JPS6320916B2 - - Google Patents
Info
- Publication number
- JPS6320916B2 JPS6320916B2 JP55149193A JP14919380A JPS6320916B2 JP S6320916 B2 JPS6320916 B2 JP S6320916B2 JP 55149193 A JP55149193 A JP 55149193A JP 14919380 A JP14919380 A JP 14919380A JP S6320916 B2 JPS6320916 B2 JP S6320916B2
- Authority
- JP
- Japan
- Prior art keywords
- manganese nodule
- present
- nodule
- manganese
- discharge
- 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
- 239000011572 manganese Substances 0.000 claims description 33
- 229910052748 manganese Inorganic materials 0.000 claims description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000006183 anode active material Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 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 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は海洋底に産出するマンガン、鉄、ニツ
ケル、コバルト、銅等を含有するマンガンノジユ
ールを電池の陽極活物質に構成することによつて
マンガンノジユール中の有価金属類を抽出回収す
る方法に関する。マンガンノジユールには主成分
であるマンガンの他に、鉄、ニツケル、コバル
ト、銅等の金属が含有されている。ニツケル、コ
バルト、銅の含有率はいずれも１％前後と低品位
であるが、これらの金属が工業上重要であり、陸
上においては枯渇しつつあること、（例えば、世
界有数のニツケル鉱床であるニユーカレドニアの
ニツケル鉱石の品位は当初９％台であつたものが
最近では２％程度になつている。しかし、消費量
は非常に速いスピードで増大している。）また、
一方マンガンノジユールの賦存量が莫大である
（例えば、資源可能量だけでも、Ni16億トン、
Co10億トン、Cu5億トン、Mn700億トンと推定
されている。）ことより、その処理法の開発は非
常に重要である。
その代表的な組成例は表−１に示すごとくであ
る。なお表−１のマンガンノジユールはカリフオ
ルニア沖の海底から採取されたものである。
The present invention is a method for extracting and recovering valuable metals in manganese nodule, which is produced on the ocean floor and contains manganese, iron, nickel, cobalt, copper, etc., by composing it as an anode active material of a battery. Regarding. In addition to manganese, which is the main component, manganese nodule contains metals such as iron, nickel, cobalt, and copper. Although the content of nickel, cobalt, and copper are all low-grade, around 1%, these metals are industrially important and are being depleted on land (for example, the world's largest nickel deposits). The grade of nickel ore in New Caledonia was originally in the 9% range, but recently it has decreased to around 2%.However, consumption is increasing at a very rapid rate.)
On the other hand, the amount of manganese nodule available is enormous (for example, the potential resource amount alone is 1.6 billion tons of Ni,
It is estimated to be 1 billion tons of Co, 500 million tons of Cu, and 70 billion tons of Mn. ), the development of treatment methods is extremely important. Typical composition examples are shown in Table 1. The manganese nodule shown in Table 1 was collected from the ocean floor off the coast of California.
【表】
周知の様にマンガンノジユールの湿式処理法で
は、回収対象となる有価金属がMn，Feの酸化物
鉱物相（マトリツクス）に分散賦存していること
から、まず上記マトリツクスを破壊し、Ni，Co，
Cuを抽出されやすい状態にすることが必要であ
る。処理法としては、苛酷な条件下での酸ある
いはアルカリによる直接浸出法、酸化焙焼、還
元焙焼後の酸あるいはアルカリで浸出する方法等
数多くの方法が提案されているが、どれも相当苛
酷な条件とそれにともなう高価な設備とを必要と
する上に、外部から多量のエネルギーを加える必
要があり、昨今のエネルギーコストの高騰が著し
い状勢では不利である。しかも、有価金属の抽出
率は高くなかつた。とくにコバルトの抽出率につ
いては従来どの方法によつても不満足であつた。
本発明者らは、種々の研究を重ねた結果、マン
ガンノジユールを電池の陽極活物質に構成し、こ
れを放電することにより、マンガンノジユールの
Mn及びFeのマトリツクス（格子）を破壊し、そ
の中に存在するニツケル、コバルト、銅などが可
溶化することを見出した。この方法は電池反応を
利用したマンガンノジユールの全く新しい金属抽
出法である。
本発明は、わざわざ還元剤を添加しなくとも、
放電により自動的にMnマトリツクス及びその中
に分散賦存する有価金属類が極めて容易に還元さ
れ、そのあと高温などの苛酷な処理を施すことな
く、きわめて温和な条件で希酸などの溶媒に短時
間に溶ける性質を帯びるという技術的特性を有す
る。また、本発明は、従来法の様に外部からの多
量のエネルギーを加えるのではなく、逆にエネル
ギーをマンガンノジユールから取出しながら、マ
ンガンノジユール中の有価金属類を回収できると
いう従来にみられない新しい効果を奏する。さら
にまた、本発明においては、放電時間を適当に選
択することにより各成分共90％以上100％近くま
での抽出率が容易に得られるという従来想到でき
なかつた効果を奏し得る。とくに従来その抽出が
困難とされていたCoの抽出率は容易に80〜90％、
あるいはそれ以上となる。
本発明において放電に使用される陽極合剤組成
は一般的には下記の通りである。
マンガンノジユール 40〜60重量％
アセチレンブラツク（AB） ５〜15
NH4Cl（塩化アンモニウム） ０〜20
ZnCl2（塩化亜鉛） ０〜８
H2O ０〜20
導電剤はABに限定されるものではなく、コー
クス粉、粉、木炭、活性炭等各種の粉状カーボン
でよい。一方、負極活物質としては例えば、亜鉛
が使用される。回収される電気エネルギーは例え
ば8mA連続放電（合剤組成；Mnノジユール59.2
％、AB7.4％、NH4Cl8.4％、ZnCl24.2％、
H2O20.8％）において約0.2W・Hh／ｇ−ノジユ
ール（0.85Vまで放電した時）である。これは蓄
電してもよいし、そのまま使用してもよい。
本発明において使用する溶出液としては、鉱酸
（H2SO4，HCl，HNO3）、アンモニア水等が利用
できるが、後処理の容易さ、高価な設備を必要と
しない、そして安価で豊富に入手できる点から、
硫酸が特に好ましい。その濃度は0.5〜10mol／
ｌ、好ましくは１〜3mol／ｌの希硫酸でよく、
マンガンノジユール中の金属成分が金属塩を形成
するのに必要な理論量よりも若干過剰使用するこ
とにより、100℃以下で短時間にマンガンノジユ
ール中の有価金属を90％以上100％近くまで抽出
できる。特に、従来その抽出が困難とされていた
Coについても80〜90％、あるいはそれ以上抽出
できる。
本発明によりマンガンノジユールから有価金属
類を溶出して得られた溶液からの各成分の分離は
公知の方法により容易に行うことができる。
本発明を実施例に基づいてさらに詳細に説明す
るが、本発明はこれによつて限定されるものでは
ない。
なお、以下の例における「％」及び「部」は特
にことわらない限り、重量による。
実施例 １
Mn19.46％、Fe15.37％、Ni0.47％、Co0.46％、
Cu0.30％を含有するマンガンノジユール（150メ
ツシユ）20ｇにAB（50％プレス）2.5ｇを添加し、
十分に混合した後、これにNH4Cl20部、ZnCl210
部、H2O70部からなる溶液を10ml添加し混練し
た合剤より５ｇを分取し、これを陽極活物質と
し、負極活物質としてZn板を使用し、電池を構
成し、定電流（5mA）にて放電させた後、この
合剤を3mol／希硫酸を３ｇ／ｇ−ノジユール
添加し、60℃×30min反応させた。その結果は次
のごとくである。[Table] As is well known, in the wet processing method for manganese nodule, since the valuable metals to be recovered are dispersed in the oxide mineral phase (matrix) of Mn and Fe, the matrix must first be destroyed. , Ni, Co,
It is necessary to put Cu in a state where it can be easily extracted. Many treatment methods have been proposed, including direct leaching with acid or alkali under harsh conditions, oxidation roasting, and leaching with acid or alkali after reduction roasting, but all of them are quite harsh. In addition to requiring the following conditions and expensive equipment, it is also necessary to add a large amount of energy from outside, which is disadvantageous in the current situation where energy costs are rapidly increasing. Moreover, the extraction rate of valuable metals was not high. In particular, the extraction rate of cobalt has been unsatisfactory with all conventional methods. As a result of various researches, the present inventors have discovered that manganese nodule can be used as an anode active material in a battery, and by discharging it, manganese nodule can be made into
It was discovered that the Mn and Fe matrix (lattice) was destroyed and the nickel, cobalt, copper, etc. present within it were solubilized. This method is a completely new method for extracting metals from manganese nodule using a battery reaction. The present invention does not require adding a reducing agent.
The Mn matrix and the valuable metals dispersed within it are automatically reduced by the electric discharge, and then they can be quickly reduced in a solvent such as a dilute acid under extremely mild conditions without harsh treatments such as high temperatures. It has the technical characteristic of melting over time. Furthermore, the present invention does not require a large amount of external energy to be applied as in the conventional method, but on the contrary, the valuable metals in the manganese nodule can be recovered while extracting energy from the manganese nodule. It produces new effects that have never existed before. Furthermore, in the present invention, by appropriately selecting the discharge time, it is possible to easily obtain an extraction rate of 90% or more to nearly 100% for each component, which is an effect previously unimaginable. In particular, the extraction rate of Co, which was previously considered difficult to extract, is easily 80-90%.
Or even more. The anode mixture composition used for discharge in the present invention is generally as follows. Manganese nodule 40-60% by weight Acetylene black (AB) 5-15 NH 4 Cl (ammonium chloride) 0-20 ZnCl 2 (zinc chloride) 0-8 H 2 O 0-20 Conductive agent is limited to AB Instead, various types of powdered carbon such as coke powder, powder, charcoal, and activated carbon may be used. On the other hand, for example, zinc is used as the negative electrode active material. The recovered electrical energy is, for example, 8 mA continuous discharge (mixture composition: Mn nodule 59.2
%, AB7.4%, NH 4 Cl 8.4%, ZnCl 2 4.2%,
H 2 O20.8%), it is approximately 0.2 W·Hh/g-nodule (when discharged to 0.85 V). This may be used to store electricity or may be used as is. As the eluent used in the present invention, mineral acids (H 2 SO 4 , HCl, HNO 3 ), ammonia water, etc. can be used, but they are easy to post-process, do not require expensive equipment, and are inexpensive and abundant. Since it is available in
Particularly preferred is sulfuric acid. Its concentration is 0.5-10mol/
1, preferably 1 to 3 mol/l of dilute sulfuric acid,
By using slightly more than the theoretical amount required for the metal components in the manganese nodule to form metal salts, the valuable metals in the manganese nodule can be increased from 90% to nearly 100% in a short time at 100℃ or below. Can be extracted. In particular, it has been difficult to extract
It is also possible to extract 80 to 90% or more of Co. Separation of each component from the solution obtained by eluting valuable metals from manganese nodule according to the present invention can be easily carried out by known methods. The present invention will be explained in more detail based on Examples, but the present invention is not limited thereto. In addition, "%" and "part" in the following examples are by weight unless otherwise specified. Example 1 Mn19.46%, Fe15.37%, Ni0.47%, Co0.46%,
Add 2.5 g of AB (50% press) to 20 g of manganese nodule (150 mesh) containing 0.30% Cu,
After mixing thoroughly, add 20 parts of NH 4 Cl and 10 parts of ZnCl 2 to this.
Add 10 ml of a solution consisting of 50% H 2 ), 3 mol/3 g/g of diluted sulfuric acid was added to this mixture, and the mixture was reacted at 60°C for 30 min. The results are as follows.
【表】
すなわち、表−２の特に試験１−２では、放電
時間10Hr後のマンガンノジユールは希硫酸浸出
処理により、Mn，Fe，Ni，CoおよびCuのいず
れの元素も90％以上の抽出率を示した。
実施例 ２
Mn18.25％、Fe11.31％、Ni0.50％、Co0.27％、
Cu0.25％を含有するMnノジユールを実施例１と
同様な方法で合剤に作製し、５ｇを分取し、これ
を陽極活物質として電池を構成し、放電電流を変
化させ70Hr放電した後、9.2mol／硫酸を16
ｇ／ｇ−ノジユール添加し、60℃×30min反応さ
せた。その結果は次のごとくであつた。[Table] In other words, especially in Test 1-2 in Table-2, the manganese nodule after a discharge time of 10 hours was subjected to dilute sulfuric acid leaching treatment, and more than 90% of the elements Mn, Fe, Ni, Co, and Cu were extracted. The rate was shown. Example 2 Mn18.25%, Fe11.31%, Ni0.50%, Co0.27%,
A mixture of Mn nodule containing 0.25% Cu was prepared in the same manner as in Example 1, 5 g was taken out, a battery was constructed using this as the anode active material, and the discharge current was varied and the battery was discharged for 70 hours. , 9.2mol/16 sulfuric acid
g/g-nodule was added and reacted at 60°C for 30 minutes. The results were as follows.
【表】
一方、比較のため、、マンガンノジユールをそ
のまま上記と同一条件で硫酸と反応させた場合の
各元素の抽出率はMn14％、Fe90％、Ni81％、
Co51％、Cu96％にとどまつた。表−３の試験に
みられるように本発明による放電の効果は顕著で
ある。
実施例 ３
実施例１と同じ組成、粒度を有するマンガンノ
ジユールをAB，NH4Cl，ZnCl2と混合、混練し
た次のごとき組成を有する陽極合剤５ｇと負極活
物質としてのZn板を使用し、電池を構成し放電
させた。その結果は表−５及び図−１のごとくで
ある。[Table] On the other hand, for comparison, when manganese nodule was directly reacted with sulfuric acid under the same conditions as above, the extraction rate of each element was Mn 14%, Fe 90%, Ni 81%,
The content remained at 51% Co and 96% Cu. As seen in the tests in Table 3, the effects of the discharge according to the present invention are remarkable. Example 3 5 g of an anode mixture having the following composition prepared by mixing and kneading manganese nodule having the same composition and particle size as in Example 1 with AB, NH 4 Cl, and ZnCl 2 and a Zn plate as a negative electrode active material were used. Then, the battery was constructed and discharged. The results are shown in Table 5 and Figure 1.
【表】【table】
【表】【table】
【表】
すなわち、表−５及び図−１から明らかなよう
に、マンガンノジユールｇ当り0.07〜0.135W・
Hr（50Hr放電時）の電力を取り出しながら、マ
ンガンノジユール中の各元素に可溶化の性質を同
時に付与することができるという従来にみられな
い本発明の技術的効果が明らかである。
比較例
本発明の効果をさらにはつきりさせるために、
実施例１と同じ組成、粒度を有するマンガンノジ
ユール３ｇを本発明の処理を行うことなく、その
まま硫酸により濃度、添加量、反応温度、時間を
種々に変化させた。その結果は次のごとくであ
る。[Table] In other words, as is clear from Table 5 and Figure 1, 0.07 to 0.135 W per gram of manganese nodule.
It is clear that the technical effect of the present invention, which has not been seen before, is that it is possible to simultaneously impart solubilizing properties to each element in the manganese nodule while extracting electric power of Hr (at the time of 50 Hr discharge). Comparative Example In order to further enhance the effect of the present invention,
3 g of manganese nodule having the same composition and particle size as in Example 1 was not subjected to the treatment of the present invention, but was directly treated with sulfuric acid while varying the concentration, amount added, reaction temperature, and time. The results are as follows.
【表】
表−６の結果にみられるように、本発明による
処理を経ない硫酸抽出のみでは各元素の抽出率は
低く、とくにMn1〜14％、Co4〜53％とこの２元
素が劣る。すなわち本発明のすぐれた抽出効果は
明らかである。[Table] As seen in the results in Table 6, the extraction rate of each element is low with sulfuric acid extraction alone without the treatment according to the present invention, and in particular, these two elements are inferior at 1 to 14% for Mn and 4 to 53% for Co. In other words, the excellent extraction effect of the present invention is obvious.
図−１は本発明によるマンガンノジユールの放
電曲線を示した。
Figure 1 shows the discharge curve of the manganese nodule according to the present invention.
Claims (1)
成し、これを放電することにより、マンガンノジ
ユール中の有価金属を可溶化し、抽出回収するこ
とを特徴とする電池反応を利用したマンガンノジ
ユールの処理方法。1 Manganese nodule is configured as an anode active material of a battery, and by discharging it, valuable metals in the manganese nodule are solubilized and extracted and recovered. Processing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55149193A JPS5773194A (en) | 1980-10-24 | 1980-10-24 | Treatment of manganese nodule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55149193A JPS5773194A (en) | 1980-10-24 | 1980-10-24 | Treatment of manganese nodule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5773194A JPS5773194A (en) | 1982-05-07 |
| JPS6320916B2 true JPS6320916B2 (en) | 1988-05-02 |
Family
ID=15469836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55149193A Granted JPS5773194A (en) | 1980-10-24 | 1980-10-24 | Treatment of manganese nodule |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5773194A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0253111U (en) * | 1988-10-11 | 1990-04-17 | ||
| JPH0586244B2 (en) * | 1989-02-27 | 1993-12-10 | Masanori Okamoto | |
| JPH07114908B2 (en) * | 1989-05-22 | 1995-12-13 | 謹造 神田 | Air cleaner cleaning equipment |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4730488B2 (en) * | 2000-04-04 | 2011-07-20 | 東ソー株式会社 | Method for producing manganese ore processed product |
| JP4734703B2 (en) * | 2000-05-19 | 2011-07-27 | 東ソー株式会社 | Method for producing reduced manganese ore |
-
1980
- 1980-10-24 JP JP55149193A patent/JPS5773194A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0253111U (en) * | 1988-10-11 | 1990-04-17 | ||
| JPH0586244B2 (en) * | 1989-02-27 | 1993-12-10 | Masanori Okamoto | |
| JPH07114908B2 (en) * | 1989-05-22 | 1995-12-13 | 謹造 神田 | Air cleaner cleaning equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5773194A (en) | 1982-05-07 |
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