JPS621578B2 - - Google Patents
Info
- Publication number
- JPS621578B2 JPS621578B2 JP9894383A JP9894383A JPS621578B2 JP S621578 B2 JPS621578 B2 JP S621578B2 JP 9894383 A JP9894383 A JP 9894383A JP 9894383 A JP9894383 A JP 9894383A JP S621578 B2 JPS621578 B2 JP S621578B2
- Authority
- JP
- Japan
- Prior art keywords
- valuable metals
- aqueous solution
- vanadium
- molybdenum
- uranium
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 150000002739 metals Chemical class 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 229910052770 Uranium Inorganic materials 0.000 claims description 18
- 239000003463 adsorbent Substances 0.000 claims description 18
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052720 vanadium Inorganic materials 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000013535 sea water Substances 0.000 claims description 9
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 239000012267 brine Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000003795 desorption Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910003174 MnOOH Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は希薄水溶液からの有価金属の回収方法
に関し、さらに詳しくは吸着剤としてオキシ水酸
化マンガンを用いて有価金属を効率よく極めて容
易に回収する方法に関するものである。
近年、有価金属資源の有効利用及び環境汚染防
止の両面から、溶液中に希薄な状態で存在してい
る有価金属を効率よく回収することが注目されて
いる。
ところで、ウラン、バナジウム、モリブデンな
どの有価金属を含む希薄水溶液から、前記有価金
属を回収するための吸着剤として、これまで多く
の金属水酸化物が知られている。しかしながら、
従来用いられてきた金属水酸化物は、分離効率、
安定度、価格などの点で必ずしも満足しうるもの
ではない。
本発明者らは、このような事情に鑑み、有価金
属を含む希薄水溶液、特にウラン、バナジウム及
びモリブデンなどの有価金属を含む海水や地下か
ん水などから、前記有価金属をそれぞれ効率よく
極めて容易に分離回収する方法を提供すべく鋭意
研究を重ねた結果、吸着剤としてオキシ水酸化マ
ンガン（MnOOH）を用いることによりその目的
を達成しうること、またこのオキシ水酸化マンガ
ンは、従来このような吸着剤として用いられた例
がないこと、さらにこのものは安価であり、かつ
空気中や水溶液中において極めて安定であること
などを見出し、この知見に基づいて本発明を完成
するに至つた。
すなわち、本発明は、有価金属を含む希薄水溶
液から該有価金属を分離回収するに当り、吸収剤
としてオキシ水酸化マンガンを用いることを特徴
とする希薄水溶液からの有価金属の回収方法、及
びウラン、バナジウム及びモリブデンを含む希薄
水溶液から前記有価金属をそれぞれ分離回収する
に当り、吸着剤としてオキシ水酸化マンガンを用
い前記有価金属を吸着させたのち、まず炭酸水素
ナトリウム水溶液を用いてウランを溶離し、次い
でPH9.5〜10の水酸化アルカリ水溶液を用いてモ
リブデンを溶離し、さらにPH12以上の水酸化アル
カリ水溶液を用いてバナジウムを溶離することを
特徴とする希薄水溶液からの有価金属の回収方法
を提供するものである。
本発明方法において用いる吸着剤は、オキシ水
酸化マンガンであつて、このものは、その調製時
に適当な酸化剤を用いて価マンガンを価マン
ガンに酸化し安定した化合物形態としたものであ
り、空気中や海水中においても極めて安定であ
る。
本発明方法においては、有価金属を含む希薄水
溶液として、ウラン、バナジウム及びモリブデン
を含む希薄水溶液、例えば海水や地下かん水が好
ましく用いられる。この希薄水溶液に前記吸着剤
を、該水溶液中の有価金属濃度によつて異なる
が、通常該水溶液に対して0.01〜１重量％添加し
て、ウラン、バナジウム及びモリブデンを十分吸
着せしめたのち、吸着剤を水溶液から分離する。
次いで、まず炭酸水素ナトリウム水溶液を用いて
ウランを溶離する。この炭酸水素ナトリウム水溶
液は、通常0.5M濃度程度のもの（PH8.2）が好ま
しく用いられる。次にPH9.5〜10の水酸化アルカ
リ水溶液を用いてモリブデンを溶離し、さらにPH
12以上の水酸化アルカリ水溶液を用いてバナジウ
ムを溶離し回収する。
あるいは、バインダーを用いて造粒して成る粒
状吸着剤を充てんしたカラムに、前記有価金属を
含む希薄水溶液を通液することによつて該有価金
属を吸着せしめたのち、前記と同様にして各有価
金属をそれぞれ溶離し回収することもできる。
本発明の吸着剤は、ウラン、バナジウム、モリ
ブデンに対し、それぞれ高い吸着率を示す適切な
PH領域を有している（第１図、第２図、第３図参
照）。すなわち、モリブデンについては弱酸性領
域（PH３〜６）で、ウラン及びバナジウムについ
てはPH５〜９の範囲で高い吸着率を示す。したが
つて、本発明の回収方法は海水（PH7.9〜8.3）中
のウラン及びバナジウムを分離回収するのに特に
適しており、工業的に極めて有益な方法である。
次に実施例によつて本発明をさらに詳細に説明
する。
実施例 １
オキシ水酸化マンガンを次のようにして調製し
た。
4.4ｇの硫酸マンガン（）を750mlの水に溶解
し、３重量％過酸化水素水68mlを加え、さらに
0.2Mアンモニア水100mlを一度に加えて加熱す
る。約４分間沸とうさせたのち、冷却後ろ過し、
次いで洗液中に硫酸イオンが認められなくなるま
で水洗する。このようにして得られたオキシ水酸
化マンガンは、結晶性の回折パターン（マンガナ
イト）を示し、γ−MnOOHである。
このオキシ水酸化マンガン200mgを２の海水
（ウラン2.8ppb、バナジウム1.7ppb、モリブデン
10ppb、PH8.1）中に添加し、２日間かきまぜ
た。
そのときの各元素の吸着量及び吸着率を第１表
に示す。
The present invention relates to a method for recovering valuable metals from a dilute aqueous solution, and more particularly to a method for efficiently and extremely easily recovering valuable metals using manganese oxyhydroxide as an adsorbent. In recent years, attention has been paid to the efficient recovery of valuable metals present in a diluted state in solutions, both from the standpoint of effective use of valuable metal resources and prevention of environmental pollution. By the way, many metal hydroxides have been known as adsorbents for recovering valuable metals such as uranium, vanadium, and molybdenum from dilute aqueous solutions containing the metals. however,
Conventionally used metal hydroxides have low separation efficiency,
It is not always satisfactory in terms of stability, price, etc. In view of these circumstances, the present inventors have devised a method for efficiently and extremely easily separating each of the valuable metals from a dilute aqueous solution containing the valuable metals, particularly from seawater or underground brine containing valuable metals such as uranium, vanadium, and molybdenum. As a result of extensive research in order to provide a method for recovery, it was discovered that this purpose could be achieved by using manganese oxyhydroxide (MnOOH) as an adsorbent, and that manganese oxyhydroxide was not used in conventional adsorbents such as MnOOH. They found that there is no example of this product being used as a compound, that it is inexpensive, and that it is extremely stable in the air or in an aqueous solution.Based on these findings, the present invention was completed. That is, the present invention provides a method for recovering valuable metals from a dilute aqueous solution, which is characterized in that manganese oxyhydroxide is used as an absorbent in separating and recovering valuable metals from a dilute aqueous solution containing uranium. In separating and recovering each of the valuable metals from a dilute aqueous solution containing vanadium and molybdenum, the valuable metals are adsorbed using manganese oxyhydroxide as an adsorbent, and then uranium is first eluted using an aqueous sodium hydrogen carbonate solution. Provided is a method for recovering valuable metals from a dilute aqueous solution, characterized in that molybdenum is then eluted using an aqueous alkali hydroxide solution with a pH of 9.5 to 10, and vanadium is further eluted using an aqueous alkali hydroxide solution with a pH of 12 or higher. It is something to do. The adsorbent used in the method of the present invention is manganese oxyhydroxide, which is obtained by oxidizing valence manganese to valence manganese using an appropriate oxidizing agent during its preparation, and converting it into a stable compound form. It is extremely stable even in water and seawater. In the method of the present invention, a dilute aqueous solution containing uranium, vanadium, and molybdenum, such as seawater or underground brine, is preferably used as the dilute aqueous solution containing valuable metals. The adsorbent is usually added to this dilute aqueous solution in an amount of 0.01 to 1% by weight (depending on the concentration of valuable metals in the aqueous solution) to sufficiently adsorb uranium, vanadium, and molybdenum. The agent is separated from the aqueous solution.
Next, uranium is first eluted using an aqueous sodium bicarbonate solution. This aqueous sodium hydrogen carbonate solution is preferably used, usually at a concentration of about 0.5M (PH8.2). Next, molybdenum is eluted using an aqueous alkali hydroxide solution with a pH of 9.5 to 10, and then
Vanadium is eluted and recovered using an aqueous alkali hydroxide solution of 12 or more. Alternatively, the valuable metals are adsorbed by passing a dilute aqueous solution containing the valuable metals through a column filled with a granular adsorbent granulated using a binder, and then each of the valuable metals is adsorbed in the same manner as above. Valuable metals can also be individually eluted and recovered. The adsorbent of the present invention is a suitable adsorbent that exhibits high adsorption rates for uranium, vanadium, and molybdenum.
It has a PH region (see Figures 1, 2, and 3). That is, molybdenum exhibits a high adsorption rate in a weakly acidic region (PH3 to 6), and uranium and vanadium exhibit a high adsorption rate in a pH range of 5 to 9. Therefore, the recovery method of the present invention is particularly suitable for separating and recovering uranium and vanadium in seawater (PH7.9 to 8.3), and is an extremely useful method industrially. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Manganese oxyhydroxide was prepared as follows. Dissolve 4.4g of manganese sulfate () in 750ml of water, add 68ml of 3% by weight hydrogen peroxide solution, and
Add 100ml of 0.2M ammonia water at once and heat. After boiling for about 4 minutes, cool and filter.
Next, the sample is washed with water until no sulfate ions are observed in the washing solution. The manganese oxyhydroxide thus obtained exhibits a crystalline diffraction pattern (manganite) and is γ-MnOOH. 200mg of this manganese oxyhydroxide was added to 2 seawater (uranium 2.8ppb, vanadium 1.7ppb, molybdenum
10ppb, PH8.1) and stirred for 2 days. Table 1 shows the adsorption amount and adsorption rate of each element at that time.
【表】
次に、各元素を吸着した吸着剤200mgを50mlの
0.5M炭酸水素ナトリウム水溶液中に添加し、２
日間かきまぜてウランを脱着し、次いでこの吸着
剤を50mlのPH10の水酸化ナトリウム水溶液中に添
加し、２日間かきまぜてモリブデンを脱着した。
さらに、この吸着剤を50mlのPH12.5の水酸化ナト
リウム水溶液中に添加し、２日間かきまぜてバナ
ジウムを脱着した。各段階におけるそれぞれの脱
着率を求め、第２表に示した。
この表から判るように、前記の脱着条件におい
て、各元素とも高い脱着率及び分離性を示した。[Table] Next, add 200 mg of the adsorbent that adsorbed each element to 50 ml of the adsorbent.
Added to 0.5M sodium hydrogen carbonate aqueous solution,
The adsorbent was stirred for 2 days to desorb uranium, and then this adsorbent was added to 50 ml of an aqueous sodium hydroxide solution with a pH of 10, and the mixture was stirred for 2 days to desorb molybdenum.
Furthermore, this adsorbent was added to 50 ml of an aqueous sodium hydroxide solution with a pH of 12.5, and the mixture was stirred for 2 days to desorb vanadium. The desorption rates at each stage were determined and shown in Table 2. As can be seen from this table, under the above desorption conditions, each element exhibited high desorption rates and separation properties.
【表】
実施例 ２
実施例１で調製したオキシ水酸化マンガン200
mgを海水２中に添加し、PHを水酸化ナトリウム
及び塩酸で調節したのち、２日間かきまぜた。そ
のときのPHと、ウラン、バナジウム及びモリブデ
ンの吸着率との関係を、それぞれ第１図、第２図
及び第３図に示した。
これらの図から明らかなように、各元素にはそ
れぞれ吸着に適したPH範囲があることが判る。[Table] Example 2 Manganese oxyhydroxide 200 prepared in Example 1
mg was added to seawater 2, the pH was adjusted with sodium hydroxide and hydrochloric acid, and the mixture was stirred for 2 days. The relationships between the pH at that time and the adsorption rates of uranium, vanadium, and molybdenum are shown in Figures 1, 2, and 3, respectively. As is clear from these figures, each element has its own PH range suitable for adsorption.
第１図、第２図及び第３図は、それぞれ本発明
の吸着剤を海水中に添加した場合のウラン、バナ
ジウム及びモリブデンの吸着率とPHとの関係を示
すグラフである。
FIG. 1, FIG. 2, and FIG. 3 are graphs showing the relationship between the adsorption rate of uranium, vanadium, and molybdenum and PH when the adsorbent of the present invention is added to seawater, respectively.
Claims (1)
分離回収するに当り、吸着剤としてオキシ水酸化
マンガンを用いることを特徴とする希薄水溶液か
らの有価金属の回収方法。 ２ 有価金属を含む希薄水溶液が海水及び地下か
ん水である特許請求の範囲第１項記載の方法。 ３ 有価金属がウラン、バナジウム及びモリブデ
ンである特許請求の範囲第１項又は第２項記載の
方法。 ４ ウラン、バナジウム及びモリブデンを含む希
薄水溶液から前記有価金属をそれぞれ分離回収す
るに当り、吸着剤としてオキシ水酸化マンガンを
用い前記有価金属を吸着させたのち、まず炭酸水
素ナトリウム水溶液を用いてウランを溶離し、次
いでPH9.5〜10の水酸化アルカリ水溶液を用いて
モリブデンを溶離し、さらにPH12以上の水酸化ア
ルカリ水溶液を用いてバナジウムを溶離すること
を特徴とする希薄水溶液からの有価金属の回収方
法。 ５ ウラン、バナジウム及びモリブデンを含む希
薄水溶液が海水及び地下かん水である特許請求の
範囲第４項記載の方法。[Scope of Claims] 1. A method for recovering valuable metals from a dilute aqueous solution, which comprises using manganese oxyhydroxide as an adsorbent in separating and recovering valuable metals from a dilute aqueous solution containing the valuable metals. 2. The method according to claim 1, wherein the dilute aqueous solution containing valuable metals is seawater or underground brine. 3. The method according to claim 1 or 2, wherein the valuable metals are uranium, vanadium, and molybdenum. 4. In separating and recovering each of the valuable metals from a dilute aqueous solution containing uranium, vanadium, and molybdenum, the valuable metals are adsorbed using manganese oxyhydroxide as an adsorbent, and then uranium is first removed using an aqueous sodium bicarbonate solution. Recovery of valuable metals from a dilute aqueous solution characterized by eluating molybdenum using an aqueous alkali hydroxide solution with a pH of 9.5 to 10, and further eluting vanadium using an aqueous alkali hydroxide solution with a pH of 12 or higher. Method. 5. The method according to claim 4, wherein the dilute aqueous solution containing uranium, vanadium and molybdenum is seawater or underground brine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9894383A JPS59227728A (en) | 1983-06-03 | 1983-06-03 | Recovery of valuable metal form dilute aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9894383A JPS59227728A (en) | 1983-06-03 | 1983-06-03 | Recovery of valuable metal form dilute aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59227728A JPS59227728A (en) | 1984-12-21 |
| JPS621578B2 true JPS621578B2 (en) | 1987-01-14 |
Family
ID=14233186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9894383A Granted JPS59227728A (en) | 1983-06-03 | 1983-06-03 | Recovery of valuable metal form dilute aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59227728A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0327974U (en) * | 1989-07-25 | 1991-03-20 |
-
1983
- 1983-06-03 JP JP9894383A patent/JPS59227728A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0327974U (en) * | 1989-07-25 | 1991-03-20 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59227728A (en) | 1984-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0688277A (en) | Lithium recovering method and electrode used therefor | |
| JPS61283342A (en) | Lithium adsorbent and its preparation | |
| JPH0626661B2 (en) | Granular lithium adsorbent and lithium recovery method using the same | |
| CA3066212C (en) | Method of adsorbing an anion of interest from an aqueous solution | |
| JPS621578B2 (en) | ||
| JP3321602B2 (en) | Selective lithium separating agent and method for producing the same | |
| JP2531790B2 (en) | Lithium recovery method | |
| JPH038443A (en) | Lithium adsorbent and method for recovering lithium with the same | |
| JPH0357814B2 (en) | ||
| JP4000370B2 (en) | Method for removing nitrate ions from various anion-containing aqueous solutions and method for recovering nitrate ions | |
| JPH0632762B2 (en) | Method for desorbing lithium from manganese oxide-based lithium adsorbent | |
| JP3412003B2 (en) | Novel lithium adsorbent and method for producing the same | |
| JPH0626660B2 (en) | New manufacturing method of lithium adsorbent | |
| JP2641239B2 (en) | Silver adsorbent and method of using the same | |
| JPH11253798A (en) | Method for regeneration of radium adsorbent | |
| JPS59195525A (en) | Recovering method of lithium from aqueous dilute solution | |
| JPS64328B2 (en) | ||
| JPS5855084B2 (en) | Metal ion adsorbent and recovery method | |
| JPS59132986A (en) | Separation of borate ion | |
| JPS58156530A (en) | Recovering method of lithium from gerothermal water and brine | |
| JP2850309B2 (en) | Method for producing lithium adsorbent | |
| JPH10182147A (en) | How to recover lithium | |
| JPS6346009B2 (en) | ||
| CN119771382A (en) | Preparation method and application of iron-manganese-titanium composite metal adsorbent for removing thallium | |
| JPH0687970B2 (en) | Lithium adsorbent and method for producing the same |