JPS6316340B2 - - Google Patents
Info
- Publication number
- JPS6316340B2 JPS6316340B2 JP23623883A JP23623883A JPS6316340B2 JP S6316340 B2 JPS6316340 B2 JP S6316340B2 JP 23623883 A JP23623883 A JP 23623883A JP 23623883 A JP23623883 A JP 23623883A JP S6316340 B2 JPS6316340 B2 JP S6316340B2
- Authority
- JP
- Japan
- Prior art keywords
- rhenium
- resin
- elution
- waste acid
- adsorbed
- 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
- 229910052702 rhenium Inorganic materials 0.000 claims description 54
- 239000011347 resin Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 49
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 40
- 239000002699 waste material Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 29
- 238000010828 elution Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052785 arsenic Inorganic materials 0.000 claims description 20
- 229910052797 bismuth Inorganic materials 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 229910052753 mercury Inorganic materials 0.000 claims description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 238000005987 sulfurization reaction Methods 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- USBWXQYIYZPMMN-UHFFFAOYSA-N rhenium;heptasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[Re].[Re] USBWXQYIYZPMMN-UHFFFAOYSA-N 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000012535 impurity Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001510 metal chloride Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 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 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、レニウムの回収方法に関するもので
あり、特には廃酸中に含まれるレニウムをイオン
交換樹脂塔を使用して回収するに当つてイオン交
換樹脂の反覆使用とレニウムの効率的回収を実現
したレニウムの回収方法に関する。
レニウムは、モリブデン原鉱の輝水鉛鉱や銅鉱
石に僅かに随伴する希少金属であるが、触媒の添
加元素、熱電対や超耐熱合金用添加元素、高真空
電子管材料等に用いられる重要な金属である。
レニウムを工業的に回収する為の有望な原料の
一つとして廃酸がある。廃酸は、銅等の非鉄金属
の製錬工程から発生する亜硫酸ガスを硫酸の製造
に利用する場合に水洗浄が為されるが、その際生
成する硫酸を定期的に一部抜出したものである。
原鉱中に含まれていたレニウムがその他の不純物
と共に廃酸中に混入している。その他の不純物と
してはHg、Mo、Bi及びAsが代表的である。
レニウムの工業的回収法についてはあまり系統
的な研究が為されていないが、一つの有力な方法
としてRe2O7を含む原料を水溶液に溶解し、陰イ
オン交換樹脂を使用してのイオン交換法によりレ
ニウムを樹脂に吸着しそして吸着したレニウムを
溶離する方法が提唱されている。
本発明者等は、レニウム回収源として廃酸を対
象として、上記陰イオン交換樹脂を使用するレニ
ウム回収法を基本とするレニウム回収法について
系統的研究を行つた。この方法においては、レニ
ウム以外の随伴する不純物とレニウムとの分離、
樹脂の再生及び繰返し使用、樹脂からのレニウム
の効率的溶離、溶離後液からのレニウムの効果的
回収等解決すべき問題点は多いが、広範な研究の
結果、工業的に有用なレニウム回収法の確立に成
功した。
廃酸中には、Reの外にHg、Mo、Bi及びAsが
不純物として含まれているが、廃酸をレニウム吸
着樹脂塔に通液した場合Reと共にこれら不純物
も吸着される。吸着した不純物のうちHgは溶離
が困難であり、樹脂塔の繰返し使用中Re吸着率
を悪化することが見出された。従つて、廃酸を吸
着樹脂塔に通す前にHgをあらかじめ除去してお
くことがレニウム回収系統を円滑に操業する上で
きわめて有利であることが判明した。
こうして脱Hgされた廃酸はRe、Mo、Bi及As
を含んでおり、これらが樹脂に吸着される。この
うちMo及びAsは水酸化ナトリウムを樹脂塔に通
液することによりきわめて効果的に樹脂から除去
しうることが見出された。このようにMo及びAs
を先に樹脂から脱着除去しておくことは後の操作
を容易とするのできわめて好都合である。
次いで、樹脂に吸着しているRe及びBi並びに
残留する少量のMo及びAsが樹脂から溶離され
る。陰イオン交換樹脂からReを溶離するのに金
属塩化物を含む塩酸溶液を溶離液として使用する
ことが本件出願人により既に提案されており（特
願昭58−82576号）、本方法においても採用するこ
とが好ましい。得られる溶離後液にはReとBiが
主体的に含まれ、少量のMo及びAsが随伴する。
溶離後液からのReの回収にはReを硫化物とし
て回収するのが一番効果的であることが判明し
た。Be、Mo及びAsはほぼ全量硫化物となるが、
Biはほぼ全量硫化後液に残るので、ReとBiとの
効果的な分離が可能となる。
溶離後の樹脂は次のサイクルに備えて再生する
ことができる。
上述した脱Hg工程、吸着工程、不純物（Mo、
As）除去工程、溶離工程、硫化工程及び再生工
程の組合せによつて廃酸中のReは硫化物の形で
効率的に回収することができると共に、樹脂の繰
返し使用が可能となる。こうして、廃酸からRe
を回収する一貫プロセスが斯界で始めて確立され
たものである。
要約すると、本発明は、レニウム、水銀、モリ
ブデン、ビスマス及び砒素を含む廃酸からレニウ
ムを硫化レニウムとして回収する方法であつて、
(イ) 廃酸から水銀を除去する脱水銀工程と、
(ロ) 脱水銀した廃酸を陰イオン交換樹脂を含む樹
脂塔に通液して、レニウム、モリブデン、ビス
マス及び砒素を該樹脂に吸着する吸着工程と、
(ハ) 前記樹脂塔に水酸化ナトリウムを通液して主
としてモリブデン及び砒素を除去する不純物除
去工程と、
(ニ) 樹脂から主としてレニウム及びビスマスを溶
離する溶離工程と、
(ホ) 溶離後液中に含まれるレニウムを硫化レニウ
ムとして回収する硫化工程と、
(ヘ) 必要に応じ、樹脂を再生する再生工程と
を包含する廃酸からのレニウムの回収法を提供す
る。
以下、本発明について具体的に説明する。
図面は本発明方法のフローシートである。前述
したように、非鉄金属精錬工場において産出する
廃酸は重要なレニウム回収源であり、出所に応じ
て５〜60mg/のレニウムを含んでいる。しかし
ながら、廃酸はReの外にHg、Mo、Bi及びAsを
主とする不純物をも含有しており、これら不純物
がReの回収の障害となつている。
本発明は基本的に陰イオン交換樹脂を使用して
Reを吸着するものであるが、Reと共に上記不純
物も吸着される。不純物のうちMo、Bi、Asは後
に樹脂から除去しうるが、Hgに関しては除去が
きわめて困難である。その為、樹脂中にHgが累
積し、Reの吸着効率を悪化する。そこで本発明
に従えば、先ず廃酸からの脱水銀が計られる。
脱水銀は、例えばユニチカ製UR−2200Hのよ
うなキレート樹脂、Amberlite IRA−400のよう
な強塩基性陰イオン交換樹脂のような水銀に対す
る吸着力の強い樹脂に廃酸を通すことによりほぼ
完全にもたらしうる。塩酸等の適当な除去剤によ
りHgの除去が可能である。
脱水銀廃酸は次いで陰イオン交換樹脂を収納し
た樹脂塔に通流される。陰イオン交換樹脂として
は、レニウムに対して吸着性の強いことが当然に
要求されるが、例えばダイヤイオンSA20A、ダ
イヤイオンPA316、ダイヤイオンPA408（三菱化
成工業(株)商品名）が効果的に使用しうる。レニウ
ムは陰イオン交換樹脂に10ｇ/樹脂までの量に
おいて強力に吸着され、廃酸中のレニウムの90〜
95％のものが吸着捕集される。レニウムの吸着と
同時に、廃酸中のMoの一部とBi及びAsの大部分
が吸着される。
廃酸の通流後、樹脂の洗浄の為例えば100ｇ/
前後の希硫酸を樹脂等に通し、続いて洗浄水にて
洗浄を為すことが好ましい。
Re、Mo、Bi及びAsを吸着した樹脂は次いで
不純物除去工程に切換えられ、ここで主として
Mo及びAsの除去が計られる。除去液としては50
〜200ｇ/の、好ましくは60〜150ｇ/の
NaOH溶液が使用される。不純物除去後液への
若干のレニウム損失は避けられないが、実質上レ
ニウムのほぼ全量を樹脂に吸着したまま、吸着
Moの95％以上が除去されると共に吸着Asも90％
近くまで除去される。吸着Biも少量除去される
が実質量は吸着したままである。不純物除去工程
の終了に際して樹脂を水洗浄しておくのがよい。
次いで樹脂塔は吸着成分を樹脂から脱着する溶
離工程に切換えられる。溶離液としては樹脂に強
固に吸着したレニウムその他の成分を容易に脱着
ししかも樹脂を破壊しないものが選定されねばな
らない。本発明においては既にMo及びAsの大半
が除去されているので溶離工程の負担が軽減され
る。溶離液としては塩酸が使用しうるが、本件出
願人は金属塩化物を含む塩酸溶液を溶離液として
用いる溶離法を先に開発し、好結果を得ている。
従つて、本方法においてもその採用が好ましい。
金属塩化物としては、銅、カドミウム或いは亜鉛
の塩化物が特に好ましく、中でも後工程の硫化処
理を行なうことを考慮すると亜鉛が特に好まし
い。亜鉛であれば簡易に精製が可能となる。３〜
９規定の塩酸濃度が使用しうる。金属塩化物添加
量は30〜150ｇ/水準で十分である。溶離用の液
量は樹脂の容量当り３〜９倍量あれば十分であ
る。金属塩化物の添加によつて塩酸のみの溶離液
に比べ、1/4の液量で100％近くの溶離が可能であ
り、高塩酸酸性としなくとも充分の溶離が可能で
ある。
溶離工程において樹脂に吸着されていたRe及
びBiは実質量溶離後液に入り、残留していたMo
及びAsは完全に溶離後液に入る。従つて、Re及
びBiを主体としそしてMo及びAsを随伴した溶離
後液が得られる。
溶離後のイオン交換樹脂は塩酸の使用により
C1型となつているので、繰返し使用の為にはOH
型に戻す再生工程が必要となる。再生は水酸化ナ
トリウム等の通流により簡易に実施しうる。その
後、充分に水洗浄を行い次のサイクルが開始され
る。
溶離後液からのレニウムの回収の為には硫化処
理を行つてレニウムを硫化物として回収するのが
有利である。溶離後液を撹拌しながら例えば硫化
水素ガスを吹込むことにより、Re、Mo及びAs
はほぼ全量硫化物となるが、Biはほぼ全量硫化
後液に残留する。塩酸濃度が3N以上の時特にBi
は液中に残留する。こうして、レニウムとビスマ
スの分離が可能となる。生成する硫化レニウムは
生成物の品位からS/Reモル比を計算してみると、
Re2S7に近い硫化物と考えられる。
硫化後液は液中のH2Sを空気で脱却して溶離液
として再使用可能であるが、Biの蓄積が考えら
れるので許容濃度を把握しておく必要がある。
以上で全工程サイクルが完結する。樹脂塔を複
数基設置することにより連続操業が可能である。
実施例
以下の組成の廃酸を本発明に従い処理した。
The present invention relates to a rhenium recovery method, and in particular, in recovering rhenium contained in waste acid using an ion exchange resin tower, it realizes repeated use of ion exchange resin and efficient recovery of rhenium. This invention relates to a method for recovering rhenium. Rhenium is a rare metal that is slightly associated with molybdenum ore and copper ore, but it is an important metal used as an additive element for catalysts, an additive element for thermocouples and super heat-resistant alloys, and materials for high-vacuum electron tubes. It is. Waste acid is one of the promising raw materials for industrially recovering rhenium. Waste acid is water-washed when sulfur dioxide gas generated in the smelting process of non-ferrous metals such as copper is used to produce sulfuric acid, and a portion of the sulfuric acid produced during that process is periodically extracted. be.
The rhenium contained in the raw ore is mixed into the waste acid along with other impurities. Other typical impurities include Hg, Mo, Bi, and As. There has not been much systematic research on the industrial recovery method of rhenium, but one promising method is to dissolve raw materials containing Re 2 O 7 in an aqueous solution and exchange them using an anion exchange resin. A method has been proposed in which rhenium is adsorbed onto a resin by a method and the adsorbed rhenium is eluted. The present inventors conducted systematic research on a rhenium recovery method based on the rhenium recovery method using the above-mentioned anion exchange resin, targeting waste acid as a rhenium recovery source. In this method, separation of accompanying impurities other than rhenium from rhenium,
Although there are many problems to be solved, such as recycling and repeated use of the resin, efficient elution of rhenium from the resin, and effective recovery of rhenium from the elution solution, extensive research has resulted in an industrially useful rhenium recovery method. was successfully established. In addition to Re, waste acid contains Hg, Mo, Bi, and As as impurities, but when waste acid is passed through a rhenium adsorption resin column, these impurities are adsorbed along with Re. It was found that among the adsorbed impurities, Hg is difficult to elute and deteriorates the Re adsorption rate during repeated use of the resin column. Therefore, it has been found that removing Hg in advance from the waste acid before passing it through the adsorption resin column is extremely advantageous for the smooth operation of the rhenium recovery system. The waste acid that has been deHg-removed in this way contains Re, Mo, Bi, and As.
, which are adsorbed by the resin. It has been found that Mo and As can be removed from the resin very effectively by passing sodium hydroxide through the resin column. In this way Mo and As
It is extremely convenient to first remove and desorb the resin from the resin because it facilitates subsequent operations. Next, the Re and Bi adsorbed on the resin and the remaining small amounts of Mo and As are eluted from the resin. The applicant has already proposed the use of a hydrochloric acid solution containing a metal chloride as an eluent to elute Re from an anion exchange resin (Japanese Patent Application No. 82576/1982), and this method is also adopted in this method. It is preferable to do so. The obtained post-elution solution mainly contains Re and Bi, with small amounts of Mo and As accompanying. It was found that the most effective way to recover Re from the elution solution was to recover Re in the form of sulfide. Almost all Be, Mo and As become sulfides, but
Since almost all of the Bi remains in the liquid after sulfurization, effective separation of Re and Bi becomes possible. The resin after elution can be regenerated for the next cycle. The above-mentioned Hg removal process, adsorption process, impurities (Mo,
As) By combining the removal process, elution process, sulfurization process, and regeneration process, Re in the waste acid can be efficiently recovered in the form of sulfide, and the resin can be used repeatedly. In this way, Re
This is the first time in this industry that an integrated process for collecting waste has been established. In summary, the present invention provides a method for recovering rhenium as rhenium sulfide from waste acids containing rhenium, mercury, molybdenum, bismuth, and arsenic, comprising (a) a demercury step for removing mercury from the waste acids; ) An adsorption step in which the mercury-depleted waste acid is passed through a resin tower containing an anion exchange resin to adsorb rhenium, molybdenum, bismuth, and arsenic to the resin; (iii) passing sodium hydroxide through the resin tower; (d) an elution step to mainly elute rhenium and bismuth from the resin; and (e) a sulfurization step to recover rhenium contained in the solution as rhenium sulfide after elution. (f) If necessary, a regeneration step of regenerating the resin is provided. The present invention will be explained in detail below. The drawing is a flow sheet of the method of the present invention. As previously mentioned, waste acids produced in non-ferrous metal smelting plants are an important source of rhenium recovery, containing between 5 and 60 mg/rhenium, depending on the source. However, waste acid also contains impurities, mainly Hg, Mo, Bi, and As, in addition to Re, and these impurities are an obstacle to the recovery of Re. The present invention basically uses an anion exchange resin.
Although it adsorbs Re, the above impurities are also adsorbed along with Re. Among the impurities, Mo, Bi, and As can be removed from the resin later, but Hg is extremely difficult to remove. Therefore, Hg accumulates in the resin, deteriorating the Re adsorption efficiency. Therefore, according to the present invention, mercury removal from waste acid is first measured. Demercury can be almost completely removed by passing the waste acid through a resin with strong adsorption power for mercury, such as a chelate resin such as Unitika's UR-2200H or a strongly basic anion exchange resin such as Amberlite IRA-400. can bring about Hg can be removed using a suitable removal agent such as hydrochloric acid. The mercury-depleted waste acid is then passed through a resin column containing an anion exchange resin. Naturally, anion exchange resins are required to have strong adsorption properties for rhenium, and for example, Diaion SA 20 A, Diaion PA316, and Diaion PA408 (product name of Mitsubishi Chemical Industries, Ltd.) are effective. It can be used for Rhenium is strongly adsorbed on anion exchange resins in amounts up to 10g/resin, and rhenium in waste acids has a
95% of it is adsorbed and collected. At the same time as rhenium is adsorbed, a portion of Mo and most of Bi and As in the waste acid are adsorbed. After flowing the waste acid, for example, 100g/ for cleaning the resin.
It is preferable to pass dilute sulfuric acid before and after the resin, etc., and then wash with washing water. The resin that has adsorbed Re, Mo, Bi and As is then switched to an impurity removal process, where the main
Mo and As are removed. 50 as a removal liquid
~200g/, preferably 60-150g/
NaOH solution is used. Although some loss of rhenium to the liquid after impurity removal is unavoidable, virtually all of the rhenium remains adsorbed on the resin.
More than 95% of Mo is removed and adsorbed As is also 90%
removed up close. A small amount of adsorbed Bi is also removed, but the substantial amount remains adsorbed. It is preferable to wash the resin with water upon completion of the impurity removal step. The resin column is then switched to an elution step in which the adsorbed components are desorbed from the resin. As the eluent, one must be selected that can easily desorb rhenium and other components strongly adsorbed to the resin, yet does not destroy the resin. In the present invention, since most of Mo and As have already been removed, the burden of the elution step is reduced. Although hydrochloric acid can be used as the eluent, the applicant has previously developed an elution method using a hydrochloric acid solution containing a metal chloride as the eluent, and has obtained good results.
Therefore, it is preferable to employ this method also in this method.
As the metal chloride, chlorides of copper, cadmium, or zinc are particularly preferable, and zinc is particularly preferable in consideration of the sulfurization treatment in the subsequent step. Zinc can be easily purified. 3～
A 9N hydrochloric acid concentration can be used. The amount of metal chloride added is sufficient at a level of 30 to 150 g/level. It is sufficient that the amount of liquid for elution is 3 to 9 times the volume of the resin. By adding a metal chloride, nearly 100% elution is possible with 1/4 the amount of liquid compared to an eluent using only hydrochloric acid, and sufficient elution is possible even without highly acidic hydrochloric acid. Substantial amounts of Re and Bi adsorbed on the resin during the elution process enter the solution after elution, and the remaining Mo
and As completely enters the solution after elution. Therefore, an elution solution containing Re and Bi as main constituents and accompanied by Mo and As is obtained. The ion exchange resin after elution is removed by using hydrochloric acid.
Since it is C1 type, it is necessary to use OH for repeated use.
A regeneration process is required to return it to the mold. Regeneration can be easily carried out by flowing sodium hydroxide or the like. Thereafter, the next cycle is started after thorough water washing. In order to recover rhenium from the solution after elution, it is advantageous to carry out a sulfurization treatment to recover rhenium as a sulfide. After elution, Re, Mo and As can be removed by blowing hydrogen sulfide gas into the solution while stirring.
Almost all of Bi becomes sulfide, but almost all of Bi remains in the liquid after sulfurization. Especially when the hydrochloric acid concentration is 3N or more, Bi
remains in the liquid. In this way, rhenium and bismuth can be separated. Calculating the S/Re molar ratio of the generated rhenium sulfide from the grade of the product, it is as follows:
It is thought to be a sulfide similar to Re 2 S 7 . The post-sulfurization solution can be reused as an eluent by removing H 2 S from the solution with air, but since Bi may accumulate, it is necessary to know the permissible concentration. The entire process cycle is thus completed. Continuous operation is possible by installing multiple resin towers. EXAMPLE A waste acid having the following composition was treated according to the present invention.
【表】
先ず、ユニチカ製キレート樹脂UR−2200Hに
よりHgを全量除去した。その後、150の陰イオ
ン交換樹脂（ダイヤイオンPA408）を収納する樹
脂塔３基を使用して吸着工程以降を実施した。各
工程条件及び分析結果を示す。
吸着工程
樹脂量：150
廃酸通液量：５m3
洗浄：100ｇ/硫酸 76
その後洗浄水 300
吸着樹脂[Table] First, all Hg was removed using Unitika's chelate resin UR-2200H. Thereafter, the adsorption step and subsequent steps were carried out using three resin towers containing 150 anion exchange resins (Diaion PA408). Each process condition and analysis result are shown. Adsorption process Resin amount: 150 Waste acid flow amount: 5 m 3 washing: 100 g/sulfuric acid 76 Then washing water 300 Adsorption resin
【表】 吸着後液【table】 Liquid after adsorption
【表】 不純物除去工程 除去液：2.5N NaOH 150 洗浄水：300 不純物除去後の樹脂【table】 Impurity removal process Removal liquid: 2.5N NaOH 150 Washing water: 300 Resin after removing impurities
【表】 不純物除去後液【table】 Liquid after removing impurities
【表】
溶離工程
溶離液：HCl（6N）＋ZnCl2（100ｇ/） 1200
洗浄水：300
溶離樹脂[Table] Elution process Eluent: HCl (6N) + ZnCl 2 (100g/) 1200
Washing water: 300 Elution resin
【表】 溶離後液【table】 After elution
【表】 硫化工程 吹込ガス：H2S 450 吹込時間：30分 撹拌：300rpm 回収硫化物（230ｇ）[Table] Sulfurization process Blow gas: H 2 S 450 Blow time: 30 minutes Stirring: 300 rpm Recovered sulfide (230 g)
【表】
再生工程
再生液：2.5N NaOH 600
洗浄水：300
こうして、出発廃酸中の150ｇのレニウムのう
ち138ｇを硫化物の形で高い純度において回収す
ることに成功した。
以上、本発明は斯界で始めて廃酸中からのレニ
ウム回収の為の効率的な一貫プロセスを確立した
ものであり、希少物質のレニウム製造にきわめて
有益な貢献を為すものである。[Table] Regeneration process Regeneration liquid: 2.5N NaOH 600 Washing water: 300 In this way, 138g of the 150g of rhenium in the starting waste acid was successfully recovered in the form of sulfide in high purity. As described above, the present invention is the first in the industry to establish an efficient integrated process for recovering rhenium from waste acid, and makes an extremely useful contribution to the production of rhenium, a rare substance.
図面は本発明方法のフローシートを示す。 The drawing shows a flow sheet of the method of the invention.
Claims (1)
砒素を含む廃酸からレニウムを硫化レニウムとし
て回収する方法であつて、 (イ) 廃酸から水銀を除去する脱水銀工程と、 (ロ) 脱水銀した廃酸を陰イオン交換樹脂を含む樹
脂塔に通液して、レニウム、モリブデン、ビス
マス及び砒素を該樹脂に吸着する吸着工程と、 (ハ) 前記樹脂塔に水酸化ナトリウムを通液して主
としてモリブデン及び砒素を除去する不純物除
去工程と、 (ニ) 樹脂から主としてレニウム及びビスマスを溶
離する溶離工程と、 (ホ) 溶離後液中に含まれるレニウムを硫化レニウ
ムとして回収する硫化工程と、 (ヘ) 必要に応じ、樹脂を再生する再生工程と を包含する廃酸からのレニウムの回収法。[Scope of Claims] 1. A method for recovering rhenium as rhenium sulfide from waste acids containing rhenium, mercury, molybdenum, bismuth, and arsenic, comprising: (a) a demercury step for removing mercury from waste acids; ) an adsorption step in which the mercury-depleted waste acid is passed through a resin column containing an anion exchange resin to adsorb rhenium, molybdenum, bismuth, and arsenic to the resin; (iii) sodium hydroxide is passed through the resin column; (d) an elution step to mainly elute rhenium and bismuth from the resin; and (e) a sulfurization step to recover rhenium contained in the solution as rhenium sulfide after elution. (f) A method for recovering rhenium from waste acid, which includes, if necessary, a regeneration step for regenerating the resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23623883A JPS60131828A (en) | 1983-12-16 | 1983-12-16 | Method for recovering rhenium from waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23623883A JPS60131828A (en) | 1983-12-16 | 1983-12-16 | Method for recovering rhenium from waste acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60131828A JPS60131828A (en) | 1985-07-13 |
| JPS6316340B2 true JPS6316340B2 (en) | 1988-04-08 |
Family
ID=16997826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23623883A Granted JPS60131828A (en) | 1983-12-16 | 1983-12-16 | Method for recovering rhenium from waste acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60131828A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012149285A (en) * | 2011-01-17 | 2012-08-09 | Pan Pacific Copper Co Ltd | Rhenium recovery method and system from waste acid |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703737B (en) * | 2012-06-28 | 2013-08-07 | 青岛阿库卡稀有金属有限公司 | Method for extracting and separating rhenium from rhenium-containing slag |
| JP6352702B2 (en) * | 2014-07-01 | 2018-07-04 | パンパシフィック・カッパー株式会社 | Method for producing perrhenic acid aqueous solution and method for producing potassium perrhenate, ammonium perrhenate and rhenium metal using the same |
-
1983
- 1983-12-16 JP JP23623883A patent/JPS60131828A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012149285A (en) * | 2011-01-17 | 2012-08-09 | Pan Pacific Copper Co Ltd | Rhenium recovery method and system from waste acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60131828A (en) | 1985-07-13 |
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