JPH0463016B2 - - Google Patents
Info
- Publication number
- JPH0463016B2 JPH0463016B2 JP5700085A JP5700085A JPH0463016B2 JP H0463016 B2 JPH0463016 B2 JP H0463016B2 JP 5700085 A JP5700085 A JP 5700085A JP 5700085 A JP5700085 A JP 5700085A JP H0463016 B2 JPH0463016 B2 JP H0463016B2
- Authority
- JP
- Japan
- Prior art keywords
- gallium
- aqueous solution
- organic phase
- nitric acid
- arsenic
- 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 57
- 229910052733 gallium Inorganic materials 0.000 claims description 57
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 28
- 229910000765 intermetallic Inorganic materials 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- 238000000605 extraction Methods 0.000 description 24
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 21
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000622 liquid--liquid extraction Methods 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- FNXKBSAUKFCXIK-UHFFFAOYSA-M sodium;hydrogen carbonate;8-hydroxy-7-iodoquinoline-5-sulfonic acid Chemical class [Na+].OC([O-])=O.C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 FNXKBSAUKFCXIK-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
（産業上の利用分野）
本発明はガリウム−砒素金属間化合物含有物か
らのガリウムの回収方法、特にトランジスタ、ダ
イオード、ICなどの電子部品を製造するときに
生じるガリウム−砒素半導体屑などからガリウム
を高純度で効率よく回収する方法に関する。
（従来の技術）
半導体などの電子材料として有用な−族金
属間化合物の研究・開発が進められている。−
族金属間化合物のなかでも、ガリウム−砒素金
属間化合物（以下、GaAs金属間化合物という）
は、電子材料としての特性に優れているため、
ICの基板用などにその需要が急増している。原
料となるガリウムは、その精鉱がほとんど存在し
ない稀少元素のひとつであり、主として、アルミ
ニウムや亜鉛の精錬副産物として得られる。その
ため、上記ICなどの電子部品を製造するときに
生じるGaAs金属間化合物屑やスクラツプからの
ガリウムの回収が望まれている。他方、砒素は有
毒物質であるため、GaAs金属間化合物屑やスク
ラツプからクローズド・システムで回収されるこ
とが公害防止の面から必要とされる。
ガリウムまたは砒素の個々についての回収方法
に関する文献や特許は過去にも知られている。例
えば、特開昭54−40212号公報には、アルミニウ
ム製錬におけるバイヤー液（アルミニウム、ナト
リウム、ガリウムを含有するアルカリ性水溶液）
からヒドロキシキノリン類を抽出剤として液−液
抽出によりガリウムを回収する方法が開示されて
いる。しかし、これらの方法はGaAs金属間化合
物からのガリウムの回収には適当ではない。この
ように、現在のところ、GaAs金属間化合物から
ガリウムを高純度で効率よく回収する方法は知ら
れていない。
（発明が解決しようとする問題点）
本発明は上記従来の欠点を解決するものであ
り、その目的とするところはGaAs金属間化合物
からガリウムを高純度で効率よく回収する方法を
提供することにある。本発明の他の目的は、上記
ガリウムの回収を操作の簡単な湿式処理により行
う方法を提供することにある。
（問題点を解決するための手段）
本発明のガリウム−砒素金属間化合物含有物か
らのガリウムの回収方法は、(a)ガリウム−砒素金
属間化合物含有物を硝酸に溶解させる工程、(b)(a)
項で得られた硝酸水溶液と酸性有機リン化合物を
含む有機溶媒とを液−液接触させ、ガリウムを有
機相に抽出する工程、および(c)(b)項で得られた有
機相を鉱酸により逆抽出しガリウム水溶液を得る
工程、を包含し、そのことにより上記目的が達成
される。
本発明方法によれば、第１図に示すように、ま
ず、第１工程（溶解工程）１においてGaAs金属
間化合物屑などのGaAs金属間化合物含有物を硝
酸に溶解させる。GaAs金属間化合物含有物は溶
解しやすいように粉砕されていることが好まし
い。通常、粉砕されたGaAs金属間化合物含有物
に水を加えてスラリー状とし、これに硝酸水溶液
を加えて溶解させる。溶解時の温度が高いほど溶
解効率が上がるため、40〜110℃に加熱して溶解
させることが好ましい。硝酸添加量がGaAs金属
間化合物１モルに対して５モル以上であれば該
GaAs金属間化合物を溶解させることができる。
通常、工業的には硝酸はGaAs金属間化合物含有
物１モルに対して５〜10モルの割合で添加される
のが有利である。添加量が過剰であると、後述の
第２において酸性有機リン化合物でガリウムを抽
出するときのPH調整に塩基が大量に必要となる。
この第１工程において、用いる水の量を少量とす
れば、砒素を亜硫酸（As2O3）として析出させる
ことができる。水溶液の容量が少量でありかつ
As2O3を濾別して得られる水溶液中には砒素量が
少なくなるため、第２工程以後におけるガリウム
と砒素との分離効率が上がる。容量効率も上がる
ため大規模の設備を必要とせず、工業的に有利と
なる。水溶液の容量は、通常、金属間化合物含有
物100ｇに対して４以上であり、As2O3を析出
させる場合には１以下である。
次に、第２工程（抽出工程）２において、上記
GaAs金属間化合物を含有する硝酸水溶液を酸性
有機リン化合物を含有する有機溶媒と接触させ、
ガリウムを有機相中に液−液抽出する。ここで、
抽出剤として用いられる酸性有機リン化合物は、
下記の構造式を有する化合物のうちの少なくとも
１種である：
（ここで、R1〜R6は、それぞれ、炭素数３〜18
のアルキル基、アルケニル基、脂環式基、アリー
ル基またはアルキルアリール基である）。
このような化合物には、例えばジ−２−エチル
ヘキシルリン酸、２−エチルヘキシルホスホン酸
モノ−２−エチルヘキシルエステル、ジ−２−エ
チルヘキシルホスフイン酸がある。
有機溶媒としては、上記抽出剤およびその金属
塩を溶解しうる通常の有機溶媒が利用されうる。
例えば、石油系炭化水素が好適に用いられ得、上
記抽出剤が、５〜90vol％、好ましくは、10〜
50vol％に希釈されて用いられる。液−液抽出を
行うときには、NaOH、Ca（OH）2、NH3などの
塩基を加えて接触時の水相のPHを0.5以上、好ま
しくは１〜２に調整する。ガリウムの抽出量は水
相のPHに依存するため、PHが低すぎるとガリウム
が有機層に抽出されにくい。水相と有機相との接
触方法は既知の方法が用いられうる。塔式あるい
は槽式の多段向流接触装置を用いると効果的に抽
出が行われうる。後述の第３工程（逆抽出工程）
および精製工程における接触方法についても同様
である。
第２工程において得られたガリウムを含有する
有機相は、次いで、第３工程（逆抽出工程）３へ
移される。この第２工程と第３工程との間に、最
終的に得られるガリウム水溶液の純度を高めるた
めに、洗浄工程４が適宜設けられる。洗浄工程４
においては、第２工程で得られたガリウムを含有
する有機相を希硝酸と接触させて、ガリウムと共
に有機相に抽出された不純物を水相へ除去する。
洗浄に用いる硝酸の濃度は高いほど優れた洗浄効
果が得られる。しかし、濃度が高いほど有機相に
含有されるガリウムも同時に、水相に移行する。
それゆえ、硝酸濃度は0.1〜1Nであることが好ま
しい。洗浄後の水相は、第１図において実線で示
すように、第１工程または第２工程へフイード・
バツクして用いることができる。洗浄水相を第１
または第２工程へフイード・バツクすることによ
りガリウムの回収率が上がる。
第２工程の抽出工程もしくはこの抽出工程と洗
浄工程を経て得られたガリウム含有有機相を、次
いで、第３工程（逆抽出工程）において鉱酸水溶
液と接触させる。それにより、ガリウムが水相に
逆抽出される。逆抽出用の鉱酸としては、塩酸、
硝酸、硫酸などが用いられる。鉱酸の濃度は高い
ほうが逆抽出効率が上がる傾向にあるが、濃度が
高すぎても逆抽出効率が低下する。通常、１〜
5Nが好適である。逆抽出後の有機相は、第１図
において点線で示すように、第２工程にフイー
ド・バツクさせて用いられうる。
このようにして99.9％以上の純度のガリウムを
含有する水溶液が得られる。このガリウム水溶液
は、必要に応じて、さらに、第２図に示す精製工
程５で精製される。この方法で精製を行う場合に
は、第３工程において鉱酸として塩酸を用いるの
が好適である。精製を行うには、まず、第３工程
で得られたガリウムの塩酸水溶液をさらに濃塩酸
を添加もしくは塩化水素ガスを吹き込み、高級ア
ルコールおよび／もしくはエーテルでガリウムを
抽出する。ガリウムは塩化物の形態で高級アルコ
ールやエーテルと錯体を形成するため、容易に抽
出されうる。高級アルコールとしては、炭素数４
〜18個のアルキル基または脂環式基を有するアル
コール、例えば、２−エチルヘキサノールが用い
られる。エーテルとしては。炭素数２〜８個のア
ルキル基を有するエーテル、例えばイソプロピル
エーテルが用いられる。この高級アルコールやエ
ーテルは溶媒に溶解させて用いられてもよい。溶
媒としては、上記高級アルコールやエーテルおよ
びそれらの金属付加物（ガリウム塩化物との錯
体）を溶解しうる有機溶媒が用いられる。これら
の有機溶媒としては。例えば、石油系炭化水素が
好適に用いられる。ガリウムの抽出量は水相の塩
酸濃度に依存し、塩酸濃度が高いほど抽出率が高
くなる。工業的には塩酸濃度を４〜10Nとするの
が有利である。次に、ガリウムを含む有機相を水
と接触させれば、ガリウムは水相に容易に逆抽出
される。逆抽出後の有機相は、第２図において点
線で示すように、精製工程における抽出にフイー
ド・バツクして利用されうる。
（作用）
本発明方法によれば、このように、GaAs金属
間化合物からガリウムが湿式処理法（液−液抽出
法）で有利に回収される。得られたガリウム水溶
液中のガリウムの純度は99.9％以上である。この
水溶液から既知の方法により高純度の金属ガリウ
ムまたはその酸化物が容易に得られうる。例え
ば、上記ガリウム水溶液もしくは精製後のガリウ
ム水溶液にアルカリを加えて水酸化ガリウムとし
てガリウムを分離した後、アルカリ電解法にて金
属ガリウムが得られる。
（実施例）
以下に本発明を実施例について説明する。
実施例 １
GaAs金属間化合物含有物として表１に示す組
成のGaAs半導体屑を用いた。この組成は原子吸
光分析法により決定された。
(Industrial Application Field) The present invention relates to a method for recovering gallium from materials containing gallium-arsenic intermetallic compounds, and in particular, a method for recovering gallium from gallium-arsenic semiconductor waste generated when manufacturing electronic components such as transistors, diodes, and ICs. It relates to a method for efficiently recovering with high purity. (Prior Art) Research and development of - group intermetallic compounds useful as electronic materials such as semiconductors is progressing. −
Among group intermetallic compounds, gallium-arsenic intermetallic compound (hereinafter referred to as GaAs intermetallic compound)
has excellent properties as an electronic material,
Demand is rapidly increasing for use in IC substrates, etc. Gallium, the raw material, is one of the rare elements that hardly exists in concentrate, and is mainly obtained as a byproduct of smelting aluminum and zinc. Therefore, it is desired to recover gallium from GaAs intermetallic compound waste and scrap generated when manufacturing electronic components such as the above-mentioned ICs. On the other hand, since arsenic is a toxic substance, it is necessary to recover it from GaAs intermetallic compound waste and scrap in a closed system to prevent pollution. Literature and patents regarding recovery methods for gallium or arsenic are known in the past. For example, JP-A No. 54-40212 describes Bayer's solution (alkaline aqueous solution containing aluminum, sodium, and gallium) used in aluminum smelting.
A method for recovering gallium by liquid-liquid extraction using hydroxyquinolines as an extractant is disclosed. However, these methods are not suitable for recovering gallium from GaAs intermetallic compounds. Thus, at present, there is no known method for efficiently recovering gallium from GaAs intermetallic compounds with high purity. (Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional drawbacks, and its purpose is to provide a method for efficiently recovering gallium from GaAs intermetallic compounds with high purity. be. Another object of the present invention is to provide a method for recovering gallium using a wet process that is easy to operate. (Means for Solving the Problems) The method of recovering gallium from a material containing a gallium-arsenic intermetallic compound of the present invention includes (a) dissolving the material containing a gallium-arsenic intermetallic compound in nitric acid; (b) (a)
A step of bringing the nitric acid aqueous solution obtained in Section 1 into liquid-liquid contact with an organic solvent containing an acidic organophosphorus compound to extract gallium into the organic phase, and adding the organic phase obtained in Section (c) and (b) with a mineral acid. The above object is achieved by performing back extraction to obtain a gallium aqueous solution. According to the method of the present invention, as shown in FIG. 1, in a first step (dissolution step) 1, GaAs intermetallic compound-containing materials such as GaAs intermetallic compound waste are dissolved in nitric acid. It is preferable that the GaAs intermetallic compound-containing material is pulverized so that it can be easily dissolved. Usually, water is added to the ground GaAs intermetallic compound-containing material to form a slurry, and a nitric acid aqueous solution is added to the slurry to dissolve it. Since the higher the temperature during dissolution, the higher the dissolution efficiency, it is preferable to heat to 40 to 110°C to dissolve. If the amount of nitric acid added is 5 mol or more per 1 mol of GaAs intermetallic compound, it is applicable.
GaAs intermetallic compounds can be dissolved.
Usually, industrially, it is advantageous to add nitric acid at a ratio of 5 to 10 moles per mole of the GaAs intermetallic compound-containing material. If the amount added is excessive, a large amount of base will be required to adjust the pH when extracting gallium with an acidic organic phosphorus compound in the second step described below.
In this first step, if the amount of water used is small, arsenic can be precipitated as sulfite (As 2 O 3 ). The volume of the aqueous solution is small and
Since the amount of arsenic in the aqueous solution obtained by filtering As 2 O 3 is reduced, the efficiency of separating gallium and arsenic in the second and subsequent steps increases. Since capacity efficiency also increases, large-scale equipment is not required, which is industrially advantageous. The volume of the aqueous solution is usually 4 or more per 100 g of the intermetallic compound-containing material, and 1 or less when depositing As 2 O 3 . Next, in the second step (extraction step) 2, the above
Contacting a nitric acid aqueous solution containing a GaAs intermetallic compound with an organic solvent containing an acidic organophosphorus compound,
Gallium is liquid-liquid extracted into the organic phase. here,
Acidic organophosphorus compounds used as extractants are
At least one compound having the following structural formula: (Here, R 1 to R 6 each have a carbon number of 3 to 18
an alkyl group, alkenyl group, alicyclic group, aryl group or alkylaryl group). Such compounds include, for example, di-2-ethylhexyl phosphoric acid, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, di-2-ethylhexylphosphinic acid. As the organic solvent, a conventional organic solvent that can dissolve the above extractant and its metal salt can be used.
For example, petroleum-based hydrocarbons can be suitably used, and the extractant is 5 to 90 vol%, preferably 10 to 90 vol%.
It is used diluted to 50vol%. When performing liquid-liquid extraction, a base such as NaOH, Ca(OH) 2 or NH 3 is added to adjust the pH of the aqueous phase during contact to 0.5 or higher, preferably 1 to 2. The amount of gallium extracted depends on the pH of the aqueous phase, so if the pH is too low, gallium will be difficult to extract into the organic layer. A known method can be used for contacting the aqueous phase and the organic phase. Extraction can be effectively carried out using a column-type or tank-type multistage countercurrent contactor. Third step (reverse extraction step) described below
The same applies to the contact method in the purification process. The gallium-containing organic phase obtained in the second step is then transferred to the third step (reverse extraction step) 3. A cleaning step 4 is appropriately provided between the second step and the third step in order to increase the purity of the finally obtained gallium aqueous solution. Washing process 4
In this step, the gallium-containing organic phase obtained in the second step is brought into contact with dilute nitric acid to remove impurities extracted into the organic phase together with gallium into the aqueous phase.
The higher the concentration of nitric acid used for cleaning, the better the cleaning effect can be obtained. However, the higher the concentration, the more gallium contained in the organic phase also migrates to the aqueous phase.
Therefore, the nitric acid concentration is preferably 0.1-1N. The aqueous phase after washing is fed to the first or second step as shown by the solid line in Figure 1.
It can be used backwards. Wash water phase first
Alternatively, the recovery rate of gallium can be increased by feeding back to the second step. The gallium-containing organic phase obtained through the second extraction step or this extraction step and washing step is then brought into contact with an aqueous mineral acid solution in the third step (reverse extraction step). Gallium is thereby extracted back into the aqueous phase. Mineral acids for back extraction include hydrochloric acid,
Nitric acid, sulfuric acid, etc. are used. The higher the mineral acid concentration, the higher the back extraction efficiency, but if the concentration is too high, the back extraction efficiency will decrease. Usually 1~
5N is preferred. The organic phase after back extraction can be used as feed back to the second step, as shown by the dotted line in FIG. In this way, an aqueous solution containing gallium with a purity of 99.9% or more is obtained. This gallium aqueous solution is further purified in a purification step 5 shown in FIG. 2, if necessary. When purifying by this method, it is preferable to use hydrochloric acid as the mineral acid in the third step. For purification, first, concentrated hydrochloric acid is further added or hydrogen chloride gas is blown into the hydrochloric acid aqueous solution of gallium obtained in the third step, and gallium is extracted with higher alcohol and/or ether. Gallium forms complexes with higher alcohols and ethers in the form of chlorides and can therefore be easily extracted. As a higher alcohol, carbon number is 4
Alcohols having ~18 alkyl or cycloaliphatic groups are used, for example 2-ethylhexanol. As ether. Ethers having an alkyl group having 2 to 8 carbon atoms, such as isopropyl ether, are used. This higher alcohol or ether may be used after being dissolved in a solvent. As the solvent, an organic solvent that can dissolve the above-mentioned higher alcohols, ethers, and their metal adducts (complexes with gallium chloride) is used. As these organic solvents. For example, petroleum hydrocarbons are preferably used. The amount of gallium extracted depends on the hydrochloric acid concentration in the aqueous phase, and the higher the hydrochloric acid concentration, the higher the extraction rate. Industrially, it is advantageous to adjust the hydrochloric acid concentration to 4 to 10N. Next, when the organic phase containing gallium is brought into contact with water, the gallium is easily back-extracted into the aqueous phase. The organic phase after the back extraction can be used as a feed back to the extraction in the purification process, as shown by the dotted line in FIG. (Function) According to the method of the present invention, gallium is thus advantageously recovered from the GaAs intermetallic compound by the wet processing method (liquid-liquid extraction method). The purity of gallium in the obtained gallium aqueous solution is 99.9% or more. High purity metallic gallium or its oxide can be easily obtained from this aqueous solution by a known method. For example, after adding an alkali to the above gallium aqueous solution or purified gallium aqueous solution to separate gallium as gallium hydroxide, metallic gallium is obtained by an alkaline electrolysis method. (Example) The present invention will be described below with reference to Examples. Example 1 GaAs semiconductor scrap having the composition shown in Table 1 was used as a material containing a GaAs intermetallic compound. The composition was determined by atomic absorption spectrometry.
【表】
この粉砕された半導体屑100ｇに水500mlを加え
てスラリーとした。これに61wt％の硝酸を284ml
加えて２時間加熱還流させた後、水を加えて４
とした。不溶物はほとんど認められなかつた。こ
の硝酸水溶液を濾過して得られた濾液の組成を表
２に示す。[Table] 500 ml of water was added to 100 g of the pulverized semiconductor chips to form a slurry. Add 284ml of 61wt% nitric acid to this.
After adding water and heating under reflux for 2 hours, water was added and refluxed for 2 hours.
And so. Almost no insoluble matter was observed. Table 2 shows the composition of the filtrate obtained by filtering this nitric acid aqueous solution.
【表】
次に、この濾液40容量部を酸性有機リン化合物
を抽出剤として含有する抽出溶媒50容量部を用い
て抽出した。抽出剤としてはジ−２−エチルヘキ
シルリン酸を用い、これをパラフイン系炭化水素
（Shellsol71、Shell社製）に0.6mol／となるよ
うに溶解させて抽出溶媒を調製した。抽出時に
は、dil NaOH10容量部を加えて接触時のPHを
1.3に調製した。得られた有機相100容量部に対し
て0.15Nの硝酸水溶液50容量部を加えて洗浄を２
回行つた。洗浄後の有機相100容量部に対して2N
塩酸50容量部を加えて逆抽出を行つた。得られた
塩酸水溶液中の金属成分の分析を行つた。なお今
回は第１表および第２には示されていない微量成
分（Cu、Na、Te、GeおよびＰ）についても測
定を行つた。その結果を表３に示す。塩酸水溶液
中のガリウムの純度は99.97％でありGaAs半導体
屑からのガリウムの回収率は85％であつた。[Table] Next, 40 parts by volume of this filtrate was extracted using 50 parts by volume of an extraction solvent containing an acidic organic phosphorus compound as an extractant. Di-2-ethylhexyl phosphoric acid was used as an extractant, and an extraction solvent was prepared by dissolving di-2-ethylhexyl phosphoric acid in a paraffinic hydrocarbon (Shellsol 71, manufactured by Shell) at a concentration of 0.6 mol/. During extraction, add 10 parts by volume of dil NaOH to adjust the PH at the time of contact.
Prepared in 1.3. Washing was carried out by adding 50 parts by volume of a 0.15N nitric acid aqueous solution to 100 parts by volume of the organic phase obtained.
I went around. 2N for 100 parts by volume of organic phase after washing
Back extraction was performed by adding 50 parts by volume of hydrochloric acid. The metal components in the obtained hydrochloric acid aqueous solution were analyzed. This time, we also measured trace components (Cu, Na, Te, Ge, and P) that are not shown in Tables 1 and 2. The results are shown in Table 3. The purity of gallium in the hydrochloric acid aqueous solution was 99.97%, and the recovery rate of gallium from GaAs semiconductor scraps was 85%.
【表】
実施例 ２
実施例１と同様の組成のGaAs半導体屑10ｇを
20mlの水を用いてスラリーとした。これに61wt
％の硝酸を45ml加えて２時間加熱還流させた。常
温にもどした後析出した沈澱物（As2O3）を濾去
し濾液に水を加えて100mlとした。この硝酸水溶
液中の金属成分の組成を表４に示す。[Table] Example 2 10g of GaAs semiconductor scraps with the same composition as Example 1 were
A slurry was prepared using 20 ml of water. 61wt for this
% nitric acid was added and the mixture was heated under reflux for 2 hours. After returning to room temperature, the precipitate (As 2 O 3 ) that had precipitated was removed by filtration, and water was added to the filtrate to make 100 ml. Table 4 shows the composition of the metal components in this nitric acid aqueous solution.
【表】
この水溶液を実施例１と同様に処理した。得ら
れた塩酸水溶液中のガリウムの純度は99.9％以上
であつた。
実施例 ３
第３工程（逆抽出工程）のあとにさらに精製工
程を設けてその効果を評価した。
実施例１で得られた塩酸水溶液にZn2+、Fe3+、
Al3+を塩化物として添加し、さらに、濃塩酸を
加えて表５に示す組成の水溶液を得た。[Table] This aqueous solution was treated in the same manner as in Example 1. The purity of gallium in the obtained hydrochloric acid aqueous solution was 99.9% or more. Example 3 A purification step was further provided after the third step (reverse extraction step) and its effect was evaluated. Zn 2+ , Fe 3+ ,
Al 3+ was added as a chloride, and concentrated hydrochloric acid was further added to obtain an aqueous solution having the composition shown in Table 5.
【表】
この水溶液100容量部に２−エチルヘキサノー
ル30vol％を含有する抽出溶媒（Shellsol71を溶
媒として使用）100容量部を加えて液−液抽出を
行つた。得られた有機相に水30容量部を加えて逆
抽出した。得られた精製ガリウム水溶液の組成を
表６に示す。[Table] To 100 parts by volume of this aqueous solution, 100 parts by volume of an extraction solvent containing 30 vol% of 2-ethylhexanol (Shellsol 71 was used as the solvent) was added to perform liquid-liquid extraction. 30 parts by volume of water was added to the obtained organic phase for back extraction. Table 6 shows the composition of the purified gallium aqueous solution obtained.
【表】
実施例 ４
抽出剤として２−エチルヘキシルホスホン酸モ
ノー２−エチルヘキシルエステルを用い、そして
2N塩酸の代わりに2N硝酸を用いたこと以外は実
施例１と同様である。得られた水溶液中のガリウ
ムの純度は99.96％であつた。
（発明の効果）
本発明によれば、このように、GaAs金属間化
合物含有物から高純度のガリウムが回収される。
操作法は簡単な液−液抽出法（湿式処理法）であ
り、クローズド・システムで処理されうるため砒
素による環境汚染がない。この方法は、ICなど
の電子部品を製造するときに生じるGaAs金属間
化合物屑やスクラツプからのガリウムの回収に有
効である。[Table] Example 4 Using 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester as the extractant, and
The procedure was the same as in Example 1 except that 2N nitric acid was used instead of 2N hydrochloric acid. The purity of gallium in the obtained aqueous solution was 99.96%. (Effects of the Invention) According to the present invention, high-purity gallium is thus recovered from a material containing a GaAs intermetallic compound.
The operation method is a simple liquid-liquid extraction method (wet processing method), and since it can be processed in a closed system, there is no environmental pollution caused by arsenic. This method is effective for recovering gallium from GaAs intermetallic compound waste and scrap generated when manufacturing electronic components such as ICs.
第１図は本発明のガリウム回収方法を説明する
工程図、第２図は第１図の第３工程で得られるガ
リウム水溶液を精製する方法を説明する工程図で
ある。
１……第１工程（溶解工程）、２……第２工程
（抽出工程）、３……第３工程（逆抽出工程）、４
……洗浄工程、５……精製工程。
FIG. 1 is a process diagram for explaining the gallium recovery method of the present invention, and FIG. 2 is a process diagram for explaining the method for purifying the gallium aqueous solution obtained in the third step of FIG. 1... 1st step (dissolution step), 2... 2nd step (extraction step), 3... 3rd step (reverse extraction step), 4
...Washing process, 5...Purification process.
Claims (1)
酸に溶解させる工程、 (b) (a)項で得られた硝酸水溶液と酸性有機リン化
合物を含む有機溶媒とを液−液接触させ、ガリ
ウムを有機相に抽出する工程、および (c) (b)項で得られた有機相を鉱酸により逆抽出し
ガリウム水溶液を得る工程、 を包含するガリウム−砒素金属間化合物含有物か
らのガリウムの回収方法。 ２ 前記(a)項で得られた硝酸水溶液から砒素を固
体の亜砒酸として分離・除去する特許請求の範囲
第１項に記載の方法。 ３ 前記(c)項で得られたガリウム水溶液を高級ア
ルコールおよび／もしくはエーテルまたは高級ア
ルコールおよび／もしくはエーテルを含有する有
機溶媒と液−液接触させ、ガリウムを有機相に抽
出する工程、および 該有機相を水により逆抽出しガリウム水溶液を
得る工程、 を包含する特許請求の範囲第１項に記載の方法。 ４ 前記酸性有機リン化合物が下記構造式を有す
る化合物のうちの少なくとも１種である特許請求
の範囲第１項に記載の方法： （ここで、R1〜R6は、それぞれ、炭素数３〜18
のアルキル基、アルケニル基、脂環式基、アリー
ル基またはアルキルアリール基である）。[Scope of Claims] 1 (a) A step of dissolving a material containing a gallium-arsenic intermetallic compound in nitric acid, (b) A step of dissolving the nitric acid aqueous solution obtained in section (a) and an organic solvent containing an acidic organophosphorus compound as a liquid. - A gallium-arsenic intermetallic compound comprising: - a step of bringing the organic phase into liquid contact and extracting gallium into an organic phase; and (c) a step of back-extracting the organic phase obtained in section (b) with a mineral acid to obtain a gallium aqueous solution. Method for recovering gallium from contained materials. 2. The method according to claim 1, wherein arsenic is separated and removed as solid arsenous acid from the nitric acid aqueous solution obtained in the above (a). 3. A step of bringing the gallium aqueous solution obtained in section (c) above into liquid-liquid contact with a higher alcohol and/or ether or an organic solvent containing a higher alcohol and/or ether to extract gallium into an organic phase; The method according to claim 1, comprising the step of back-extracting the phase with water to obtain an aqueous gallium solution. 4. The method according to claim 1, wherein the acidic organophosphorus compound is at least one compound having the following structural formula: (Here, R 1 to R 6 each have a carbon number of 3 to 18
an alkyl group, alkenyl group, alicyclic group, aryl group or alkylaryl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60057000A JPS61215214A (en) | 1985-03-20 | 1985-03-20 | Recovery of gallium from material containing intermetallic compound of gallium and arsenic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60057000A JPS61215214A (en) | 1985-03-20 | 1985-03-20 | Recovery of gallium from material containing intermetallic compound of gallium and arsenic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61215214A JPS61215214A (en) | 1986-09-25 |
| JPH0463016B2 true JPH0463016B2 (en) | 1992-10-08 |
Family
ID=13043213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60057000A Granted JPS61215214A (en) | 1985-03-20 | 1985-03-20 | Recovery of gallium from material containing intermetallic compound of gallium and arsenic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61215214A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63206312A (en) * | 1987-02-23 | 1988-08-25 | Mitsubishi Kasei Corp | Extraction method of rare earth elements |
| FR2624524B1 (en) * | 1987-11-24 | 1990-05-18 | Metaleurop Sa | METHOD FOR HYDROMETALLURGICAL TREATMENT OF GALLIFER MATERIAL SOLUTION |
-
1985
- 1985-03-20 JP JP60057000A patent/JPS61215214A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61215214A (en) | 1986-09-25 |
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