JP2020143329A - Treatment equipment and treatment method for waste lithium-ion battery and heat-resistant container - Google Patents

Treatment equipment and treatment method for waste lithium-ion battery and heat-resistant container Download PDF

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JP2020143329A
JP2020143329A JP2019040341A JP2019040341A JP2020143329A JP 2020143329 A JP2020143329 A JP 2020143329A JP 2019040341 A JP2019040341 A JP 2019040341A JP 2019040341 A JP2019040341 A JP 2019040341A JP 2020143329 A JP2020143329 A JP 2020143329A
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heat
resistant container
cooling
waste lithium
ion battery
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JP7174652B2 (en
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充志 中村
Mitsuji Nakamura
充志 中村
本間　健一
Kenichi Honma
健一 本間
泰之 石田
Yasuyuki Ishida
泰之 石田
誠司 福田
Seiji Fukuda
誠司 福田
浦田　泰裕
Yasuhiro Urata
泰裕 浦田
章宏 大河内
Akihiro Okochi
章宏 大河内
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Taiheiyo Cement Corp
Matsuda Sangyo Co Ltd
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Matsuda Sangyo Co Ltd
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    • 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

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Abstract

To treat waste lithium ion batteries safely and efficiently.SOLUTION: There is provided a waste lithium ion battery processing device 1 comprising: a heat-resistant container 2 for storing waste lithium ion batteries, a heat treatment furnace 3 for heating the heat-resistant container, a container transport device 4 for loading and unloading the heat-resistant container into the heat treatment furnace, and a cooling device 32 that cools with cooling water the lower part of the heat-resistant container which has been unloaded from the heat treatment furnace by the container transport device. It may be provided with a pressure control device that controls the inside of a cooling chamber 31 that surrounds the heat-resistant container being cooled by the cooling device so that the pressure is negative, and it may be provided with an exhaust gas treatment device that supplies exhaust gas from the cooling chamber to an exhaust gas treatment system of cement kiln. It may be provided with a path to release water vapor generated upon cooling the lower part of the heat-resistant container with cooling water to the outside of the system.SELECTED DRAWING: Figure 1

Description

本発明は、電気自動車やハイブリッド自動車等の電源として使用された廃リチウムイオン電池の処理装置及び処理方法、並びに廃リチウムイオン電池を処理する際に用いられる耐熱容器に関する。 The present invention relates to a processing apparatus and processing method for a waste lithium ion battery used as a power source for an electric vehicle, a hybrid vehicle, or the like, and a heat-resistant container used for processing the waste lithium ion battery.

リチウムイオン電池は、アルミ箔にリチウム、コバルト、ニッケル等を塗布した正極材と、銅箔に黒鉛等を塗布した負極材と、電解液と、セパレーター等で構成される。リチウムイオン電池は、リチウム、コバルト、ニッケル、銅、アルミニウム等の有価物を含むため、廃棄されたリチウム電池からこれらの有価物を回収することは、資源に乏しいわが国にとって極めて有益である。そこで、廃リチウムイオン電池から上記有価物を回収するため、焙焼、破砕又は粉砕、篩分け、選別等による分離回収が行われている。 A lithium ion battery is composed of a positive electrode material in which lithium, cobalt, nickel or the like is coated on an aluminum foil, a negative electrode material in which graphite or the like is coated on a copper foil, an electrolytic solution, a separator or the like. Since lithium-ion batteries contain valuable resources such as lithium, cobalt, nickel, copper, and aluminum, it is extremely beneficial for Japan, which is scarce in resources, to recover these valuable resources from discarded lithium batteries. Therefore, in order to recover the valuable resources from the waste lithium ion battery, separation and recovery by roasting, crushing or crushing, sieving, sorting and the like are performed.

しかし、リチウムイオン電池の電解液には、電解質となるフッ素化合物（ＬｉＰＦ6等）が含まれており、ＬｉＰＦ6は水と反応すると加水分解して有毒なフッ化水素を発生する。そこで、特許文献１には、複数個のリチウムイオン電池セルが配列された電池モジュールが箱型筺体内に複数収納されてなる電池パックを排気口が設けられた耐熱容器に格納した後、耐熱容器を熱処理炉に投入して還元雰囲気下で３００℃〜６５０℃で加熱することで、耐熱容器部の電池パックを乾留して炭化混合物を分離すると共に、電池内の電解液を揮発化して耐熱容器の排気口から熱処理炉内に排出させることで、極めて簡易な作業で廃リチウムイオン電池をリサイクル処理する方法が開示されている。 However, the electrolytic solution of the lithium ion battery contains a fluorine compound (LiPF 6 or the like) that serves as an electrolyte, and when LiPF 6 reacts with water, it hydrolyzes to generate toxic hydrogen fluoride. Therefore, in Patent Document 1, a battery pack in which a plurality of battery modules in which a plurality of lithium ion battery cells are arranged is housed in a box-shaped housing is stored in a heat-resistant container provided with an exhaust port, and then the heat-resistant container is provided. Is put into a heat treatment furnace and heated at 300 ° C. to 650 ° C. in a reducing atmosphere to dry-distill the battery pack in the heat-resistant container to separate the carbonized mixture, and volatilize the electrolytic solution in the battery to heat the heat-resistant container. A method of recycling a waste lithium-ion battery by discharging it into a heat treatment furnace from the exhaust port of the above is disclosed.

一方、特許文献２には、廃リチウムイオン電池を処理する際に、揮発性のフッ素化合物（ＬｉＰＦ6等）等を安全に処理するため、放電処理を行った後、安全弁を開口し、フッ素化合物を含む電解液の揮発成分を減圧下で加熱して気化させる気化工程、気化したガスに含まれるフッ素成分をカルシウムと反応させてフッ化カルシウムとして固定するフッ素固定工程等を備えるフッ素含有電解液の処理方法が記載されている。 On the other hand, in Patent Document 2, in order to safely treat volatile fluorine compounds (LiPF 6 etc.) and the like when treating waste lithium ion batteries, after performing discharge treatment, a safety valve is opened and the fluorine compounds are treated. A fluorine-containing electrolytic solution comprising a vaporization step of heating the volatile component of the electrolytic solution containing the above to vaporize it under reduced pressure, a fluorine fixing step of reacting the fluorine component contained in the vaporized gas with calcium and fixing it as calcium fluoride, and the like. The processing method is described.

特開２０１６−２２３９５号公報Japanese Unexamined Patent Publication No. 2016-22395 特開２０１３−２２９３２６号公報Japanese Unexamined Patent Publication No. 2013-229326

しかし、特許文献１及び特許文献２に記載の技術で加熱処理を行った後、大気下で自然冷却を行うと、加熱した廃リチウムイオン電池からフッ化水素、塩化水素等を含む有害なガスが発生する可能性があるため安全面で課題が残る。また、自然冷却に長時間を要するため、効率的な処理の妨げになっていた。さらに、廃リチウムイオン電池等に冷却水を噴霧して冷却し、発生した蒸気をセメント製造工程に導入すると、セメント製造工程での熱損失や、セメントクリンカの減産に繋がるおそれがあった。 However, when heat treatment is performed by the techniques described in Patent Document 1 and Patent Document 2 and then natural cooling is performed in the atmosphere, harmful gases including hydrogen fluoride, hydrogen chloride, etc. are released from the heated waste lithium ion battery. Since it may occur, safety issues remain. In addition, it takes a long time for natural cooling, which hinders efficient processing. Further, if cooling water is sprayed on a waste lithium ion battery or the like to cool it and the generated steam is introduced into the cement manufacturing process, there is a risk of causing heat loss in the cement manufacturing process and reducing the production of cement clinker.

そこで、本発明は、上記従来の技術における問題点に鑑みてなされたものであって、安全かつ効率的に廃リチウムイオン電池を処理することができ、セメント製造工程に悪影響を与えることもない廃リチウムイオン電池の処理装置等を提供することを目的とする。 Therefore, the present invention has been made in view of the above-mentioned problems in the prior art, and can safely and efficiently treat the waste lithium ion battery and does not adversely affect the cement manufacturing process. An object of the present invention is to provide a processing device for a lithium ion battery or the like.

上記目的を達成するため、本発明は、廃リチウムイオン電池の処理装置であって、廃リチウムイオン電池を収容する耐熱容器と、該耐熱容器を加熱する熱処理炉と、該熱処理炉に前記耐熱容器を投入及び排出する容器搬送装置と、該容器搬送装置によって前記熱処理炉から排出された耐熱容器の下部を冷却水を用いて冷却する冷却装置とを備えることを特徴とする。 In order to achieve the above object, the present invention is a waste lithium ion battery processing apparatus, which comprises a heat-resistant container for accommodating the waste lithium-ion battery, a heat treatment furnace for heating the heat-resistant container, and the heat-resistant container in the heat treatment furnace. It is characterized by including a container transport device for loading and unloading, and a cooling device for cooling the lower part of the heat-resistant container discharged from the heat treatment furnace by the container transport device using cooling water.

本発明によれば、熱処理炉から排出された耐熱容器の下部を冷却水を用いて冷却するため、熱処理後の廃リチウムイオン電池を短時間で冷却することができ、効率的に廃リチウムイオン電池を処理することができる。 According to the present invention, since the lower part of the heat-resistant container discharged from the heat treatment furnace is cooled by using cooling water, the waste lithium ion battery after the heat treatment can be cooled in a short time, and the waste lithium ion battery can be efficiently cooled. Can be processed.

上記廃リチウムイオン電池の処理装置において、前記冷却装置で冷却中の耐熱容器を囲繞する冷却室の内部が負圧になるように制御する圧力制御装置を備えることができ、これによって、フッ化水素、塩化水素等を含む有害ガスが冷却室から放出されるのを防止することができる。 The waste lithium-ion battery processing device may be provided with a pressure control device that controls the inside of the cooling chamber surrounding the heat-resistant container being cooled by the cooling device so that the pressure becomes negative, thereby hydrogen fluoride. , Hazardous gas containing hydrogen chloride and the like can be prevented from being released from the cooling chamber.

また、前記冷却室の排ガスをセメントキルンの排ガス処理系統に供給する排ガス処理装置を備えることができ、これによって、フッ化水素、塩化水素等を含む有害ガスをセメント製造工程内のセメント原料に固定化して無害化することができる。 In addition, an exhaust gas treatment device that supplies the exhaust gas from the cooling chamber to the exhaust gas treatment system of the cement kiln can be provided, whereby harmful gas containing hydrogen fluoride, hydrogen chloride, etc. is fixed to the cement raw material in the cement manufacturing process. It can be made harmless.

さらに、前記耐熱容器の下部を冷却水で冷却した際に発生した水蒸気を系外に放出する経路を有することで、発生した蒸気をセメント製造工程に導入する必要がなく、セメント製造工程での熱損失や、セメントクリンカの減産を回避することができる。 Further, by having a path for releasing the steam generated when the lower part of the heat-resistant container is cooled with cooling water to the outside of the system, it is not necessary to introduce the generated steam into the cement manufacturing process, and the heat in the cement manufacturing process is not required. Losses and reductions in cement clinker production can be avoided.

また、本発明は、廃リチウムイオン電池の処理方法であって、廃リチウムイオン電池を収容した耐熱容器を加熱し、加熱後の耐熱容器の下部を冷却水を用いて冷却することを特徴とする。本発明によれば、加熱後の耐熱容器の下部を冷却することで熱処理後の廃リチウムイオン電池を短時間で冷却することができ、効率的に廃リチウムイオン電池を処理することができる。 Further, the present invention is a method for treating a waste lithium ion battery, which comprises heating a heat-resistant container containing the waste lithium-ion battery and cooling the lower portion of the heated heat-resistant container with cooling water. .. According to the present invention, the waste lithium ion battery after heat treatment can be cooled in a short time by cooling the lower part of the heat-resistant container after heating, and the waste lithium ion battery can be treated efficiently.

さらに、本発明は、廃リチウムイオン電池を収容した後熱処理炉で加熱され、加熱後に下部を冷却水を用いて冷却される耐熱容器であって、廃リチウムイオン電池を収容する収容部と、該収容部の下方に、前記冷却水が導入される空間を有することを特徴とする。この耐熱容器を用いることで、効率的に廃リチウムイオン電池を処理することができる。 Further, the present invention is a heat-resistant container in which a waste lithium ion battery is housed and then heated in a heat treatment furnace, and the lower part is cooled by using cooling water after heating. It is characterized by having a space below the accommodating portion into which the cooling water is introduced. By using this heat-resistant container, the waste lithium ion battery can be treated efficiently.

以上のように、本発明によれば、安全かつ効率的に廃リチウムイオン電池を処理することができ、セメント製造工程に悪影響を与えることもない。 As described above, according to the present invention, the waste lithium ion battery can be treated safely and efficiently, and the cement manufacturing process is not adversely affected.

本発明に係る廃リチウムイオン電池の処理装置の一実施の形態を示す全体横断面図である。It is an overall cross-sectional view which shows one Embodiment of the waste lithium ion battery processing apparatus which concerns on this invention. 本発明に係る廃リチウムイオン電池の処理装置の一実施の形態を示す全体縦断面図である。It is an overall vertical sectional view which shows one Embodiment of the processing apparatus of the waste lithium ion battery which concerns on this invention. 図２のＡ矢視図であって、炉前室及び冷却室等を示す概略図である。FIG. 2 is a view taken along the arrow A of FIG. 2, which is a schematic view showing a furnace front chamber, a cooling chamber, and the like. 本発明に係る廃リチウムイオン電池の処理装置の冷却装置を示す全体構成図である。It is an overall block diagram which shows the cooling apparatus of the processing apparatus of the waste lithium ion battery which concerns on this invention. 本発明に係る廃リチウムイオン電池の処理装置で用いる耐熱容器を示す縦断面図である。It is a vertical sectional view which shows the heat-resistant container used in the processing apparatus of the waste lithium ion battery which concerns on this invention. 熱処理炉に投入される直前の耐熱容器を示す横断面図である。It is a cross-sectional view which shows the heat-resistant container just before being put into a heat treatment furnace. 熱処理炉に投入される直前の耐熱容器を示す縦断面図である。It is a vertical cross-sectional view which shows the heat-resistant container just before being put into a heat treatment furnace. 熱処理炉への耐熱容器の投入動作を説明するための概略図である。It is the schematic for demonstrating the operation of putting a heat-resistant container into a heat treatment furnace. 熱処理炉への耐熱容器の投入・排出動作を説明するための概略図である。It is a schematic diagram for demonstrating the operation of putting and discharging a heat-resistant container into a heat treatment furnace. 熱処理炉への耐熱容器の投入・排出動作を説明するための概略図である。It is a schematic diagram for demonstrating the operation of putting and discharging a heat-resistant container into a heat treatment furnace. 冷却室及び熱処理炉への耐熱容器の投入・排出動作を説明するための概略図である。It is the schematic for demonstrating the charge | charge operation of the heat-resistant container into a cooling chamber and a heat treatment furnace. 冷却室からの耐熱容器の排出動作を説明するための概略図である。It is the schematic for demonstrating the discharge operation of the heat-resistant container from a cooling chamber.

次に、本発明の一実施の形態について図面を参照しながら詳細に説明する。 Next, an embodiment of the present invention will be described in detail with reference to the drawings.

図１〜図３に示すように、本発明に係る廃リチウムイオン電池の処理装置１は、複数個のリチウムイオン電池セルが配列された電池モジュールが箱型筐体内に複数収納された電池パック５０に加熱処理を施して有用金属を回収するものであって、主に電池パック５０を格納する複数の耐熱容器２と、熱処理炉３と、熱処理炉３に耐熱容器２を投入及び排出する容器搬送装置４と、熱処理後の耐熱容器２を冷却する冷却室３１等を備える。 As shown in FIGS. 1 to 3, the waste lithium ion battery processing device 1 according to the present invention has a battery pack 50 in which a plurality of battery modules in which a plurality of lithium ion battery cells are arranged are housed in a box-shaped housing. A plurality of heat-resistant containers 2 mainly for storing the battery pack 50, a heat treatment furnace 3, and a container transport for charging and discharging the heat-resistant container 2 into the heat treatment furnace 3 are used to recover useful metals. The apparatus 4 is provided with a cooling chamber 31 and the like for cooling the heat-resistant container 2 after heat treatment.

熱処理炉３は円筒状の縦型炉であり、４本のガスバーナー８（８Ａ〜８Ｄ）によって加熱される。ガスバーナー８の近傍にはノズル１１（１１Ａ〜１１Ｄ）が設けられ、ファン（不図示）によって燃焼用及び冷却用の空気Ａが炉内に供給される。熱処理炉３の炉床１７は、電動モータ（不図示）を備えた炉床回転装置１９によって鉛直軸回りに回転し、位置決めセンサ（不図示）によって所定の位置に位置決めされる。排気管２８の下流側には二次燃焼室、排気用の煙突等が設けられる。 The heat treatment furnace 3 is a cylindrical vertical furnace, and is heated by four gas burners 8 (8A to 8D). Nozzles 11 (11A to 11D) are provided in the vicinity of the gas burner 8, and air A for combustion and cooling is supplied into the furnace by a fan (not shown). The hearth 17 of the heat treatment furnace 3 is rotated about a vertical axis by a hearth rotating device 19 provided with an electric motor (not shown), and is positioned at a predetermined position by a positioning sensor (not shown). A secondary combustion chamber, a chimney for exhaust, and the like are provided on the downstream side of the exhaust pipe 28.

熱処理炉３の炉壁７の一部には、上下に開閉式の炉体扉７ｂで外部と仕切られた開口部７ａが形成される。開口部７ａに対向する位置に、開口部７ａから熱処理炉３内に耐熱容器２を投入すると共に、耐熱容器２を熱処理炉３から排出する容器搬送装置４が設けられる。 An opening 7a is formed in a part of the furnace wall 7 of the heat treatment furnace 3 so as to be separated from the outside by a furnace body door 7b that can be opened and closed vertically. At a position facing the opening 7a, a container transport device 4 is provided in which the heat-resistant container 2 is put into the heat treatment furnace 3 from the opening 7a and the heat-resistant container 2 is discharged from the heat treatment furnace 3.

容器搬送装置４は、図１、図２及び図７に示すように、熱処理炉３の開口部７ａと熱処理炉３の中心を結ぶ線上の方向（図１では左右方向）に延びると共に、モーター１８の正回転によって耐熱容器２に当接して耐熱容器２を熱処理炉３内に押し入れるプッシャー部４ａと、耐熱容器２の容器本体２Ａの外周に設けられたハンガー２ｐを係止する爪４ｃが先端に設けられ、モーター１８の負回転によって耐熱容器２を熱処理炉３内から引っ張り出すプルアウト部４ｂを備えている。プッシャー部４ａはプルアウト部４ｂの真上に位置する。 As shown in FIGS. 1, 2 and 7, the container transport device 4 extends in the direction on the line connecting the opening 7a of the heat treatment furnace 3 and the center of the heat treatment furnace 3 (left-right direction in FIG. 1), and the motor 18 A pusher portion 4a that abuts the heat-resistant container 2 and pushes the heat-resistant container 2 into the heat treatment furnace 3 by the forward rotation of the heat-resistant container 2, and a claw 4c that locks the hanger 2p provided on the outer periphery of the container body 2A of the heat-treated container 2 It is provided with a pull-out portion 4b for pulling out the heat-resistant container 2 from the heat treatment furnace 3 by the negative rotation of the motor 18. The pusher portion 4a is located directly above the pullout portion 4b.

開閉式の炉体扉７ｂに隣接して（図１において左方に）炉前室２３が設けられ、炉前室２３に隣接して（図３において右方に）冷却室３１が設けられる。熱処理炉３の接線方向（図１では上下方向に）搬送装置２９によって移動自在のスライドベース２１が設置され、スライドベース２１は、図３において、炉前室２３の左方空間と、開閉式の扉２４、２５を隔て炉前室２３及び冷却室３１の間を移動可能に構成される。尚、扉２５を設けずに炉前室２３及び冷却室３１を一つの室としてもよい。 The furnace front chamber 23 is provided adjacent to the openable furnace body door 7b (on the left in FIG. 1), and the cooling chamber 31 is provided adjacent to the furnace front chamber 23 (on the right in FIG. 3). A slide base 21 that can be moved by the transfer device 29 in the tangential direction (vertical direction in FIG. 1) of the heat treatment furnace 3 is installed, and the slide base 21 is openable and closable with the left space of the furnace front chamber 23 in FIG. It is configured to be movable between the furnace front chamber 23 and the cooling chamber 31 with the doors 24 and 25 separated from each other. The furnace front chamber 23 and the cooling chamber 31 may be combined into one chamber without providing the door 25.

冷却室３１は、開閉式の扉２５を隔てて炉前室２３に隣接し、内部には、図４に示すように、熱処理炉３から排出された耐熱容器２を冷却するための冷却装置３２が配置される。冷却装置３２は、耐熱容器２の冷却空間２ｃに冷却水を噴霧するための噴霧ノズル３３と、先端に噴霧ノズル３３を備える給水管３４と、給水管３４を内部に保持し、先端にパッキン３６を備えた排水管３５と、排水管３５を上下方向に移動させるエアシリンダ３７と、冷却水の量を調整するための流調弁３８と、給水管３４及び排水管３５に各々接続されるフレキシブルホース３９、４０とで構成され、フレキシブルホース３９に冷却水が供給され、フレキシブルホース４０から耐熱容器２の冷却で生じた蒸気が排出される。 The cooling chamber 31 is adjacent to the furnace front chamber 23 with an openable door 25 interposed therebetween, and inside, as shown in FIG. 4, a cooling device 32 for cooling the heat-resistant container 2 discharged from the heat treatment furnace 3. Is placed. The cooling device 32 holds a spray nozzle 33 for spraying cooling water into the cooling space 2c of the heat-resistant container 2, a water supply pipe 34 having a spray nozzle 33 at the tip, and a water supply pipe 34 inside, and a packing 36 at the tip. A drain pipe 35 provided with a water pipe 35, an air cylinder 37 for moving the drain pipe 35 in the vertical direction, a flow control valve 38 for adjusting the amount of cooling water, and flexible connections to the water supply pipe 34 and the drain pipe 35, respectively. It is composed of hoses 39 and 40, cooling water is supplied to the flexible hose 39, and steam generated by cooling the heat-resistant container 2 is discharged from the flexible hose 40.

また、冷却室３１の内部が負圧になるように制御する圧力制御装置（不図示）が設けられ、圧力制御装置は、冷却室３１の内部の圧力を測定する圧力計と、冷却室３１の排ガスを吸引する吸引装置と、前記圧力計の測定値が負圧になるように吸引装置を制御するコントローラ等を備える。さらに、冷却室３１の排ガスをセメントキルンの排ガス処理系統に供給する排ガス処理装置（不図示）が設けられる。 Further, a pressure control device (not shown) for controlling the inside of the cooling chamber 31 so as to have a negative pressure is provided, and the pressure control device includes a pressure gauge for measuring the pressure inside the cooling chamber 31 and a cooling chamber 31. It includes a suction device that sucks exhaust gas, a controller that controls the suction device so that the measured value of the pressure gauge becomes a negative pressure, and the like. Further, an exhaust gas treatment device (not shown) for supplying the exhaust gas from the cooling chamber 31 to the exhaust gas treatment system of the cement kiln is provided.

耐熱容器２は、図５〜図７に示すように、容器本体２Ａと蓋２Ｂとで構成され、少なくとも６５０℃の耐熱温度を有する。また、耐熱容器２は、熱伝導の高い一般構造圧延鋼（ＳＳ）、ステンレス鋼（ＳＵＳ３０４）、銅合金等の金属合金が材料として好ましいが、廃ＬＩＢモジュールＭを回転炉で加熱する際の熱に耐えるため、ステンレス鋼（ＳＵＳ３０４）等の少なくとも６５０℃の温度に耐えることができる材料からなることがより好ましい。 As shown in FIGS. 5 to 7, the heat-resistant container 2 is composed of a container body 2A and a lid 2B, and has a heat-resistant temperature of at least 650 ° C. Further, the heat-resistant container 2 is preferably made of a metal alloy such as general structure rolled steel (SS), stainless steel (SUS304), or copper alloy having high thermal conductivity, but the heat generated when the waste LIB module M is heated in a rotary furnace. It is more preferable that the material is made of a material that can withstand a temperature of at least 650 ° C., such as stainless steel (SUS304).

容器本体２Ａは、上方に開口して円筒状に形成された内筒２ａと、内筒２ａよりも大径で内筒２ａを囲繞するように配置された外筒２ｂと、内筒２ａの下方に位置する冷却空間２ｃと、冷却空間２ｃの底面視で中心部に位置する突出管２ｄと、外筒２ｂの底面に配置された複数の車輪２ｊと、外筒２ｂの周面２ｋに固定された２本の取っ手２ｅと、外筒２ｂの周面２ｋから突出するハンガー２ｐとで構成される。 The container body 2A has an inner cylinder 2a that opens upward and is formed in a cylindrical shape, an outer cylinder 2b that has a diameter larger than that of the inner cylinder 2a and is arranged so as to surround the inner cylinder 2a, and a lower portion of the inner cylinder 2a. It is fixed to the cooling space 2c located in, the protruding pipe 2d located in the center of the cooling space 2c when viewed from the bottom surface, the plurality of wheels 2j arranged on the bottom surface of the outer cylinder 2b, and the peripheral surface 2k of the outer cylinder 2b. It is composed of two handles 2e and a hanger 2p protruding from the peripheral surface 2k of the outer cylinder 2b.

一方、蓋２Ｂは、下方に開口する円筒状に形成された本体２ｎと、本体２ｎの周面に開口して斜め上方に突出する排気管２ｇと、本体２ｎの天井面２ｈに設けられた取っ手２ｍとで構成される。 On the other hand, the lid 2B has a cylindrical main body 2n that opens downward, an exhaust pipe 2g that opens diagonally upward on the peripheral surface of the main body 2n, and a handle provided on the ceiling surface 2h of the main body 2n. It is composed of 2m.

次に、上記構成を有する廃リチウムイオン電池の処理装置１を用いた廃リチウムイオン電池の処理方法について説明する。尚、以下の説明では、処理装置１によってハイブリッド自動車や電気自動車等から取外されたままの電池パック５０を処理する場合を例示する。 Next, a method for processing the waste lithium ion battery using the waste lithium ion battery processing device 1 having the above configuration will be described. In the following description, a case where the processing device 1 processes the battery pack 50 as it is removed from the hybrid vehicle, the electric vehicle, or the like will be illustrated.

熱処理炉３の内部を６５０℃に昇温し、クレーン等（不図示）を使用して、図８に示すように、電池パック５０を格納した耐熱容器２Ｎをスライドベース２１の右端部に載置する。扉２４を開放した後、搬送装置２９を介してスライドベース２１を右方に移動させ、耐熱容器２Ｎを炉体扉７ｂの正面まで移動させた後、扉２４を閉じて炉体扉７ｂを開放し、容器搬送装置４のプッシャー部４ａ（図７参照）を前進させて耐熱容器２Ｎを熱処理炉３内に投入する。これにより、耐熱容器２Ｎは熱処理炉３の炉床１７上、図１では９時の位置に載置される。 The inside of the heat treatment furnace 3 is heated to 650 ° C., and a heat-resistant container 2N containing the battery pack 50 is placed on the right end of the slide base 21 using a crane or the like (not shown) as shown in FIG. To do. After opening the door 24, the slide base 21 is moved to the right via the transport device 29, the heat-resistant container 2N is moved to the front of the furnace body door 7b, and then the door 24 is closed and the furnace body door 7b is opened. Then, the pusher portion 4a (see FIG. 7) of the container transport device 4 is advanced to put the heat-resistant container 2N into the heat-resistant furnace 3. As a result, the heat-resistant container 2N is placed on the hearth 17 of the heat treatment furnace 3 at the 9 o'clock position in FIG.

容器搬送装置４のプッシャー部４ａを後退させた後、炉体扉７ｂを閉鎖し、炉床回転装置１９を介して炉床１７を４５゜左回転させる。この４５゜の回転は、特に限定されるものではないが、例えば、３７．５分毎に炉床１７を４５゜ずつ回転させることで、５時間で炉床１７が１回転するように設定している。 After retracting the pusher portion 4a of the container transport device 4, the furnace body door 7b is closed, and the hearth 17 is rotated counterclockwise by 45 ° via the hearth rotating device 19. This rotation of 45 ° is not particularly limited, but for example, by rotating the hearth 17 by 45 ° every 37.5 minutes, the hearth 17 is set to rotate once in 5 hours. ing.

上記動作をさらに、７回繰り返すことで、熱処理炉３の炉床１７上には、図１に示したように、隣接する耐熱容器２が一定の間隔を開けた状態で８個の耐熱容器２が環状に載置される。 By further repeating the above operation 7 times, as shown in FIG. 1, eight heat-resistant containers 2 are placed on the hearth 17 of the heat treatment furnace 3 with adjacent heat-resistant containers 2 at regular intervals. Is placed in a ring.

上記動作の間、耐熱容器２は熱処理炉３内で１周する間に外側から加熱されることで、耐熱容器２内は還元雰囲気となり、耐熱容器２に格納された電池パック５０の樹脂製の筐体等のプラスチック類は、乾留により炭化混合物としてリチウム、コバルト、ニッケル、マンガン等の有用金属が含まれた材料から分離された状態となっている。尚、耐熱容器２はアルミニウムの融点（６６０℃）よりも低い温度（６５０℃）で加熱されるので、電池パック５０内で使用されたアルミニウム成分が溶け出すことはない。また、電池内の電解液は揮発し、プラスチック等の可燃性物質が熱分解することによって発生したガスと共に、耐熱容器２の排気管２ｇから熱処理炉３内に排出される。熱処理炉３内の未燃焼ガスは二次燃焼室に導かれ、熱処理炉３の温度（６５０℃）よりも高い温度（８００℃）で燃焼する。 During the above operation, the heat-resistant container 2 is heated from the outside while making one round in the heat-resistant container 3, so that the inside of the heat-resistant container 2 becomes a reducing atmosphere, and the battery pack 50 stored in the heat-resistant container 2 is made of resin. The plastics such as the housing are in a state of being separated from the material containing useful metals such as lithium, cobalt, nickel and manganese as a carbonization mixture by carbonization. Since the heat-resistant container 2 is heated at a temperature (650 ° C.) lower than the melting point of aluminum (660 ° C.), the aluminum component used in the battery pack 50 does not melt out. Further, the electrolytic solution in the battery volatilizes and is discharged into the heat treatment furnace 3 from the exhaust pipe 2g of the heat-resistant container 2 together with the gas generated by the thermal decomposition of the flammable substance such as plastic. The unburned gas in the heat treatment furnace 3 is guided to the secondary combustion chamber and burns at a temperature (800 ° C.) higher than the temperature (650 ° C.) of the heat treatment furnace 3.

耐熱容器２が熱処理炉３内で１周する前に、図９に示すように、電池パック５０を格納した新たな耐熱容器２Ｎを左端部に載置したスライドベース２１の右半分を炉前室２３に挿入する。この際、扉２４は閉じられている。 As shown in FIG. 9, the right half of the slide base 21 on which the new heat-resistant container 2N containing the battery pack 50 is placed on the left end is placed in the furnace front chamber before the heat-resistant container 2 makes one round in the heat treatment furnace 3. Insert into 23. At this time, the door 24 is closed.

耐熱容器２が熱処理炉３内で１周すると、炉体扉７ｂを開放して容器搬送装置４のプルアウト部４ｂを耐熱容器２の位置まで前進させ、図７に示すように、プルアウト部４ｂ先端に設けられた爪４ｃを、耐熱容器２に設けられたハンガー２ｐに係止させる。そして、プルアウト部４ｂを後退させ、図１０に示すように、熱処理後の耐熱容器２Ｔを熱処理炉３から引き出してスライドベース２１上に載置し、炉体扉７ｂを閉鎖する。 When the heat-resistant container 2 makes one round in the heat treatment furnace 3, the furnace body door 7b is opened and the pull-out portion 4b of the container transport device 4 is advanced to the position of the heat-resistant container 2, and as shown in FIG. 7, the tip of the pull-out portion 4b is advanced. The claw 4c provided in the heat-resistant container 2 is locked to the hanger 2p provided in the heat-resistant container 2. Then, the pullout portion 4b is retracted, and as shown in FIG. 10, the heat-resistant container 2T after the heat treatment is pulled out from the heat treatment furnace 3 and placed on the slide base 21, and the furnace body door 7b is closed.

次に、扉２４、２５を開放した後、スライドベース２１を右方に移動し、電池パック５０を格納した新たな耐熱容器２Ｎを炉体扉７ｂの正面まで移動させると共に、熱処理済みの耐熱容器２Ｔを冷却室３１に移動させて扉２４、２５を閉じる。この状態を図１１に示す。 Next, after opening the doors 24 and 25, the slide base 21 is moved to the right, the new heat-resistant container 2N containing the battery pack 50 is moved to the front of the furnace body door 7b, and the heat-treated heat-treated container is moved. The 2T is moved to the cooling chamber 31 and the doors 24 and 25 are closed. This state is shown in FIG.

図１１の状態から、新たな耐熱容器２Ｎを上述の要領で熱処理炉３内に投入して加熱すると共に、熱処理済みの耐熱容器２Ｔを冷却室３１で冷却する。冷却室３１において、図４に示すように、エアシリンダ３７で排水管３５を上昇させ、排水管３５の先端のパッキン３６に耐熱容器２の突出管２ｄを挿入する。その状態で、フレキシブルホース３９に冷却水を供給し、流調弁３８で冷却水の量を調整しながら給水管３４を経て噴霧ノズル３３から冷却水を耐熱容器２の冷却空間２ｃ内に万遍なく噴霧する。これによって、耐熱容器２の内筒２ａ内の電池パック５０が冷却される。電池パック５０を冷却することで生じた水蒸気は、耐熱容器２の突出管２ｄの内部を通過して排水管３５、フレキシブルホース４０を経て外部に排出される。尚、電池パック重量や加熱温度が変化した場合でも、流調弁３８で水の噴霧量を調整することで冷却時間を調整することができる。また、排出した水蒸気を凝縮させて冷却水として循環使用することもできる。 From the state of FIG. 11, a new heat-resistant container 2N is put into the heat treatment furnace 3 and heated as described above, and the heat-treated heat-resistant container 2T is cooled in the cooling chamber 31. In the cooling chamber 31, as shown in FIG. 4, the drain pipe 35 is raised by the air cylinder 37, and the protruding pipe 2d of the heat-resistant container 2 is inserted into the packing 36 at the tip of the drain pipe 35. In that state, the cooling water is supplied to the flexible hose 39, and the cooling water is uniformly supplied into the cooling space 2c of the heat-resistant container 2 from the spray nozzle 33 via the water supply pipe 34 while adjusting the amount of the cooling water with the flow control valve 38. Spray without. As a result, the battery pack 50 in the inner cylinder 2a of the heat-resistant container 2 is cooled. The water vapor generated by cooling the battery pack 50 passes through the inside of the protruding pipe 2d of the heat-resistant container 2, passes through the drain pipe 35, and the flexible hose 40, and is discharged to the outside. Even if the weight of the battery pack or the heating temperature changes, the cooling time can be adjusted by adjusting the amount of water sprayed by the flow control valve 38. It is also possible to condense the discharged water vapor and circulate it as cooling water.

次に、扉２４、２５を開放した後、冷却済みの耐熱容器２Ｃが載置されたスライドベース２１を左方に移動させ（図１２参照）、クレーン等で次工程へ搬送する。 Next, after opening the doors 24 and 25, the slide base 21 on which the cooled heat-resistant container 2C is placed is moved to the left (see FIG. 12) and transported to the next process by a crane or the like.

冷却後の加熱処理済みの耐熱容器２Ｃは、内部の電池パック５０を破砕、分級して炭化混合物を取り除いた後、リチウム、コバルト、ニッケル、マンガン等の有用金属をさらに分離する処理が行われる。また、電池パック５０の破砕物を磁選機にかけて、鉄筐体、ねじ等の磁着物と、銅とアルミニウムからなるミックメタルに分離し、ミックメタルを比重選別してアルミ塊及び銅塊と、銅箔及びアルミ箔の積層物とに分けた後、選別機でさらに銅箔とアルミ箔とに分けることができる。 The heat-resistant container 2C that has been heat-treated after cooling is subjected to a treatment of crushing and classifying the internal battery pack 50 to remove a carbonized mixture, and then further separating useful metals such as lithium, cobalt, nickel, and manganese. Further, the crushed material of the battery pack 50 is subjected to a magnetic separator to separate a magnetic material such as an iron housing and a screw and a mic metal composed of copper and aluminum, and the mic metal is sorted by specific gravity to form an aluminum block, a copper block, and copper. After separating into a laminate of foil and aluminum foil, it can be further separated into copper foil and aluminum foil by a sorter.

また、冷却室３１からのフッ化水素、塩化水素等を含む有害ガスは、排ガス処理装置によってセメントキルンの排ガス処理系統に供給し、セメント製造工程内のセメント原料に固定化して無害化する。 In addition, harmful gas containing hydrogen fluoride, hydrogen chloride, etc. from the cooling chamber 31 is supplied to the exhaust gas treatment system of the cement kiln by the exhaust gas treatment device, and is immobilized on the cement raw material in the cement manufacturing process to make it harmless.

尚、熱処理炉３は、炉床１７が回転するものでなくてもよく、バッチ式のものでも適用可能である。また、耐熱容器２は熱処理炉３内で一周するものではなくてもよく、所定の時間を経過したものは熱処理炉３から排出してもよい。また、熱源として電気や重油を使用した各種炉を使用することもでき、既存の製造設備、例えば、セメント焼成装置からの排ガスを熱源として用いてもよい。 As the heat treatment furnace 3, the hearth 17 does not have to rotate, and a batch type can also be applied. Further, the heat-resistant container 2 does not have to go around in the heat treatment furnace 3, and the heat-resistant container 2 may be discharged from the heat treatment furnace 3 after a predetermined time has passed. Further, various furnaces using electricity or heavy oil can be used as a heat source, and exhaust gas from an existing manufacturing facility, for example, a cement firing device may be used as a heat source.

また、本実施の形態では、電池パック５０を電池セルを個々に取外すことなくそのままの状態のものに対して加熱処理したが、電池パック５０から分解した電池モジュール単位のものや、電池セルを個々に取外したものを格納した耐熱容器２を熱処理炉３に投入して加熱処理してもよい。 Further, in the present embodiment, the battery pack 50 is heat-treated as it is without removing the battery cells individually, but the battery pack 50 is disassembled from the battery pack 50 and the battery cells are individually removed. The heat-resistant container 2 containing the removed one may be put into the heat treatment furnace 3 for heat treatment.

１ 廃リチウムイオン電池の処理装置
２ 耐熱容器
３ 熱処理炉
４ 容器搬送装置
７ 炉壁
８（８Ａ〜８Ｄ） ガスバーナー
１１（１１Ａ〜１１Ｄ） ノズル
１７ 炉床
１８ モーター
１９ 炉床回転装置
２１ スライドベース
２３ 炉前室
２４、２５ 扉
２８ 排気管
２９ 搬送装置
３１ 冷却室
３２ 冷却装置
３３ 噴霧ノズル
３４ 給水管
３５ 排水管
３６ パッキン
３７ エアシリンダ
３８ 流調弁
３９、４０ フレキシブルホース
５０ 電池パック
1 Waste lithium ion battery processing device 2 Heat resistant container 3 Heat treatment furnace 4 Container transfer device 7 Furnace wall 8 (8A to 8D) Gas burner 11 (11A to 11D) Nozzle 17 Hearth 18 Motor 19 Hearth rotation device 21 Slide base 23 Furnace front chamber 24, 25 Door 28 Exhaust pipe 29 Conveyor device 31 Cooling chamber 32 Cooling device 33 Spray nozzle 34 Water supply pipe 35 Drain pipe 36 Packing 37 Air cylinder 38 Flow control valve 39, 40 Flexible hose 50 Battery pack

Claims (6)

廃リチウムイオン電池を収容する耐熱容器と、
該耐熱容器を加熱する熱処理炉と、
該熱処理炉に前記耐熱容器を投入及び排出する容器搬送装置と、
該容器搬送装置によって前記熱処理炉から排出された耐熱容器の下部を冷却水を用いて冷却する冷却装置とを備えることを特徴とする廃リチウムイオン電池の処理装置。 A heat-resistant container that houses waste lithium-ion batteries,
A heat treatment furnace that heats the heat-resistant container and
A container transport device for charging and discharging the heat-resistant container into the heat treatment furnace,
A waste lithium ion battery processing device including a cooling device for cooling the lower portion of a heat-resistant container discharged from the heat treatment furnace by the container transport device using cooling water. 前記冷却装置で冷却中の耐熱容器を囲繞する冷却室の内部が負圧になるように制御する圧力制御装置を備えることを特徴とする請求項１に記載の廃リチウムイオン電池の処理装置。 The waste lithium ion battery processing apparatus according to claim 1, further comprising a pressure control device that controls the inside of the cooling chamber surrounding the heat-resistant container being cooled by the cooling device so that the pressure becomes negative. 前記冷却室の排ガスをセメントキルンの排ガス処理系統に供給する排ガス処理装置を備えることを特徴とする請求項１又は２に記載の廃リチウムイオン電池の処理装置。 The waste lithium ion battery treatment apparatus according to claim 1 or 2, further comprising an exhaust gas treatment apparatus for supplying the exhaust gas from the cooling chamber to the exhaust gas treatment system of the cement kiln. 前記耐熱容器の下部を冷却水で冷却した際に発生した水蒸気を系外に放出する経路を有することを特徴とする請求項１、２又は３に記載の廃リチウムイオン電池の処理装置。 The waste lithium ion battery processing apparatus according to claim 1, 2 or 3, further comprising a path for releasing water vapor generated when the lower portion of the heat-resistant container is cooled with cooling water to the outside of the system. 廃リチウムイオン電池を収容した耐熱容器を加熱し、
加熱後の耐熱容器の下部を冷却水を用いて冷却することを特徴とする廃リチウムイオン電池の処理方法。 Heat the heat-resistant container containing the waste lithium-ion battery,
A method for treating a waste lithium ion battery, which comprises cooling the lower part of a heat-resistant container after heating with cooling water. 廃リチウムイオン電池を収容した後熱処理炉で加熱され、加熱後に下部を冷却水を用いて冷却される耐熱容器であって、
廃リチウムイオン電池を収容する収容部と、
該収容部の下方に、前記冷却水が導入される空間を有することを特徴とする耐熱容器。 A heat-resistant container that contains a waste lithium-ion battery, is then heated in a heat treatment furnace, and then the lower part is cooled with cooling water.
A housing unit that houses waste lithium-ion batteries,
A heat-resistant container having a space below the accommodating portion into which the cooling water is introduced.
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JP6990753B1 (en) 2020-09-16 2022-01-12 Ｄｏｗａエコシステム株式会社 How to recover valuables from lithium-ion secondary batteries
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