JPH1171111A - Extraction of rare earth metallic compound - Google Patents
Extraction of rare earth metallic compoundInfo
- Publication number
- JPH1171111A JPH1171111A JP24334697A JP24334697A JPH1171111A JP H1171111 A JPH1171111 A JP H1171111A JP 24334697 A JP24334697 A JP 24334697A JP 24334697 A JP24334697 A JP 24334697A JP H1171111 A JPH1171111 A JP H1171111A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth metal
- acid
- earth metallic
- metallic element
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は廃棄される蛍光管や
ブラウン管等の希土類金属化合物を含有する物からから
希土類金属化合物を抽出する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for extracting a rare earth metal compound from a substance containing a rare earth metal compound such as a fluorescent tube or a cathode ray tube which is discarded.
【０００２】[0002]
【従来の技術】原子番号５７のＬａ（ランタン）から原
子番号７１のＬｕ（ルテチウム）までの１５元素と、化
学的性質が類似したＳｃ（スカンジウム）とＹ（イット
リウム）の２元素を加えた１７元素を総称する希土類金
属元素は、蛍光材や触媒、光学ガラス、セラミックス、
磁石等の機能性材料に広く利用されており、いわゆる先
端産業分野を支える重要な元素群の一つになっている。
これらの元素は、通常、モナザイトやバストネサイト、
ゼノタイムなどの鉱石から高温度、高濃度酸による抽出
操作により精製されている。2. Description of the Related Art Fifteen elements from La (lanthanum) having an atomic number of 57 to Lu (lutetium) having an atomic number of 71 and two elements of Sc (scandium) and Y (yttrium) having similar chemical properties are added. Rare earth metal elements, which are collectively called elements, are fluorescent materials, catalysts, optical glasses, ceramics,
It is widely used in functional materials such as magnets, and is one of the important elements that support the so-called advanced industrial field.
These elements are usually found in monazite, bastnaesite,
It is refined from ore such as Xenotime by extraction with high temperature and high concentration acid.
【０００３】これら希土類金属元素含有鉱石の産地は世
界中でも主に中国、北米、ロシアなどに限定さており、
しかも産出量が少ないので、希土類金属元素の入手をこ
れのみに依存していたのでは早晩枯渇してしまうおそれ
がある。[0003] The production areas of these rare earth metal-containing ores are limited mainly to China, North America, Russia, etc., all over the world.
Moreover, since the amount of production is small, there is a risk that the rare earth metal element will be depleted immediately if it is solely used to obtain the rare earth metal element.
【０００４】そこで、希土類金属元素が三波長高演色蛍
光管用蛍光材として広く利用され、年々これを用いた蛍
光管の需要が増大するにともない、使用済みとなって廃
棄される蛍光管の量が増加の一途をたどっていることに
着目し、廃棄される蛍光管から希土類金属元素を分離回
収し、再利用することが考えられている。これまでの回
収技術は高温度、高濃度酸による処理法であるので、作
業環境上問題があり、より温和な条件下での回収法の確
立が望まれている。[0004] Therefore, rare earth metal elements are widely used as fluorescent materials for three-wavelength high color rendering fluorescent tubes, and as the demand for fluorescent tubes using them increases year by year, the amount of used and discarded fluorescent tubes is reduced. Focusing on the ever-increasing increase, it has been considered to separate and recover rare earth metal elements from the discarded fluorescent tubes and reuse them. Since the conventional recovery technique is a treatment method using a high-temperature, high-concentration acid, there is a problem in the working environment, and it is desired to establish a recovery method under milder conditions.
【０００５】本発明者らは最近、メカノケミカル反応に
より固相での交換反応をおこない、バストネサイトから
希土類金属元素を非加熱で弱酸性溶液により抽出する方
法を提案した。しかしながら、バストネサイトは炭酸塩
であり、蛍光材は酸化物であるので、蛍光材から希土類
金属元素を回収するのにこれをそのまま適用することは
困難である。The present inventors have recently proposed a method in which a solid phase exchange reaction is carried out by a mechanochemical reaction to extract a rare earth metal element from bastnaesite without heating using a weakly acidic solution. However, since bastnaesite is a carbonate and the fluorescent material is an oxide, it is difficult to apply it as it is to recover a rare earth metal element from the fluorescent material.
【０００６】[0006]
【発明が解決しようとする課題】本発明は希土類金属元
素を含有する蛍光材などから、希土類金属元素を温和な
条件下で抽出する方法を提供せんとするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for extracting a rare earth metal element from a fluorescent material containing the rare earth metal element under mild conditions.
【０００７】メカノケミカルとは、一般に固体物質に加
えた機械的ネネルギ−、たとえば、せん断、圧縮、衝
撃、粉砕、曲げ延伸などによって、固体表面が物理化学
的変化をきたし、その周囲に存在する気体、液体物質に
化学的変化をもたらすか、あるいはそれらと固体表面と
の化学的変化を直接誘起し、または促進するなどして、
化学的状態に影響をおよぼす現象として知られている。[0007] Mechanochemicals are generally defined as mechanical energy added to a solid substance, for example, shear, compression, impact, crushing, bending or stretching, etc., causing the physicochemical change of the solid surface and the gas existing around it. , Causing chemical changes in liquid substances, or directly inducing or promoting chemical changes between them and the solid surface,
It is known as a phenomenon that affects the chemical state.
【０００８】[0008]
【課題を解決するための手段】ここにおいて本発明者
は、希土類金属元素含有物を所定時間メカノケミカル処
理し、結晶構造を破壊して漬出しやすい形態に変え、こ
れを低濃度酸に浸出させることにより希土類金属化合物
を効果的に抽出できることを見出した。そして、希土類
金属がＹ、Ｓｃおよびランタノイド系元素であり、メカ
ノケミカル処理が高エネルギ−型粉砕機によりおこなわ
れ、低濃度酸が１Ｎ以下の塩酸または硫酸であると好適
であることを見出すにいたった。これにより、廃棄蛍光
管の蛍光材成分、あるいは廃棄されるブラウン管など電
子部品に含まれる希土類金属化合物を、メカノケミカル
処理して、低濃度酸で抽出できるにいたった。Here, the inventor of the present invention mechanochemically treats a rare earth metal element-containing substance for a predetermined period of time to break the crystal structure into a form easy to be immersed, and to leach it into a low-concentration acid. As a result, it has been found that the rare earth metal compound can be effectively extracted. Then, it has been found that the rare earth metal is Y, Sc and a lanthanoid element, the mechanochemical treatment is performed by a high energy type pulverizer, and the low concentration acid is preferably 1N or less hydrochloric acid or sulfuric acid. Was. As a result, the fluorescent material component of the waste fluorescent tube or the rare earth metal compound contained in the electronic component such as the discarded cathode ray tube can be extracted with a low-concentration acid by mechanochemical treatment.
【０００９】[0009]
【発明の実施の形態】本発明者は廃棄蛍光管を将来の有
望な希土類金属元素の都市資源と位置付け、廃棄蛍光管
の含有蛍光材を乾式メカノケミカル処理し、結晶構造を
変化させてから、従来にない温和な酸処理によって、希
土類金属化合物を高収率で抽出することができるにいた
った。BEST MODE FOR CARRYING OUT THE INVENTION The present inventor has positioned waste fluorescent lamps as a promising urban resource for rare earth metal elements in the future, and has performed dry mechanochemical treatment on the fluorescent material contained in the waste fluorescent tubes to change the crystal structure. It has been possible to extract rare earth metal compounds in high yield by unprecedented mild acid treatment.
【００１０】[0010]
【実施例】以下、実施例により本発明を具体的に説明す
る。 〔蛍光材〕廃棄される三波長高演色蛍光管に含まれる蛍
光材（以下、蛍光材と略記する）は、下記４種類の複合
酸化物の混合物であることが知られている。 青色蛍光体・・・ＢａＭｇＡｌ10Ｏ17：Ｅｕ2+ 緑色蛍光体・・・ＬａＰＯ4 ：Ｃｅ3+、Ｔｂ3+ 緑色蛍光体・・・ＣｅＭｇＡｌ11Ｏ19：Ｔｂ3+ 赤色蛍光体・・・Ｙ2 Ｏ3 ：Ｅｕ3+ 混合物の化学分析結果から、混合物を酸化物からなると
仮定して、その組成比を表示すると第１表のようにな
る。The present invention will be described below in detail with reference to examples. [Fluorescent Material] It is known that a fluorescent material (hereinafter abbreviated as a fluorescent material) contained in a discarded three-wavelength high color rendering fluorescent tube is a mixture of the following four types of composite oxides. Blue phosphor ··· BaMgAl 10 O 17: Eu 2+ Green phosphor ··· LaPO 4: Ce 3+, Tb 3+ green phosphor ··· CeMgAl 11 O 19: Tb 3+ red phosphor.. From the results of chemical analysis of the Y 2 O 3 : Eu 3+ mixture, assuming that the mixture is composed of an oxide, the composition ratio is shown in Table 1.
【００１１】[0011]
【表１】 [Table 1]
【００１２】第１表には示していないが、希土類金属元
素以外のＳｒＯやＢａＯ、ＭｇＯ、Ａｌ2 Ｏ3 などの酸
化物と仮定される元素化合物は不純物とみなされる。そ
の一部の元素は乾式メカノケミカル処理後の酸浸出でも
検出され、注目元素に加えた。なお、未処理蛍光材の粒
度分布を第２図中に示す。Although not shown in Table 1, elemental compounds which are assumed to be oxides such as SrO, BaO, MgO and Al 2 O 3 other than rare earth metal elements are regarded as impurities. Some of the elements were also detected in acid leaching after dry mechanochemical treatment and were added to the elements of interest. The particle size distribution of the untreated fluorescent material is shown in FIG.
【００１３】廃棄蛍光管から蛍光材のみを機械的に取出
すことは煩雑であり、大量処理する場合には実用的でな
い。廃棄蛍光管から希土類金属化合物を取出す際は、予
め金具と管内の水銀成分を除き、全体を粗砕してから乾
式メカノケミカル処理にかける。シリカ成分が多いと乾
式メカノケミカル処理効果が上がることが判明している
が、ここでは、別途得られた蛍光材相当の試料を対象物
として、これより希土類金属化合物を取出すことを試み
た。It is complicated to mechanically take out only the fluorescent material from the waste fluorescent tube, and it is not practical for mass processing. When removing the rare earth metal compound from the waste fluorescent tube, the whole is coarsely crushed except for the mercury component in the metal fittings and the tube, and then subjected to dry mechanochemical treatment. It has been found that the dry mechanochemical treatment effect increases when the silica content is large, but here, an attempt was made to extract a rare earth metal compound from a separately obtained sample corresponding to a fluorescent material.
【００１４】〔乾式メカノケミカル処理〕蛍光材の乾式
メカノケミカル処理（以下、メカノケミカル処理とい
う）における高エネルギ−型粉砕機として、遊星ミル
（Ｆｒｉｔｓｃｈ社製、Ｐｕｌｖｅｒｉｓｓｅｔｅ−
７）を用いた。この遊星ミルは内容量５０ｃｍ3 からな
る２個のジルコニア製ポットを回転方向が時計回りで、
回転半径７０ｍｍの回転円盤に取付けたもので、ポット
自身も回転方向が反時計回りで、回転円盤と同じ速度で
回転できるようになっている。ポットには直径１４ｍｍ
のジルコニア製ボ−ル７個と蛍光材粉末５ｇを装填し、
回転速度７００ｒｐｍで、蛍光材粉末についてメカノケ
ミカル処理をおこなった。粉砕は回分法でおこない、所
定時間処理して得られた産物は全量回収した。最長処理
時間は２時間であり、とくに、ポット内の過度の発熱を
避けるため、１５分運転後は３０分停止して自然冷却す
る操作をくりかえした。各粉砕処理時間後の産物は、粒
度分布測定、Ｘ線回析（ＸＲＤ）解析、熱分析等をおこ
なって、メカノケミカル処理による粉体特性の変化を評
価した。[Dry Mechanochemical Treatment] As a high-energy type pulverizer for dry mechanochemical treatment of fluorescent material (hereinafter referred to as mechanochemical treatment), a planetary mill (Pulverisset, manufactured by Fritsch) is used.
7) was used. In this planetary mill, two zirconia pots having a content of 50 cm 3 are rotated clockwise,
The pot is mounted on a rotating disk having a rotating radius of 70 mm. The rotating direction of the pot itself is also counterclockwise, and the pot can rotate at the same speed as the rotating disk. 14mm diameter in the pot
Of zirconia balls and 5 g of phosphor powder,
Mechanochemical treatment was performed on the phosphor powder at a rotation speed of 700 rpm. The pulverization was carried out by a batch method, and all the products obtained by treating for a predetermined time were recovered. The longest processing time was 2 hours. In particular, in order to avoid excessive heat generation in the pot, the operation of stopping for 30 minutes after the 15-minute operation and repeating the natural cooling operation was repeated. The product after each pulverization treatment time was subjected to particle size distribution measurement, X-ray diffraction (XRD) analysis, thermal analysis, and the like to evaluate changes in powder characteristics due to mechanochemical treatment.
【００１５】第１図に乾式メカノケミカル処理産物のＸ
ＲＤパタ−ンを示す。これにより、処理時間の増大とと
もに構成成分の特徴的な回折ピ−ク強度が徐々に低下し
ていることがわかる。たとえば、ＹＯＸ（Ｙ2 Ｏ3 ）の
ピ−ク強度は粉砕初期で急激に低下しているが、２時間
処理でも完全には消滅していない。また、ＢＡＴ（Ｂａ
ＭｇＡｌ10Ｏ17：Ｅｕ2+）については、顕著な変化は認
められない。これに対して、ＬＡＰ（ＬａＰＯ4 ：Ｃｅ
3+、Ｔｂ3+）、ＭＡＴ（ＣｅＭｇＡｌ11Ｏ19：Ｔｂ3+）
のピ−クはいずれも低いが、処理時間とともに小さくな
り、非結晶化が進行しているものと予想される。このよ
うに、メカノケミカル処理により希土類金属元素複合酸
化物の結晶構造は一部維持しながらもかなり歪んだ状態
になることがわかる。FIG. 1 shows X of the dry mechanochemically treated product.
RD pattern is shown. This indicates that the characteristic diffraction peak intensity of the component gradually decreases as the processing time increases. For example, the peak strength of YOX (Y 2 O 3 ) sharply decreases at the beginning of pulverization, but does not completely disappear even after 2 hours of treatment. Also, BAT (Ba
MgAl 10 O 17 : Eu 2+ ) shows no significant change. On the other hand, LAP (LaPO 4 : Ce)
3+ , Tb 3+ ), MAT (CeMgAl 11 O 19 : Tb 3+ )
Although the peaks are low in each case, the peaks decrease with the processing time, and it is expected that non-crystallization has progressed. Thus, it can be seen that the mechanochemical treatment causes the rare earth metal element composite oxide to be in a considerably distorted state while partially maintaining the crystal structure.
【００１６】第２図には未処理蛍光材と２時間処理産物
の粒度分布を示す。これにより、処理時間の増大ととも
に、産物中、粒度分布の中位の径は細粒側へ移行する
が、同時に分布の幅が大となり、その粗粒部分は未処理
蛍光材の最大径よりも粗粒側にひろがっていることがわ
かる。このことは、処理によって機械的活性が大とな
り、粉体の一部が凝集したためであると思われる。FIG. 2 shows the particle size distribution of the untreated fluorescent material and the product treated for 2 hours. As a result, as the processing time increases, the median diameter of the particle size distribution in the product shifts to the fine grain side, but at the same time the width of the distribution increases, and the coarse grain portion becomes larger than the maximum diameter of the untreated fluorescent material. It can be seen that it spreads to the coarse grain side. This is considered to be because the mechanical activity was increased by the treatment, and a part of the powder was aggregated.
【００１７】〔酸処理〕メカノケミカル処理して得られ
た産物から希土類金属化合物を抽出するにあたり、従来
よりも極端に低濃度の酸として、１Ｎの塩酸を用いた。
ここで、塩酸にかえ硫酸を使用することもできる。酸液
２５ｍｌにメカノケミカル処理粉末０．５ｇを投入し、
室温下で１時間攪拌後、ろ過して固液を分離し、ろ液中
の含有元素をＩＣＰで分析するとともに、固体残査はＸ
ＲＤ解析によって構成成分を同定し、評価した。なお、
メカノケミカル処理していない蛍光材粉末についても同
様に酸浸出をおこない、同様な分析をおこなった。[Acid Treatment] In extracting a rare earth metal compound from a product obtained by mechanochemical treatment, 1N hydrochloric acid was used as an acid having an extremely lower concentration than before.
Here, sulfuric acid may be used instead of hydrochloric acid. 0.5 g of mechanochemically treated powder is added to 25 ml of the acid solution,
After stirring at room temperature for 1 hour, the mixture was filtered to separate a solid and a liquid, and the elements contained in the filtrate were analyzed by ICP.
The components were identified and evaluated by RD analysis. In addition,
Acid leaching was similarly performed on the fluorescent material powder not subjected to the mechanochemical treatment, and the same analysis was performed.
【００１８】第３図には１Ｎ塩酸により抽出され、塩化
物として溶解している各希土類金属元素の収率とメカノ
ケミカル処理時間との関係を示す。これによれば、メカ
ノケミカル未処理の場合Ｙ、Ｅｕが約２０％抽出される
が、その他の希土類金属元素は殆ど抽出されない。これ
に対して、メカノケミカル処理時間が３分では、Ｙ、Ｅ
ｕの収率が急激に増加し、それぞれ８０％、７０％に達
する。さらに処理時間が長くなり３０分では、収率がＹ
で９８％、Ｅｕで８５％以上になる。これがその他の希
土類金属元素の場合、処理時間が３分で約２０％、３０
分でも６０％以下である。さらに、処理時間を延長する
と収率は次第に増大し、Ｙ、Ｅｕの場合に近付くが、２
時間でもようやく８０〜９０％の範囲である。これは、
蛍光材粉末をメカノケミカル処理することによって、そ
の結晶構造が歪み、かつ、微粒化したことと深く関連す
る。とくにＹ、Ｅｕの収率が高いのは、メカノケミカル
処理によってＹＯＸが溶解しやすくなることによるもの
であり、また、ＥｕがＹより収率が僅かに低いのは、溶
解しにくいＢＡＴにＥｕ2+が含まれるからと推察され
る。なお、ここには示さないが、硫酸処理の場合も同様
の傾向があった。FIG. 3 shows the relationship between the yield of each rare earth metal element extracted with 1N hydrochloric acid and dissolved as chloride and the mechanochemical treatment time. According to this, about 20% of Y and Eu are extracted in the case of no mechanochemical treatment, but other rare earth metal elements are hardly extracted. On the other hand, if the mechanochemical processing time is 3 minutes, Y, E
The yield of u increases sharply, reaching 80% and 70% respectively. Further, the processing time becomes longer, and in 30 minutes, the yield is Y.
98% in Eu and 85% or more in Eu. When this is another rare earth metal element, the treatment time is about 20% in 3 minutes, and 30%.
Even less than 60%. Further, when the treatment time is extended, the yield gradually increases and approaches the case of Y and Eu,
The time is finally in the range of 80-90%. this is,
The mechanochemical treatment of the phosphor powder is closely related to the fact that the crystal structure is distorted and atomized. Especially Y, the Eu yield is high is due to the fact that easily dissolved YOX by mechanochemical processing, also, Eu that is slightly lower yields than Y is Eu 2 to less soluble BAT It is presumed that + is included. Although not shown here, there was a similar tendency in the case of sulfuric acid treatment.
【００１９】第４図には、ＡｌとＭｇの２元素に注目
し、それらの塩酸浸出における収率とメカノケミカル処
理時間との関係を示す。それによれば、メカノケミカル
処理６０分でも収率はＡｌで約３０％、Ｍｇでは２０％
未満と低く、メカノケミカル処理をおこなっても、これ
ら２元素はさほど酸には溶解しないことがわかる。FIG. 4 focuses on two elements, Al and Mg, and shows the relationship between the yield in leaching with hydrochloric acid and the mechanochemical treatment time. According to the results, the yield is about 30% for Al and 20% for Mg even after 60 minutes of mechanochemical treatment.
It can be seen that these two elements do not dissolve so much in the acid even when the mechanochemical treatment is performed.
【００２０】第５図には、メカノケミカル処理を２時間
おこなったものの酸浸出後の残渣のＸＲＤパタ−ンをＢ
ＡＴ単品のＸＲＤパタ−ンとともに示す。それによれ
ば、残査のＸＲＤパタ−ンの各ピ−ク位置は未処理のＢ
ＡＴのそれらと同一であり、したがって、残査にはＢＡ
Ｔの結晶系がかなり残存していることがわかる。このこ
とは、ＢＡＴに含まれるＡｌ、Ｍｇ等の各酸化物もある
程度残査中にとどまっていることを示唆し、第４図の結
果とよく対応する。FIG. 5 shows the XRD pattern of the residue after acid leaching after the mechanochemical treatment for 2 hours.
This is shown together with the XRD pattern of AT alone. According to this, each peak position of the XRD pattern of the residue is represented by an unprocessed B
Are identical to those of AT, so the residue
It can be seen that a considerable amount of the T crystal system remains. This suggests that the oxides such as Al and Mg contained in the BAT also remain in the residue to some extent, which corresponds well to the results in FIG.
【００２１】塩酸に浸出した希土類金属化合物が塩化物
として溶解しているところから希土類金属元素を析出さ
せるには、溶液のｐＨを制御することによって、水酸化
物として取出す。さらに各成分を分離するには、析出段
階で他の硫酸イオンや硝酸イオン等との反応における選
択性を利用し、逐次析出をおこない、使用目的の形態に
合わせて分離・回収する。析出物を焼成すれば酸化物を
得ることができる。In order to precipitate the rare earth metal element from the place where the rare earth metal compound leached in hydrochloric acid is dissolved as chloride, the rare earth metal element is extracted as hydroxide by controlling the pH of the solution. Further, in order to separate each component, the separation is carried out successively by utilizing the selectivity in the reaction with other sulfate ions or nitrate ions in the precipitation stage, and separated / recovered according to the intended use form. By firing the precipitate, an oxide can be obtained.
【００２２】[0022]
【発明の効果】本発明により、希土類金属元素を含む廃
蛍光管から、これを温和な条件下で抽出できるので、作
業環境を安全にすることができる。とくに、廃棄蛍光管
を将来の有望な希土類金属元素都市資源と位置付けるこ
とができ、希少資源の循環使用を可能にする。According to the present invention, a waste fluorescent tube containing a rare earth metal element can be extracted under a mild condition, so that the working environment can be made safe. In particular, waste fluorescent tubes can be positioned as promising rare earth metal element city resources in the future, enabling the recycling of rare resources.
【図１】 メカノケミカル処理時間による蛍光材粉末の
ＸＲＤパタ−ンである。FIG. 1 is an XRD pattern of a phosphor powder according to a mechanochemical treatment time.
【図２】 メカノケミカル未処理および１２０分処理蛍
光材の粒度分布である。FIG. 2 is a particle size distribution of a mechanochemical untreated phosphor and a phosphor treated for 120 minutes.
【図３】 メカノケミカル処理時間と酸抽出された希土
類金属元素の収率との関係を示すものである。FIG. 3 shows the relationship between the mechanochemical treatment time and the yield of acid-extracted rare earth metal elements.
【図４】 メカノケミカル処理時間と酸抽出されたＡ
ｌ、Ｍｇの収率との関係を示すものである。FIG. 4. Mechanochemical treatment time and acid extracted A
1 shows the relationship with the yield of Mg.
【図５】 メカノケミカル１２０分処理後における酸抽
出残渣のＸＲＤパタ−ンと比較のために示す未処理ＢＡ
Ｔ単品のＸＲＤパタ−ンである。FIG. 5: XRD pattern of acid extraction residue after mechanochemical treatment for 120 minutes and untreated BA shown for comparison
This is the XRD pattern of T alone.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成９年１１月１２日[Submission date] November 12, 1997
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００１[Correction target item name] 0001
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００１】[0001]
【発明の属する技術分野】本発明は廃棄される蛍光管や
ブラウン管等の希土類金属化合物を含有する物から希土
類金属化合物を抽出する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for extracting a rare earth metal compound from a material containing a rare earth metal compound, such as a fluorescent tube or a cathode ray tube, which is discarded.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００７】メカノケミカルとは、一般に固体物質に加
えた機械的エネルギー、たとえば、せん断、圧縮、衝
撃、粉砕、曲げ延伸などによって、固体表面が物理化学
的変化をきたし、その周囲に存在する気体、液体物質に
化学的変化をもたらすか、あるいはそれらと固体表面と
の化学的変化を直接誘起し、または促進するなどして、
化学的状態に影響をおよぼす現象として知られている。[0007] Mechanochemicals are generally defined as physicochemical changes in the surface of a solid caused by mechanical energy applied to a solid material, for example, shear, compression, impact, crushing, bending and stretching, and the gas existing around the solid. Cause chemical changes in liquid substances, or directly induce or promote chemical changes between them and the solid surface,
It is known as a phenomenon that affects the chemical state.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１７】〔酸処理〕メカノケミカル処理して得られ
た産物から希土類金属化合物を抽出するにあたり、従来
よりも極端に低濃度の酸として、１Ｎの塩酸を用いた。
ここで、塩酸にかえ硫酸を使用することもできる。酸液
２５ｍｌにメカノケミカル処理粉末０．５ｇを投入し、
室温下で１時間攪拌後、ろ過して固液を分離し、ろ液中
の含有元素をＩＣＰで分析するとともに、固体残渣はＸ
ＲＤ解析によって構成成分を同定し、評価した。なお、
メカノケミカル処理していない蛍光材粉末についても同
様に酸浸出をおこない、同様な分析をおこなった。[Acid Treatment] In extracting a rare earth metal compound from a product obtained by mechanochemical treatment, 1N hydrochloric acid was used as an acid having an extremely lower concentration than before.
Here, sulfuric acid may be used instead of hydrochloric acid. 0.5 g of mechanochemically treated powder is added to 25 ml of the acid solution,
After stirring at room temperature for 1 hour, the mixture was filtered to separate a solid and a liquid, and the elements contained in the filtrate were analyzed by ICP.
The components were identified and evaluated by RD analysis. In addition,
Acid leaching was similarly performed on the fluorescent material powder not subjected to the mechanochemical treatment, and the same analysis was performed.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２０】第５図には、メカノケミカル処理を２時間
おこなったものの酸浸出後の残渣のＸＲＤパターンをＢ
ＡＴ単品のＸＲＤパターンとともに示す。それによれ
ば、残渣のＸＲＤパターンの各ピーク位置は未処理のＢ
ＡＴのそれらと同一であり、したがって、残渣にはＢＡ
Ｔの結晶系がかなり残存していることがわかる。このこ
とは、ＢＡＴに含まれるＡｌ、Ｍｇ等の各酸化物もある
程度残渣中にとどまっていることを示唆し、第４図の結
果とよく対応する。FIG. 5 shows the XRD pattern of the residue after acid leaching after mechanochemical treatment for 2 hours.
It is shown together with the XRD pattern of the AT alone. According to this, each peak position in the XRD pattern of the residue is untreated B
Identical to those of AT and therefore the residue contains BA
It can be seen that a considerable amount of the T crystal system remains. This suggests that the oxides such as Al and Mg contained in the BAT also remain in the residue to some extent, which corresponds well to the results in FIG.
Claims (4)
ケミカル処理し、結晶構造を変化させたのち、低濃度酸
に浸出させることを特徴とする希土類金属化合物の抽出
方法。1. A method for extracting a rare earth metal compound, comprising subjecting a rare earth metal element-containing substance to a mechanochemical treatment for a predetermined time to change its crystal structure and then leaching it in a low-concentration acid.
ノイド系元素である請求項１記載の希土類金属化合物の
抽出方法。2. The method for extracting a rare earth metal compound according to claim 1, wherein the rare earth metal element is a Y, Sc or lanthanoid element.
砕機によりおこなわれる請求項１又は２記載の希土類金
属化合物の抽出方法。3. The method for extracting a rare earth metal compound according to claim 1, wherein the mechanochemical treatment is performed by a high energy type pulverizer.
ある請求項１、２又は３記載の希土類金属化合物の抽出
方法。4. The method for extracting a rare earth metal compound according to claim 1, wherein the low-concentration acid is hydrochloric acid or sulfuric acid of 1N or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24334697A JPH1171111A (en) | 1997-08-25 | 1997-08-25 | Extraction of rare earth metallic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24334697A JPH1171111A (en) | 1997-08-25 | 1997-08-25 | Extraction of rare earth metallic compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1171111A true JPH1171111A (en) | 1999-03-16 |
Family
ID=17102471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24334697A Pending JPH1171111A (en) | 1997-08-25 | 1997-08-25 | Extraction of rare earth metallic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1171111A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100412397B1 (en) * | 2001-11-05 | 2003-12-24 | 한국화학연구원 | La and Eu separation method of useless three wave fluorescent lamp |
| EP1215260A3 (en) * | 2000-12-18 | 2004-03-03 | Osram Sylvania Inc. | Recovery of electroluminescent phosphor from encapsulated material |
| WO2007141177A1 (en) | 2006-06-02 | 2007-12-13 | Osram Gesellschaft mit beschränkter Haftung | Method for recovery of rare earths from fluorescent lamps |
| JP2010042346A (en) * | 2008-08-12 | 2010-02-25 | Jfe Mineral Co Ltd | Pretreatment method for recovering rare earth element from disposed fluorescent lamp and method of recovering rare earth element using solid matter obtained by the pretreatment method |
| US8034319B2 (en) | 2003-05-30 | 2011-10-11 | Jfe Mineral Co., Ltd. | Method for producing complex oxide of metal |
| WO2012016511A1 (en) * | 2010-08-03 | 2012-02-09 | 江西稀有金属钨业控股集团有限公司 | Process for in-situ leaching by liquid injection |
| WO2014066668A1 (en) * | 2012-10-24 | 2014-05-01 | Rare Earth Salts Separation And Refining, Llc | Method for rare earth and actinide element recovery, extraction and separations from natural and recycled resources |
| DE102014101766A1 (en) | 2014-02-12 | 2015-08-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the recovery and optionally separation of lanthanides in the form of their chlorides or oxides from mineral wastes and residues |
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1997
- 1997-08-25 JP JP24334697A patent/JPH1171111A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1215260A3 (en) * | 2000-12-18 | 2004-03-03 | Osram Sylvania Inc. | Recovery of electroluminescent phosphor from encapsulated material |
| KR100412397B1 (en) * | 2001-11-05 | 2003-12-24 | 한국화학연구원 | La and Eu separation method of useless three wave fluorescent lamp |
| US8034319B2 (en) | 2003-05-30 | 2011-10-11 | Jfe Mineral Co., Ltd. | Method for producing complex oxide of metal |
| US8628734B2 (en) | 2006-06-02 | 2014-01-14 | Osram Gesellschaft Mit Beschraenkter Haftung | Method for recovery of rare earths from fluorescent lamps |
| WO2007141177A1 (en) | 2006-06-02 | 2007-12-13 | Osram Gesellschaft mit beschränkter Haftung | Method for recovery of rare earths from fluorescent lamps |
| JP2009538949A (en) * | 2006-06-02 | 2009-11-12 | オスラム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Recovery method of rare earth from fluorescent lamp |
| US7976798B2 (en) | 2006-06-02 | 2011-07-12 | Osram Gesellschaft Mit Beschraenkter Haftung | Method for recovery of rare earths from fluorescent lamps |
| EP2363873A1 (en) | 2006-06-02 | 2011-09-07 | Osram Gesellschaft mit Beschränkter Haftung | Method for recovering rare earths from illuminant lamps |
| CN102496545A (en) * | 2006-06-02 | 2012-06-13 | 欧司朗股份有限公司 | Method for recovery of rare earths from fluorescent lamps |
| JP2010042346A (en) * | 2008-08-12 | 2010-02-25 | Jfe Mineral Co Ltd | Pretreatment method for recovering rare earth element from disposed fluorescent lamp and method of recovering rare earth element using solid matter obtained by the pretreatment method |
| WO2012016511A1 (en) * | 2010-08-03 | 2012-02-09 | 江西稀有金属钨业控股集团有限公司 | Process for in-situ leaching by liquid injection |
| KR101407349B1 (en) * | 2010-08-03 | 2014-06-13 | 지앙시 레어 어스 앤드 레어 메탈스 텅스텐 그룹 홀딩 컴퍼니 리미티드 | A liquid injection process for in-situ leaching and extracting ion-adsorption type rare earth |
| WO2014066668A1 (en) * | 2012-10-24 | 2014-05-01 | Rare Earth Salts Separation And Refining, Llc | Method for rare earth and actinide element recovery, extraction and separations from natural and recycled resources |
| DE102014101766A1 (en) | 2014-02-12 | 2015-08-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the recovery and optionally separation of lanthanides in the form of their chlorides or oxides from mineral wastes and residues |
| EP2910654A1 (en) | 2014-02-12 | 2015-08-26 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for recovering and optionally separating lanthanides in the form of their chlorides or oxides from mineral waste and residual materials |
| DE102020100243A1 (en) | 2020-01-08 | 2021-07-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Process for reconditioning glass-plastic-metal composite materials |
| DE102020100243B4 (en) | 2020-01-08 | 2023-06-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Process for processing glass-plastic-metal composite materials |
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