JPH0249770B2 - URANIRUIONYUSOYOFUKUGOKOBUNSHIMAKU - Google Patents
URANIRUIONYUSOYOFUKUGOKOBUNSHIMAKUInfo
- Publication number
- JPH0249770B2 JPH0249770B2 JP22259982A JP22259982A JPH0249770B2 JP H0249770 B2 JPH0249770 B2 JP H0249770B2 JP 22259982 A JP22259982 A JP 22259982A JP 22259982 A JP22259982 A JP 22259982A JP H0249770 B2 JPH0249770 B2 JP H0249770B2
- Authority
- JP
- Japan
- Prior art keywords
- substance
- quaternary ammonium
- uranyl
- ammonium group
- substance containing
- 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 - Lifetime
Links
- 239000000126 substance Substances 0.000 claims description 37
- -1 uranyl ions Chemical class 0.000 claims description 20
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 7
- 229920005597 polymer membrane Polymers 0.000 claims description 6
- 125000005289 uranyl group Chemical group 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 239000012528 membrane Substances 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000002394 hexacarboxylic acid derivatives Chemical class 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N hexane carboxylic acid Natural products CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- COQLPRJCUIATTQ-UHFFFAOYSA-N Uranyl acetate Chemical compound O.O.O=[U]=O.CC(O)=O.CC(O)=O COQLPRJCUIATTQ-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SGUFBJTXUSTOJB-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-ethenylpyridine;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=N1.C=CC1=CC=CC=C1C=C SGUFBJTXUSTOJB-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- PDOUPBSKRAFWOU-UHFFFAOYSA-N cycloheptacosane-1,1,10,10,19,19-hexacarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCCCCCC(C(O)=O)(C(O)=O)CCCCCCCCC(C(O)=O)(C(O)=O)CCCCCCCC1 PDOUPBSKRAFWOU-UHFFFAOYSA-N 0.000 description 1
- VPBZLNMWXCLXOB-UHFFFAOYSA-N cyclotetracosane-1,3,9,11,17,19-hexone Chemical compound O=C1CCCCCC(=O)CC(=O)CCCCCC(=O)CC(=O)CCCCCC(=O)C1 VPBZLNMWXCLXOB-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は、海水中のウラニルイオンを効率よく
輸送、濃縮し得る高分子膜に関するものである。
より詳しくは、アニオン性の解離基を含むウラニ
ルイオン吸着性物質と四級アンモニウム基を含む
物質とを組合せた複合材料の膜に関するものであ
る。本発明の目的とするところは、ウラニルイオ
ンに対して大きい輸送速度を有する高分子膜を提
供せんとする点にある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer membrane capable of efficiently transporting and concentrating uranyl ions in seawater.
More specifically, the present invention relates to a membrane made of a composite material that combines a uranyl ion-adsorbing substance containing an anionic dissociative group and a substance containing a quaternary ammonium group. An object of the present invention is to provide a polymer membrane having a high transport rate for uranyl ions.
所謂石油シヨツク以来、原子力エネルギーへの
依存度の高まりにつれて、海水、貧鉱、ダム排水
からウラニルイオンを採取することのできる吸着
剤の開発が先進各国で競つて研究されている。こ
れら吸着剤としては、本発明者らの発明に係る大
環状ヘキサケトンを官能基として有するポリマ
ー、大環状ヘキサカルボン酸類を官能基として有
するポリマーが公知の他、アミドオキシム基を有
するウラニルイオン吸着用樹脂、ジチオカバマー
トを有する樹脂等が知られている。 Since the advent of so-called oil shocks, and with increasing dependence on nuclear energy, advanced countries are competing in research to develop adsorbents that can extract uranyl ions from seawater, poor mines, and dam drainage. As these adsorbents, there are known polymers having a macrocyclic hexaketone as a functional group according to the invention of the present inventors, polymers having a macrocyclic hexacarboxylic acid as a functional group, and resins for adsorbing uranyl ions having an amidoxime group. , resins having dithiocabamate, etc. are known.
これら吸着剤は、従来の含水チタン酸等の無機
吸着剤に比べはるかに優れた吸着速度を有してい
るが、なおかつ１日当りの吸着剤単位重量当りの
吸着速度について、工業的実施を直ちに可能にす
るような値は得られていない。 These adsorbents have a much superior adsorption rate compared to conventional inorganic adsorbents such as hydrous titanic acid, but the adsorption rate per unit weight of adsorbent per day is such that it is immediately possible to implement them industrially. No value has been obtained that would make it possible.
このような現状を打開するものとして、本発明
者らは、膜を用いたウラニルイオンの捕捉方法を
提唱したが（特願昭56−148315号（特公平２−
8969号）に係る発明）、これを更に改良して、ウ
ラニルイオンを吸着できる機能物質と四級アンモ
ニウム塩を共存させた膜を使用することにより、
より高い輸送速度が得られることを見出したもの
である。 In order to overcome this current situation, the present inventors have proposed a method for capturing uranyl ions using a membrane (Japanese Patent Application No. 148315/1982).
8969), by further improving this and using a membrane in which a functional substance capable of adsorbing uranyl ions and a quaternary ammonium salt coexist.
It was discovered that a higher transport speed can be obtained.
即ち本発明はアニオン性の解離基を含むウラニ
ルイオン吸着性物質と、四級アンモニウム基を含
む物質とが共存し、四級アンモニウム基を含む物
質が疎水性であるときは前記共存物質の少くとも
一方が水不溶性の高分子物質に担持され、四級ア
ンモニウム基を含む物質が親水性であるときは前
記共存物質の少くとも親水性四級アンモニウム基
を含む物質が水不溶性の高分子物質に担持されて
いることを特徴とするウラニルイオン輸送用複合
高分子膜である。 That is, in the present invention, a uranyl ion-adsorbing substance containing an anionic dissociative group and a substance containing a quaternary ammonium group coexist, and when the substance containing a quaternary ammonium group is hydrophobic, at least one of the coexisting substances When one of the coexisting substances is supported on a water-insoluble polymeric substance and the substance containing a quaternary ammonium group is hydrophilic, the substance containing at least a hydrophilic quaternary ammonium group is supported on the water-insoluble polymeric substance. This is a composite polymer membrane for transporting uranyl ions.
本発明において用いるウラニルイオン吸着性物
質としては、現在まで公知のウラニルイオン吸着
剤のうち、酸解離してアニオン種を与える官能基
を含むヘキサケトン、ヘキサカルボン酸、アミド
キシム、ジチオカルバマート等を用いることがで
きる。これらウラニルイオン吸着性物質は、水と
任意にまざり合わない疎水性を有し、海水中の塩
素イオン、リン酸イオン等によつて容易に置き換
わらないものであればよい。一方、四級アンモニ
ウム基を含む物質としては、トリオクチルメチル
アンモニウムクロリド、ステアリルトリメチルア
ンモニウムブロミド、トリドデシルメチルアンモ
ニウムクロリド、ステアリル化ポリエチレンイミ
ン等を用いることができる。これら四級アンモニ
ウム基を含む物質も、水と任意にまざり合わない
適当な疎水性を有していることが必要で、Na、
Ｋ、Mg、Caなどの海水中に多量存在するカチオ
ンと容易に置き変わらないものであればよい。こ
れら両者を複合して、膜状物質とするためには両
成分のうち少なくとも一方が水に不溶の高分子物
質であることが必要である。 As the uranyl ion adsorbing substance used in the present invention, among the uranyl ion adsorbents known to date, hexaketone, hexacarboxylic acid, amidoxime, dithiocarbamate, etc. containing a functional group that gives an anion species by acid dissociation may be used. Can be done. These uranyl ion adsorbing substances may be of any kind as long as they have hydrophobic properties that do not mix with water and are not easily replaced by chlorine ions, phosphate ions, etc. in seawater. On the other hand, as the substance containing a quaternary ammonium group, trioctylmethylammonium chloride, stearyltrimethylammonium bromide, tridodecylmethylammonium chloride, stearylated polyethyleneimine, etc. can be used. These substances containing quaternary ammonium groups also need to have appropriate hydrophobicity so that they do not mix with water arbitrarily.
Any material may be used as long as it is not easily replaced by cations such as K, Mg, and Ca that are present in large amounts in seawater. In order to combine these two components to form a film-like substance, at least one of the two components must be a water-insoluble polymeric substance.
先づ、ウラニルイオン吸着性物質が高分子物質
に担持されている場合には、スチレンのゲル状共
重合体から出発してヘキサケトン、ヘキサカルボ
ン酸を担持させたもの、アミドキシム樹脂、ジチ
オカルバマート樹脂等と前記四級アンモニウム基
を含む物質とをそのまま、または任意の有機溶媒
を加えて、溶解または膨潤させて複合した後、膜
状に成型すればよい。 First, when the uranyl ion adsorbing substance is supported on a polymeric substance, it is possible to start from a gel copolymer of styrene and support hexaketone or hexacarboxylic acid, amidoxime resin, or dithiocarbamate resin. etc. and the substance containing the quaternary ammonium group may be combined as is or by adding an arbitrary organic solvent to dissolve or swell the compound, and then mold the compound into a film.
次に、四級アンモニウム基が高分子物質に担持
されている場合には、スチレン―ジビニルベンゼ
ン―ビニルピリジンを重合、四級化処理して得ら
れるもの、ポリエチレンイミンの四級化物等を一
方の成分とし、上記のウラニルイオン吸着物質を
担持した高分子の他ヘキサケトン（１、３、９、
11、17、19―ヘキサオキソシクロテトラコサン）
とその長鎖アルキル誘導体、１、３、９、11、
17、19―ヘキサオキソ―２―ｎ―ラウリル―シク
ロテトラコサン、またヘキサカルボン酸（１、
１、10、10、19、19―ヘキサカルボキシシクロヘ
プタコサン）とその長鎖アルキル誘導体、１―ス
テアリルアミノカルボニル―１、10、10、19、19
―ペンタカルボキシシクロヘプタコサン、１、10
―ビス（ステアリルアミノカルボニル）―１、
10、19、19―テトラカルボキシシクロヘプタコサ
ン、１、10―ビス（ラウリルアミノカルボニル）
―１、10、19、19―テトラカルボキシシクロヘプ
タコサン、ドデカン酸アミドキシム、テトラエチ
レンペンタミン―１、４、７、10、13―ペンタプ
ロピオン酸アミドキシムピペラジン―Ｎ，N′―
ジチオカルバミン酸ジアンモニウム塩、Ｎ，
N′―ジメチルエチレンジアミン―Ｎ、N′―ジチ
オカルバミン酸ジカリウム塩、１、13―ジメチル
―テトラエチレンペンタミン―１、４、７、10、
13―ペンタジチオカルバミン酸ペンタアンモニウ
ム塩等をもう一つの成分として、両成分をそのま
ままたは任意の有機溶媒を加えて溶解または膨潤
させて複合した後膜状に成型すればよい。 Next, when a quaternary ammonium group is supported on a polymeric substance, one obtained by polymerizing and quaternizing styrene-divinylbenzene-vinylpyridine, a quaternized product of polyethyleneimine, etc. In addition to polymers supporting the above-mentioned uranyl ion adsorbing substances, hexaketones (1, 3, 9,
11, 17, 19-hexaoxocyclotetracosane)
and its long-chain alkyl derivatives, 1, 3, 9, 11,
17,19-hexaoxo-2-n-lauryl-cyclotetracosane, also hexacarboxylic acid (1,
1,10,10,19,19-hexacarboxycycloheptacosane) and its long chain alkyl derivatives, 1-stearylaminocarbonyl-1,10,10,19,19
-Pentacarboxycycloheptacosane, 1, 10
-bis(stearylaminocarbonyl)-1,
10,19,19-tetracarboxycycloheptacosane, 1,10-bis(laurylaminocarbonyl)
-1, 10, 19, 19-tetracarboxycycloheptacosane, amidoxime dodecanoate, tetraethylenepentamine -1, 4, 7, 10, 13-pentapropionic acid amidoxime piperazine -N,N'-
Dithiocarbamic acid diammonium salt, N,
N'-dimethylethylenediamine-N,N'-dithiocarbamic acid dipotassium salt, 1,13-dimethyl-tetraethylenepentamine-1,4,7,10,
The two components may be combined as they are or by adding an arbitrary organic solvent to dissolve or swell the two components, using another component such as 13-pentadithiocarbamic acid pentaammonium salt, and then forming the composite into a film.
上記の方法による複合、次いで膜状に成型する
工程は順序を逆にしてもよい。即ちウラニルイオ
ン吸着物質を担持した高分子物質または四級アン
モニウム基を担持した高分子物質の一方をあらか
じめ膜状に成型した後、高分子でないもう一方の
成分と接触させて複合化を行つてもよい。但し両
成分が共に高分子物質である場合には複合後改め
て成型工程が必要となるので両成分をあらかじめ
膜に成型することは実際的でない。 The order of the steps of combining by the above method and then forming into a film may be reversed. In other words, even if one of the polymer material supporting a uranyl ion adsorbing substance or the polymer material supporting a quaternary ammonium group is formed into a membrane in advance, it is brought into contact with the other non-polymer component to form a composite. good. However, if both components are polymeric substances, it is not practical to mold both components into a film in advance because a new molding step is required after the composite.
これら高分子の膜厚は、高分子の種類、使用場
所等によつて区々であるが、通常0.1mm〜0.5mmで
充分である。 The film thickness of these polymers varies depending on the type of polymer, the place of use, etc., but 0.1 mm to 0.5 mm is usually sufficient.
次に本発明の作用効果について説明する。 Next, the effects of the present invention will be explained.
本発明によるウラニルイオン吸着性物質と四級
アンモニウム基を含む物質とを複合した高分子膜
はウラニルイオン吸着性物質のみから成る高分子
物質膜に比べ、輸送速度の大きいことが特徴であ
る。この理由については更に研究を続けなければ
早急な結論を出すことはできないが現在のところ
次のように考えられる。ウラニルイオンはアニオ
ン性の錯イオンを形成し易く海水中では（トリ炭
酸ウラニル）4-として存在しており、ウラニルイ
オン吸着剤とも錯アニオンを形成するものと考え
られている。このため、この電荷を中和するカチ
オンが必要であり、親水性の高いナトリウム、カ
リウム等を膜内に持ち込むよりも、四級塩を膜内
に共存させておくことにより、とくに吸着速度及
び／又は吸着平衡においてウラニルイオンのとり
込みに有利に作用し、輸送速度を増大させるもの
と考えられる。 The polymer membrane according to the present invention, which is a composite of a uranyl ion-adsorbing substance and a substance containing a quaternary ammonium group, is characterized by a higher transport rate than a polymer membrane consisting only of a uranyl ion-adsorbing substance. Although it is not possible to draw a quick conclusion as to the reason for this without further research, the following is currently thought to be the reason. Uranyl ions tend to form anionic complex ions and exist as (uranyl tricarbonate) 4- in seawater, and are thought to form complex anions with uranyl ion adsorbents. For this reason, cations that neutralize this charge are required, and rather than bringing highly hydrophilic sodium, potassium, etc. into the membrane, allowing quaternary salts to coexist within the membrane will improve the adsorption rate and/or Alternatively, it is thought to have an advantageous effect on the uptake of uranyl ions in the adsorption equilibrium, increasing the transport rate.
実施例 １
ニトリル基をアミドキシム基に変換する変性処
理として、35％のニトリル含量を有するアクリロ
ニトリル―ブタジエン共重合体ラテツクスを膜状
に成型（厚さ0.1mm）したニトリルゴム（イオウ
加硫）を、メタノール中において15％のヒドロキ
シルアミンと80℃で５時間反応させた後、1N
NaOH溶液に室温で一夜浸漬した。水洗後トリ
オクチルメチルアンモニウムクロリドのメタノー
ル溶液（1.0mol・-1）中に一夜浸漬した。この
膜を水で十分洗滌後支持枠に保持し、ウラン濃度
が4.8ppmになるよう酢酸ウラニルを添加した海
水（原液）と５％のNaHCO3水溶液（受液）と
の間に介在させたところ、1.5時間の接触で原液
から受液側に1.8mg―Ｕ／ｇ―膜のウラニルイオ
ンの輸送・濃縮がみられた。Example 1 As a modification treatment to convert nitrile groups into amidoxime groups, nitrile rubber (sulfur vulcanization) obtained by molding an acrylonitrile-butadiene copolymer latex having a nitrile content of 35% into a film shape (thickness 0.1 mm), After reacting with 15% hydroxylamine in methanol at 80°C for 5 hours, 1N
Soaked in NaOH solution overnight at room temperature. After washing with water, it was immersed overnight in a methanol solution (1.0 mol· -1 ) of trioctylmethylammonium chloride. After thoroughly washing this membrane with water, it was held in a support frame and placed between seawater to which uranyl acetate had been added (undiluted solution) so that the uranium concentration was 4.8 ppm, and a 5% NaHCO 3 aqueous solution (receiving solution). After 1.5 hours of contact, transport and concentration of uranyl ions of 1.8 mg-U/g membrane from the stock solution to the receiving side was observed.
実施例 ２
１、10―ビス（ステアリルアミノカルボニル）
―１、10、19、19―テトラカルボキシシクロヘプ
タコサン１部とトリエチルアミン４部のクロロホ
ルム溶液に、第４級ピリジニウム塩基を有した陰
イオン交換膜ネオセプタAV―4T（徳山曹達製）
を10分間浸漬させた後、風乾し、再び浸漬・風乾
を２回繰り返した後、支持枠で保持し、これを
6.7ppmの酢酸ウラニル強化海水（原液）と５％
のNaHCO3水溶液（受液）との間に介在させて
ウラニルイオンの輸送を行なつたところ、２時間
の接触で原液から受液側に2.8mg―Ｕ／ｇ―膜の
ウラニルイオンの輸送がみられた。Example 2 1,10-bis(stearylaminocarbonyl)
- Anion exchange membrane Neoceptor AV-4T (manufactured by Tokuyama Soda) containing a quaternary pyridinium base in a chloroform solution of 1 part of 1, 10, 19, 19-tetracarboxycycloheptacosane and 4 parts of triethylamine.
After soaking for 10 minutes, air drying, repeating soaking and air drying twice, hold it with a support frame, and
6.7ppm uranyl acetate enriched seawater (undiluted solution) and 5%
When transporting uranyl ions between NaHCO 3 aqueous solution (receiving liquid), 2.8 mg-U/g of uranyl ions were transported from the raw solution to the receiving liquid side in 2 hours of contact. It was seen.
Claims (1)
着性物質と、四級アンモニウム基を含む物質とが
共存し、四級アンモニウム基を含む物質が疎水性
であるときは前記共存物質の少くとも一方が水不
溶性の高分子物質に担持され、四級アンモニウム
基を含む物質が親水性であるときは前記共存物質
の少くとも親水性四級アンモニウム基を含む物質
が水不溶性の高分子物質に担持されていることを
特徴とするウラニルイオン輸送用複合高分子膜。1. When a uranyl ion-adsorbing substance containing an anionic dissociative group and a substance containing a quaternary ammonium group coexist, and the substance containing a quaternary ammonium group is hydrophobic, at least one of the coexisting substances is water. When the substance supported on an insoluble polymeric substance and containing a quaternary ammonium group is hydrophilic, at least the substance containing a hydrophilic quaternary ammonium group among the coexisting substances is supported on the water-insoluble polymeric substance. A composite polymer membrane for transporting uranyl ions characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22259982A JPH0249770B2 (en) | 1982-12-17 | 1982-12-17 | URANIRUIONYUSOYOFUKUGOKOBUNSHIMAKU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22259982A JPH0249770B2 (en) | 1982-12-17 | 1982-12-17 | URANIRUIONYUSOYOFUKUGOKOBUNSHIMAKU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59112804A JPS59112804A (en) | 1984-06-29 |
| JPH0249770B2 true JPH0249770B2 (en) | 1990-10-31 |
Family
ID=16784993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22259982A Expired - Lifetime JPH0249770B2 (en) | 1982-12-17 | 1982-12-17 | URANIRUIONYUSOYOFUKUGOKOBUNSHIMAKU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0249770B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4956740B2 (en) * | 2006-07-14 | 2012-06-20 | 国立大学法人弘前大学 | Uranium recovery method |
-
1982
- 1982-12-17 JP JP22259982A patent/JPH0249770B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59112804A (en) | 1984-06-29 |
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