JPH0471597B2 - - Google Patents
Info
- Publication number
- JPH0471597B2 JPH0471597B2 JP6774485A JP6774485A JPH0471597B2 JP H0471597 B2 JPH0471597 B2 JP H0471597B2 JP 6774485 A JP6774485 A JP 6774485A JP 6774485 A JP6774485 A JP 6774485A JP H0471597 B2 JPH0471597 B2 JP H0471597B2
- Authority
- JP
- Japan
- Prior art keywords
- gallium
- resin
- arsenic
- chelate
- group
- 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
- 239000011347 resin Substances 0.000 claims description 57
- 229920005989 resin Polymers 0.000 claims description 57
- 229910052733 gallium Inorganic materials 0.000 claims description 54
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 53
- 239000013522 chelant Substances 0.000 claims description 36
- 229910052785 arsenic Inorganic materials 0.000 claims description 31
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 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 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000006294 amino alkylene group Chemical group 0.000 claims description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000002351 wastewater Substances 0.000 description 11
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- -1 sodium and potassium Chemical class 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IRCKLQBEVKCOOS-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;prop-2-enenitrile Chemical compound C=CC#N.C=CC1=CC=CC=C1C=C IRCKLQBEVKCOOS-UHFFFAOYSA-N 0.000 description 1
- JQSXBKFLDFIUPJ-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2lambda5-dioxaphosphetan-4-amine Chemical group NC1OP(O)(=O)O1 JQSXBKFLDFIUPJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
〔産業上の利用分野〕
本発明はガリウムとヒ素を含有する水より、ガ
リウムを分離除去して、ガリウムとヒ素を分離す
る方法に関する。さらに詳しくはキレート樹脂を
用いて、ガリウムとヒ素を含む水を処理して、ガ
リウムをキレート樹脂に吸着させ、ガリウムとヒ
素を分離する方法である。
〔従来の技術〕
近年、電子工業で半導体素子としてガリウム・
ヒ素が広く使用されるようになつて、それらの工
業の廃水中にガリウムとヒ素を含有するケースが
増加しており、その処理に迫られている。ガリウ
ムは希少元素として回収利用することに価値があ
り、またヒ素は有害物質として廃水基準0.5ppm
以下に厳しく規制されている。
(1)ヒ素の処理方法としては、一般に鉄化合物を
併用した中和凝集沈殿法が使用されている。ガリ
ウムを回収する方法としては、(2)有機溶媒を用
い、液−液抽出によつてガリウムを回収する方法
（特開昭59−186683）。(3)アミノカルボン酸基を有
するキレート性イオン交換樹脂を使用する方法
（特開昭59−186686）などが知られている。
〔発明が解決しようとする問題点〕
しかしながら(1)の方法はヒ素と共に高価金属で
あるガリウムも共に凝集沈殿してしまい、両者を
分離することはできない。(2)の方法は溶媒の寿命
が非常に短いことと、抽出後に溶媒が微量だが混
入してくること、および溶媒の処理による公害上
の問題等があり、実用化に難点がある。
また(3)の方法は、アミノカルボン酸基を使用す
るため、ガリウムの吸着量が低く、またガリウム
とのキレート結合が弱く、ヒ素とガリウムを完全
に分離できず、本発明の目的には適当でない。
〔発明の概要〕
本発明者らは、これらの問題点を解決し、さら
に効率よくガリウムとヒ素を分離すべき方法を検
討した結果、本発明に到達したものである。
すなわち、本発明はガリウムとヒ素を含有する
水をPH５以下でキレート樹脂と接触させることに
より、ガリウムをキレート樹脂に選択的に吸着さ
せることができ、ガリウムとヒ素を完全に分離す
ることが出来ることを見出したものである。それ
に用いるキレート樹脂として、その母体がジビニ
ルベンゼン系共重合体、エポキシ樹脂、フエノー
ル樹脂、塩化ビニル樹脂のいずれかよりなり、そ
の母体に結合する官能基がリン酸基、アルキレン
リン酸基、アミノアルキレンリン酸基、イミノア
ルキレンリン酸基、アミドオキシム基より成る群
より選ばれたる少くとも一種を有するものであ
る。上で用いるジビニルベンゼン系共重合体とし
ては、スチレン−ジビニルベンゼン共重合体、ア
クリル酸メチル−ジビニルベンゼン共重合体、メ
タクリル酸メチル−ジビニルベンゼン共重合体、
アクリロニトリル−ジビニルベンゼン共重合体等
が挙げられる。
上記のキレート樹脂を用いてガリウムとヒ素を
分離できる原理について述べると、ガリウムはア
ルミニウム族に属し、アルミニウムと同様に３価
の陽イオンとなる。またヒ素は窒素族に属し、原
子価は３価と５価になり、As2O3やAs2O5などの
酸化物となり易く、水中ではAsO2 -、AsO3 -、
AsO4 -の形で陰イオンとして存在するが、上記の
キレート樹脂はこのような陰イオンを吸着しない
ので、ガリウムを吸着分離出来るのである。樹脂
母体並びに官能基により、その吸着分離機能が異
なるが、上記の樹脂母体に官能基にリン酸基、ア
ルキレンリン酸基、アミノアルキレンリン酸基、
イミノアルキレンリン酸基、アミドオキシム基よ
り選ばれたる少くとも一種を持つキレート樹脂
は、ガリウムとヒ素の分離能がすぐれていると共
に、従来のアミノカルボン酸型のキレート樹脂に
比較してガリウムに対して高い吸着量を示す。上
に掲げた官能基は酸型、または塩型、すなわちナ
トリウム、カリウム等のアルカリ金属、カルシウ
ム、マグネシウム等のアルカリ土類金属の塩とし
て、用い得る。
また、ガリウムとヒ素の吸着分離能とガリウム
吸着量はPHにより影響を受ける。本発明におい
て、樹脂を接触させる時の処理水のPHは５以下が
好ましい。PHが５以上であると、ガリウムの水酸
化物が生成するため、ガリウムに対する吸着能が
低下してしまい、それに伴いヒ素との分離能も低
下するため、目的を達成できない。従つてキレー
ト樹脂のガリウムに対する吸着能力および水酸化
物の生成などより考えて、処理水のPHは５以下、
好ましくは１〜４の範囲でキレート樹脂と接触さ
せることにより、ガリウムとヒ素との最も高い分
離効率を得ることができる。
ガリウムとヒ素を含有する水と上記キレート樹
脂とを接触せしめる方法としては、例えばガリウ
ムとヒ素を含有する処理水中にキレート樹脂を浸
漬せしめるバツチ式方法、キレート樹脂を充填し
たカラムに処理水を通過せしめるカラム式方法等
が挙げられ、またカラム式の場合には一過方式と
循環方式があり、さらに通液方法としては上向
流、下向流があり、いずれの方法も採用できる。
このようにしてガリウムを吸着したキレート樹
脂は酸または／およびアルカリで処理することに
より、容易にガリウムを溶離でき、そのキレート
樹脂はくり返し、何度でも使用が可能である。ま
た溶離液中のガリウムは電解工程を経て、金属ガ
リウムとして回収される。
実施例 １
スチレン−ジビニルベンゼン（8wt％）を懸濁
重合して得られたMR型の球状樹脂（10〜60メツ
シユ）をエチレンジクロリド中で膨潤させ、無水
塩化亜鉛の存在下でクロロメチルエーテルにより
上記球状樹脂をクロロメチル化した（塩素含有率
＝21.8wt％）。得られたクロロメチル化球状樹脂
とジエチレントリアミン（DETA）を反応させ、
DETA型球状樹脂を得た。この樹脂と０−亜リ
ン酸およびパラホルムアルデヒドとを塩酸水溶液
中で反応させて、キレート形成基としてアミノメ
チレンリン酸基とイミノメチレンリン酸基を有す
るMR型のキレート樹脂を得た。得られたキレー
ト樹脂を分級して、10〜48メツシユのものを分取
し、吸着実験に供した。
As：18ppm、Ga：43ppm、NaCl：1000ppm
を含有する模擬廃水（PH3.2）を調製した後、キ
レート樹脂100mlを充填したカラム（内径25mm）
に模擬廃水を下向流、通液速度SV5で通液した。
第１表に示す如く50〜400／−Ｒの各通液量
に達する毎に100mlの流出液サンプルを採取し、
ガリウムとヒ素の濃度を測定した。その結果を第
１表に示す。また樹脂１当たりの通液量が350
（以下樹脂１当たりの通液量の単位を／
−Ｒで表す）となつた時のキレート樹脂へのガリ
ウム吸着量は15.0ｇ／−Resinであり、それよ
り計算するとこの時点での吸着率は99.7％であつ
た。
次いでカラム内に残留した模擬廃水を水で押し
出した後、3NHCl水溶液を通液速度SV2、下向
流で樹脂容積の５倍量（500ml）を通液してキレ
ート樹脂に吸着されたガリウムを溶離し、溶離液
中のガリウムイオン濃度を測定した結果、キレー
ト樹脂に吸着されたガリウムの99.8％が溶離回収
された。溶離液中には3380ppmのガリウムと
0.02ppmのヒ素が含まれ、純度高くガリウムが濃
度分離された。
[Industrial Application Field] The present invention relates to a method for separating gallium and arsenic from water containing gallium and arsenic by separating and removing gallium. More specifically, it is a method in which water containing gallium and arsenic is treated using a chelate resin, gallium is adsorbed onto the chelate resin, and gallium and arsenic are separated. [Prior art] In recent years, gallium and gallium have been used as semiconductor elements in the electronics industry.
As arsenic has become widely used, gallium and arsenic are increasingly found in industrial wastewater, and there is an urgent need to treat them. Gallium is a rare element that has value in recovering and reusing, and arsenic is considered a hazardous substance and has a wastewater standard of 0.5ppm.
The following are strictly regulated. (1) As a method for treating arsenic, a neutralization coagulation precipitation method using iron compounds is generally used. Methods for recovering gallium include (2) a method of recovering gallium by liquid-liquid extraction using an organic solvent (Japanese Patent Application Laid-Open No. 186683/1983); (3) A method using a chelating ion exchange resin having an aminocarboxylic acid group (Japanese Unexamined Patent Publication No. 186686/1986) is known. [Problems to be Solved by the Invention] However, in the method (1), gallium, which is an expensive metal, coagulates and precipitates together with arsenic, making it impossible to separate the two. Method (2) is difficult to put into practical use because the lifetime of the solvent is very short, a small amount of solvent is mixed in after extraction, and there are problems with pollution due to the treatment of the solvent. In addition, since method (3) uses an aminocarboxylic acid group, the adsorption amount of gallium is low, and the chelate bond with gallium is weak, making it impossible to completely separate arsenic and gallium, and therefore it is not suitable for the purpose of the present invention. Not. [Summary of the Invention] The present inventors solved these problems and studied a method for more efficiently separating gallium and arsenic, and as a result, they arrived at the present invention. That is, the present invention allows gallium to be selectively adsorbed to the chelate resin by bringing water containing gallium and arsenic into contact with the chelate resin at a pH of 5 or less, thereby completely separating gallium and arsenic. This is what we discovered. The chelate resin used for this purpose has a base made of divinylbenzene copolymer, epoxy resin, phenol resin, or vinyl chloride resin, and the functional group bonded to the base is a phosphate group, an alkylene phosphate group, or an aminoalkylene group. It has at least one type selected from the group consisting of a phosphoric acid group, an iminoalkylene phosphoric acid group, and an amidoxime group. Examples of the divinylbenzene copolymer used above include styrene-divinylbenzene copolymer, methyl acrylate-divinylbenzene copolymer, methyl methacrylate-divinylbenzene copolymer,
Examples include acrylonitrile-divinylbenzene copolymer. Describing the principle by which gallium and arsenic can be separated using the above-mentioned chelate resin, gallium belongs to the aluminum group and is a trivalent cation like aluminum. Furthermore, arsenic belongs to the nitrogen group, and has trivalent and pentavalent valences, and easily forms oxides such as As 2 O 3 and As 2 O 5. In water, it forms AsO 2 - , AsO 3 - ,
Gallium exists as an anion in the form of AsO 4 - , but the above-mentioned chelate resin does not adsorb such anions, so it can adsorb and separate gallium. The adsorption/separation function differs depending on the resin matrix and the functional group, but the functional groups on the resin matrix mentioned above include phosphoric acid groups, alkylene phosphoric acid groups, aminoalkylene phosphoric acid groups,
Chelate resins that have at least one type selected from iminoalkylene phosphate groups and amidoxime groups have excellent separation ability for gallium and arsenic, and are more effective against gallium than conventional aminocarboxylic acid type chelate resins. shows high adsorption amount. The functional groups listed above can be used in acid form or salt form, ie, salts of alkali metals such as sodium and potassium, and alkaline earth metals such as calcium and magnesium. In addition, the adsorption separation ability of gallium and arsenic and the amount of gallium adsorbed are affected by pH. In the present invention, the pH of the treated water during contact with the resin is preferably 5 or less. If the pH is 5 or more, hydroxide of gallium is generated, which lowers the adsorption ability for gallium, and accordingly reduces the ability to separate it from arsenic, making it impossible to achieve the objective. Therefore, considering the chelate resin's ability to adsorb gallium and the generation of hydroxide, the pH of the treated water should be 5 or less.
The highest separation efficiency between gallium and arsenic can be obtained by contacting the chelate resin preferably in the range of 1 to 4. Examples of methods for bringing the chelate resin into contact with water containing gallium and arsenic include a batch method in which the chelate resin is immersed in treated water containing gallium and arsenic, and a method in which the treated water is passed through a column filled with the chelate resin. Examples include a column method, and in the case of a column method, there are a transient method and a circulation method, and furthermore, there are an upward flow method and a downward flow method as a liquid passing method, and either method can be adopted. By treating the chelate resin that has adsorbed gallium in this manner with acid and/or alkali, gallium can be easily eluted, and the chelate resin can be used repeatedly. Further, gallium in the eluent is recovered as metallic gallium through an electrolytic process. Example 1 MR type spherical resin (10 to 60 mesh) obtained by suspension polymerization of styrene-divinylbenzene (8 wt%) was swollen in ethylene dichloride, and swollen with chloromethyl ether in the presence of anhydrous zinc chloride. The above spherical resin was chloromethylated (chlorine content = 21.8 wt%). The obtained chloromethylated spherical resin is reacted with diethylenetriamine (DETA),
DETA type spherical resin was obtained. This resin was reacted with 0-phosphorous acid and paraformaldehyde in an aqueous hydrochloric acid solution to obtain an MR type chelate resin having an aminomethylene phosphate group and an iminomethylene phosphate group as chelate forming groups. The obtained chelate resin was classified and 10 to 48 meshes were collected and used for adsorption experiments. As: 18ppm, Ga: 43ppm, NaCl: 1000ppm
After preparing simulated wastewater (PH3.2) containing
Simulated wastewater was passed through the tube in a downward flow at a flow rate of SV5.
As shown in Table 1, a 100 ml sample of the effluent was collected every time a flow rate of 50 to 400/-R was reached.
Gallium and arsenic concentrations were measured. The results are shown in Table 1. In addition, the amount of liquid passed per resin is 350
(Hereinafter, the unit of liquid flow rate per resin is /
-R), the amount of gallium adsorbed on the chelate resin was 15.0 g/-Resin, and when calculated from this, the adsorption rate at this point was 99.7%. Next, after pushing out the simulated wastewater remaining in the column with water, 3NHCl aqueous solution was passed in a downward flow at a flow rate of SV2 in an amount 5 times the resin volume (500 ml) to elute the gallium adsorbed on the chelate resin. However, as a result of measuring the gallium ion concentration in the eluent, 99.8% of the gallium adsorbed to the chelate resin was recovered by elution. The eluent contains 3380ppm gallium and
Contains 0.02ppm of arsenic, and gallium was separated in high purity.
【表】
比較例 １
MR型のスチレン−ジビニルベンゼン共重合樹
脂を母体樹脂とした10〜48メツシユのイミノジ酢
酸型キレート樹脂（酸型）を用いて、実施例１と
同じ廃水を用い同じ条件にて吸着実験を行なつ
た。結果を第２表に示す。また樹脂１当たりの
通液量が300となつた時のキレート樹脂へのガ
リウム吸着量は、11.8ｇ／−Resinであり、吸
着回収率は91.4％であつた。[Table] Comparative Example 1 Using the same wastewater as in Example 1, using an iminodiacetic acid type chelate resin (acid type) of 10 to 48 meshes using MR type styrene-divinylbenzene copolymer resin as the base resin, and under the same conditions. An adsorption experiment was conducted. The results are shown in Table 2. Further, when the amount of liquid passed per resin was 300, the amount of gallium adsorbed to the chelate resin was 11.8 g/-Resin, and the adsorption recovery rate was 91.4%.
【表】
この結果、上記のイミノジ酢酸型のキレート樹
脂は、ヒ素を吸着せずにガリウムを吸着するが、
その吸着量が低く、廃水中よりガリウムをヒ素か
ら効率より回収することは出来ない。
実施例 ２
実施例１で得たクロロメチル化樹脂に塩化アル
ミニウムの存在下、三塩化リンを反応させ、キレ
ート形成基としてリン酸基とメチレンリン酸基を
有するキレート樹脂を得た。これを10〜48メツシ
ユに分級し、試験に用いた。
As：20ppm、Ga：10ppm、NaCl：1000ppm
を含有する模擬廃水（PH1.0）を調製した後、キ
レート樹脂100mlを充填したカラム（内径25mmφ）
に模擬廃水を下向流、通液速度SV10で通液した。
通液量が1000／−Ｒに達するまでの間に流出
した流出液中のガリウムイオン濃度とヒ素イオン
濃度を測定したところ、ガリウムイオンは検出さ
れず、ヒ素イオンは原水と同じ20ppmで完全にガ
リウムとヒ素とを分離することができた。
実施例 ３
アクリロニトリル−ジビニルベンゼン（10wt.
％）をトルエン存在下で懸濁重合して得られる
MR型の球状樹脂にヒドロキシルアミンを反応さ
せ、アミドオキシム基を有するキレート樹脂を得
た。これを分級して10〜48メツシユのものを得
た。
実施例１と同じ模擬廃水200mlに10〜48メツシ
ユのキレート樹脂を0.2ml添加し、1.5時間振とう
後、水溶液中のガリウムイオン濃度およびヒ素イ
オン濃度を測定し、それぞれの吸着量を求めたと
ころ、ガリウムは12.5ｇ／−Ｒであり、ヒ素は
まつたく吸着されていなかつた。
また、樹脂の添加量を２mlに増し、３時間振と
う後水溶液中のガリウムイオン濃度およびヒ素イ
オン濃度を測定したところ、Gaは検出されず、
Asは18ppmであり、ガリウムは完全に吸着分離
されていた。
実施例 ４
チツ素原子に結合する活性水素を少なくとも２
個有するように、テトラエチレンペンタミンにＯ
−亜リン酸とホルマリンを反応させ、次いでレゾ
ルシンとホルマリンを反応させ、得られた反応生
成物につきポリビニルアルコール水溶液中で懸濁
重合、硬化を行い、球状樹脂を得た。この球状樹
脂はキレート形成基としてイミノメチレンリン酸
基を有するキレート樹脂である。これを分級して
10〜48メツシユのものを得た。
このキレート樹脂100mlをカラム（内径25mmφ）
に充填し、実施例１と同じ模擬廃水を同様の条件
で通液量300／−Ｒまで通液し、この間に流
出した流出液中のガリウムイオン濃度とヒ素イオ
ン濃度を測定する。
次にカラム内に残留した廃水を水で押し出し、
3N−HNO3水溶液を、通液速度SV2、下向流で
樹脂量の５倍量（500ml）通液し、溶離液中のガ
リウムイオン濃度を測定し、溶離回収率を求め
た。次いでカラムを水洗する。
以上の通液−吸着−押出し−溶離−水洗の操作
を繰り返し、計３回の吸着一溶離試験を行つた。
その結果を第３表に示す。[Table] As a result, the above iminodiacetic acid type chelate resin adsorbs gallium without adsorbing arsenic, but
Due to its low adsorption amount, it is not possible to efficiently recover gallium from arsenic from wastewater. Example 2 The chloromethylated resin obtained in Example 1 was reacted with phosphorus trichloride in the presence of aluminum chloride to obtain a chelate resin having a phosphoric acid group and a methylene phosphoric acid group as chelate forming groups. This was classified into 10 to 48 meshes and used in the test. As: 20ppm, Ga: 10ppm, NaCl: 1000ppm
After preparing simulated wastewater (PH1.0) containing
Simulated wastewater was passed through the tube in a downward flow at a flow rate of SV10.
When we measured the gallium ion and arsenic ion concentrations in the effluent until the flow rate reached 1000/-R, no gallium ions were detected, and the arsenic ions were completely gallium at 20 ppm, the same as in the raw water. and arsenic could be separated. Example 3 Acrylonitrile-divinylbenzene (10wt.
%) in the presence of toluene.
A chelate resin having an amidoxime group was obtained by reacting MR type spherical resin with hydroxylamine. This was classified to obtain 10 to 48 meshes. 0.2 ml of 10 to 48 mesh chelate resin was added to 200 ml of the same simulated wastewater as in Example 1, and after shaking for 1.5 hours, the gallium ion concentration and arsenic ion concentration in the aqueous solution were measured, and the adsorption amount of each was determined. , gallium was 12.5 g/-R, and arsenic was not adsorbed at all. In addition, when the amount of resin added was increased to 2 ml and the gallium ion concentration and arsenic ion concentration in the aqueous solution was measured after shaking for 3 hours, no Ga was detected.
As was 18 ppm, and gallium was completely adsorbed and separated. Example 4 At least two active hydrogen atoms bonded to a nitrogen atom
Tetraethylenepentamine has O
- Phosphorous acid and formalin were reacted, then resorcinol and formalin were reacted, and the resulting reaction product was subjected to suspension polymerization and curing in an aqueous polyvinyl alcohol solution to obtain a spherical resin. This spherical resin is a chelate resin having an iminomethylene phosphate group as a chelate forming group. Classify this
Got one for 10-48 metsushiyu. Column (inner diameter 25mmφ) 100ml of this chelate resin
The same simulated wastewater as in Example 1 was passed under the same conditions up to a flow rate of 300/-R, and the gallium ion concentration and arsenic ion concentration in the effluent that flowed out during this period was measured. Next, the wastewater remaining in the column is pushed out with water,
A 3N-HNO 3 aqueous solution was passed in an amount five times the resin amount (500 ml) at a flow rate of SV2 in a downward flow, and the gallium ion concentration in the eluent was measured to determine the elution recovery rate. The column is then washed with water. The above operations of liquid passage, adsorption, extrusion, elution, and water washing were repeated, and adsorption and elution tests were conducted three times in total.
The results are shown in Table 3.
Claims (1)
キレート樹脂としてその樹脂母体がジビニルベン
ゼン系共重合体、エポキシ樹脂、フエノール樹
脂、塩化ビニル樹脂のいずれかであり、該樹脂母
体に結合する官能基がリン酸基、アルキレンリン
酸基、アミノアルキレンリン酸基、イミノアルキ
レンリン酸基、アミドオキシム基より成る群より
選ばれたる少なくとも一種であるキレート樹脂と
接触させることにより、ガリウムをキレート樹脂
に選択的に吸着させてヒ素と分離することを特徴
とするガリウムとヒ素の分離方法。1 Water containing gallium and arsenic at a pH of 5 or less,
As a chelate resin, the resin base is either a divinylbenzene copolymer, an epoxy resin, a phenol resin, or a vinyl chloride resin, and the functional group bonded to the resin base is a phosphoric acid group, an alkylene phosphoric acid group, or an aminoalkylene phosphoric acid group. The method is characterized in that gallium is selectively adsorbed to the chelate resin and separated from arsenic by contacting it with a chelate resin that is at least one selected from the group consisting of acid groups, iminoalkylene phosphate groups, and amidoxime groups. How to separate gallium and arsenic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6774485A JPS61227888A (en) | 1985-03-30 | 1985-03-30 | Separation of gallium from arsenic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6774485A JPS61227888A (en) | 1985-03-30 | 1985-03-30 | Separation of gallium from arsenic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61227888A JPS61227888A (en) | 1986-10-09 |
| JPH0471597B2 true JPH0471597B2 (en) | 1992-11-16 |
Family
ID=13353758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6774485A Granted JPS61227888A (en) | 1985-03-30 | 1985-03-30 | Separation of gallium from arsenic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61227888A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003001275A (en) * | 2001-06-19 | 2003-01-07 | Kurita Water Ind Ltd | Gallium-arsenic wastewater treatment equipment |
-
1985
- 1985-03-30 JP JP6774485A patent/JPS61227888A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61227888A (en) | 1986-10-09 |
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