JP3113307B2 - Method for separating and recovering zinc and manganese from waste dry batteries - Google Patents
Method for separating and recovering zinc and manganese from waste dry batteriesInfo
- Publication number
- JP3113307B2 JP3113307B2 JP10390391A JP10390391A JP3113307B2 JP 3113307 B2 JP3113307 B2 JP 3113307B2 JP 10390391 A JP10390391 A JP 10390391A JP 10390391 A JP10390391 A JP 10390391A JP 3113307 B2 JP3113307 B2 JP 3113307B2
- Authority
- JP
- Japan
- Prior art keywords
- manganese
- zinc
- solution
- recovered
- gypsum
- 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
- 239000011701 zinc Substances 0.000 title claims description 77
- 239000011572 manganese Substances 0.000 title claims description 75
- 229910052725 zinc Inorganic materials 0.000 title claims description 74
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 69
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 68
- 229910052748 manganese Inorganic materials 0.000 title claims description 68
- 238000000034 method Methods 0.000 title claims description 18
- 239000002699 waste material Substances 0.000 title claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 229910052602 gypsum Inorganic materials 0.000 claims description 26
- 239000010440 gypsum Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 239000010812 mixed waste Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000006148 magnetic separator Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000002697 manganese compounds Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 238000002386 leaching Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011656 manganese carbonate Substances 0.000 description 3
- 235000006748 manganese carbonate Nutrition 0.000 description 3
- 229940093474 manganese carbonate Drugs 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005868 electrolysis reaction 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing 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
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、廃乾電池から亜鉛およ
びマンガンを分離回収する方法に関する。The present invention relates to a method for separating and recovering zinc and manganese from waste dry batteries.
【０００２】[0002]
【従来の技術】わが国における乾電池の生産量は、昭和
63年度で37億5000万個に達し、年々その生産量は増加し
ている。また、わが国で生産される乾電池の種類は多
く、構成要素も多岐にわたっているが、マンガン乾電池
およびアルカリ・マンガン乾電池が全生産量の90％以上
を占めている。2. Description of the Related Art Dry battery production in Japan
It reached 3.75 billion in fiscal 63, and its production has been increasing year by year. Although there are many types of batteries produced in Japan and their components are also diverse, manganese batteries and alkaline manganese batteries account for more than 90% of the total production.
【０００３】国内で消費される乾電池は約60％程度と見
られており、廃乾電池は水銀公害を防止するため全国的
に集荷され、北海道のイトカムなどで処理されている。
わが国で生産している乾電池のほとんどが輸入原材料か
ら製造されているため、廃乾電池中に含まれている亜
鉛、鉄、マンガン等の有価物の回収および再資源化が注
目されている。廃乾電池中の有価物の回収および再資源
化方法は、これまでにもいくつか考え出されているが、
中でも野村興産（株）の焙焼法が広く用いられている。
この焙焼法とは、廃乾電池を焙焼することにより、揮発
物や可燃物を燃焼、揮発させて水銀を回収し、さらに鉄
屑を回収した後の粉末を製錬して亜鉛を回収するという
ものである。It is estimated that about 60% of batteries are consumed in Japan, and waste batteries are collected nationwide in order to prevent mercury pollution and are treated at Itocam in Hokkaido.
Since most dry batteries manufactured in Japan are manufactured from imported raw materials, attention has been focused on the recovery and recycling of valuable resources such as zinc, iron, and manganese contained in waste dry batteries. Several methods have been devised to recover and recycle valuable resources in waste batteries.
Above all, the roasting method of Nomura Kosan Co., Ltd. is widely used.
The roasting method is to roast a waste dry battery to burn and volatilize volatiles and combustibles to recover mercury, and further recover zinc by recovering powder after collecting iron scraps. That is.
【０００４】しかしながら、上記焙焼後得られる粉末の
主要成分は亜鉛が30〜40％、マンガンが25〜30％である
ため、製錬による亜鉛の回収において、該粉末は亜鉛原
料としてはやや品位が低く、しかも上記焙焼法によると
レア・メタル備蓄制度の対象鉱種となっているマンガン
が廃棄処分されてしまっていた。そのため、該粉末中の
亜鉛とマンガンとを経済的に分離し、亜鉛およびマンガ
ンを有効に利用する好適な処理技術の開発が求められて
いた。However, the main components of the powder obtained after the above-mentioned roasting are 30 to 40% of zinc and 25 to 30% of manganese. Therefore, in the recovery of zinc by smelting, the powder is used as a raw material for zinc. In addition, according to the above-mentioned roasting method, manganese, which is the target ore of the rare metal stockpile system, was disposed of. Therefore, there has been a demand for the development of a suitable treatment technique for economically separating zinc and manganese in the powder and effectively using zinc and manganese.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上述従来の
技術の問題点を解決し、廃乾電池中の亜鉛およびマンガ
ンを効率良くかつ経済的に分離回収することができる方
法の提供を目的としている。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a method for efficiently and economically separating and recovering zinc and manganese in a waste dry battery. I have.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記目的
を達成するため鋭意研究したところ、破砕混合した廃乾
電池を焙焼し、さらに鉄屑を除去した粉末から亜鉛およ
びマンガンを浸出し、その浸出液を pH5.5〜7.0 に中和
して浸出液中の亜鉛を石膏として沈殿させてマンガンと
固液分離することにより、亜鉛およびマンガンを効率良
く回収できることを見い出し、本発明に到達した。Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and found that zinc and manganese were leached from the powder obtained by roasting a crushed and mixed waste dry battery and further removing iron chips. The inventors have found that zinc and manganese can be efficiently recovered by neutralizing the leachate to pH 5.5 to 7.0, precipitating zinc in the leachate as gypsum, and performing solid-liquid separation with manganese.
【０００７】すなわち、本発明は、破砕混合した廃乾電
池を焙焼して得られる焼滓を、磁選機にかけて鉄屑を除
去した粉末原料から亜鉛およびマンガンを分離回収する
方法であって、希硫酸によって上記粉末原料から亜鉛お
よびマンガンをほぼ完全に浸出し、その浸出液に中和剤
を投入して pH5.5〜7.0 に中和することにより、浸出液
中の亜鉛を含亜鉛石膏として沈殿させてマンガンと固液
分離し、得られた含亜鉛石膏中の亜鉛を希硫酸で再溶解
させた後、その溶液を湿式亜鉛製錬工程における電解液
調製工程に合流させることによって石膏中の亜鉛を電気
亜鉛として回収し、一方、亜鉛の分離後に得られた脱亜
鉛浸出液中に硫化水素ガスを吹き込んでマンガン以外の
金属を硫化物として沈殿分離した後、この溶液中のマン
ガンを含マンガン石膏、金属マンガンまたはマンガン化
合物として回収することを特徴とする廃乾電池からの亜
鉛およびマンガンの分離回収方法を提供するものであ
る。That is, the present invention relates to a method for separating and recovering zinc and manganese from a powdery material from which iron swarf has been removed by subjecting slag obtained by roasting a crushed and mixed waste dry battery to a magnetic separator, comprising dilute sulfuric acid. Zinc and manganese are almost completely leached from the above powdered raw material, and a neutralizing agent is added to the leaching solution to neutralize the pH to 5.5 to 7.0, thereby precipitating zinc in the leaching solution as zinc-containing gypsum to form manganese. After solid-liquid separation with zinc, the zinc in the resulting zinc-containing gypsum is redissolved with dilute sulfuric acid, and the solution is combined with the electrolytic solution preparation step in the wet zinc smelting step to convert the zinc in the gypsum into electric zinc. As the other hand, hydrogen sulfide gas is blown into the dezincified leachate obtained after the separation of zinc to precipitate and separate metals other than manganese as sulfides, and then the manganese-containing gypsum containing manganese in this solution And a method for separating and recovering zinc and manganese from waste dry batteries, wherein the method recovers zinc and manganese as metal manganese or a manganese compound.
【０００８】[0008]
【作用】本発明によると、破砕混合した廃乾電池を焙焼
して得られる焼滓を、磁選機にかけて鉄屑を除去した粉
末を原料としており、 100〜400g/lパルプ濃度となる量
の原料を 5〜20重量％希硫酸中に投入し、攪拌浸出を行
っている。なお、この工程における反応温度は、室温で
浸出を開始しても原料の溶解熱により70〜90℃に上昇す
るため特に加熱設備等は必要とせず、また、反応時間は
攪拌回転数が300rpm程度であれば 0.5〜２時間程度で十
分である。このようにして攪拌浸出を行うと、原料中の
亜鉛およびマンガンが希硫酸溶液中に90％以上浸出され
る。また、この工程において、希硫酸は亜鉛およびマン
ガンの浸出に伴って消費され、浸出終了時にはpH 3.5〜
4.0 程度まで中和されるため、次の中和工程における中
和剤の消費量が少なく、経済的である。According to the present invention, the slag obtained by roasting a crushed and mixed waste dry battery is subjected to a magnetic separator to remove powdered iron as a raw material, and the raw material has an amount of 100 to 400 g / l pulp concentration. Is poured into 5 to 20% by weight of diluted sulfuric acid to perform stirring leaching. Incidentally, the reaction temperature in this step, even if the leaching is started at room temperature, because the heat of dissolution of the raw material rises to 70-90 ° C, no special heating equipment is required, and the reaction time is about 300 rpm with stirring rotation speed. In this case, about 0.5 to 2 hours is sufficient. When the stirring and leaching are performed in this manner, 90% or more of zinc and manganese in the raw material are leached in the diluted sulfuric acid solution. In this step, the diluted sulfuric acid is consumed along with the leaching of zinc and manganese, and at the end of the leaching, pH 3.5 to
Since it is neutralized to about 4.0, the consumption of the neutralizing agent in the next neutralization step is small and economical.
【０００９】上記浸出工程において、原料のパルプ濃度
を100g/l以下にすると、取扱い液容量が増加するため装
置が大型化してしまい、原料のパルプ濃度を400g/l以上
にすると、浸出液の粘性が増大して攪拌や濾過が困難に
なってしまう。また、溶媒とする希硫酸の濃度は、亜鉛
およびマンガンの浸出に伴って消費される硫酸量から必
然的に決定されるものであって、原料のパルプ濃度が 1
00〜400g/lであれば、相対的な初硫酸濃度として５〜20
重量％が適当である。In the above leaching step, if the pulp concentration of the raw material is set to 100 g / l or less, the volume of the liquid to be handled increases, and the apparatus becomes large. If the pulp concentration of the raw material is set to 400 g / l or more, the viscosity of the leached liquid becomes It increases and stirring and filtration become difficult. The concentration of dilute sulfuric acid as a solvent is inevitably determined from the amount of sulfuric acid consumed in leaching zinc and manganese.
If it is 00 to 400 g / l, the relative primary sulfuric acid concentration is 5 to 20
% By weight is appropriate.
【００１０】次に、中和工程においては、上記浸出液に
消石灰等の中和剤を投入してpH 5.5〜7.0 まで攪拌中和
し、浸出液中の亜鉛を含亜鉛石膏として沈殿させ、亜鉛
とマンガンとを固液分離させている。なお、この工程に
おける反応温度は、中和熱によって液温が60℃程度まで
上昇するため加熱設備等は必要とせず、また反応時間
は、攪拌回転数が300rpm程度であれば２時間程度で十分
である。この中和工程における浸出液のpHが 5.5以下で
あると、亜鉛の石膏中への回収率が低下してしまい、浸
出液のpHが 7.0以上であると亜鉛の石膏中への回収率は
ほぼ完全であるが、同時にマンガンも沈殿分離してしま
う。Next, in the neutralization step, a neutralizing agent such as slaked lime is added to the above leachate to neutralize by stirring to pH 5.5 to 7.0, and zinc in the leachate is precipitated as zinc-containing gypsum, and zinc and manganese are removed. And solid-liquid separation. The reaction temperature in this step does not require heating equipment because the liquid temperature rises to about 60 ° C. due to the heat of neutralization, and the reaction time is about 2 hours if the stirring rotation speed is about 300 rpm. It is. If the pH of the leachate in this neutralization step is 5.5 or less, the recovery rate of zinc in gypsum decreases, and if the pH of the leachate is 7.0 or more, the recovery rate of zinc in gypsum is almost complete. However, manganese precipitates out at the same time.
【００１１】中和工程で得られた含亜鉛石膏は、希硫酸
溶液で処理することにより石膏中の亜鉛を希硫酸溶液中
に再溶解させ、この希硫酸溶液を公知の湿式亜鉛製錬工
程における電解液調製工程に挿入して該溶液中の亜鉛を
電気亜鉛として回収している。以上の工程はすべて容易
に実施し得る上、亜鉛の回収効率は極めて良い。一方、
上記のようにして亜鉛を沈殿分離した後の浸出液は、続
く洗浄工程において硫化水素ガス等の吹き込みが行わ
れ、該溶液中に少量残存している亜鉛等を硫化物として
沈殿分離し、その後以下に示す方法等により溶液中のマ
ンガンを含マンガン石膏、金属マンガンあるいはマンガ
ン化合物として回収している。The zinc-containing gypsum obtained in the neutralization step is treated with a dilute sulfuric acid solution to redissolve zinc in the gypsum in the dilute sulfuric acid solution, and this dilute sulfuric acid solution is used in a known wet zinc smelting step. The zinc in the solution is recovered as electro-zinc by being inserted into the electrolyte solution preparation step. All of the above steps can be easily carried out, and the zinc recovery efficiency is extremely good. on the other hand,
The leachate obtained by precipitating and separating zinc as described above is blown with hydrogen sulfide gas or the like in the subsequent washing step to precipitate and separate zinc and the like remaining in the solution in small amounts as sulfide, and then The manganese in the solution is recovered as manganese-containing gypsum, metallic manganese or a manganese compound by the method shown in (1).
【００１２】上記マンガン含有溶液にカセイソーダおよ
び炭酸ソーダを投入して pH 9.0 〜11.0まで攪拌中和
し、炭酸マンガンとして回収、カセイソーダのみを投入
してpH9.0 〜11.0まで攪拌中和し、酸化マンガンとして
回収、亜硫酸ガスを吹き込むなどして還元雰囲気のも
と、カセイソーダのみを投入してpH 9.0〜11.0まで攪拌
中和し、水酸化マンガンとして回収、または消石灰を投
入してpH 9.0〜11.0まで攪拌中和し、含マンガン石膏と
して回収することができる。また、該含マンガン石膏中
のマンガンを希硫酸溶液中に再溶解させ、そのマンガン
濃縮液を従来からの電解マンガン法により、金属マンガ
ンあるいは二酸化マンガンとして回収することもでき、
さらに、該マンガン濃縮液を加熱濃縮することにより、
硫酸マンガンとして晶析回収することもできる。Caustic soda and sodium carbonate are added to the manganese-containing solution and neutralized by stirring to pH 9.0 to 11.0, and recovered as manganese carbonate. Only caustic soda is added and neutralized by stirring to pH 9.0 to 11.0, and manganese oxide is added. In a reducing atmosphere, such as by blowing in sulfurous acid gas, add only caustic soda to neutralize with stirring to pH 9.0 to 11.0, recover as manganese hydroxide, or add slaked lime and stir to pH 9.0 to 11.0 It can be neutralized and recovered as gypsum containing manganese. Further, manganese in the manganese-containing gypsum can be redissolved in a diluted sulfuric acid solution, and the manganese concentrated solution can be recovered as metal manganese or manganese dioxide by a conventional electrolytic manganese method,
Further, by heating and concentrating the manganese concentrate,
It can also be crystallized and recovered as manganese sulfate.
【００１３】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は、以下の実施例により
制限されるものではない。Hereinafter, the present invention will be described in more detail by way of examples. However, the scope of the present invention is not limited by the following examples.
【００１４】[0014]
【実施例１】本発明の廃乾電池からの亜鉛およびマンガ
ンの分離回収方法の一実施例を以下に示す。Embodiment 1 One embodiment of the method for separating and recovering zinc and manganese from a waste dry battery according to the present invention will be described below.
【００１５】破砕混合した廃乾電池を焙焼し、磁選機に
かけて鉄屑を除去して得たＺｎ33.0％、Ｍｎ25.5％、Ｃ
9.5％、Ｆｅ 3.5％の組成からなる粉末原料を、200g/l
パルプ濃度となるように10重量％の希硫酸中に投入し、
攪拌回転数300rpmで２時間浸出を行った。その際、特に
加熱は行わなかったが液温は溶解熱により80℃まで上昇
し、浸出終了時の溶液のpHは 3.7となった。また、得ら
れた浸出液中の亜鉛およびマンガンの濃度は、65g/l お
よび49g/lであり、浸出率は99％および97％であった。The crushed and mixed waste dry battery is roasted and subjected to a magnetic separator to remove iron scraps. Zn 33.0%, Mn 25.5%, C
Powder material consisting of 9.5% and 3.5% Fe, 200g / l
Pour into dilute sulfuric acid of 10% by weight so that the pulp concentration becomes,
Leaching was performed for 2 hours at a stirring rotation speed of 300 rpm. At that time, no heating was performed, but the temperature of the solution rose to 80 ° C. due to heat of dissolution, and the pH of the solution at the end of the leaching was 3.7. The concentrations of zinc and manganese in the obtained leachate were 65 g / l and 49 g / l, and the leaching rates were 99% and 97%.
【００１６】次に、得られた浸出液に消石灰を投入し、
攪拌回転数300rpmで２時間、pH 6.0まで中和した。その
際、特に加熱は行わなかったが液温は中和熱により60℃
まで上昇した。この中和反応により、浸出液中の亜鉛は
石膏中に回収されて沈殿し、含亜鉛石膏とマンガン含有
溶液とに固液分離した。得られた含亜鉛石膏中の亜鉛は
19.1％であり、マンガン含有溶液中のマンガンは 49.0g
/l、亜鉛は0.7g/lであった。Next, slaked lime is added to the obtained leachate,
Neutralized to pH 6.0 at 300 rpm with stirring rotation for 2 hours. At that time, no heating was performed, but the liquid temperature was 60 ° C due to the heat of neutralization.
Up. By this neutralization reaction, zinc in the leachate was collected in gypsum and precipitated, and solid-liquid separated into zinc-containing gypsum and a manganese-containing solution. Zinc in the obtained zinc-containing gypsum is
19.1%, manganese in solution containing manganese is 49.0g
/ l and zinc was 0.7 g / l.
【００１７】上記中和反応により得られた含亜鉛石膏
は、希硫酸で処理することにより石膏中の亜鉛を完全に
再溶解させ、この希硫酸溶液を公知の湿式亜鉛製錬工程
における電解液調製工程に挿入することによって溶液中
の亜鉛を電気亜鉛として回収した。一方、マンガン含有
溶液は、硫化水素ガスを吹き込むことによって溶液中に
少量残存していた亜鉛等を硫化物として沈殿分離した。
分離後、得られたマンガン含有溶液にカセイソーダおよ
び炭酸ソーダを投入し、pH10.0まで攪拌中和することに
より、溶液中のマンガンを炭酸マンガンとして回収し
た。なお、回収した炭酸マンガンの組成はＭｎ42.6％、
Ｚｎ４ppm であった。The zinc-containing gypsum obtained by the above neutralization reaction is treated with dilute sulfuric acid to completely dissolve zinc in the gypsum, and this dilute sulfuric acid solution is used to prepare an electrolytic solution in a known wet zinc smelting process. Zinc in the solution was recovered as electro-zinc by inserting into the process. On the other hand, in the manganese-containing solution, a small amount of zinc and the like remaining in the solution was precipitated and separated as sulfide by blowing hydrogen sulfide gas.
After separation, caustic soda and sodium carbonate were added to the obtained manganese-containing solution, and the mixture was neutralized with stirring to pH 10.0, whereby manganese in the solution was recovered as manganese carbonate. The composition of the recovered manganese carbonate was Mn 42.6%,
Zn was 4 ppm.
【００１８】[0018]
【実施例２】硫化水素ガスを吹き込み、亜鉛等を硫化物
として沈殿分離した後のマンガン含有溶液に、カセイソ
ーダのみを投入したこと以外は実施例１と同様にして酸
化マンガンを回収した。回収した酸化マンガンの組成は
Ｍｎ66.8％、Ｚｎ６ppm であった。Example 2 Manganese oxide was recovered in the same manner as in Example 1 except that only caustic soda was added to the manganese-containing solution after hydrogen sulfide gas was blown therein to precipitate and separate zinc and the like as sulfides. The composition of the recovered manganese oxide was Mn 66.8% and Zn 6 ppm.
【００１９】[0019]
【実施例３】硫化水素ガスを吹き込み、亜鉛等を硫化物
として沈殿分離した後のマンガン含有溶液に、亜硫酸ガ
スを吹き込みながらカセイソーダのみを投入したこと以
外は実施例１と同様にして水酸化マンガンを回収した。
回収した水酸化マンガンの組成はＭｎ51.8％、Ｚｎ８pp
m であった。Example 3 Manganese hydroxide was prepared in the same manner as in Example 1 except that sulfuric acid gas was blown into the manganese-containing solution after injecting hydrogen sulfide gas to precipitate and separate zinc and the like as sulfides. Was recovered.
The composition of the recovered manganese hydroxide is Mn 51.8%, Zn 8pp
m.
【００２０】[0020]
【実施例４】硫化水素ガスを吹き込み、亜鉛等を硫化物
として沈殿分離した後のマンガン含有溶液に、消石灰を
投入したこと以外は実施例１と同様にして含マンガン石
膏を回収した。なお、回収した含マンガン石膏中におけ
るマンガンは23.7％であった。次いで、希硫酸溶液中に
該石膏を入れ、石膏中のマンガンを希硫酸溶液中に完全
に再溶解させてマンガン濃縮液を得た。Example 4 A manganese-containing gypsum was recovered in the same manner as in Example 1 except that slaked lime was added to a manganese-containing solution obtained by injecting hydrogen sulfide gas to precipitate and separate zinc and the like as sulfides. The manganese content in the collected manganese-containing gypsum was 23.7%. Next, the gypsum was put into a dilute sulfuric acid solution, and manganese in the gypsum was completely redissolved in the dilute sulfuric acid solution to obtain a manganese concentrate.
【００２１】次に、上記マンガン濃縮液を電解浴成分と
してＭｎ 15g/l、（ＮＨ4 ）2 ＳＯ4 130g/l、pH7.0に
調整し、アノードとして１％銀含有鉛板、カソードとし
てSUS-316 板を用い、陽極室と陰極室を隔膜で仕切り、
電解浴温度37℃、電流密度550A/m2 で12時間電気分解を
行い、金属マンガンを回収した。その際、電流効率は53
％であり、金属マンガンはカソード上に析出した。回収
した金属マンガンの品質は、不純物としてＺｎ 22ppm、
Ｆｅ 11ppm、Ｐｂ２ppm 、Ｃｕ１ppm 以下であった。Next, the manganese concentrated solution was adjusted to 15 g / l of Mn and 130 g / l of (NH 4 ) 2 SO 4 as an electrolytic bath component, pH 7.0, and a lead plate containing 1% silver as an anode and SUS as a cathode. -316 plate, the anode compartment and cathode compartment are separated by a diaphragm,
Electrolysis was performed at an electrolytic bath temperature of 37 ° C. and a current density of 550 A / m 2 for 12 hours to recover metallic manganese. At that time, the current efficiency is 53
%, And the metallic manganese was deposited on the cathode. The quality of the recovered metal manganese is Zn 22ppm as impurities,
Fe was less than 11 ppm, Pb was less than 2 ppm, and Cu was less than 1 ppm.
【００２２】[0022]
【実施例５】マンガン濃縮液を電解浴成分としてＭｎ 4
0g/l、Ｈ2 ＳＯ4 70g/lに調整し、アノードとしてチタ
ン板、カソードとして SUS-316板を用い、電解浴温度95
℃、電流密度100A/m2 で５日間電気分解を行ったこと以
外は実施例４と同様にして二酸化マンガンを回収した。
その際、電流効率は95％であり、二酸化マンガンはアノ
ード上に析出した。回収した二酸化マンガンの品質はＭ
ｎ60.2％、不純物としてＦｅ 0.012％、Ｐｂ 0.007％で
あった。Example 5 A manganese concentrated solution was used as an electrolytic bath component and Mn 4
0 g / l, H 2 SO 4 70 g / l, titanium plate as anode, SUS-316 plate as cathode, electrolytic bath temperature 95
Manganese dioxide was recovered in the same manner as in Example 4 except that electrolysis was performed at 100 ° C. and a current density of 100 A / m 2 for 5 days.
At that time, the current efficiency was 95% and manganese dioxide was deposited on the anode. The quality of the recovered manganese dioxide is M
n60.2%, Fe 0.012% and Pb 0.007% as impurities.
【００２３】[0023]
【実施例６】本実施例では、実施例４と同様にして得た
マンガン濃縮液を80℃で加熱濃縮し、一水塩の硫酸マン
ガンを晶析回収した。回収した硫酸マンガンの品質は、
Ｍｎ32.0％、不純物としてＺｎ８ppm 、Ｆｅ７ppm 、Ｐ
ｂ８ppm であった。Example 6 In this example, a manganese concentrated solution obtained in the same manner as in Example 4 was heated and concentrated at 80 ° C., and manganese sulfate as a monohydrate was crystallized and recovered. The quality of the recovered manganese sulfate
Mn 32.0%, Zn 8 ppm, Fe 7 ppm, P as impurities
b was 8 ppm.
【００２４】[0024]
【発明の効果】本発明の開発により、廃乾電池中の亜鉛
とマンガンとをほぼ完全に分離回収することができるよ
うになった。また、本発明によると、亜鉛およびマンガ
ンの回収効率が極めて良く、しかも経済的に回収するこ
とができるため再資源化や環境保全に大きく寄与し得る
ものである。According to the development of the present invention, zinc and manganese in a waste dry battery can be almost completely separated and recovered. Further, according to the present invention, zinc and manganese can be recovered extremely efficiently and can be recovered economically, which can greatly contribute to recycling and environmental conservation.
フロントページの続き (72)発明者 田口 良一 秋田県河辺郡河辺町赤平字田中90 (56)参考文献 特開 昭62−29072（ＪＰ，Ａ) 特開 昭63−36885（ＪＰ，Ａ) 特開 昭49−21632（ＪＰ，Ａ) 特開 昭51−69261（ＪＰ，Ａ) 特開 昭61−261443（ＪＰ，Ａ) 特開 昭61−136639（ＪＰ，Ａ) 特開 昭60−96734（ＪＰ，Ａ) 特開 昭61−74692（ＪＰ，Ａ) 特開 昭61−118182（ＪＰ，Ａ) 特開 昭50−60414（ＪＰ，Ａ) 特開 昭50−1094（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B09B 5/00 C22B 7/00 C22B 19/22 C22B 47/00 H01M 6/52 Continuation of the front page (72) Inventor Ryoichi Taguchi 90, Tanaka, Akahira, Kawabe-cho, Kawabe-gun, Akita (56) References JP-A-62-29072 (JP, A) JP-A-63-36885 (JP, A) JP-A-49-21632 (JP, A) JP-A-51-69261 (JP, A) JP-A-61-261443 (JP, A) JP-A-61-136639 (JP, A) JP-A-60-96734 (JP JP-A-61-74692 (JP, A) JP-A-61-118182 (JP, A) JP-A-50-60414 (JP, A) JP-A-50-1094 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B09B 5/00 C22B 7/00 C22B 19/22 C22B 47/00 H01M 6/52
Claims (1)
る焼滓を、磁選機にかけて鉄屑を除去した粉末原料から
亜鉛およびマンガンを分離回収する方法であって、希硫
酸によって上記粉末原料から亜鉛およびマンガンをほぼ
完全に浸出し、その浸出液に中和剤を投入して pH5.5〜
7.0 に中和することにより、浸出液中の亜鉛を含亜鉛石
膏として沈殿させてマンガンと固液分離し、得られた含
亜鉛石膏中の亜鉛を希硫酸で再溶解させた後、その溶液
を湿式亜鉛製錬工程における電解液調製工程に合流させ
ることによって石膏中の亜鉛を電気亜鉛として回収し、
一方、亜鉛の分離後に得られた脱亜鉛浸出液中に硫化水
素ガスを吹き込んでマンガン以外の金属を硫化物として
沈殿分離した後、この溶液中のマンガンを含マンガン石
膏、金属マンガンまたはマンガン化合物として回収する
ことを特徴とする廃乾電池からの亜鉛およびマンガンの
分離回収方法。1. A method for separating and recovering zinc and manganese from a powdery material from which iron swarf has been removed by subjecting a slag obtained by roasting a crushed and mixed waste dry battery to a magnetic separator, wherein the powdery material is diluted with dilute sulfuric acid. Almost completely leaches zinc and manganese from
By neutralizing to 7.0, the zinc in the leachate was precipitated as zinc-containing gypsum and solid-liquid separated from manganese.The zinc in the resulting zinc-containing gypsum was redissolved with dilute sulfuric acid, and the solution was wet-processed. The zinc in the gypsum is recovered as electric zinc by joining the electrolyte preparation step in the zinc smelting step,
On the other hand, after hydrogen sulfide gas is blown into the dezincified leachate obtained after the separation of zinc to precipitate and separate metals other than manganese as sulfides, the manganese in this solution is recovered as manganese-containing gypsum, metallic manganese or manganese compound A method for separating and recovering zinc and manganese from waste dry batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10390391A JP3113307B2 (en) | 1991-04-08 | 1991-04-08 | Method for separating and recovering zinc and manganese from waste dry batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10390391A JP3113307B2 (en) | 1991-04-08 | 1991-04-08 | Method for separating and recovering zinc and manganese from waste dry batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04310280A JPH04310280A (en) | 1992-11-02 |
| JP3113307B2 true JP3113307B2 (en) | 2000-11-27 |
Family
ID=14366389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10390391A Expired - Lifetime JP3113307B2 (en) | 1991-04-08 | 1991-04-08 | Method for separating and recovering zinc and manganese from waste dry batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3113307B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4337747A1 (en) * | 1993-11-05 | 1995-05-11 | Gewerk Keramchemie | Process for the hydrometallurgical treatment of used household and appliance batteries |
| CN100431720C (en) * | 2003-03-14 | 2008-11-12 | 于之涛 | Method for producing metal compound by waste zinc-manganese dioxide dry cell |
| JP7004091B2 (en) * | 2019-10-18 | 2022-02-04 | Ｊｆｅスチール株式会社 | Manganese recovery method and recovery equipment from waste batteries |
| JP7036229B2 (en) * | 2019-10-18 | 2022-03-15 | Ｊｆｅスチール株式会社 | Manganese recovery method and recovery equipment from waste batteries |
| KR20230098861A (en) * | 2021-03-04 | 2023-07-04 | 제이에프이 스틸 가부시키가이샤 | Manganese recovery method and recovery equipment from waste batteries |
| WO2022185974A1 (en) * | 2021-03-04 | 2022-09-09 | Ｊｆｅスチール株式会社 | Method and facility for recovering manganese from waste dry battery |
| CN113846219B (en) * | 2021-09-06 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for extracting lithium from waste lithium batteries |
| CN115092923A (en) * | 2022-08-10 | 2022-09-23 | 六盘水师范学院 | A kind of comprehensive recovery and recycling method of waste dry battery |
| CN115572159B (en) * | 2022-08-25 | 2023-06-02 | 安徽格派锂电循环科技有限公司 | Method for preparing manganese-zinc ferrite material from copper-manganese waste liquid |
-
1991
- 1991-04-08 JP JP10390391A patent/JP3113307B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04310280A (en) | 1992-11-02 |
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