JPS63137128A - Acid treatment of manganese nodule - Google Patents
Acid treatment of manganese noduleInfo
- Publication number
- JPS63137128A JPS63137128A JP61282930A JP28293086A JPS63137128A JP S63137128 A JPS63137128 A JP S63137128A JP 61282930 A JP61282930 A JP 61282930A JP 28293086 A JP28293086 A JP 28293086A JP S63137128 A JPS63137128 A JP S63137128A
- Authority
- JP
- Japan
- Prior art keywords
- hydrazine
- nodule
- reducing agent
- carbonaceous material
- carbon material
- 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.)
- Pending
Links
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 16
- 229910052748 manganese Inorganic materials 0.000 title claims description 16
- 239000011572 manganese Substances 0.000 title claims description 16
- 238000010306 acid treatment Methods 0.000 title description 4
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 abstract description 11
- 239000000654 additive Substances 0.000 abstract description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003610 charcoal Substances 0.000 abstract description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 abstract description 2
- 239000012493 hydrazine sulfate Substances 0.000 abstract description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 abstract description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明はマンガン団塊に含まれるコバルト、ニッケル、
銅などの有価金属を酸処理により抽出する方法である。[Detailed Description of the Invention] [Technical Field] The present invention relates to cobalt, nickel, and cobalt contained in manganese nodules.
This is a method of extracting valuable metals such as copper through acid treatment.
〔従来技術）
マンガン団塊の製錬法については、すでに溶錬−浸出法
、焙焼−浸出法、直接浸出法などいくつかの方法が提案
されている。溶練−浸出法は１３００℃〜１４００℃の
高温でマンガン団塊を溶融する工程がふくまれており、
エネルギー消費が大きい、焙焼−浸出法も還元焙焼、硫
酸化焙焼、塩化焙焼などの焙焼工程を経て浸出するが選
択性などの点でそれぞれ一長一短がある。直接浸出法に
は塩酸あるいは硫酸による処理法があるが、前者は耐食
性容器の必要性や塩素の副生による処理が障害となる。[Prior Art] Several methods have already been proposed for smelting manganese nodules, including the smelting-leaching method, the roasting-leaching method, and the direct leaching method. The smelting-leaching method includes a process of melting manganese nodules at a high temperature of 1300°C to 1400°C.
The roasting-leaching method, which consumes a large amount of energy, also involves leaching through roasting processes such as reduction roasting, sulfation roasting, and chloride roasting, but each has advantages and disadvantages in terms of selectivity. Direct leaching methods include treatment with hydrochloric acid or sulfuric acid, but the former is hampered by the need for corrosion-resistant containers and by-products of chlorine.
後者は取扱いは比較的簡単ではあるが、有価金属の抽出
率を高めるには硫酸濃度を高くするか、オートクレーブ
などによる高温高圧装置を必要とする。Although the latter is relatively easy to handle, increasing the extraction rate of valuable metals requires either increasing the sulfuric acid concentration or using a high-temperature, high-pressure device such as an autoclave.
本発明は、簡単な方法により有価金属の抽出率を高める
方法を提供することを目的とする。An object of the present invention is to provide a method for increasing the extraction rate of valuable metals using a simple method.
本発明はマンガン団塊の処理に上記のような特別の焙焼
工程や加圧浸出工程を必要とせず、マンガン団塊を硫酸
処理する前に、活性炭などの炭素材又は炭素材とヒドラ
ジン系あるいはヒドロキシルアミン系還元剤を添加する
ことにより、マンガン団塊からコバルト、ニッケル、銅
などの有価金属を効率よく抽出するものであり次のよう
な特長がある。The present invention does not require the above-mentioned special roasting process or pressure leaching process to treat manganese nodules, and before treating manganese nodules with sulfuric acid, a carbon material such as activated carbon or a carbon material and a hydrazine-based or hydroxylamine By adding a system reducing agent, valuable metals such as cobalt, nickel, and copper can be efficiently extracted from manganese nodules, and it has the following features.
（１）マンガン団塊を硫酸で浸出処理する際に活性炭な
どの炭素材又は炭素材とヒドラジン系還元剤あるいはヒ
ドロキシルアミン系還元剤を添加した場合には、添加剤
のない場合と比較してコバルト、ニッケル、銅、とくに
コバルトの抽出率が高くなる。(1) When a carbon material such as activated carbon or a carbon material and a hydrazine-based reducing agent or a hydroxylamine-based reducing agent are added when manganese nodules are leached with sulfuric acid, cobalt, The extraction rate of nickel, copper, and especially cobalt increases.
（２）添加する炭素材は活性炭、木炭などでいずれもマ
ンガン団塊から有価金属の抽出率を高くする。粒度は１
００〜２００メツシユのものが望ましいが、２０〜４８
メツシユのものでも有価金属の抽出には効果がある。た
だし、この場合には抽出速度は多少低下する。炭素材の
添加量は炭素材の種類により異なるが、マンガン団塊１
０ｇ／ｊ！当たり０．５〜２ｇ程度が適当である。(2) The carbon material to be added is activated carbon, charcoal, etc., both of which increase the extraction rate of valuable metals from manganese nodules. Particle size is 1
00 to 200 mesh is preferable, but 20 to 48
Methushi's products are also effective in extracting valuable metals. However, in this case, the extraction speed will decrease somewhat. The amount of carbon material added varies depending on the type of carbon material, but manganese nodules 1
0g/j! Approximately 0.5 to 2 g per serving is appropriate.
（３）炭素材に併用される還元剤の中、ヒドラジン系と
してヒドラジン水和物、硫酸ヒドラジンが、ヒドロキシ
ルアミン系として硫酸ヒドロキシルアンモニウム、塩酸
ヒドロキシルアンモニウムなどが使用される。(3) Among the reducing agents used in combination with the carbon material, hydrazine hydrate and hydrazine sulfate are used as hydrazine-based reducing agents, and hydroxylammonium sulfate and hydroxylammonium hydrochloride are used as hydroxylamine-based reducing agents.
（４）第１段の硫酸処理によりマンガン団塊からニッケ
ル、銅の大部分を抽出したあと、第２段の硫酸処理で炭
素材または炭素材と還元剤を併用して添加することによ
りコバルトの大部分を抽出し、抽出段階でニッケル、銅
とコバルトを分離することができる。(4) After most of the nickel and copper are extracted from the manganese nodules in the first stage of sulfuric acid treatment, a large amount of cobalt is extracted by adding carbon material or a combination of carbon material and reducing agent in the second stage of sulfuric acid treatment. The nickel, copper and cobalt can be separated in the extraction stage.
本発明で使用されたマンガン団塊はハワイ諸島西方で採
取されたもので、マンガン２１．５％、銅０゜７９％、
ニッケル０．７１％、コバルト０．１７％を有する。The manganese nodules used in the present invention were collected west of the Hawaiian Islands, and contained 21.5% manganese, 0.79% copper,
It contains 0.71% nickel and 0.17% cobalt.
これを１００〜２００メツシユに粒度を調製したのち、
この２ｇを所定頃度の硫酸溶液２００ｒｒｌ！をエルレ
ンマイヤーフラスコに装入し、添加剤として炭素材ある
いは炭素材と還元剤を添加し、所定温度に保ちながらか
くはん操作を行った。この実験結果を表１〜３に示す、
この実験結果は本発明を限定するものではない。After adjusting the particle size to 100 to 200 mesh,
Add this 2g to 200rrl of a sulfuric acid solution of the specified temperature! was charged into an Erlenmeyer flask, a carbon material or a carbon material and a reducing agent were added as additives, and stirring was performed while maintaining a predetermined temperature. The experimental results are shown in Tables 1 to 3.
This experimental result is not intended to limit the invention.
（抽出率と反応時間の関係〕
マンガン団塊２ｇ／２００ｍ Ａ’ 、 Ｈ２Ｓ０ａ
１．５ａ＋ｏｌ／ １温度 ６０°Ｃ
（１）添加剤のない場合
表１
（２）炭素材（市販粒状活性炭）
０．４ｇ／２００ｍ１ 添加の場合
表２
（３）炭素材（市販粒状活性炭） ０．４ｇ／２００
ｎ＋ １２及び硫酸ヒドラジン０．２ｇ／２００糟Ｅ添
加の場合
表３
〔抽出率と硫酸濃度の関係〕
マンガン団塊２ｇ／２００閘２．温度６０°Ｃ，１時間
（１）添加剤のない場合
表 ４
（２）炭素材（市販粒状活性炭） ０．４ｇ／２００
＋ Ａ添加の場合
表 ５
（３）炭素材（市販粒状活性炭） ０．４ｇ／２００
ｍ ｌ及び硫酸ヒドラジン０．２ｇ／２０抛ｌ添加の場
合
表６
〔抽出率と還元剤の種類の関係〕
マンガン団塊： ２ｇ／２００ｎ＋ １ 、温度６０”
ＣＨｘＳＯａ： １．５ｍｏ Ｉｔ ／ ｌ 、攪拌１
時間還元剤 ０．２ｇ、炭素剤０．４ｇ／２００ｍ １
表７
〔効果〕
以上のように、本発明によれば、簡単な操作により、有
価金属の高い抽出率を得ることができる。(Relationship between extraction rate and reaction time) Manganese nodules 2g/200m A', H2S0a
1.5a+ol/1 Temperature 60°C (1) Table 1 without additives (2) Table 2 with carbon material (commercially available granular activated carbon) 0.4g/200m1 (3) Carbon material (commercially available granular activated carbon) 0 .4g/200
Table 3 [Relationship between extraction rate and sulfuric acid concentration] Manganese nodules 2g/200 sieve 2. Temperature 60°C, 1 hour (1) Table 4 without additives (2) Carbon material (commercially available granular activated carbon) 0.4g/200
+ In the case of A addition Table 5 (3) Carbon material (commercially available granular activated carbon) 0.4g/200
Table 6 [Relationship between extraction rate and type of reducing agent] Manganese nodules: 2g/200n+1, temperature 60"
CHxSOa: 1.5mo It/l, stirring 1
Time reducing agent 0.2g, carbon agent 0.4g/200m 1
Table 7 [Effects] As described above, according to the present invention, a high extraction rate of valuable metals can be obtained with a simple operation.
Claims (1)
とヒドラジン系あるいはヒドロキシルアミン系還元剤を
添加することによりコバルト、ニッケル、銅などの有価
金属を抽出する方法。A method of extracting valuable metals such as cobalt, nickel, and copper by adding a carbon material or a carbon material and a hydrazine-based or hydroxylamine-based reducing agent during acid leaching treatment of manganese nodules.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61282930A JPS63137128A (en) | 1986-11-27 | 1986-11-27 | Acid treatment of manganese nodule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61282930A JPS63137128A (en) | 1986-11-27 | 1986-11-27 | Acid treatment of manganese nodule |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63137128A true JPS63137128A (en) | 1988-06-09 |
Family
ID=17658954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61282930A Pending JPS63137128A (en) | 1986-11-27 | 1986-11-27 | Acid treatment of manganese nodule |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63137128A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009197298A (en) * | 2008-02-25 | 2009-09-03 | Sumitomo Metal Mining Co Ltd | Wet-smelting method for nickel-oxide ore |
| CN103882226A (en) * | 2014-04-14 | 2014-06-25 | 北京矿冶研究总院 | Economic, clean and simple method for leaching cobalt from high-valence cobalt oxide |
| CN107513613A (en) * | 2017-08-31 | 2017-12-26 | 广东佳纳能源科技有限公司 | A kind of technique of normal temperature reducing leaching Africa heterogenite |
| CN107739845A (en) * | 2017-08-31 | 2018-02-27 | 广东佳纳能源科技有限公司 | A kind of cleaning procedure of reducing leaching Africa heterogenite |
| CN113227417A (en) * | 2018-12-21 | 2021-08-06 | 尤米科尔公司 | Method for recovering metals from polymetallic nodules |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5776136A (en) * | 1980-10-31 | 1982-05-13 | Mitsui Mining & Smelting Co Ltd | Wet processing of manganese nodule |
-
1986
- 1986-11-27 JP JP61282930A patent/JPS63137128A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5776136A (en) * | 1980-10-31 | 1982-05-13 | Mitsui Mining & Smelting Co Ltd | Wet processing of manganese nodule |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009197298A (en) * | 2008-02-25 | 2009-09-03 | Sumitomo Metal Mining Co Ltd | Wet-smelting method for nickel-oxide ore |
| CN103882226A (en) * | 2014-04-14 | 2014-06-25 | 北京矿冶研究总院 | Economic, clean and simple method for leaching cobalt from high-valence cobalt oxide |
| CN107513613A (en) * | 2017-08-31 | 2017-12-26 | 广东佳纳能源科技有限公司 | A kind of technique of normal temperature reducing leaching Africa heterogenite |
| CN107739845A (en) * | 2017-08-31 | 2018-02-27 | 广东佳纳能源科技有限公司 | A kind of cleaning procedure of reducing leaching Africa heterogenite |
| CN113227417A (en) * | 2018-12-21 | 2021-08-06 | 尤米科尔公司 | Method for recovering metals from polymetallic nodules |
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