JPH0785898A - Method for used sodium-sulfur battery disposal - Google Patents
Method for used sodium-sulfur battery disposalInfo
- Publication number
- JPH0785898A JPH0785898A JP19607893A JP19607893A JPH0785898A JP H0785898 A JPH0785898 A JP H0785898A JP 19607893 A JP19607893 A JP 19607893A JP 19607893 A JP19607893 A JP 19607893A JP H0785898 A JPH0785898 A JP H0785898A
- Authority
- JP
- Japan
- Prior art keywords
- sulfur
- sodium
- recovered
- sulfur battery
- aluminum
- 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
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 9
- 239000011734 sodium Substances 0.000 claims abstract description 51
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 30
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000012188 paraffin wax Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 48
- 229910052717 sulfur Inorganic materials 0.000 claims description 48
- 239000011593 sulfur Substances 0.000 claims description 48
- 238000000926 separation method Methods 0.000 claims description 20
- 230000002093 peripheral effect Effects 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 229910001347 Stellite Inorganic materials 0.000 abstract description 4
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 229910000997 High-speed steel Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電力貯蔵用電池や電気
自動車用電源として開発が進められているナトリウム硫
黄電池の廃棄物から有用物質を回収することを目的とし
た使用済みナトリウム硫黄電池の処理方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a used sodium-sulfur battery for recovering useful substances from the waste of a sodium-sulfur battery which is being developed as a power storage battery or a power source for electric vehicles. It relates to a processing method.
【０００２】[0002]
【従来の技術】ナトリウム硫黄電池は、β−アルミナ製
の固体電解質管の両側に陰極活物質としてのナトリウム
と、陽極活物質としての硫黄を充填したもので、その外
周をアルミニウム製の外周容器により保護した構造の二
次電池である。このナトリウム硫黄電池は電力貯蔵用電
池として最も適したものとして開発が進められている
が、充放電を繰り返す間に徐々に劣化するため、耐用年
数である１０年を経過した後には使用済みのナトリウム
硫黄電池が大量に発生することが考えられる。2. Description of the Prior Art A sodium-sulfur battery is a solid electrolyte tube made of β-alumina filled with sodium as a cathode active material and sulfur as an anode active material on both sides, and its outer circumference is made of an aluminum outer container. It is a secondary battery with a protected structure. This sodium-sulfur battery is being developed as the most suitable battery for electric power storage, but since it gradually deteriorates during repeated charging and discharging, it is used sodium after a useful life of 10 years. It is conceivable that a large amount of sulfur batteries will be generated.
【０００３】このような使用済みのナトリウム硫黄電池
の処理技術は未だ完成されていないため、そのままの状
態で保管しておくことも考えられる。しかしナトリウム
硫黄電池の内部には消防法で危険物に指定されているナ
トリウムや硫黄が含まれているため、一箇所に保管でき
る量には限度があり、大量の使用済みのナトリウム硫黄
電池をそのまま保管することは困難である。Since the treatment technology for such a used sodium-sulfur battery has not been completed yet, it may be possible to store it as it is. However, since the sodium-sulfur battery contains sodium and sulfur that are specified as dangerous substances by the Fire Service Law, there is a limit to the amount that can be stored in one place, and a large amount of used sodium-sulfur battery can be used as is. It is difficult to store.
【０００４】なお、使用済みのナトリウム硫黄電池の処
理に関する唯一の従来技術が特開平3-88281 号公報に公
開されている。この公報には、使用済みのナトリウム硫
黄電池からナトリウムを回収した後、外周容器を陽極部
分から分離し、外周容器はアルコール浴で洗浄して再使
用するとともに、陽極部分は焼却して硫酸を回収すると
記載されている。しかし長期間にわたり使用されてきた
ナトリウム硫黄電池の外周容器は損傷されている可能性
があるため、アルコール浴で洗浄しただけで再使用する
ことは、我が国では受け入れられないと想定される。ま
た硫酸の回収工程では設備が酸腐食されるおそれがあ
る。The only conventional technique for treating used sodium-sulfur batteries is disclosed in Japanese Patent Laid-Open No. 3-88281. In this publication, after recovering sodium from a used sodium-sulfur battery, the outer container is separated from the anode part, the outer container is washed with an alcohol bath and reused, and the anode part is incinerated to recover sulfuric acid. Then it is described. However, since the outer container of the sodium-sulfur battery that has been used for a long period of time may be damaged, it is assumed that it is unacceptable in Japan to reuse the container after cleaning it with an alcohol bath. Moreover, there is a possibility that the facility is acid-corroded in the sulfuric acid recovery process.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記した従来
の問題点を解決し、使用済みのナトリウム硫黄電池から
設備を腐食させることなく、アルミニウム、その表面の
金属皮膜、ナトリウム、硫黄、多硫化ソーダ（Na2Sx )
等をそれぞれ分離して回収することができる使用済みナ
トリウム硫黄電池の処理方法を提供するために完成され
たものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems and allows aluminum, its surface metal film, sodium, sulfur, polysulfide to be used without corroding equipment from a used sodium-sulfur battery. Soda (Na 2 S x )
It was completed in order to provide a method for treating a used sodium-sulfur battery in which the above substances can be separated and recovered.
【０００６】[0006]
【課題を解決するための手段】上記の課題を解決するた
めになされた第１の発明は、使用済みナトリウム硫黄電
池のキャップを切断し、パラフィン中でナトリウムを回
収したのち外周容器をはぎ取り、この外周容器を加熱炉
内の分離媒体上で700 〜1200℃に加熱してアルミニウム
を滴下させ、このアルミニウムと分離媒体上に残存した
金属皮膜とを分離回収することを特徴とするものであ
る。The first invention made to solve the above problems is to cut a cap of a used sodium-sulfur battery, collect sodium in paraffin, and then peel off an outer peripheral container. The outer peripheral container is heated to 700 to 1200 ° C. on a separation medium in a heating furnace to drop aluminum, and the aluminum and the metal film remaining on the separation medium are separated and recovered.
【０００７】また第２の発明は、使用済みナトリウム硫
黄電池のキャップを切断し、パラフィン中でナトリウム
を回収したのち外周容器をはぎ取り、残部を不活性雰囲
気中で加熱して硫黄を蒸発させるとともに、蒸発した硫
黄を冷却固化して固体硫黄として回収することを特徴と
するものである。A second aspect of the invention is to cut the cap of a used sodium-sulfur battery, collect sodium in paraffin, strip off the outer peripheral container, heat the rest in an inert atmosphere to evaporate sulfur, and It is characterized in that the evaporated sulfur is cooled and solidified and recovered as solid sulfur.
【０００８】また第３の発明は、使用済みナトリウム硫
黄電池のキャップを切断し、パラフィン中でナトリウム
を回収したのち外周容器をはぎ取り、残部を不活性雰囲
気中で目的とするNa2Sx のｘ値に対応する温度に加熱し
て硫黄を蒸発させるとともに、蒸発した硫黄を冷却固化
して固体硫黄を回収し、硫黄分離後の部分をアルコール
又は水中に浸漬してNa2Sx を抽出・回収することを特徴
とするものである。なお、この第１の発明と第２の発明
とは一連の工程で行うことができ、第１の発明と第３の
発明とを一連の工程で行うこともできる。In a third aspect of the present invention, the cap of a used sodium-sulfur battery is cut, sodium is recovered in paraffin, the outer peripheral container is stripped off, and the remainder is x in the target Na 2 S x in an inert atmosphere. While heating to a temperature corresponding to the value to evaporate sulfur, the evaporated sulfur is cooled and solidified to recover solid sulfur, and the portion after sulfur separation is immersed in alcohol or water to extract and recover Na 2 S x. It is characterized by doing. The first invention and the second invention can be carried out in a series of steps, and the first invention and the third invention can also be carried out in a series of steps.
【０００９】[0009]
【作用】第１の発明によれば、使用済みナトリウム硫黄
電池から、ナトリウムと、アルミニウムと、その表面の
高価な金属皮膜とをそれぞれ分離して回収することがで
きる。第２の発明によれば、使用済みナトリウム硫黄電
池から、ナトリウムと硫黄とをそれぞれ分離して回収す
ることができる。第３の発明によれば、使用済みナトリ
ウム硫黄電池から、ナトリウムと、有価物質である多硫
化ソーダとをそれぞれ分離して回収することができる。
なおいずれの発明においても、設備が酸腐食されるおそ
れはない。以下に各発明を順次詳細に説明するが、図１
に各発明を総合した使用済みナトリウム硫黄電池の処理
フローの全体を示す。According to the first aspect of the present invention, sodium, aluminum and an expensive metal film on the surface of the used sodium-sulfur battery can be separated and recovered. According to the second aspect of the invention, sodium and sulfur can be separated and recovered from the used sodium-sulfur battery. According to the third invention, sodium and sodium polysulfide, which is a valuable substance, can be separated and recovered from the used sodium-sulfur battery.
In any of the inventions, there is no risk of acid corrosion of equipment. Each of the inventions will be described in detail below.
Shows the entire processing flow of the used sodium-sulfur battery, which is a synthesis of each invention.
【００１０】[0010]
（第１の発明）図２は使用済みナトリウム−硫黄電池の
断面構造を示す図であって、１はアルミニウム製の外周
容器、２はその内部に収納されたβ−アルミナ製の固体
電解質管、３は陽極活物質としての硫黄、４は陰極活物
質としてのナトリウム、５はキャップ、６は集電棒であ
る。この外周容器１の内面には、ステライト（Co-Cr-W-
C 系合金) 等の金属皮膜がコーティングされている。(First Invention) FIG. 2 is a view showing a cross-sectional structure of a used sodium-sulfur battery, wherein 1 is an outer peripheral container made of aluminum, 2 is a solid electrolyte tube made of β-alumina housed therein, 3 is sulfur as an anode active material, 4 is sodium as a cathode active material, 5 is a cap, and 6 is a collector rod. On the inner surface of the outer container 1, stellite (Co-Cr-W-
A metal film such as C type alloy) is coated.
【００１１】まず、使用済みナトリウム−硫黄電池のキ
ャップ５を機械的に切断し、必要に応じて上部からドリ
ル等で孔を明けて電極上部を開口し、図３のように陰極
部を露出させる。次にこれを図４のようにナトリウムの
融点以上の温度に加温されたパラフィン８の入った槽７
の内部に開口部を下向きとして浸漬する。するとパラフ
ィン８よりも比重の大きいナトリウムは槽７の底部に流
下し、回収できる。なお、ナトリウムは水分との接触に
より激しく反応するが、パラフィン８は全く水分を含有
しないので反応が生ずることはなく、陰極部のナトリウ
ムは容易に回収される。First, the used sodium-sulfur battery cap 5 is mechanically cut, and if necessary, a hole is drilled from the upper part to open the upper part of the electrode to expose the cathode part as shown in FIG. . Next, as shown in FIG. 4, this was placed in a tank 7 containing paraffin 8 heated to a temperature above the melting point of sodium.
Immerse the inside of the container with the opening facing downward. Then, sodium having a higher specific gravity than the paraffin 8 flows down to the bottom of the tank 7 and can be collected. It should be noted that sodium reacts violently with contact with water, but paraffin 8 does not contain water at all, so no reaction occurs, and sodium in the cathode portion is easily recovered.
【００１２】このようにしてナトリウムを回収した後、
使用済みナトリウム−硫黄電池の外周容器１をβ−アル
ミナ製の固体電解質管２から機械的にはぎ取り、外周容
器１を例えば縦方向に２等分して断面半円状とする。こ
れを図５のように加熱炉９内のすのこ状あるいは網状の
分離媒体10上に載せ、700 〜1200℃に加熱する。すると
融点が約660 ℃のアルミニウムは溶融して分離媒体10か
ら下方の容器11内へ滴下し、融点が1200℃よりも高いス
テライト等の金属皮膜のみが分離媒体10上に残ることと
なる。このようにして完全にアルミニウムと金属皮膜と
が分離された後、分離媒体10上から金属皮膜を取り出せ
ばよい。なお、容器11に回収されたアルミニウムの純度
は99％以上であって利用価値が高く、またステライト等
の金属皮膜は高速度鋼の製造原料等として再利用するこ
とができる。After recovering sodium in this way,
The outer peripheral container 1 of a used sodium-sulfur battery is mechanically stripped from the solid electrolyte tube 2 made of β-alumina, and the outer peripheral container 1 is divided into, for example, two parts in the vertical direction to have a semicircular cross section. As shown in FIG. 5, this is placed on a saw-shaped or mesh-shaped separation medium 10 in a heating furnace 9 and heated to 700 to 1200 ° C. Then, aluminum having a melting point of about 660 ° C. is melted and dropped from the separation medium 10 into the container 11 below, and only a metal film such as stellite having a melting point higher than 1200 ° C. remains on the separation medium 10. After the aluminum and the metal film are completely separated in this way, the metal film may be taken out from the separation medium 10. The aluminum recovered in the container 11 has a purity of 99% or more and is highly useful, and a metal film such as stellite can be reused as a raw material for producing high speed steel.
【００１３】（第２の発明）一方、外周容器１をはぎ取
られた残部は図６のように陽極部の硫黄３を露出させ
る。そしてこれを図７に示すように電気炉のような加熱
炉12に入れ、不活性ガス雰囲気中で200 〜1000℃に加熱
する。すると陽極部の硫黄３は酸化されることなく蒸発
するので、発生した硫黄の蒸気をヒータ14付きのパイプ
15で冷却固化装置16へ導き、冷却して固化させる。この
結果、純度が99.9％以上の硫黄が得られるので、この硫
黄はナトリウム硫黄電池の陽極活性物質として再利用す
ることができる。なお、加熱炉12の排ガスはスクラバー
17を通したうえで大気中へ放出すればよい。この方法に
よれば、硫黄を蒸発させて冷却固化し固体硫黄として回
収するので、従来法のように設備を腐食させるおそれの
ある硫酸等を生じさせることがない。(Second invention) On the other hand, the remaining part of the outer peripheral container 1 stripped off exposes the sulfur 3 in the anode part as shown in FIG. Then, as shown in FIG. 7, it is placed in a heating furnace 12 such as an electric furnace and heated to 200 to 1000 ° C. in an inert gas atmosphere. Then, the sulfur 3 in the anode part evaporates without being oxidized, so the generated sulfur vapor is piped with the heater 14.
At 15 it is led to the cooling and solidifying device 16 where it is cooled and solidified. As a result, sulfur having a purity of 99.9% or more can be obtained, and this sulfur can be reused as the anode active material of the sodium-sulfur battery. The exhaust gas from the heating furnace 12 is a scrubber.
It may be released through the air after passing through 17. According to this method, since sulfur is evaporated, cooled and solidified to be recovered as solid sulfur, sulfuric acid or the like which may corrode equipment unlike the conventional method is not generated.
【００１４】（第３の発明）上記の第２の発明は硫黄の
回収を目的としたものであるが、第３の発明はNa2S
x （多硫化ソーダ）の回収を目的としたものである。第
３の発明でも、外周容器１をはぎ取られた残部（陽極部
分）の硫黄３を露出させ、図７に示すように電気炉のよ
うな加熱炉12に入れ、不活性ガス雰囲気中で200 〜1000
℃に加熱し、陽極部分の硫黄を蒸発させる。しかし第３
の発明では、回収目的とするNa2Sx のｘ値に対応する温
度に加熱して硫黄を蒸発させる。これは、加熱温度と後
工程において回収されるNa2Sx のｘ値との間に、図８の
通りの関係があることが確認されたためである。このた
め、例えば後工程においてNa2S6 を回収したい場合には
約350 ℃で加熱すればよく、後工程においてNa2S3 を回
収したい場合には約1000℃で加熱すればよい。(Third Invention) The second invention described above is intended to recover sulfur, but the third invention is Na 2 S.
The purpose is to recover x (sodium polysulfide). Also in the third invention, the peripheral container 1 is exposed to the remaining sulfur 3 (anode portion) that has been stripped off, and placed in a heating furnace 12 such as an electric furnace as shown in FIG. ~ 1000
Heat to ° C to evaporate the sulfur in the anode part. But the third
In the invention, the sulfur is evaporated by heating to a temperature corresponding to the x value of Na 2 S x to be recovered. This is because it was confirmed that there is a relationship as shown in FIG. 8 between the heating temperature and the x value of Na 2 S x recovered in the subsequent step. Therefore, for example, if it is desired to recover Na 2 S 6 in the subsequent step, it may be heated at about 350 ° C., and if it is desired to recover Na 2 S 3 in the subsequent step, it may be heated at about 1000 ° C.
【００１５】このようにして硫黄３を蒸発させ、第２の
発明と同様に硫黄の蒸気を冷却固化し固体硫黄を回収し
た後、図９のように硫黄分離後の陽極部分を粉砕してア
ルコール又は水18に浸漬して陽極部分に含まれるNa2Sx
を抽出し、その後、ろ過により固体を除きNa2Sx を回収
したり、図10の例のように硫黄分離後の陽極部分をその
ままアルコール又は水18に浸漬して陽極部分に含まれる
Na2Sx を抽出し回収する。抽出の際のアルコール又は水
の量は陽極部分１ｇ当り100cc 程度とすればよく、陽極
部分を室温で30分程度浸漬する。なお、図10は硫黄分離
後の陽極部分をコンベヤ19に載せてアルコール又は水18
の中を移動させる方法を示しており、コンベヤ19のスピ
ードは陽極部分が必要な時間浸漬できるスピードに調整
されている。In this way, the sulfur 3 is evaporated, the vapor of sulfur is cooled and solidified in the same manner as in the second aspect of the invention, and the solid sulfur is recovered. Then, as shown in FIG. Alternatively, Na 2 S x contained in the anode part by immersing in water 18
And then remove the solid by filtration to recover Na 2 S x , or as in the example of FIG. 10, the anode part after sulfur separation is immersed in alcohol or water 18 as it is and contained in the anode part.
Extract and recover Na 2 S x . The amount of alcohol or water at the time of extraction may be about 100 cc per 1 g of the anode part, and the anode part is immersed at room temperature for about 30 minutes. In FIG. 10, the anode part after sulfur separation is placed on the conveyor 19 and the alcohol or water 18
The speed of the conveyor 19 is adjusted so that the anode part can be dipped for the required time.
【００１６】Na2Sx はそのｘ値に応じて染料や薬品等の
種々の用途があり、大３の発明ではこのNa2Sx のｘ値を
前工程の温度によって自由に制御できるので、目的とす
るｘ値を持ったNa2Sx を得ることができる。なお、濾過
された固形物中には陽極を構成しているカーボンマット
が含まれるので、これは乾燥後再びカーボンマットとし
て使用することができる。Na 2 S x has various uses such as dyes and chemicals depending on its x value, and in the three major inventions, the x value of Na 2 S x can be freely controlled by the temperature of the previous step. It is possible to obtain Na 2 S x having the target x value. Since the filtered solid matter contains the carbon mat which constitutes the anode, it can be reused as a carbon mat after drying.
【００１７】[0017]
【発明の効果】以上に詳細に説明したように、第１の発
明によれば、使用済みナトリウム硫黄電池から、ナトリ
ウムと、アルミニウムと、その表面の高価な金属皮膜と
をそれぞれ分離して回収することができる。また第２の
発明によれば、使用済みナトリウム硫黄電池から、ナト
リウムと硫黄とをそれぞれ分離して回収することがで
き、第３の発明によれば、使用済みナトリウム硫黄電池
から、ナトリウムと、有価物質である多硫化ソーダとを
それぞれ分離して回収することができる。なおいずれの
発明においても、従来法のように処理工程で硫酸が発生
することがないので、設備が酸腐食されるおそれはな
い。よって本発明は従来の問題点を解消した使用済みナ
トリウム硫黄電池の処理方法として、産業の発展に寄与
するところはきわめて大きいものがある。As described in detail above, according to the first invention, sodium, aluminum, and an expensive metal film on the surface of the used sodium-sulfur battery are separated and recovered. be able to. Further, according to the second invention, it is possible to separate and collect sodium and sulfur from the used sodium-sulfur battery, respectively, and according to the third invention, the used sodium-sulfur battery is used to collect sodium and valuable sodium. Sodium polysulfide, which is the substance, can be separated and recovered. In any of the inventions, sulfuric acid is not generated in the treatment step as in the conventional method, and therefore there is no risk of acid corrosion of equipment. Therefore, the present invention has an extremely great contribution to the industrial development as a method of treating a used sodium-sulfur battery that solves the conventional problems.
【図１】使用済みナトリウム硫黄電池の処理フローの全
体を示すブロック図である。FIG. 1 is a block diagram showing an overall processing flow of a used sodium-sulfur battery.
【図２】使用済みナトリウム硫黄電池を示す断面図であ
る。FIG. 2 is a sectional view showing a used sodium-sulfur battery.
【図３】使用済みナトリウム硫黄電池のキャップを切断
し、ドリルで穴明けをした状態を示す断面図である。FIG. 3 is a cross-sectional view showing a state where a cap of a used sodium-sulfur battery is cut and a hole is drilled.
【図４】使用済みナトリウム硫黄電池からナトリウムを
回収する工程を示す断面図である。FIG. 4 is a cross-sectional view showing a step of recovering sodium from a used sodium-sulfur battery.
【図５】使用済みナトリウム硫黄電池からアルミニウム
と金属皮膜とを分離回収する工程を示す断面図である。FIG. 5 is a cross-sectional view showing a step of separating and recovering aluminum and a metal film from a used sodium-sulfur battery.
【図６】使用済みナトリウム硫黄電池の外周容器を剥ぎ
取った状態を示す断面図である。FIG. 6 is a cross-sectional view showing a state in which a peripheral container of a used sodium-sulfur battery is stripped off.
【図７】硫黄の回収工程を示す断面図である。FIG. 7 is a cross-sectional view showing a sulfur recovery step.
【図８】硫黄回収工程における加熱温度と、後工程にお
いて回収されるNa2Sx のｘ値との関係を示すグラフであ
る。FIG. 8 is a graph showing the relationship between the heating temperature in the sulfur recovery step and the x value of Na 2 S x recovered in the subsequent step.
【図９】硫黄分離後の陽極部分の破砕品よりNa2Sx を抽
出する工程の一例を示す断面図である。FIG. 9 is a cross-sectional view showing an example of a step of extracting Na 2 S x from the crushed product of the anode portion after sulfur separation.
【図10】硫黄分離後の陽極部分よりNa2Sx を抽出する工
程の一例を示す断面図である。FIG. 10 is a cross-sectional view showing an example of a step of extracting Na 2 S x from the anode portion after sulfur separation.
１ 外周容器、２ 固体電解質管、３ 陽極活性物質で
ある硫黄、４ 陰極活性物質であるナトリウム、５ キ
ャップ、６ 集電棒、７ 槽、８ パラフィン、９ 加
熱炉、10 分離媒体、11 容器、12 加熱炉、14 ヒー
タ、15 パイプ、16 冷却固化装置、17 スクラバー、
18 アルコール又は水、19 コンベヤ1 outer peripheral container, 2 solid electrolyte tube, 3 sulfur as an anode active substance, 4 sodium as a cathode active substance, 5 cap, 6 collector rod, 7 tank, 8 paraffin, 9 heating furnace, 10 separation medium, 11 container, 12 Heating furnace, 14 heaters, 15 pipes, 16 cooling and solidifying equipment, 17 scrubbers,
18 alcohol or water, 19 conveyor
───────────────────────────────────────────────────── フロントページの続き (72)発明者 蔵島 吉彦 愛知県名古屋市熱田区花表町17番20号 花 表団地314号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiko Kurashima 17-20 Hanaomote-cho, Atsuta-ku, Aichi Prefecture
Claims (5)
切断し、パラフィン中でナトリウムを回収したのち外周
容器をはぎ取り、この外周容器を加熱炉内の分離媒体上
で700 〜1200℃に加熱してアルミニウムを滴下させ、こ
のアルミニウムと分離媒体上に残存した金属皮膜とを分
離回収することを特徴とする使用済みナトリウム硫黄電
池の処理方法。1. A cap of a used sodium-sulfur battery is cut, sodium is recovered in paraffin, and then an outer peripheral container is stripped off. The outer peripheral container is heated to 700 to 1200 ° C. on a separation medium in a heating furnace, and aluminum is heated. A method for treating a used sodium-sulfur battery, characterized in that the aluminum and the metal film remaining on the separation medium are separated and recovered.
切断し、パラフィン中でナトリウムを回収したのち外周
容器をはぎ取り、残部を不活性雰囲気中で加熱して硫黄
を蒸発させるとともに、蒸発した硫黄を冷却固化して固
体硫黄として回収することを特徴とする使用済みナトリ
ウム硫黄電池の処理方法。2. A cap of a used sodium-sulfur battery is cut, sodium is recovered in paraffin, an outer peripheral container is stripped off, the rest is heated in an inert atmosphere to evaporate sulfur, and the evaporated sulfur is cooled. A method for treating a used sodium-sulfur battery, which comprises solidifying and recovering it as solid sulfur.
切断し、パラフィン中でナトリウムを回収したのち外周
容器をはぎ取り、残部を不活性雰囲気中で目的とするNa
2Sx のｘ値に対応する温度に加熱して硫黄を蒸発させる
とともに、蒸発した硫黄を冷却固化して固体硫黄を回収
し、硫黄分離後の部分をアルコール又は水中に浸漬して
Na2Sx を抽出・回収することを特徴とする使用済みナト
リウム硫黄電池の処理方法。3. The cap of a used sodium-sulfur battery is cut off, sodium is recovered in paraffin, the outer peripheral container is stripped off, and the remaining portion of the target sodium
2 S x is heated to a temperature corresponding to the x value to evaporate sulfur, and the evaporated sulfur is cooled and solidified to recover solid sulfur, and the portion after sulfur separation is immersed in alcohol or water.
A method for treating a used sodium-sulfur battery, which comprises extracting and recovering Na 2 S x .
切断し、パラフィン中でナトリウムを回収したのち外周
容器をはぎ取り、この外周容器を加熱炉内の分離媒体上
で700 〜1200℃に加熱してアルミニウムを滴下させ、こ
のアルミニウムと分離媒体上に残存した金属皮膜とを分
離回収する一方、残部を不活性雰囲気中で加熱して硫黄
を蒸発させるとともに、蒸発した硫黄を冷却固化して固
体硫黄として回収することを特徴とする使用済みナトリ
ウム硫黄電池の処理方法。4. A cap of a used sodium-sulfur battery is cut, sodium is recovered in paraffin, and then an outer peripheral container is stripped off. The outer peripheral container is heated to 700 to 1200 ° C. on a separation medium in a heating furnace and aluminum is removed. While the aluminum and the metal film remaining on the separation medium are separated and recovered, the rest is heated in an inert atmosphere to evaporate sulfur, and the evaporated sulfur is cooled and solidified to be recovered as solid sulfur. A method for treating a used sodium-sulfur battery, comprising:
切断し、パラフィン中でナトリウムを回収したのち外周
容器をはぎ取り、この外周容器を加熱炉内の分離媒体上
で700 〜1200℃に加熱してアルミニウムを滴下させ、こ
のアルミニウムと分離媒体上に残存した金属皮膜とを分
離回収する一方、残部を不活性雰囲気中で目的とするNa
2Sx のｘ値に対応する温度に加熱して硫黄を蒸発させる
とともに、蒸発した硫黄を冷却固化して固体硫黄を回収
し、硫黄分離後の部分をアルコール又は水中に浸漬して
Na2Sx を抽出・回収することを特徴とする使用済みナト
リウム硫黄電池の処理方法。5. A cap of a used sodium-sulfur battery is cut, sodium is recovered in paraffin, and then an outer peripheral container is stripped off. The outer peripheral container is heated to 700 to 1200 ° C. on a separation medium in a heating furnace, and aluminum is removed. While the aluminum and the metal film remaining on the separation medium are separated and collected, the remainder is the target Na in an inert atmosphere.
2 S x is heated to a temperature corresponding to the x value to evaporate sulfur, and the evaporated sulfur is cooled and solidified to recover solid sulfur, and the portion after sulfur separation is immersed in alcohol or water.
A method for treating a used sodium-sulfur battery, which comprises extracting and recovering Na 2 S x .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19607893A JP2740621B2 (en) | 1992-08-14 | 1993-08-06 | How to treat used sodium-sulfur batteries |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21692592 | 1992-08-14 | ||
| JP22728492 | 1992-08-26 | ||
| JP5-127164 | 1993-05-28 | ||
| JP4-216925 | 1993-05-28 | ||
| JP4-227284 | 1993-05-28 | ||
| JP12716493 | 1993-05-28 | ||
| JP19607893A JP2740621B2 (en) | 1992-08-14 | 1993-08-06 | How to treat used sodium-sulfur batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0785898A true JPH0785898A (en) | 1995-03-31 |
| JP2740621B2 JP2740621B2 (en) | 1998-04-15 |
Family
ID=27471277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19607893A Expired - Lifetime JP2740621B2 (en) | 1992-08-14 | 1993-08-06 | How to treat used sodium-sulfur batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2740621B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5785732A (en) * | 1995-10-03 | 1998-07-28 | Ngk Insulators, Ltd. | process and apparatus for recovering Na from spent NaS cells |
| JP2012003979A (en) * | 2010-06-17 | 2012-01-05 | Mitsubishi Materials Corp | DISPOSAL FACILITY FOR NaS BATTERY AND PREPROCESSING DEVICE FOR NaS BATTERY |
| CN105811039A (en) * | 2016-05-09 | 2016-07-27 | 上海电气钠硫储能技术有限公司 | Sodium-sulfur battery recovery method |
| CN111106359A (en) * | 2020-01-17 | 2020-05-05 | 三门踱哒环保设备有限公司 | Automatic metal collecting device in waste battery |
-
1993
- 1993-08-06 JP JP19607893A patent/JP2740621B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5785732A (en) * | 1995-10-03 | 1998-07-28 | Ngk Insulators, Ltd. | process and apparatus for recovering Na from spent NaS cells |
| JP2012003979A (en) * | 2010-06-17 | 2012-01-05 | Mitsubishi Materials Corp | DISPOSAL FACILITY FOR NaS BATTERY AND PREPROCESSING DEVICE FOR NaS BATTERY |
| CN105811039A (en) * | 2016-05-09 | 2016-07-27 | 上海电气钠硫储能技术有限公司 | Sodium-sulfur battery recovery method |
| CN105811039B (en) * | 2016-05-09 | 2018-06-05 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery recovery method |
| CN111106359A (en) * | 2020-01-17 | 2020-05-05 | 三门踱哒环保设备有限公司 | Automatic metal collecting device in waste battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2740621B2 (en) | 1998-04-15 |
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