JPS6386824A - Method for recovering valuable metal from manganese nodule or cobalt crust by separation - Google Patents
Method for recovering valuable metal from manganese nodule or cobalt crust by separationInfo
- Publication number
- JPS6386824A JPS6386824A JP61229509A JP22950986A JPS6386824A JP S6386824 A JPS6386824 A JP S6386824A JP 61229509 A JP61229509 A JP 61229509A JP 22950986 A JP22950986 A JP 22950986A JP S6386824 A JPS6386824 A JP S6386824A
- Authority
- JP
- Japan
- Prior art keywords
- valuable components
- eluate
- filtrate
- cobalt
- separated
- 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.)
- Granted
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 39
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 241001283150 Terana caerulea Species 0.000 title claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 title claims description 8
- 239000002184 metal Substances 0.000 title claims description 8
- 238000000926 separation method Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 title description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009854 hydrometallurgy Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000011656 manganese carbonate Substances 0.000 abstract description 3
- 235000006748 manganese carbonate Nutrition 0.000 abstract description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract description 3
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 101100500679 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cot-3 gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- QKMGIVQNFXRKEE-UHFFFAOYSA-L sodium;copper(1+);3-[(n-prop-2-enyl-c-sulfidocarbonimidoyl)amino]benzoate Chemical compound [Na+].[Cu+].[O-]C(=O)C1=CC=CC(NC([S-])=NCC=C)=C1 QKMGIVQNFXRKEE-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は深海底マンガンノジュールまたはコバルトクラ
ストから、銅、ニッケル、コバルト等の有価金属を回収
する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for recovering valuable metals such as copper, nickel, and cobalt from deep-sea manganese nodules or cobalt crusts.
マンガンノジュールやコバルトクラストからＣｕ、 Ｎ
ｉ、 Ｃｏなどの有価金属を分離回収する方法は種々試
みられており、例えばマンガンノジュールからこれらを
回収する方法としては次の方法が知られているが、未だ
工業化されるに到っていない。Cu, N from manganese nodules and cobalt crust
Various methods have been tried to separate and recover valuable metals such as i and Co. For example, the following method is known as a method for recovering these from manganese nodules, but it has not yet been industrialized.
例えば（１）ｉイオンの存在下でＣＯガスによって湿式
還元浸出を行いＭｎをＭｎＣＯ３として除き、ＣＬＩ
＋ Ｎ Ｉ ＋Ｃｏを回収する方法。For example, (1) perform wet reduction leaching with CO gas in the presence of i ions to remove Mn as MnCO3, and CLI
+N I +Method of recovering Co.
（２）２４５℃、３５ａｔｍの高温、高圧下で３０％硫
酸によってＣｕ、Ｎｉ、Ｃｏを浸出する方法。(2) A method of leaching Cu, Ni, and Co with 30% sulfuric acid at a high temperature and pressure of 245° C. and 35 atm.
＜３）５００”ｃで）ＩＩガスを作用させて還元後、水
又はＨＣ７！溶？＆で浸出する方法。<3) Method of reducing with II gas (at 500"c) and then leaching with water or HC7! solution?&.
！４１６２５〜１０００℃でコークス、ＣＯガスの存在
下で予備加熱還元し、さらに１４２５°ＣでＣｕ。! Coke was preheated and reduced in the presence of CO gas at 41625-1000°C, and Cu was further heated at 1425°C.
Ｎｉ、 ＣｏをＦｅ合金とし、Ｍｎ、Ｆｅを酸化させス
ラグとして除去する。次に、石膏とコークスを加えＣｕ
。Ni and Co are made into an Fe alloy, and Mn and Fe are oxidized and removed as slag. Next, add gypsum and coke and Cu
.
Ｎｉ、Ｃｏを硫化物マントに変え、１１０℃、５％Ｈ２
ＳＯ，で浸出する方法
（５）亜硫酸液で浸出させた後、Ｆ ｅ ＋ Ｍ ｎを
（ＮＨ４）ｚＣｏ、で沈澱させ濾過分離し、濾液は従来
の溶媒抽出や電気分解の湿式製錬で各金属を分離回収す
る方法。Change Ni and Co to sulfide cloak, 110℃, 5%H2
Method of leaching with SO (5) After leaching with sulfite solution, Fe + Mn is precipitated with (NH4)zCo and separated by filtration, and the filtrate is leached using conventional solvent extraction or electrolysis hydrometallurgy. A method of separating and recovering metals.
などがあげられる。etc. can be mentioned.
（１）の方法はＫｅｎｎｅｃｏｔｔ Ｃｕｐｒｉｏｎ
Ｐｒｏｃｅｓｓと言われ常温、常圧反応で環境への影響
は少ないがＣ。Method (1) is based on Kennecott Cuprion.
It is called Process and has little impact on the environment as it reacts at room temperature and pressure.
の収率は極めて低い。The yield is extremely low.
しかも有害な一酸化炭素を使用するため、環境衛生上の
問題があり、コストの面でも割高となる。Moreover, since it uses harmful carbon monoxide, it poses environmental health problems and is relatively expensive.
また、（２）の高温・高圧・硫酸浸出法は硫酸のリサイ
クルが困難であるばかりでな（、反応容器の耐蝕性が問
題となる。Furthermore, in the high temperature, high pressure, sulfuric acid leaching method (2), not only is it difficult to recycle the sulfuric acid (but also the corrosion resistance of the reaction vessel is a problem).
さらに（３）の高温下１１１！ガス還元−水又はＨＣｌ
による浸出法はほとんどの有価金属成分を浸出させるこ
とができるとは言うものの、ＨＣｌの回収が困難であっ
て（２）の方法と同様反応容器の耐蝕性の点でも問題が
ある。Furthermore, (3) 111 under high temperature! Gas reduction - water or HCl
Although the leaching method is capable of leaching most of the valuable metal components, it is difficult to recover HCl and, like method (2), there are also problems in terms of corrosion resistance of the reaction vessel.
（４）の乾式製錬・硫酸浸出法は、Ｍｎの回収廃棄を市
況に応じて選択でき、既設のＮｉ製錬設備が活用できる
が、原料の加熱乾燥に莫大なエネルギーを必要とする問
題点がある。(4) Pyrometallurgical smelting/sulfuric acid leaching method allows Mn recovery and disposal to be selected depending on market conditions, and existing Ni smelting equipment can be used, but the problem is that it requires a huge amount of energy to heat and dry the raw material. There is.
（５）の亜硫酸浸出法は、常温、常圧で行なえる利点が
あるが、濾液中からＭｎを沈澱１分離、除去する際に、
Ｃｏが共沈し、Ｃｏの回収率が７０％と低くなる問題点
がある。The sulfite leaching method (5) has the advantage of being able to be carried out at room temperature and pressure, but when precipitating and removing Mn from the filtrate,
There is a problem that Co precipitates and the recovery rate of Co becomes as low as 70%.
文献：溝田忠人、藤井雄二部、河野好美日本鉱業会春季
大会講演要旨集
Ｐ３４７〜３４８ １９８５
このように、従来方法は高温・高圧その他反応条件が厳
しかったり、エネルギー消費が大であったりし、かつ特
に共通する欠点は、Ｃｏの収率がいずれも５０〜７０％
と低い点である。Literature: Tadato Mizota, Yujibu Fujii, Yoshimi Kono, Abstracts of the Japan Mining Society Spring Conference, P347-348 1985 As described above, conventional methods require severe reaction conditions such as high temperature and pressure, and consume a large amount of energy. A particularly common drawback is that the Co yield is 50 to 70% in all cases.
This is a low point.
本発明の目的はこれらの従来法の問題点をすべて解決し
、低コストでしかも環境汚染を生せず、有価金属を高収
率で回収できる方法を提供するにある。The object of the present invention is to solve all of the problems of these conventional methods and to provide a method that is low cost, does not cause environmental pollution, and can recover valuable metals at a high yield.
〔問題点を解決するための具体的手段〕本発明は、亜硫
酸液を用いて有価成分、特にＣｏ、 Ｃｕ、 Ｎｉが９
０％以上の収率で回収できる方法である。[Specific means for solving the problem] The present invention uses a sulfurous acid solution to dissolve valuable components, especially Co, Cu, and Ni.
This method allows recovery with a yield of 0% or more.
まず粉砕した原鉱は、常温常圧下でＨｇＳＯ４濃度０．
０１ｉｏ１／ １以上の亜硫酸溶液中で攪拌する。First, the crushed raw ore is processed at room temperature and pressure with a HgSO4 concentration of 0.
Stir in a sulfite solution of 01io1/1 or more.
本発明において亜硫酸液は、ＨｇＳＯ４濃度０．０１ｍ
ｏｌ／ｆ以上のものが用いられ、粉砕原鉱はこの中で少
なくとも１分以上撹拌される。亜硫酸液と原鉱との重量
比は、有価成分の含有量によって異なるが、ＭＯ２＋ｌ
（□ＳＯ：ｌ −Ｍ”＋ＳＯ４”−＋ ｆｌＺｏ（Ｍ
：金属イオン）の反応に見合う当量以上のｌＩ□ＳＯ１
であればよい。また亜硫酸液の液量と原鉱重量との比は
機械的に撹拌できればよく特に制約はない。In the present invention, the sulfite solution has a HgSO4 concentration of 0.01 m
ol/f or more is used, and the crushed raw ore is stirred in this for at least 1 minute. The weight ratio of sulfite liquid and raw ore varies depending on the content of valuable components, but MO2 + l
(□SO:l −M”+SO4”−+ flZo(M
: metal ion)
That's fine. Further, the ratio between the amount of the sulfite solution and the weight of the raw ore is not particularly limited as long as it can be mechanically stirred.
温度は常温、圧力も常圧で行うことができ、反応装置等
に特別の配慮を払う必要はない。The reaction can be carried out at room temperature and pressure, and there is no need to pay special attention to the reaction equipment.
亜硫酸液で浸出され、遠心分離、フィルタープレスなど
で、固液分離された濾液には、Ｇｏ、 Ｎｉ。The filtrate, which has been leached with sulfite solution and separated into solid and liquid by centrifugation, filter press, etc., contains Go and Ni.
Ｃｕなどの有価成分をはじめＦｅ、Ｍｎの金属イオンが
含まれる。It contains valuable components such as Cu as well as metal ions such as Fe and Mn.
得た濾液に空気を吹き込みＦｅ２＋をＦｅ３＋に全部酸
化させ、酸性領域でＦｅ （ＯＨ） ３の沈澱を生成さ
せ濾過分離させる。Air is blown into the obtained filtrate to completely oxidize Fe2+ to Fe3+, and a precipitate of Fe(OH)3 is generated in an acidic region and separated by filtration.
酸化した酸性領域で沈澱させる理由は、アルカリ側での
Ｆｅ （ＯＢ） ３の沈澱にＣｏ、 Ｎｉ、 Ｃｕ等の
有価成分が共沈し、回収率の向上を不可能ならしめるた
めである。The reason for precipitating in the oxidized acidic region is that valuable components such as Co, Ni, and Cu are co-precipitated with the precipitation of Fe (OB) 3 on the alkaline side, making it impossible to improve the recovery rate.
そのためＦｅ”＋を酸化しＦｅ”にして酸性側で沈澱を
生成しなければならない。Therefore, Fe"+ must be oxidized to Fe" to form a precipitate on the acidic side.
酸化にあっては、０□、０３．空気いずれも酸素を含む
気体を吸込むことによって行える。For oxidation, 0□, 03. Air can be done by inhaling a gas containing oxygen.
次に鉄の除去された濾液に炭酸アンモニウムを加える。Ammonium carbonate is then added to the iron-free filtrate.
これは、ＭｎをＭｎＣ０１として沈に２させ、Ｃｕ、
Ｎｉ、およびＣｏをアンミン錯体とするためである。This causes Mn to precipitate as MnC01, Cu,
This is to make Ni and Co into an ammine complex.
Ｃｕ、 ＮｉおよびＣｏのアンミン錯体をさらに安定化
するためには、特にＣｏのアンミン錯体を安定化するた
めには、亜硫酸アンモニウム、硫酸アンモニラム、など
のアンモニウム塩を加えるか、または、アンモニウム水
を加える。To further stabilize the ammine complexes of Cu, Ni and Co, in particular to stabilize the ammine complex of Co, add ammonium salts such as ammonium sulfite, ammonium sulfate, or add ammonium water. .
上記の添加剤を加え、酸化雰囲気で撹拌を行いＭｎＣＯ
３を生成、沈澱させ静置し、はとんどのＭｎ分を濾過分
離させる。Add the above additives and stir in an oxidizing atmosphere to obtain MnCO
3 is produced, precipitated and allowed to stand, and most of the Mn components are separated by filtration.
酸化雰囲気で攪拌する理由は、Ｃｏのアミン錯体である
（Ｃｏ（Ｎ）Ｉ−） ｂ〕”を酸化することによ、より
安定な（Ｃｏ（ＮＨｔ）Ｊ ”にするためである。The reason for stirring in an oxidizing atmosphere is to oxidize the amine complex of Co (Co(N)I-) b]'' to make it more stable (Co(NHt)J'').
安定度定数が（ｃｏ（Ｎｏｓ）ｂ） ３”では、ｌｏｇ
Ｋ＝１３３゜（Ｃｏ（ＮＨｔ）ｂ） ” では、ｌ
ｏｇＫ＝２５．８となり２価の場合は安定度が低く操作
中に分解しやすいことからＭｎを沈澱させる際、安定な
コバルトアミン錯体にしておくため、積極的に（Ｃｏ（
ＮＨ４）６） ”に酸化させた方がよい。When the stability constant is (co(Nos)b) 3”, log
K=133°(Co(NHt)b)”, then l
ogK = 25.8, and if it is divalent, it has low stability and is easily decomposed during operation.
It is better to oxidize to NH4)6).
なお、（Ｃｏ（ＮＨ４）ｂ） ”から（Ｃｏ（ＮＨｔ）
Ｊ ”に酸化する・にあたって酸化還元電位を調べると
、（Ｃｏ（ＮＨ４）ｈ） ”＋ ｅ−＝ （Ｃｏ（ＮＨ
ｔ）ｂ ”Ｅｏ＝０．０６Ｖとなり（Ｃｏ（ＮＨ４，）
６） ”の酸化還元電位が極めて低いことがわかる。In addition, from (Co(NH4)b)'' to (Co(NHt)
When examining the redox potential for oxidation to J'', we find that (Co(NH4)h)
t)b ”Eo=0.06V (Co(NH4,)
6) It can be seen that the redox potential of `` is extremely low.
この電位程度なら容易に酸化することが可能であるので
、空気吹き込み、あるいは大気中での振とうや強い攪拌
で十分である。さらにこの操作における静置の理由は、
ＭｎからＭｎＣＯ３の反応が非常に遅いために、十分Ｍ
ｎＣＯ５が沈澱熟成できるようにするためである。Since it is possible to easily oxidize at this potential level, blowing air, shaking in the atmosphere, or strong stirring is sufficient. Furthermore, the reason for standing still in this operation is
Since the reaction from Mn to MnCO3 is very slow, sufficient Mn
This is to enable nCO5 to undergo precipitation ripening.
また加温して沈澱生成を促進することが可能である。It is also possible to promote precipitation formation by heating.
このようにすることによりＦｅ、 Ｍｎを含まずＣｏ。By doing this, Co does not contain Fe or Mn.
Ｃｕ、 Ｎｉを９０％以上の回収率で溶液中に回収でき
る。Cu and Ni can be recovered into the solution with a recovery rate of 90% or more.
なお、Ｍｎを分離回収しない場合には、Ｆｅ、 Ｍｎの
同時分離方法も考えられる。Note that if Mn is not separated and recovered, a method for simultaneously separating Fe and Mn may also be considered.
この方法は、原鉱を亜硫酸液で浸出後、浸出液中に溶解
したＣｏ、 Ｃｕ、 Ｎｉ、 Ｆｅ、 Ｍｎと浸出残渣
を濾過分離し、その濾液を空気酸化によりＦｐ ２゛を
Ｆｅｆｆ＋に酸化し、その溶液にアンモニア水、炭酸ア
ンモニウム等で有価成分を錯体化しＭｎ分をＭｎＣ０１
にし沈澱させ、同時にｐＨを上げることによりＦｅ（Ｏ
Ｈ）：＋の沈澱とＭｎＣ０ｚの沈澱を一諸に沈澱分離す
る方法である。This method involves leaching the raw ore with a sulfite solution, then filtering and separating the Co, Cu, Ni, Fe, and Mn dissolved in the leaching solution and the leaching residue, and oxidizing the filtrate with air to oxidize Fp 2゛ to Feff+. Complex valuable components in the solution with ammonia water, ammonium carbonate, etc. to reduce the Mn content to MnC01.
Fe(O
H): This is a method in which the + precipitate and the MnC0z precipitate are precipitated and separated at the same time.
また、細砕酸液浸出残渣、ＦｅおよびＭｎを有価成分と
一括分離する方法、つまり細砕酸液浸出残渣を除去せず
有価成分を含む溶液に含まれているＦｅ２＋をＦｅ３＋
とし、次にＭｎ分をＭｎＣ０，に生成、同時にｐＨを上
げてＦｅ （ＯＨ） ３を沈澱させて有価成分と分離を
行うと、沈澱物にを傷成分がＣｏ １９．３％、 Ｃｕ
９．８％、Ｎｉ ５．８％と残るが、有価成分を溶液中
に回収することができる。In addition, there is a method in which the pulverized acid solution leaching residue, Fe and Mn are separated from the valuable components at once, that is, the Fe2+ contained in the solution containing the valuable components is removed from the Fe3+ without removing the pulverized acid solution leaching residue.
Next, the Mn content was converted to MnC0, and at the same time the pH was raised to precipitate Fe (OH) 3 and separate it from valuable components.
9.8% and 5.8% Ni remain, but valuable components can be recovered into solution.
ＭｎおよびＦｅの原鉱品位が高いので、上記のいずれの
方法によってもＣｏ、 ＣｕおよびＮｉの前液中には、
Ｃｕ、 Ｎｉと同程度のＭｎと微量のＦｅが残る。Since the raw ore grade of Mn and Fe is high, Co, Cu and Ni preliquids contain
Mn and a trace amount of Fe remain in the same amount as Cu and Ni.
これらをさらに分離する方法としてこの前液中にＭｎＣ
Ｏ３との共沈効果の期待できる共沈剤を添加することも
可能である。As a method to further separate these, MnC is added to this preliquid.
It is also possible to add a coprecipitant that can be expected to have a coprecipitation effect with O3.
この場合の共沈剤はＣａＣ１，である。The coprecipitant in this case is CaCl.
Ｆｅ、 Ｍｎと有価成分の分離は、次の反応に見合うだ
けの（ＮＨｔ）ｚｃＯｉとＣａＣ（１２を添加し、１時
間以上沈澱熟成させ濾過分離する。To separate Fe, Mn and valuable components, (NHt)zcOi and CaC (12) are added in an amount suitable for the next reaction, and the mixture is precipitated and aged for over 1 hour, followed by filtration separation.
Ｍｎ”＋ＣａＣ１２＋ ２ （ＮＨ４）ｚｃ（ｈ ＝Ｍ
ｎＣＯ３Ｌ＋ ＣａＣＯ３↓＋２ＮＨｎＣｊ２ ＋ ２
Ｎ）Ｉｓ ’ Ｆｅ、 Ｍｎは、ＣａＣＯ３の沈澱に効
率よく共沈し、前液中のＦｅ、 Ｍｎ？震度を著しく低
下せしめる。Mn”+CaC12+ 2 (NH4)zc(h = M
nCO3L+ CaCO3↓+2NHnCj2 + 2
N)Is' Fe, Mn are efficiently co-precipitated with the CaCO3 precipitate, and Fe, Mn? Significantly reduces seismic intensity.
以上のように、Ｆｅ、 Ｍｎを同時に分離する方法もあ
るが、Ｆｅ、 Ｍｎをそれぞれ個別的に有効に利用し−
ル１ｇにＨ２３０３９１４度０．２ｍｏ１７７！の亜硫
酸水を１００ｍｌ入れ、２５℃で１時間振とうして有価
成分の浸出を行なった。As mentioned above, there is a method to separate Fe and Mn at the same time, but it is also possible to effectively utilize Fe and Mn individually.
H2303914 degrees 0.2mo177 in 1g! 100 ml of sulfurous acid water was added thereto, and the mixture was shaken at 25° C. for 1 hour to leach out valuable components.
浸出後、遠心分離機で固液分離を行なった。°濾液には
Ｃｕ、 Ｎｉ、 Ｃｏ、 Ｍｎ、 Ｆｅイオンが存在す
る。残渣には原鉱に含まれるＦｅ分の２６．７％が残っ
た。After leaching, solid-liquid separation was performed using a centrifuge. °Cu, Ni, Co, Mn, and Fe ions are present in the filtrate. The residue contained 26.7% of the Fe contained in the raw ore.
次に濾液に空気を５００ ｍ ｆｆ／ｍｉｎ、２．５時
間吹き込み酸化させた。空気酸化させた濾液に濃度０．
５ｍｏｌ／βのＮａ、ＣＯｔ ３ ｍ ｌを入れ、ｐｉ
ｔを４．０４として１時間空気酸化させた。Next, air was blown into the filtrate at 500 mff/min for 2.5 hours to oxidize it. The air oxidized filtrate has a concentration of 0.
Add 5 mol/β Na, COt 3 ml, pi
Air oxidation was performed for 1 hour at t of 4.04.
これにより、ＦｅはＦｅ （ＯＨ） ３ として沈≦２
した。このＦｅ （ＯＨ） ：ｌ沈澱物を含む液を遠心
分離機にかけ、この水酸化沈澱物を分離した。As a result, Fe is precipitated as Fe (OH) 3 ≦2
did. The liquid containing the Fe(OH):l precipitate was centrifuged to separate the hydroxylated precipitate.
除鉄した濾液に、（ＮＨ４）２ＣＯ３を５ｇ入れ、濃度
２８％の５Ｈ４０１１１５ｍ ｐを入れた。5 g of (NH4)2CO3 and 5H401115mp with a concentration of 28% were added to the iron-removed filtrate.
さらに、（ＮＨａ） ｚｓＱａ ５ ｇｒを濾液に入
れ、１００ｒ、ｐ、ｍ １．５時間で振とうした。Furthermore, (NHa) zsQa 5 gr was added to the filtrate and shaken at 100 r, p, m for 1.5 hours.
振とう後溶液は２日間静置させ、１ｎを沈澱分離した。After shaking, the solution was allowed to stand for 2 days, and 1N was separated by precipitation.
最終濾液で、Ｃｕ、 Ｎｉ、 Ｃｏの回収率は、それぞ
れ９４．０％、 ９４．２％、 ９４．４％であった。In the final filtrate, the recoveries of Cu, Ni, and Co were 94.0%, 94.2%, and 94.4%, respectively.
結果をまとめて表２に示す。The results are summarized in Table 2.
表１ 原料マンガンノジュールの品位（ｗｔ％）表２
処理結果
（合計回収分）
〔発明の効果〕
亜硫酸水浸出によって常・品、常圧下で浸出できるので
設備も簡単であり、環境汚染の問題もな（、実施上極め
て有利であるのみならず、有価金属時ニＣｏ、 Ｎｉ、
Ｃｕ等を９０％以上という高い収率でしかもＭｎ、
Ｆｅの存在の少ない状態で分離回収することができる。Table 1 Quality of raw manganese nodules (wt%) Table 2
Treatment results (total recovered amount) [Effects of the invention] Sulfurous acid water leaching allows leaching under normal pressure, so the equipment is simple and there is no problem of environmental pollution (not only is it extremely advantageous in terms of implementation, but Valuable metals: Co, Ni,
With a high yield of over 90% of Cu, etc., Mn,
Separation and recovery can be performed in a state where the presence of Fe is small.
Claims (1)
ら有価成分を分離するにあたり、マンガンノジュールま
たは、コバルトクラストの原鉱をＨ＿２ＳＯ＿３濃度０
．０１ｍｏｌ／ｌ以上の亜硫酸液中で有価成分を溶出せ
しめ溶解残渣と溶出液を濾過分離し、次いでその溶出液
に酸化性気体を吹き込み、Ｆｅ＾２＾＋をＦｅ＾３＾＋
に酸化させ、酸性領域内でＦｅ（ＯＨ）＿３の水酸化物
を沈澱させ、鉄分を分離させ、鉄分を除去した濾液に炭
酸アンモニウムを加え、さらに、アンモニウム塩、また
はアンモニア水を加えて、空気酸化後、静置し、マンガ
ンをＭｎＣＯ＿３の沈澱物として分離し、銅、ニッケル
、コバルト等の有価成分を湿式製錬用に濾液中に残すこ
とを特徴とするマンガンノジュールまたはコバルトクラ
ストから有価金属を分離回収する方法。In separating valuable components from manganese nodules or cobalt crust raw ore, the manganese nodule or cobalt crust raw ore is heated to 0 H_2SO_3 concentration.
．． Valuable components are eluted in a sulfite solution of 01 mol/l or more, the dissolved residue and the eluate are separated by filtration, and then an oxidizing gas is blown into the eluate to convert Fe^2^+ to Fe^3^+
The hydroxide of Fe(OH)_3 is precipitated in an acidic region, the iron content is separated, ammonium carbonate is added to the filtrate from which the iron content has been removed, ammonium salt or aqueous ammonia is added, and air Valuable metals are removed from manganese nodules or cobalt crusts by leaving to stand after oxidation, separating manganese as a precipitate of MnCO_3, and leaving valuable components such as copper, nickel, and cobalt in the filtrate for hydrometallurgy. How to separate and collect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22950986A JPH086150B2 (en) | 1986-09-30 | 1986-09-30 | Method for separating and recovering valuable metals from manganese nodules or cobalt crusts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22950986A JPH086150B2 (en) | 1986-09-30 | 1986-09-30 | Method for separating and recovering valuable metals from manganese nodules or cobalt crusts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6386824A true JPS6386824A (en) | 1988-04-18 |
| JPH086150B2 JPH086150B2 (en) | 1996-01-24 |
Family
ID=16893289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22950986A Expired - Fee Related JPH086150B2 (en) | 1986-09-30 | 1986-09-30 | Method for separating and recovering valuable metals from manganese nodules or cobalt crusts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH086150B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009009825A1 (en) * | 2007-07-13 | 2009-01-22 | Metaleach Limited | Method for ammoniacal leaching |
| WO2011014930A1 (en) * | 2009-08-07 | 2011-02-10 | Metaleach Limited | Method for leaching cobalt from oxidised cobalt ores |
| CN114207160A (en) * | 2019-08-09 | 2022-03-18 | 尤米科尔公司 | Method for recovering metals from oxidized ores |
Families Citing this family (1)
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|---|---|---|---|---|
| KR101514837B1 (en) * | 2014-11-06 | 2015-04-28 | 한국지질자원연구원 | The preparation method of sulfides using oxide flux from deep ocean manganese nodules |
-
1986
- 1986-09-30 JP JP22950986A patent/JPH086150B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009009825A1 (en) * | 2007-07-13 | 2009-01-22 | Metaleach Limited | Method for ammoniacal leaching |
| CN102649997A (en) * | 2007-07-13 | 2012-08-29 | 梅塔里奇有限公司 | Method for ammoniacal leaching |
| US8388729B2 (en) | 2007-07-13 | 2013-03-05 | Metaleach Limited | Method for ammoniacal leaching |
| WO2011014930A1 (en) * | 2009-08-07 | 2011-02-10 | Metaleach Limited | Method for leaching cobalt from oxidised cobalt ores |
| AU2010254596B2 (en) * | 2009-08-07 | 2012-04-19 | Metaleach Limited | Method for leaching cobalt from oxidised cobalt ores |
| US8486355B2 (en) | 2009-08-07 | 2013-07-16 | Metaleach Limited | Method for leaching cobalt from oxidised cobalt ores |
| CN114207160A (en) * | 2019-08-09 | 2022-03-18 | 尤米科尔公司 | Method for recovering metals from oxidized ores |
| CN114207160B (en) * | 2019-08-09 | 2023-10-31 | 尤米科尔公司 | Method for recovering metals from oxidized ores |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH086150B2 (en) | 1996-01-24 |
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