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and M 3+ is at least one type selected from the group consisting of Al ions and Fe ions) A n− is made of an n-valent anion. X is a number satisfying 0.20 ≦ x ≦ 0.25.) And the surface spacing (003) is 8. A method for producing a nitrate ion selective adsorbent, comprising precipitating a mixed metal hydroxide of 05 to 8.15 kg and separating the precipitate.
Item 3. A trivalent metal water-soluble compound selected from the group consisting of Mg and Zn, and at least one trivalent metal water-soluble compound selected from the group consisting of Al and Fe. A solution mixed so that the molar ratio of the water-soluble compound of the divalent metal to the water-soluble compound of the metal is 3.0 to 4.0 is mixed with an alkali or a solution thereof to be reacted, and the following general formula ( 1):
M 2+ 1-x M 3+ x (OH) 2 [A n− ] x / n · mH 2 O (1)
( Wherein M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and M 3+ is at least one type selected from the group consisting of Al ions and Fe ions) A n− is made of an n-valent anion. X is a number satisfying 0.20 ≦ x ≦ 0.25.) And the surface spacing (003) is 8. A method for producing a selective nitrate ion adsorbent, comprising precipitating 05 to 8.15 kg of composite metal hydroxide, followed by hydrothermal treatment.
Item 4. A method for removing nitrate ions, comprising adding the nitrate ion selective adsorbent according to Item 1 to a nitrate ion-containing solution and selectively adsorbing nitrate ions, followed by solid-liquid separation.
Item 5. The nitrate ion selective adsorbent according to Item 1 is added to a nitrate ion-containing solution to selectively adsorb nitrate ions, and then the adsorbent on which nitrate ions are adsorbed is separated and heated at a temperature of 100 to 500 ° C. A method for desorbing nitrate ions and regenerating an adsorbent, characterized in that after treatment, the solution is brought into contact with a solution containing chloride ions.
Item 6. The nitrate ion selective adsorbent according to Item 1 is added to a nitrate ion-containing solution to selectively adsorb nitrate ions, and then the adsorbent on which nitrate ions are adsorbed is brought into contact with a solution containing a desorbent. A method for recovering nitrate ions, comprising desorbing and recovering nitrate ions.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の硝酸イオン選択的吸着剤は、下記一般式（１）で表され、面間隔（００３）が８．０５〜８．１５Åの複合金属水酸化物およびその水熱処理物からなる群より選択される少なくとも１種を有効成分とする。（面間隔（００３）は、Ｍ2+、Ｍ3+およびＯＨ-からなる層の層間隔を意味する。）
Ｍ2+ 1-xＭ3+ x（ＯＨ）2［Ａn-］x/n・ｍＨ2Ｏ （１）
式中、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンであり、Ａn-はｎ価の陰イオンからなる。ｘは０．２０≦ｘ≦０．２５を満たす数である。
The nitrate ion selective adsorbent of the present invention is selected from the group consisting of a composite metal hydroxide represented by the following general formula (1) and having an interplanar spacing (003) of 8.05 to 8.15 mm and a hydrothermally treated product thereof. At least one of these is used as an active ingredient. (Surface spacing (003) means the layer spacing of layers composed of M 2+ , M 3+ and OH − )
M 2+ 1-x M 3+ x (OH) 2 [A n− ] x / n · mH 2 O (1)
In the formula, M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and M 3+ is at least one type selected from the group consisting of Al ions and Fe ions. It is a metal trivalent ion, and A n− consists of an n-valent anion. x is a number satisfying 0.20 ≦ x ≦ 0.25.
一般式（１）において、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍｇイオンが好ましい。 In the general formula (1), M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and Mg ions are preferable.
一般式（１）において、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンである。 In the general formula (1), M 3+ is at least one metal trivalent ion selected from the group consisting of Al ions and Fe ions.
一般式（１）において、Ａn-はｎ価の陰イオンからなり、Ｃｌ-が主であるのが好ましく、ＣＯ3 2-が微量含まれていてもよい。複合金属水酸化物の層間には、Ｃｌ-が存在するのが好ましく、吸着剤として用いる際に他の陰イオンと交換が可能である。 In the general formula (1), A n- is an n-valent anion, Cl - is preferably is a primary, CO 3 2-may also contain minor amounts. The layers of the composite metal hydroxide, Cl - is preferably present is a possible exchange with other anions when used as an adsorbent.
一般式（１）中のｘは０．２０≦ｘ≦０．２５を満たす数である。また、一般式（１）において、（１−ｘ）／ｘは３．０〜４．０であるのが好ましい。 X in the general formula (1) is a number satisfying 0.20 ≦ x ≦ 0.25. In the general formula (1), (1-x) / x is preferably 3.0 to 4.0.
一般式（１）中のｍは、０．１≦ｍ≦１．０を満たす数であるのが好ましい。 M in the general formula (1) is preferably a number satisfying 0.1 ≦ m ≦ 1.0.
一般式（１）で表される複合金属水酸化物は、ＭｇおよびＺｎからなる群より選択される少なくとも１種の２価金属の水溶性化合物と、ＡｌおよびＦｅからなる群より選択される少なくとも１種の３価金属の水溶性化合物とを、該３価金属の水溶性化合物に対する該２価金属の水溶性化合物のモル比（２価金属の水溶性化合物／３価金属の水溶性化合物）が３．０〜４．０となるように混合し、該混合物を加水分解することによって製造することができるが、好ましくは加水分解反応後、さらに熟成するのがよい。これら２価金属の水溶性化合物と３価金属の水溶性化合物としては、金属のハロゲン化物、硝酸塩、硫酸塩、炭酸水素塩などを挙げることができるが、後の処理を考えると塩化物、硝酸塩、炭酸水素塩が好ましい。 The composite metal hydroxide represented by the general formula (1) is at least one selected from the group consisting of at least one divalent metal water-soluble compound selected from the group consisting of Mg and Zn, and the group consisting of Al and Fe. One water-soluble compound of a trivalent metal and a molar ratio of the water-soluble compound of the divalent metal to the water-soluble compound of the trivalent metal (water-soluble compound of divalent metal / water-soluble compound of trivalent metal) Can be prepared by hydrolyzing the mixture, and preferably after the hydrolysis reaction, further aging. Examples of these divalent metal water-soluble compounds and trivalent metal water-soluble compounds include metal halides, nitrates, sulfates, bicarbonates, and the like. Hydrogen carbonate is preferred.
加水分解反応は適当なアルカリ、例えば水酸化ナトリウムなどのアルカリ金属水酸化物、炭酸ナトリウムなどのアルカリ金属炭酸塩、炭酸水素ナトリウムなどのアルカリ金属炭酸水素塩、アンモニアや、これらの溶液等を用いて行うことができるが、一般には水酸化ナトリウムなどのアルカリ金属水酸化物の水溶液が用いられる。反応を均一化させるために、２価金属の水溶性化合物と３価金属の水溶性化合物を混合水溶液とし、この水溶液とアルカリ金属水酸化物の水溶液とを同時滴下するのが好ましい。 The hydrolysis reaction is carried out using a suitable alkali, for example, an alkali metal hydroxide such as sodium hydroxide, an alkali metal carbonate such as sodium carbonate, an alkali metal bicarbonate such as sodium bicarbonate, ammonia, or a solution thereof. In general, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide is used. In order to make the reaction uniform, it is preferable that a water-soluble compound of a divalent metal and a water-soluble compound of a trivalent metal are used as a mixed aqueous solution, and this aqueous solution and an aqueous solution of an alkali metal hydroxide are added dropwise simultaneously.
加水分解反応において、溶液のｐＨは８〜１２、中でも９〜１１に保つのが好ましく、特に沈殿時の溶液のｐＨをそのようにするのがよい。 In the hydrolysis reaction, the pH of the solution is preferably 8 to 12, and particularly preferably 9 to 11, and the pH of the solution during precipitation is particularly preferably set as such.
加水分解反応により沈殿が生成され、この沈殿をろ過または遠心分離により分取し、中性になるまで水洗した後に、風乾することにより、複合金属水酸化物が粉末として得られる。 A precipitate is generated by the hydrolysis reaction, and this precipitate is collected by filtration or centrifugation, washed with water until neutral, and then air-dried to obtain a composite metal hydroxide as a powder.
このようにして得られた複合金属水酸化物は、そのままでも吸着剤として用いることができるが、これを水熱処理したものも良好な硝酸イオン吸着性を示す。水熱処理は、耐圧容器（オートクレーブ）中、通常０．１１〜１ＭＰａの範囲の加圧下、１００〜２５０℃の範囲の温度、好ましくは０．１５〜０．５ＭＰａの範囲の加圧下、１１０〜１８０℃の範囲の温度で行われる。 The composite metal hydroxide thus obtained can be used as an adsorbent as it is, but a hydrothermally treated product of the composite metal hydroxide also exhibits good nitrate ion adsorptivity. The hydrothermal treatment is usually performed in a pressure vessel (autoclave) under a pressure in the range of 0.11 to 1 MPa, at a temperature in the range of 100 to 250 ° C., preferably under a pressure in the range of 0.15 to 0.5 MPa. Performed at a temperature in the range of ° C.
本発明の硝酸イオン選択的吸着剤を用いて溶液中の硝酸イオンを除去するには、該吸着剤を硝酸イオン含有溶液に添加し、十分撹拌混合して硝酸イオンを吸着させ、さらにはほぼ吸着平衡に達しめた後に、固液分離すればよい。それにより、溶液中の硝酸イオンは吸着剤に取り込まれ、吸着剤ごと固体として液体より分別除去される。このような吸着処理において、溶液のｐＨは４〜１０の範囲に調整されるのが好ましい。 In order to remove nitrate ions in a solution using the nitrate ion selective adsorbent of the present invention , the adsorbent is added to a nitrate ion-containing solution, and mixed sufficiently with stirring to adsorb nitrate ions. After reaching equilibrium, solid-liquid separation may be performed. Thereby, nitrate ions in the solution are taken into the adsorbent, and the adsorbent is separated and removed from the liquid as a solid. In such an adsorption treatment, the pH of the solution is preferably adjusted to a range of 4-10.
吸着剤に吸着された硝酸イオンは、吸着剤を適当な脱着剤、通常アルカリ、例えば水酸化ナトリウムなどのアルカリ金属水酸化物、炭酸ナトリウムなどのアルカリ金属炭酸塩、炭酸水素ナトリウムなどのアルカリ金属炭酸水素塩等や、塩化ナトリウムなどのハロゲン化アルカリ等の溶液、好ましくは水溶液で処理すれば、脱着されて溶液中に溶出してくる。脱着剤の溶液濃度は、硝酸イオン吸着量によっても異なるが、通常０．１〜５Ｍ、好ましくは０．１〜２Ｍの範囲で選ばれる。脱着と同時に吸着剤の再生を行う場合には、脱着剤溶液として塩化物イオンを含む溶液を用いるのが好ましい。 Nitrate ions adsorbed on the adsorbent are used as a suitable desorbent, usually an alkali such as an alkali metal hydroxide such as sodium hydroxide, an alkali metal carbonate such as sodium carbonate, or an alkali metal carbonate such as sodium bicarbonate. When treated with a solution such as a hydrogen salt or an alkali halide such as sodium chloride, preferably an aqueous solution, it is desorbed and eluted into the solution. The solution concentration of the desorbent varies depending on the nitrate ion adsorption amount, but is usually 0.1 to 5M, preferably 0.1 to 2M. When regenerating the adsorbent simultaneously with desorption, it is preferable to use a solution containing chloride ions as the desorbent solution.
また、吸着剤に吸着された硝酸イオンは、吸着剤を加熱処理することで脱着することができる。すなわち、硝酸イオンを吸着した吸着剤を１００〜５００℃、好ましくは２００〜３５０℃で加熱処理すれば、層間の硝酸イオンは分解しガスとして放出される。その後に、吸着剤を、塩化ナトリウム、塩化マグネシウム等の塩化物イオンを含む水溶液に添加することにより、再生することができる。 The nitrate ions adsorbed on the adsorbent can be desorbed by heat-treating the adsorbent. That is, if the adsorbent adsorbing nitrate ions is heat-treated at 100 to 500 ° C., preferably 200 to 350 ° C., the nitrate ions between the layers are decomposed and released as gas. Thereafter, the adsorbent can be regenerated by adding it to an aqueous solution containing chloride ions such as sodium chloride and magnesium chloride.
本発明の硝酸イオン選択的吸着剤によれば、硝酸イオン含有溶液、中でも他の陰イオンの共存する硝酸イオン含有溶液において、高い硝酸イオン選択吸着性を有する。従って、共存する陰イオン、例えば硫酸イオン、塩素イオン、リン酸水素イオン、炭酸イオンなどの通常硝酸イオンの吸着を妨害すると考えられている陰イオンが共存していても、硝酸イオンを高い効率で吸着することができる。さらに、多量の陰イオンが存在する海水においても硝酸イオンを選択的に吸着し得る高選択吸着性を有するので、全水域の硝酸イオンの除去に有効である。 The nitrate ion selective adsorbent of the present invention has a high nitrate ion selective adsorption property in a nitrate ion-containing solution, particularly a nitrate ion-containing solution in which other anions coexist. Therefore, even in the presence of coexisting anions, such as sulfate ions, chloride ions, hydrogen phosphate ions, carbonate ions, and the like, which are normally thought to interfere with the adsorption of nitrate ions, nitrate ions are highly efficient. Can be adsorbed. Furthermore, even in seawater where a large amount of anions are present, it has a high selective adsorption property capable of selectively adsorbing nitrate ions, which is effective in removing nitrate ions in the entire water area.
また、既に吸着処理に使用済みの硝酸イオン選択的吸着剤は、簡単に硝酸イオンを脱着、再生して繰り返し使用することができる。 In addition, the nitrate ion selective adsorbent that has already been used for the adsorption treatment can be repeatedly used by simply desorbing and regenerating nitrate ions.
以下、実施例を挙げて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
なお、以下の実施例および比較例において、面間隔は、Ｘ線回折（ＸＲＤ）測定より求めた。Ｘ線回折測定は、粉末Ｘ線回折装置を使用し、管電圧４０ｋＶ、管電流２４ｍＡ、走査速度２θ＝２°／ｍｉｎの条件下で行った。面間隔は（００３）の回折ピーク位置から求めた。 In the following examples and comparative examples, the surface spacing was determined by X-ray diffraction (XRD) measurement. X-ray diffraction measurement was performed using a powder X-ray diffractometer under conditions of a tube voltage of 40 kV, a tube current of 24 mA, and a scanning speed of 2θ = 2 ° / min. The surface spacing was determined from the diffraction peak position at (003).
実施例１
１Ｍの塩化マグネシウム溶液１２ｍｌと１Ｍの塩化アルミニウム溶液３ｍｌとを含む混合溶液と、１Ｍ水酸化ナトリウム水溶液とを、水５０ｍｌにｐＨ１０に保ちながら同時に滴下し、１時間撹拌した後、遠心分離し、水溶液と析出物を分離した。析出物は８０ｍｌの水溶液と共に１５０℃で１日間水熱処理させ、沈殿生成物を得た。沈殿生成物を遠心分離し、中性になるまで水洗いし、室温で１日間乾燥した（１．５ｇ）。生成物は、粉末Ｘ線回折、組成分析、熱分析により、［Ｍｇ0.799Ａｌ0.201（ＯＨ）2］［Ｃｌ0.176（ＣＯ3）0.013］・０．４９６Ｈ2Ｏの化学組成の複合金属水酸化物と同定され、これを吸着剤試料とした。
Example 1
A mixed solution containing 12 ml of 1M magnesium chloride solution and 3 ml of 1M aluminum chloride solution and 1M aqueous sodium hydroxide solution were added dropwise to 50 ml of water while keeping the pH at 10 and stirred for 1 hour, followed by centrifugation to obtain an aqueous solution. And the precipitate were separated. The precipitate was hydrothermally treated with 150 ml of an aqueous solution at 150 ° C. for 1 day to obtain a precipitated product. The precipitated product was centrifuged, washed with water until neutral and dried at room temperature for 1 day (1.5 g). The product is a composite metal hydroxide having a chemical composition of [Mg 0.799 Al 0.201 (OH) 2 ] [Cl 0.176 (CO 3 ) 0.013 ] · 0.496H 2 O by powder X-ray diffraction, composition analysis, and thermal analysis. This was identified as an adsorbent sample.
実施例２
１Ｍの塩化マグネシウム溶液１２ｍｌと１Ｍの塩化鉄溶液３ｍｌとを含む混合溶液と、１Ｍ水酸化ナトリウム水溶液とを、水５０ｍｌにｐＨ１０に保ちながら同時に滴下し、１時間撹拌した後、遠心分離し、水溶液と析出物を分離した。析出物は８０ｍｌの水溶液と共に１５０℃で１日間水熱処理させ、沈殿生成物を得た。沈殿生成物を遠心分離し、中性になるまで水洗いし、室温で１日間乾燥した（１．７ｇ）。生成物は、粉末Ｘ線回折、組成分析、熱分析により、［Ｍｇ0.752Ｆｅ0.248（ＯＨ）2］［Ｃｌ0.215（ＣＯ3）0.016］・０．５１８Ｈ2Ｏの化学組成の複合金属水酸化物と同定され、これを吸着剤試料とした。
Example 2
A mixed solution containing 12 ml of 1M magnesium chloride solution and 3 ml of 1M iron chloride solution and 1M aqueous sodium hydroxide solution were simultaneously added dropwise to 50 ml of water while keeping the pH at 10 and stirred for 1 hour, followed by centrifugation to obtain an aqueous solution. And the precipitate were separated. The precipitate was hydrothermally treated with 150 ml of an aqueous solution at 150 ° C. for 1 day to obtain a precipitated product. The precipitated product was centrifuged, washed with water until neutral and dried at room temperature for 1 day (1.7 g). The product, a powder X-ray diffraction, composition analysis, thermal analysis, [Mg 0.752 Fe 0.248 (OH ) 2] [Cl 0.215 (CO 3) 0.016] · 0.518H 2 composite metal hydroxide of O chemical composition This was identified as an adsorbent sample.
比較例１
吸着剤試料として、冨田製薬株式会社製の商品名「ＴＰＥＸ」を用いた。
Comparative Example 1
The brand name “TPEX” manufactured by Iwata Pharmaceutical Co., Ltd. was used as the adsorbent sample.
実施例１、２および比較例１の吸着剤試料を用いて、以下のようにして、硝酸飽和吸着容量、海水からの硝酸吸着容量、および分配係数（Ｋｄ）を求めた。結果を表１に示す。 Using the adsorbent samples of Examples 1 and 2 and Comparative Example 1, the nitric acid saturated adsorption capacity, the nitric acid adsorption capacity from seawater, and the distribution coefficient (Kd) were determined as follows. The results are shown in Table 1.
［硝酸飽和吸着容量］
吸着剤試料０．２ｇに対して０．１Ｍ硝酸ナトリウム水溶液１００ｍｌを加え、吸着実験を２７℃で３日間行い、硝酸イオンの飽和吸着容量を求めた。
[Nitric acid saturated adsorption capacity]
100 mL of 0.1 M sodium nitrate aqueous solution was added to 0.2 g of the adsorbent sample, and the adsorption experiment was performed at 27 ° C. for 3 days to determine the saturated adsorption capacity of nitrate ions.
［海水からの硝酸吸着容量］
吸着剤試料０．１ｇに対して０．０３ｍＭ硝酸ナトリウムを添加した天然海水１Ｌを加え、吸着実験を２７℃で３日間行い、海水からの硝酸イオンの吸着容量を求めた。
[Nitric acid adsorption capacity from seawater]
1 L of natural seawater added with 0.03 mM sodium nitrate was added to 0.1 g of the adsorbent sample, and the adsorption experiment was conducted at 27 ° C. for 3 days to determine the adsorption capacity of nitrate ions from seawater.
［分配係数（Ｋｄ）］
吸着剤試料０．１ｇを、濃度各１ｍＭの、塩化物イオン、硝酸イオン、リン酸二水素イオン、硫酸イオン（何れもナトリウム塩として供用）を含む混合溶液１０ｍｌに加え、混合陰イオン吸着実験を２７℃で３日間行った。次いで、上澄みの陰イオン濃度を陰イオンクロマトグラフィーで分析した。
[Distribution coefficient (Kd)]
Add 0.1 g of adsorbent sample to 10 ml of a mixed solution containing chloride ion, nitrate ion, dihydrogen phosphate ion, and sulfate ion (all used as sodium salts) at a concentration of 1 mM, and perform mixed anion adsorption experiments. 3 days at 27 ° C. Subsequently, the anion concentration of the supernatant was analyzed by anion chromatography.
なお、表１における（１−ｘ）／ｘは、吸着剤試料における３価金属に対する２価金属のモル比（２価金属／３価金属）である。 In Table 1, (1-x) / x is the molar ratio of divalent metal to trivalent metal in the adsorbent sample (divalent metal / trivalent metal).
実施例３（加熱脱着による再生）
硝酸イオン吸着後の吸着剤０．２ｇを、３００℃で２時間加熱した（０．１８ｇ）。加熱処理後の吸着剤０．０５ｇを０．１Ｍ塩化ナトリウム水溶液１００ｍｌに添加し、室温で２日間撹拌して再生した。以下同様にして、硝酸イオンの吸脱着を５回以上繰り返すことができた。
Example 3 (Regeneration by heat desorption)
After adsorption of nitrate ions, 0.2 g of the adsorbent was heated at 300 ° C. for 2 hours (0.18 g). 0.05 g of the adsorbent after the heat treatment was added to 100 ml of a 0.1 M sodium chloride aqueous solution, and the mixture was regenerated by stirring at room temperature for 2 days. In the same manner, the adsorption and desorption of nitrate ions could be repeated 5 times or more.
実施例４（脱着剤による再生）
硝酸イオン吸着後の吸着剤０．０５ｇを０．１Ｍ塩化ナトリウム水溶液１００ｍｌに添加し、室温で２日間撹拌して脱着・再生した。硝酸イオンは８０％以上脱着した。以下同様にして、硝酸イオンの吸脱着を５回以上繰り返すことができた。
Example 4 (Regeneration with Desorbent)
0.05 g of adsorbent after adsorption of nitrate ions was added to 100 ml of 0.1 M aqueous sodium chloride solution, and the mixture was stirred for 2 days at room temperature for desorption / regeneration. Nitrate ions were desorbed by 80% or more. In the same manner, the adsorption and desorption of nitrate ions could be repeated 5 times or more.
Claims (6)
Ｍ2+ 1-xＭ3+ x（ＯＨ）2［Ａn-］x/n・ｍＨ2Ｏ （１）
（式中、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンであり、Ａn-はｎ価の陰イオンからなる。ｘは０．２０≦ｘ≦０．２５を満たす数である。）で表され、面間隔（００３）が８．０５〜８．１５Åの複合金属水酸化物およびその水熱処理物からなる群より選択される少なくとも１種を有効成分とする硝酸イオン選択的吸着剤。 The following general formula (1):
M 2+ 1-x M 3+ x (OH) 2 [A n− ] x / n · mH 2 O (1)
( Wherein M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and M 3+ is at least one type selected from the group consisting of Al ions and Fe ions) A n− is made of an n-valent anion. X is a number satisfying 0.20 ≦ x ≦ 0.25.) And the surface spacing (003) is 8. A nitrate ion selective adsorbent comprising as an active ingredient at least one selected from the group consisting of a mixed metal hydroxide of 05 to 8.15 kg and a hydrothermally treated product thereof.
Ｍ2+ 1-xＭ3+ x（ＯＨ）2［Ａn-］x/n・ｍＨ2Ｏ （１）
（式中、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンであり、Ａn-はｎ価の陰イオンからなる。ｘは０．２０≦ｘ≦０．２５を満たす数である。）で表され、面間隔（００３）が８．０５〜８．１５Åの複合金属水酸化物を沈殿させ、この沈殿を分離することを特徴とする硝酸イオン選択的吸着剤の製造方法。 A trivalent metal water-soluble compound selected from the group consisting of Mg and Zn, and at least one trivalent metal water-soluble compound selected from the group consisting of Al and Fe. A solution mixed so that the molar ratio of the water-soluble compound of the divalent metal to the water-soluble compound of the metal is 3.0 to 4.0 is mixed with an alkali or a solution thereof to be reacted, and the following general formula ( 1):
M 2+ 1-x M 3+ x (OH) 2 [A n− ] x / n · mH 2 O (1)
( Wherein M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and M 3+ is at least one type selected from the group consisting of Al ions and Fe ions) A n− is made of an n-valent anion. X is a number satisfying 0.20 ≦ x ≦ 0.25.) And the surface spacing (003) is 8. A method for producing a nitrate ion selective adsorbent, comprising precipitating a mixed metal hydroxide of 05 to 8.15 kg and separating the precipitate.
Ｍ2+ 1-xＭ3+ x（ＯＨ）2［Ａn-］x/n・ｍＨ2Ｏ （１）
（式中、Ｍ2+はＭｇイオンおよびＺｎイオンからなる群より選択される少なくとも１種の金属２価イオンであり、Ｍ3+はＡｌイオンおよびＦｅイオンからなる群より選択される少なくとも１種の金属３価イオンであり、Ａn-はｎ価の陰イオンからなる。ｘは０．２０≦ｘ≦０．２５を満たす数である。）で表され、面間隔（００３）が８．０５〜８．１５Åの複合金属水酸化物を沈殿させ、次いで水熱処理することを特徴とする硝酸イオン選択的吸着剤の製造方法。 A trivalent metal water-soluble compound selected from the group consisting of Mg and Zn, and at least one trivalent metal water-soluble compound selected from the group consisting of Al and Fe. A solution mixed so that the molar ratio of the water-soluble compound of the divalent metal to the water-soluble compound of the metal is 3.0 to 4.0 is mixed with an alkali or a solution thereof to be reacted, and the following general formula ( 1):
M 2+ 1-x M 3+ x (OH) 2 [A n− ] x / n · mH 2 O (1)
( Wherein M 2+ is at least one metal divalent ion selected from the group consisting of Mg ions and Zn ions, and M 3+ is at least one type selected from the group consisting of Al ions and Fe ions) A n− is made of an n-valent anion. X is a number satisfying 0.20 ≦ x ≦ 0.25.) And the surface spacing (003) is 8. A method for producing a nitrate ion- selective adsorbent, comprising precipitating 05 to 8.15 kg of a composite metal hydroxide, followed by hydrothermal treatment.
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