JPH0154094B2 - - Google Patents
Info
- Publication number
- JPH0154094B2 JPH0154094B2 JP13602681A JP13602681A JPH0154094B2 JP H0154094 B2 JPH0154094 B2 JP H0154094B2 JP 13602681 A JP13602681 A JP 13602681A JP 13602681 A JP13602681 A JP 13602681A JP H0154094 B2 JPH0154094 B2 JP H0154094B2
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- anion
- chelate
- inorganic
- anions
- 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.)
- Expired
Links
- 239000003463 adsorbent Substances 0.000 claims description 39
- 150000001449 anionic compounds Chemical class 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000013522 chelant Substances 0.000 claims description 17
- -1 phosphate anion Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 9
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- OWTFKEBRIAXSMO-UHFFFAOYSA-N arsenite(3-) Chemical compound [O-][As]([O-])[O-] OWTFKEBRIAXSMO-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IDVRZFQYOSGBAF-UHFFFAOYSA-N monophenyl phosphonate Chemical compound O=P(=O)OC1=CC=CC=C1 IDVRZFQYOSGBAF-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KPRZOPQOBJRYSW-UHFFFAOYSA-N o-hydroxybenzylamine Natural products NCC1=CC=CC=C1O KPRZOPQOBJRYSW-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Description
本発明は、特にリン酸アニオン、フツ素アニオ
ン、亜ヒ酸アニオン、等の有害な無機アニオンを
選択的に吸着する吸着剤とその製造法及びその利
用法に関するものである。
従来、これらの有害無機アニオンを除去するた
めの吸着剤としては、活性炭、活性アルミナ、水
酸化鉄などの金属水酸化物、ゼオライト、アニオ
ン交換樹脂、シリコン合金、金属担持型陽イオン
交換樹脂、金属を担持したイミノジ酢酸キレート
型キレート樹脂などがあり、これらを用いて上記
有害な無機アニオンを吸着除去する研究がなされ
ている。しかしながら、これらは、いずれも吸着
量が少なく、吸着剤を多量に必要とし、吸着剤の
寿命が低いなどの欠点を有している。したがつ
て、従来、公知の上記吸着剤を、上水、下水、工
業用水、工場廃液、ポイラー用水等から有害な無
機アニオンを除去するためには、コスト高とな
り、実用的には、不適当であつた。
そこで、本発明者らは、かかる欠点を解消すべ
く鋭意研究した結果、特定のキレート樹脂に金属
イオンを担持させると、無機アニオンに対して高
い吸着能を有し、かつ吸着剤の寿命がすぐれた吸
着剤が得られることを見い出し、また得られた吸
着剤が水中の無機アニオンをきわめて効率良く除
去できることを見い出し、本発明に到達した。
すなわち、本発明は、フエノール核に導入され
た一級及び／又は二級のアルキルアミノ基の水素
原子の一部又は全部がメチレンホスホン酸基で置
換されたキレート形成基を有するフエノール系キ
レート樹脂に金属イオンを担持せしめてなる無機
アニオン吸着剤及びフエノール核に導入された一
級及び／又は二級のアルキルアミノ基の水素原子
の一部又は全部がメチレンホスホン酸基で置換さ
れたキレート形成基を有するフエノール系キレー
ト樹脂（以下含リンフエノール系キレート樹脂と
いう。）と金属イオンを含有する金属塩水溶液と
を接触させることを特徴とする無機アニオン吸着
剤の製造法ならびにかかる吸着剤を用いて、水溶
液中の無機アニオンを吸着せしめることを特徴と
する吸着処理法である。
本発明に用いられる含リンフエノール系キレー
ト樹脂は先に特許出願した（特願昭55−36358号
（特公昭60−51491号公報参照））樹脂であり、た
とえば、次のような方法で製造することができ
る。すなわち、一級又は二級アルキルアミノ基を
含有するフエノール誘導体に、鉱酸の存在下で、
ホルムアルデヒドと亜リン酸を反応させ、アミノ
基のプロトンの一部又は全部をメチレンホスホン
酸に置換させ、しかる後、フエノール類とアルデ
ヒド類とを反応させゲル化させることにより製造
することができる。そのときに用いる一級又は二
級のアルキルアミノ基を含有するフエノール誘導
体としては、チロシン、アンモニアレゾール、サ
リチルアミン等、鉱酸としては、塩酸、硫酸、フ
エノール類としては、フエノール、レゾルシン、
アルデヒド類としては、ホルムアルデヒド、アセ
トアルドヒドが好ましい。また、本発明に用いら
れる含リンフエノール系キレート樹脂の形状は、
好ましくは、粒状が用いられるが、繊維状、板状
等いかなる状でもよい。
本発明において、前記の含リンフエノール系キ
レート樹脂に担持させる金属イオンとしては、い
かなる金属イオンであつてもよいが、その中でも
Fe3+，Sn4+，Ti4+，Al3+が好ましい。
本発明の吸着剤を製造するには、たとえば前記
の含リンフエノール系キレート樹脂と上記の金属
イオンを含有する金属塩水溶液とを接触させれば
よい。その接触させる方法としては、カラム法、
パツチ法のいずれの方法でもよい。また、接触さ
せる時の温度としては、５〜40℃が適当で、10〜
30℃が好ましい。また、金属塩水溶液としては、
たとえば塩化物の水溶液、硫酸塩の水溶液、硝酸
塩の水溶液があげられ、その濃度としては、0.5
〜10wt％が適当で、２〜5wt％が好ましく、PHと
しては、２〜７が適当で、３〜５が好ましい。
このようにして得られる吸着剤は無機アニオ
ン、特にリン酸アニオン、亜ヒ酸アニオン、フツ
素アニオンに対して高い吸着能を有するので、通
常のイオン交換樹脂と同様にして、無機アニオン
含有水溶液と接触させて、これを除去することが
できる。接触させる方法としては、パツチ法、カ
ラム法のいずれの方法を用いてもよい。また、そ
の時の接触温度としては、５℃〜40℃が適当で、
10℃〜30℃が好ましく、無機アニオンを含有する
水溶液のPHとしては、２〜８が適当で、４〜７が
好ましい。また、無機アニオンを吸着した吸着剤
から無機アニオンを脱着させるには、たとえば、
0.2〜１規定の塩酸又は硫酸水溶液を吸着剤に接
触させ、続いて、水洗すればよく、この方法によ
り、吸着剤は再生され、何回もくり返して使用す
ることができる。
本発明によれば、きわめて簡単で、かつ経済的
な方法で無機アニオン吸着剤を得ることができ、
また得られた吸着剤はリン酸アニオン、亜ヒ酸ア
ニオン、フツ素アニオンなどの無機アニオンに対
して高い吸着能を有し、かつ吸着剤の寿命もすぐ
てれいる。
次に実施例により本発明をさらに具体的に説明
する。
参考例 １
チロシン１モルと亜リン酸２モルとを20％塩酸
水溶液に溶解させて、撹拌しながら加熱還流させ
ておいた。この状態で、37％ホルマリン水溶液６
mlを１時間かかつて滴下し、さらに１時間還流さ
せながら、撹拌を続けた。ついで、室温に冷却し
た後、カ性ソーダを加えて、PH11のアルカリ性に
した。この液に、レゾルシン1.5モル、37％ホル
マリン５モルを加え、さらに、撹拌下ｎ−パラフ
インを加えた。次いで、撹拌を続けながら、60℃
で１時間、80℃で１時間、90℃で１時間おのおの
加熱すると、内容物は粒状に固化を始めた。しか
る後、オートクレープに内容物をうつし、120℃
で５時間反応させて、ゲル化を完了させた。この
得られた粒状の樹脂をロ過により単離し、風乾、
水洗後、1NH2SO4溶液に浸漬し、樹脂をNa型か
らＨ型に変換させた。その後、この樹脂をロ別す
るとビーズ状の含リンフエノール系キレート樹脂
が得られた。
実施例 １
参考例１で製造した磁含リンフエノール系キレ
ート樹脂100c.c.を5wt％の塩化第二鉄水溶液（PH
３）500c.c.に25℃で48時間浸漬し、Fe3+イオンを
担持させた（以下この吸着剤をＡとする。）。ま
た、同様にして含リンフエノール系キレート樹脂
100c.c.を5wt％の塩化第二スズ水溶液（PH５）500
c.c.に25℃で48時間浸漬しSn4+イオンを担持させ
た（以下この吸着剤をＢとする。）。また、同様に
して四塩化チタン水溶液、塩化アルミニウム水溶
液を用いてTi4+イオン、Al3+イオンをそれぞれ
担持させた（以下これらの吸着剤をおのおのＣ，
Ｄとする。）。
比較例 １
イミノジ酢酸型キレート樹脂である三菱化成社
製ダイアイオンCR−10にも実施例１と同様にし
てFe3+イオン、Sn4+イオン、Ti4+イオン、Al3+
イオンをれぞれ担持せしめた（以下これらをおの
おの吸着剤Ｅ，Ｆ，Ｇ，Ｈとする。）。
実施例２〜５、比較例２〜５
実施例１で得た吸着剤Ａ，Ｂ，Ｃ，Ｄ、及び比
較例１で得た吸着剤のＥ，Ｆ，Ｇ，Ｈ、おのおの
10c.c.を10mmφ×50mmのカラムに詰め、リン酸アニ
オン含有水溶液を、SV51／hr25℃で通液した。
このときのリン酸アニオン含有水溶液としては、
リンとして20ppmの濃度となるように、正リン酸
を用いて調整したものであり、また、この液のPH
は酢酸ソーダと塩酸でPHが６となるように調整し
たものである。
通液後、液中のリン酸濃度を測定することによ
りおのおのの吸着剤の0.5ppm破過点吸着容量を
求めた。
その結果を表１に示す。
The present invention particularly relates to an adsorbent that selectively adsorbs harmful inorganic anions such as phosphate anions, fluorine anions, arsenite anions, etc., and methods for producing and using the same. Conventionally, adsorbents for removing these harmful inorganic anions include activated carbon, activated alumina, metal hydroxides such as iron hydroxide, zeolites, anion exchange resins, silicon alloys, metal-supported cation exchange resins, and metals. There are iminodiacetic acid chelate type chelate resins that carry , and research is being conducted to adsorb and remove the harmful inorganic anions using these. However, all of these have drawbacks such as a small amount of adsorption, a large amount of adsorbent, and a short lifespan of the adsorbent. Therefore, the conventionally known adsorbents described above are expensive and unsuitable for practical use in order to remove harmful inorganic anions from tap water, sewage, industrial water, factory waste water, boiler water, etc. It was hot. Therefore, as a result of intensive research in order to eliminate such drawbacks, the present inventors found that when metal ions are supported on a specific chelate resin, it has a high adsorption capacity for inorganic anions and the life of the adsorbent is excellent. The inventors have now discovered that an adsorbent can be obtained, and that the obtained adsorbent can remove inorganic anions in water very efficiently, leading to the present invention. That is, the present invention provides a phenolic chelate resin having a chelate-forming group in which some or all of the hydrogen atoms of the primary and/or secondary alkylamino groups introduced into the phenol nucleus are substituted with methylenephosphonic acid groups. An inorganic anion adsorbent carrying ions and a phenol having a chelate-forming group in which some or all of the hydrogen atoms of the primary and/or secondary alkylamino group introduced into the phenol nucleus are substituted with a methylenephosphonic acid group. A method for producing an inorganic anion adsorbent characterized by contacting an aqueous solution of a metal salt containing a metal ion with an aqueous solution of a metal salt containing a metal ion, and a method for producing an inorganic anion adsorbent, which is characterized by bringing an aqueous solution of a metal salt containing a metal ion into contact with an aqueous chelate resin (hereinafter referred to as a phosphophenol-containing chelate resin). This is an adsorption treatment method characterized by adsorbing inorganic anions. The phosphophenol-containing chelate resin used in the present invention is a resin for which a patent application has been previously applied (Japanese Patent Application No. 55-36358 (see Japanese Patent Publication No. 60-51491)), and can be produced, for example, by the following method. be able to. That is, in the presence of a mineral acid, a phenol derivative containing a primary or secondary alkylamino group,
It can be produced by reacting formaldehyde and phosphorous acid to replace some or all of the protons of amino groups with methylenephosphonic acid, and then reacting phenols and aldehydes to form a gel. Phenol derivatives containing a primary or secondary alkylamino group used at that time include tyrosine, ammonia aresol, salicylamine, etc. Mineral acids include hydrochloric acid, sulfuric acid, and phenols include phenol, resorcinol,
As the aldehydes, formaldehyde and acetaldehyde are preferred. Furthermore, the shape of the phosphophenol-containing chelate resin used in the present invention is as follows:
Preferably, a granular shape is used, but any shape such as a fibrous shape or a plate shape may be used. In the present invention, any metal ion may be supported on the phosphor-containing chelate resin, but among them,
Fe 3+ , Sn 4+ , Ti 4+ , and Al 3+ are preferred. In order to produce the adsorbent of the present invention, for example, the above-mentioned phosphor-containing chelate resin and the above-mentioned metal salt aqueous solution containing the metal ions may be brought into contact with each other. The contact method includes column method,
Any patch method may be used. In addition, the appropriate temperature for contact is 5 to 40℃, and 10 to 40℃.
30°C is preferred. In addition, as a metal salt aqueous solution,
For example, chloride aqueous solutions, sulfate aqueous solutions, and nitrate aqueous solutions are mentioned, and their concentration is 0.5
-10wt% is suitable, preferably 2-5wt%, and the pH is suitably 2-7, preferably 3-5. The adsorbent obtained in this way has a high adsorption capacity for inorganic anions, especially phosphate anions, arsenite anions, and fluorine anions, so it can be used in the same manner as ordinary ion exchange resins to absorb inorganic anion-containing aqueous solutions. It can be removed by contacting it. As the contacting method, either a patch method or a column method may be used. In addition, the appropriate contact temperature at that time is 5°C to 40°C.
The temperature is preferably 10°C to 30°C, and the pH of the aqueous solution containing the inorganic anion is suitably 2 to 8, preferably 4 to 7. In addition, in order to desorb inorganic anions from an adsorbent that has adsorbed inorganic anions, for example,
The adsorbent may be brought into contact with a 0.2 to 1 N aqueous solution of hydrochloric acid or sulfuric acid, and then washed with water. By this method, the adsorbent is regenerated and can be used repeatedly. According to the present invention, an inorganic anion adsorbent can be obtained in an extremely simple and economical manner,
Furthermore, the obtained adsorbent has a high adsorption capacity for inorganic anions such as phosphate anions, arsenite anions, and fluorine anions, and has an excellent adsorbent life. Next, the present invention will be explained in more detail with reference to Examples. Reference Example 1 1 mole of tyrosine and 2 moles of phosphorous acid were dissolved in a 20% aqueous hydrochloric acid solution, and the solution was heated to reflux with stirring. In this state, 37% formalin aqueous solution 6
ml was added dropwise over an hour and continued stirring while refluxing for an additional hour. Then, after cooling to room temperature, caustic soda was added to make the mixture alkaline to pH 11. To this solution, 1.5 mol of resorcin and 5 mol of 37% formalin were added, and further, n-paraffin was added with stirring. Then, while stirring, the temperature was increased to 60°C.
After heating for 1 hour at 100°C, 1 hour at 80°C, and 1 hour at 90°C, the contents began to solidify into granules. After that, transfer the contents to an autoclave and heat at 120℃.
The gelation was completed by reacting for 5 hours. The resulting granular resin was isolated by filtration, air-dried,
After washing with water, the resin was immersed in a 1NH 2 SO 4 solution to convert the resin from Na type to H type. Thereafter, this resin was filtered to obtain bead-shaped phosphophenol-containing chelate resin. Example 1 100 c.c. of the magnetic phosphorphenol chelate resin produced in Reference Example 1 was mixed with a 5 wt% ferric chloride aqueous solution (PH
3) It was immersed in 500c.c. at 25°C for 48 hours to support Fe 3+ ions (hereinafter, this adsorbent will be referred to as A). In addition, in the same way, phosphorus-containing chelate resin
100c.c. 5wt% stannic chloride aqueous solution (PH5) 500
cc at 25° C. for 48 hours to support Sn 4+ ions (hereinafter, this adsorbent will be referred to as B). Similarly, titanium tetrachloride aqueous solution and aluminum chloride aqueous solution were used to support Ti 4+ ions and Al 3+ ions, respectively (hereinafter, these adsorbents were used to support C, C, and Al 3+ ions, respectively).
Let it be D. ). Comparative Example 1 In the same manner as in Example 1, Fe 3+ ions, Sn 4+ ions, Ti 4+ ions, and Al 3+ were added to Diaion CR-10 manufactured by Mitsubishi Kasei, which is an iminodiacetic acid type chelate resin.
Each adsorbent was made to support ions (hereinafter, these will be referred to as adsorbents E, F, G, and H, respectively). Examples 2 to 5, Comparative Examples 2 to 5 Adsorbents A, B, C, and D obtained in Example 1, and E, F, G, and H of the adsorbent obtained in Comparative Example 1, respectively.
10 c.c. was packed into a 10 mmφ x 50 mm column, and an aqueous solution containing phosphate anions was passed therethrough at SV51/hr25°C.
The phosphate anion-containing aqueous solution at this time is
The concentration of phosphorus was adjusted to 20ppm using orthophosphoric acid, and the pH of this solution was
The pH was adjusted to 6 using sodium acetate and hydrochloric acid. After passing through the solution, the 0.5 ppm breakthrough adsorption capacity of each adsorbent was determined by measuring the phosphoric acid concentration in the solution. The results are shown in Table 1.
【表】【table】
【表】
表１より本発明の吸着剤が高い吸着能を有して
いることが明らかである。
実施例６〜９、比較例６〜９
実施例１で得た吸着剤Ａ，Ｂ，Ｃ，Ｄ、及び比
較例１で得た吸着剤Ｅ，Ｆ，Ｇ，Ｈ、おのおの10
c.c.を10mmφ×50mmのカラムに詰め、フツ素アニオ
ン含有水溶液をＳ，V51／hr25℃で通液した。こ
のときのフツ素アニオン含有水溶液は、Ｆとし
て、10ppmの濃度となるように、フツ化ソーダを
用いて調整したものであり、また、この液のPH
は、酢酸ソーダと塩酸でPHが６となるように調整
したものである。
通液後、液中のフツ素アニオン濃度を測定する
ことにより、おのおのの吸着剤の0.5ppm破過点
吸着容量を求めた。
その結果を表２に示す。[Table] It is clear from Table 1 that the adsorbent of the present invention has high adsorption capacity. Examples 6 to 9, Comparative Examples 6 to 9 Adsorbents A, B, C, and D obtained in Example 1, and adsorbents E, F, G, and H obtained in Comparative Example 1, each with 10
cc was packed into a column of 10 mmφ x 50 mm, and an aqueous solution containing fluorine anions was passed therethrough at S, V51/hr25°C. The aqueous solution containing fluorine anions at this time was adjusted using sodium fluoride to have a concentration of 10 ppm as F, and the pH of this solution was
The pH was adjusted to 6 using sodium acetate and hydrochloric acid. After passing through the solution, the fluorine anion concentration in the solution was measured to determine the 0.5 ppm breakthrough adsorption capacity of each adsorbent. The results are shown in Table 2.
【表】
実施例10〜13、比較例10〜13
実施例１で得た吸着剤Ａ，Ｂ，Ｃ，Ｄ、及び比
較例１で得た吸着剤Ｅ，Ｆ，Ｇ，Ｈ、おのおの10
c.c.を10mmφ×50mmのカラムに詰め、亜ヒ酸アニオ
ン含有水溶液をＳ，Ｖ，51／hr25℃で通液した。
亜ヒ酸アニオン含有水力液は、Asとして、
20ppmの濃度となるように三酸化二ヒ素を用いて
調整したものであり、また、この液のPHは酢酸ソ
ーダと塩酸でPHが６となるように調整したもので
ある。
通液後、液中のヒ素濃度を測定することによ
り、おのおのの吸着剤の0.5ppm破過点吸着容量
を求めた。
その結果を表３に示す。[Table] Examples 10 to 13, Comparative Examples 10 to 13 Adsorbents A, B, C, D obtained in Example 1, and Adsorbents E, F, G, H obtained in Comparative Example 1, each 10
cc was packed in a 10 mmφ x 50 mm column, and an arsenite anion-containing aqueous solution was passed therethrough at S, V, 51/hr at 25°C.
Hydraulic fluid containing arsenite anion, as As,
The concentration was adjusted to 20 ppm using diarsenic trioxide, and the pH of this liquid was adjusted to 6 using sodium acetate and hydrochloric acid. After passing through the solution, the arsenic concentration in the solution was measured to determine the 0.5 ppm breakthrough adsorption capacity of each adsorbent. The results are shown in Table 3.
【表】【table】
Claims (1)
級のアルキルアミノ基の水素原子の一部又は全部
がメチレンホスホン酸基で置換されたキレート形
成基を有するフエノール系キレート樹脂に金属イ
オンを担持せしめてなる無機アニオン吸着剤。 ２ 金属イオンが、Fe3+，Al3+，Ti4+又はSn4+
である特許請求の範囲第１項記載の吸着剤。 ３ フエノール核に導入された一級及び／又は二
級のアルキルアミノ基の水素原子の一部又は全部
がメチレンホスホン酸基で置換されたキレート形
成基を有するフエノール系キレート樹脂と金属イ
オンを含有する金属塩水溶液とを接触させること
を特徴とする無機アニオン吸着剤の製造法。 ４ 金属イオンが、Fe3+，Al3+，Ti4+又はSn4+
である特許請求の範囲第３項記載の製造法。 ５ フエノール核に導入された一級及び／又は二
級のアルキルアミノ基の水素原子の一部又は全部
がメチレンホスホン酸基で置換されたキレート形
成基を有するフエノール系キレート樹脂に金属イ
オンを担持せしめてなる無機アニオン吸着剤を用
いて、水溶液中の無機アニオンを吸着せしめるこ
とを特徴とする吸着処理法。 ６ 無機アニオンが、リン酸アニオン、亜ヒ酸ア
ニオンまたはフツ素アニオンである特許請求の範
囲第５項記載の吸着処理法。[Scope of Claims] 1. A phenolic chelate resin having a chelate-forming group in which some or all of the hydrogen atoms of a primary and/or secondary alkylamino group introduced into a phenol nucleus are substituted with a methylenephosphonic acid group. An inorganic anion adsorbent that supports metal ions. 2 The metal ion is Fe 3+ , Al 3+ , Ti 4+ or Sn 4+
The adsorbent according to claim 1. 3 A phenolic chelate resin having a chelate-forming group in which some or all of the hydrogen atoms of the primary and/or secondary alkylamino group introduced into the phenol nucleus are substituted with a methylene phosphonic acid group, and a metal containing a metal ion. A method for producing an inorganic anion adsorbent, which comprises contacting the adsorbent with an aqueous salt solution. 4 The metal ion is Fe 3+ , Al 3+ , Ti 4+ or Sn 4+
The manufacturing method according to claim 3. 5. Metal ions are supported on a phenolic chelate resin having a chelate-forming group in which some or all of the hydrogen atoms of the primary and/or secondary alkylamino groups introduced into the phenol nucleus are substituted with methylene phosphonic acid groups. An adsorption treatment method characterized by adsorbing inorganic anions in an aqueous solution using an inorganic anion adsorbent. 6. The adsorption treatment method according to claim 5, wherein the inorganic anion is a phosphate anion, an arsenite anion, or a fluorine anion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13602681A JPS5836632A (en) | 1981-08-28 | 1981-08-28 | Inorganic anion adsorbent, its manufacture, and adsorption treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13602681A JPS5836632A (en) | 1981-08-28 | 1981-08-28 | Inorganic anion adsorbent, its manufacture, and adsorption treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5836632A JPS5836632A (en) | 1983-03-03 |
| JPH0154094B2 true JPH0154094B2 (en) | 1989-11-16 |
Family
ID=15165445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13602681A Granted JPS5836632A (en) | 1981-08-28 | 1981-08-28 | Inorganic anion adsorbent, its manufacture, and adsorption treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5836632A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6168307A (en) * | 1984-09-13 | 1986-04-08 | Unitika Ltd | Purification of sulfuric acid solution |
| US4830837A (en) * | 1987-08-03 | 1989-05-16 | Olin Corporation | Process for removing aluminum from concentrated alkali metal halide brines |
| JPH01156752U (en) * | 1988-04-21 | 1989-10-27 | ||
| JP3999596B2 (en) * | 2002-08-02 | 2007-10-31 | 中部キレスト株式会社 | Arsenic-trapping fiber and arsenic-containing water treatment method using the same |
-
1981
- 1981-08-28 JP JP13602681A patent/JPS5836632A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5836632A (en) | 1983-03-03 |
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