JPH033751B2 - - Google Patents
Info
- Publication number
- JPH033751B2 JPH033751B2 JP60204476A JP20447685A JPH033751B2 JP H033751 B2 JPH033751 B2 JP H033751B2 JP 60204476 A JP60204476 A JP 60204476A JP 20447685 A JP20447685 A JP 20447685A JP H033751 B2 JPH033751 B2 JP H033751B2
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- mercury
- solution
- recovering
- hydrochloric acid
- 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
- 229910052797 bismuth Inorganic materials 0.000 claims description 24
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 16
- 229910052753 mercury Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000003480 eluent Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011550 stock solution Substances 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
- Electrolytic Production Of Metals (AREA)
Description
発明の目的
本発明は、ビスマス及び又は水銀の回収法に関
する。
従来技術
従来ビスマス及び又は水銀の回収法で簡易にビ
スマス、水銀を液中から回収する方法がなかつ
た。
このため、例えば塩酸酸性の液でイオン交換樹
脂もしくはキレート樹脂に吸着した金属を溶離
し、目的金属を回収する方法においては、溶離液
を循環使用することが好ましいが、好ましい回収
方法がなかつたためこの再循環液中にビスマスが
濃縮残存した場合次のような問題を生じていた。
即ち、レニウムの回収法において、液中にビスマ
スが濃縮するとイオン交換樹脂の吸着性能が劣化
し、好ましい回収処理を行うことができなくな
る。
そこで、ビスマス及び又は水銀を系外に回収す
る好ましい方法が要望されていた。
また本発明は、上記の場合のみに限定されるこ
となく、液中のビスマス及び又は水銀を効率よく
回収する方法である。
発明の構成
即ち、本発明は、イオン交換樹脂からレニウム
を溶離した塩酸酸性の液中のビスマス及又は水銀
の回収法において、ビスマス及び又は水銀の含有
するに前記酸性液を電解液とし、該液を電解する
に際し、陽極側にH2Sおよび又はH2C2O4を吹き
込み、電解を行い、該液を硫酸根等の蓄積なく再
び溶離液として使用可能とすることを特徴とする
ビスマス及び又は水銀の回収法に関するものであ
る。
発明の作用
本発明で対象となる溶液は、塩酸酸性浴（１規
定以上）である。ビスマス、水銀の濃度は、特に
限定を要しない。例えば、レニウムをイオン交換
樹脂で回収する方法において、その溶離液を塩酸
酸性とし、レニウムを溶離回収するが、この場合
循環使用されると１〜５ｇ／のビスマス、及び
0.07〜0.04ｇ／の水銀が蓄積される。
このような液を処理する場合は、陽極に例えば
不溶性陽極を用いる。例えば、カーボン電極等で
ある。さらに陰極には、例えば銅板が用いられ
る。
本発明におけるH2Sおよび又はH2C2O4の添加
は、上記陽極側に添加する。これは、電解により
陽極に発生するCl2ガスが陽極面で式の反応に
より溶解し、陰極に析出するBiを式の反応
により溶解するためBiの回収率が低下するため
であり、H2SおよびH2C2O4等の還元剤を添加す
ることにより、HClOを式の反応により分解
することによりBiの回収率が大幅に高められる
ものと思われる。
Cl2＋H2O→HCl＋HClO …
3HClO＋2Bi→Bi2O3＋3HCl …
Bi2O3＋6HCl→2BiCl3＋3H2O …
HClO＋H2S→HCl＋S0＋H2O …
HClO＋H2C2O4→HCl＋2Co2＋H2O …
H2Sおよび又はH2C2O4の吹き込み量は、
H2C2O4については、反応当量の1.0倍〜1.7倍程
度、H2Sについては、電解液にCl2臭が着臭しな
いように吹き込むことが好ましい。
電解条件は、電流密度が30〜250A／m2、電解
液温度は常温、等の条件であることが好ましい。
発明の効果
以上のように本発明を実施することにより以下
の効果を有する。
(1) 溶液中のビスマス及び又は水銀を効率良く回
収できる。
(2) レニウムの回収工程において循環使用する塩
酸酸性溶離液から、ビスマスや水銀等を効率良
く回収できる。
(3) 銅電解液のキレート樹脂によるSb等の除去
工程において循環使用する塩酸酸性溶離液か
ら、ビスマス及び又は水銀を効率良く回収でき
る。
(4) 溶離液の有害成分の蓄積がなく繰り返し使用
が可能となる。
実施例 １
ビスマスを含む塩酸溶液にH2C2O4，H2Sをそ
れぞれ反応当量の1.5倍添加し、４条件で処理し
た結果、表１のごとくビスマスの回収が効率良く
行われた。
原液中のビスマスは、3.5〜3.66ｇ／のもの
を供試料として、約22時間後の液中のビスマス
は、0.93〜0.12ｇ／と効率の良い回収ができ
た。特にH2Sを添加したものがビスマスの回収率
が高い値を示した。
また同様に水銀の回収率も高い値を示した。
比較例 １
実施例１と同様な条件で、H2C2O4およびH2S
のいずれも添加しない条件で行つた結果、表２の
ごとくビスマスの回収率は22時間後であつても悪
い値であつた。
OBJECTS OF THE INVENTION The present invention relates to a method for recovering bismuth and/or mercury. Prior Art Conventionally, there has been no method for easily recovering bismuth and/or mercury from a liquid. For this reason, for example, in a method of recovering the target metal by eluting the metal adsorbed on an ion exchange resin or chelate resin with an acidic solution of hydrochloric acid, it is preferable to recycle the eluent, but there has been no suitable recovery method for this method. When bismuth remains concentrated in the recirculating liquid, the following problems occur.
That is, in the rhenium recovery method, if bismuth is concentrated in the liquid, the adsorption performance of the ion exchange resin deteriorates, making it impossible to perform a preferable recovery process. Therefore, there has been a need for a preferable method for recovering bismuth and/or mercury out of the system. Furthermore, the present invention is not limited to the above-mentioned cases, but is a method for efficiently recovering bismuth and/or mercury in a liquid. Components of the Invention That is, the present invention provides a method for recovering bismuth and/or mercury from an acidic solution of hydrochloric acid in which rhenium has been eluted from an ion exchange resin, in which the acidic solution containing bismuth and/or mercury is used as an electrolytic solution. When electrolyzing bismuth and bismuth, H 2 S and/or H 2 C 2 O 4 are blown into the anode side, electrolysis is performed, and the solution can be used again as an eluent without accumulation of sulfuric acid groups, etc. or related to mercury recovery methods. Effect of the Invention The solution targeted by the present invention is a hydrochloric acid bath (1 normal or more). The concentrations of bismuth and mercury are not particularly limited. For example, in a method for recovering rhenium using an ion exchange resin, the eluent is made acidic with hydrochloric acid to elute and recover rhenium, but in this case, when recycled, 1 to 5 g/bismuth and
0.07-0.04 g/mercury is accumulated. When processing such a liquid, an insoluble anode, for example, is used as the anode. For example, it is a carbon electrode. Furthermore, a copper plate, for example, is used for the cathode. In the present invention, H 2 S and/or H 2 C 2 O 4 is added to the anode side. This is because the Cl 2 gas generated at the anode due to electrolysis is dissolved on the anode surface by the reaction of the formula, and the Bi deposited on the cathode is dissolved by the reaction of the formula, resulting in a decrease in the recovery rate of Bi. It is thought that by adding a reducing agent such as H 2 C 2 O 4 and the like, the recovery rate of Bi can be greatly increased by decomposing HClO by the reaction of the formula. Cl 2 +H 2 O→HCl+HClO … 3HClO+2Bi→Bi 2 O 3 +3HCl … Bi 2 O 3 +6HCl→2BiCl 3 +3H 2 O … HClO+H 2 S→HCl+S 0 +H 2 O … HClO+H 2 C 2 O 4 →HCl+2Co 2 +H 2 O …The amount of H 2 S and or H 2 C 2 O 4 blown into
For H 2 C 2 O 4 , it is preferable to blow about 1.0 to 1.7 times the reaction equivalent, and for H 2 S, it is preferable to blow into the electrolyte so as not to give off a Cl 2 odor. The electrolytic conditions are preferably such that the current density is 30 to 250 A/m 2 and the electrolyte temperature is room temperature. Effects of the Invention By implementing the present invention as described above, the following effects can be obtained. (1) Bismuth and/or mercury in solution can be efficiently recovered. (2) Bismuth, mercury, etc. can be efficiently recovered from the hydrochloric acid acidic eluent that is recycled in the rhenium recovery process. (3) Bismuth and/or mercury can be efficiently recovered from the hydrochloric acid acidic eluent that is recycled in the process of removing Sb, etc. using a chelate resin in the copper electrolyte. (4) The eluent does not accumulate harmful components and can be used repeatedly. Example 1 H 2 C 2 O 4 and H 2 S were each added in an amount of 1.5 times the reaction equivalent to a hydrochloric acid solution containing bismuth, and as a result of treatment under four conditions, bismuth was efficiently recovered as shown in Table 1. The amount of bismuth in the stock solution was 3.5 to 3.66 g per sample, and after about 22 hours, the amount of bismuth in the solution was 0.93 to 0.12 g per sample, which was able to be efficiently recovered. Particularly, the one to which H 2 S was added showed a high bismuth recovery rate. Similarly, the recovery rate of mercury also showed a high value. Comparative Example 1 Under the same conditions as Example 1, H 2 C 2 O 4 and H 2 S
As a result of conducting the experiment without adding any of the above, as shown in Table 2, the recovery rate of bismuth was a poor value even after 22 hours.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
酸性の液中のビスマス及び又は水銀の回収法にお
いて、ビスマス及び又は水銀の含有するに前記酸
性液を電解液とし、該液を電解するに際し、陽極
側にH2Sおよび又はH2C2O4を吹き込み、電解を
行い、該液を硫酸根等の蓄積なく再び溶離液とし
て使用可能とすることを特徴とするビスマス及び
又は水銀の回収法。1. In a method for recovering bismuth and/or mercury from an acidic solution of hydrochloric acid that has eluted rhenium from an ion exchange resin, the acidic solution containing bismuth and/or mercury is used as an electrolytic solution, and when electrolyzing the solution, the anode side is A method for recovering bismuth and/or mercury, which comprises blowing in H 2 S and/or H 2 C 2 O 4 to perform electrolysis, and making the solution usable as an eluent again without accumulation of sulfuric acid radicals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204476A JPS62161989A (en) | 1985-09-18 | 1985-09-18 | Method for recovering bismuth and/or mercury |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204476A JPS62161989A (en) | 1985-09-18 | 1985-09-18 | Method for recovering bismuth and/or mercury |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62161989A JPS62161989A (en) | 1987-07-17 |
| JPH033751B2 true JPH033751B2 (en) | 1991-01-21 |
Family
ID=16491157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60204476A Granted JPS62161989A (en) | 1985-09-18 | 1985-09-18 | Method for recovering bismuth and/or mercury |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62161989A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52128804A (en) * | 1976-04-22 | 1977-10-28 | Stanley Electric Co Ltd | Electrolytic recovery of metal |
-
1985
- 1985-09-18 JP JP60204476A patent/JPS62161989A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52128804A (en) * | 1976-04-22 | 1977-10-28 | Stanley Electric Co Ltd | Electrolytic recovery of metal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62161989A (en) | 1987-07-17 |
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