JP3134896B2 - Production method of high purity rare earth fluoride - Google Patents
Production method of high purity rare earth fluorideInfo
- Publication number
- JP3134896B2 JP3134896B2 JP04053905A JP5390592A JP3134896B2 JP 3134896 B2 JP3134896 B2 JP 3134896B2 JP 04053905 A JP04053905 A JP 04053905A JP 5390592 A JP5390592 A JP 5390592A JP 3134896 B2 JP3134896 B2 JP 3134896B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- rare earth
- exchange resin
- cation exchange
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/265—Fluorides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は超低損失のフッ化物ガラ
ス光ファイバを製造する際、構成原料として用いられる
高純度希土類フッ化物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-purity rare earth fluoride used as a raw material for producing an ultra-low loss fluoride glass optical fiber.
【０００２】[0002]
【従来の技術】フッ化物ガラス光ファイバは石英光ファ
イバを凌ぐ１０-2ｄＢ／km以下の伝送損失が期待されて
おり、長距離無中継が可能な伝送媒体として有望視され
ている。しかし、これまで報告されているフッ化物ガラ
ス光ファイバの損失値は１ｄＢ／km前後である。フッ化
物光ファイバの超低損失化を阻害する要因としてＮｄ，
Ｐｒなどの希土類不純物、Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕなど
の遷移金属不純物による吸収損失と酸化物不純物による
散乱損失がある。これらの不純物は出発フッ化物原料に
含まれていることが多いと考えられるため、Ｎｄ，Ｐｒ
などの希土類不純物、Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕなどの遷
移金属不純物、酸化物不純物を含まない高純度フッ化物
原料の製造が望まれている。2. Description of the Related Art Fluoride glass optical fibers are expected to have a transmission loss of 10 -2 dB / km or less more than quartz optical fibers, and are regarded as promising as transmission media capable of long-distance non-repeating. However, the fluoride glass optical fiber reported to date has a loss value of around 1 dB / km. Nd and Nd are factors that hinder ultra-low loss of fluoride optical fibers.
There are absorption loss due to rare earth impurities such as Pr, transition metal impurities such as Fe, Co, Ni and Cu, and scattering loss due to oxide impurities. Since it is considered that these impurities are often contained in the starting fluoride material, Nd, Pr
It is desired to produce a high-purity fluoride raw material containing no rare earth impurities such as, for example, transition metal impurities such as Fe, Co, Ni, and Cu, and oxide impurities.
【０００３】光ファイバ用フッ化物ガラスの組成はＺｒ
Ｆ4 ，ＢａＦ2 ，ＬａＦ3 ，ＹＦ3，ＡｌＦ3 ，ＬｉＦ
あるいはＮａＦからなる。このうち、ＬａＦ3 ，ＹＦ3
などの希土類フッ化物の従来の精製法と、その欠点を述
べる。The composition of fluoride glass for optical fibers is Zr
F 4 , BaF 2 , LaF 3 , YF 3 , AlF 3 , LiF
Or it consists of NaF. Of these, LaF 3 , YF 3
Conventional purification methods for rare earth fluorides and the like and their disadvantages are described.
【０００４】（１）希土類フッ化物の精製〔D.R.Gabbe,
“Purification of Ba and Rare Earth Fluorides for
Optical Fibers”Materials Science Forum,vol 5 (198
5) pp85〜90〕 ゾーン精製法により、ＹＦ3 中のＰｒ，Ｎｄの除去を検
討したが、出発ＹＦ3中のＰｒ１ppm ，Ｎｄ２ppm に対
し精製ＹＦ3 中のＰｒ１ppm 以下、Ｎｄ１ppm以下が得
られ、１ppm レベル程度の高純度化しか行えない欠点が
あった。また、ＬａＦ3 中のＮｄ，Ｐｒのゾーン精製法
による除去についてはＬａＦ3 の融点が１４９３℃と高
く、精製装置に制限を受ける欠点があった。(1) Purification of rare earth fluorides [DRGabbe,
“Purification of Ba and Rare Earth Fluorides for
Optical Fibers ”Materials Science Forum, vol 5 (198
By 5) pp85~90] zone refining method, Pr in YF 3, has been studied in the removal of Nd, Pr1ppm in the starting YF 3, following Pr1ppm in the purified YF 3 to Nd2ppm, following is obtained Nd1ppm, 1ppm There is a drawback that only high-level purification can be performed. Also, Nd in LaF 3, the melting point of the LaF 3 for removal by zone refining method Pr high as 1493 ° C., there is a disadvantage that restricted to the purification device.
【０００５】（２）ＬａＦ3 の精製〔K.J.Ewing,J.Jaga
nathan,R.M.Rourke,I.D.Aggarwal,P.Paulson,E.Beary,
“Purification and Analysis of Fluoride Raw Materi
als atSub ppb levels ”Materials Science Forum,vol
32 (1988) pp19 〜24〕は、出発物質のＬａ2 Ｏ3 をＨ
ＮＯ3 に溶解後、アンモニア水を加え不純物のＦｅ，Ｃ
ｏ，Ｎｉ，ＣｕをＬａ（ＯＨ）3 に共沈させ、残った水
溶液に（ＮＨ4 ）2 ＣＯ3 水溶液を添加し、Ｌａ2 （Ｃ
Ｏ3 ）3 を生成後、フッ化水素酸との反応でＬａＦ3 と
する精製法である。このような精製過程で得られるＬａ
2 （ＣＯ3 ）3 は、Ｆｅ，Ｃｏ，Ｎｉについては精製さ
れているが，Ｃｕについては出発物質のＬａ2 Ｏ3 での
１０ｐｐｂに対し、２０ｐｐｂとＣｕが汚染される欠点
があった。さらに、この精製法ではＮｄ，Ｐｒの除去が
できないという欠点があった。(2) Purification of LaF 3 [KJ Ewing, J. Jaga
nathan, RMRourke, IDAggarwal, P.Paulson, E.Beary,
“Purification and Analysis of Fluoride Raw Materi
als atSub ppb levels ”Materials Science Forum, vol
32 (1988) pp. 19-24] describes the conversion of La 2 O 3
After dissolving in NO 3 , ammonia water is added and impurities such as Fe and C
o, Ni, and Cu are coprecipitated with La (OH) 3, and an aqueous solution of (NH 4 ) 2 CO 3 is added to the remaining aqueous solution to obtain La 2 (C
This is a purification method in which after producing O 3 ) 3 , it is converted into LaF 3 by reaction with hydrofluoric acid. La obtained in such a purification process
2 (CO 3 ) 3 has been refined for Fe, Co and Ni, but has a drawback that Cu is contaminated with 20 ppb as opposed to 10 ppb in the starting material La 2 O 3 . Further, this purification method has a disadvantage that Nd and Pr cannot be removed.
【０００６】また、希土類不純物相互の分離については
以下ような方法がある。 α−ヒドロキシイソ酪酸による核分裂生成物の希土類の
イオン交換分離〔M.M.Zeligman,Anal.Chem.,37 (1965)
pp524 〜525 〕 Ｙ，Ｔｂ，Ｇｄ，Ｅｕ，Ｓｍ，Ｐｍ，Ｎｄ，Ｐｒ，Ｃ
ｅ，Ｌａの軽希土類の相互分離は、陽イオン交換樹脂の
Ｄｏｗｅｘ５０Ｗ−Ｘ８の１００〜２００メッシュを交
換カラム（内径７mm，長さ３０インチ）に入れ、溶離剤
としてα−ヒドロキシイソ酪酸を用いて行なう方法であ
る。しかしながら、このような方法は、交換カラムの容
量が小さく分離できる希土類は数mg程度であり、１０ｇ
程度の希土類の分離ができないという欠点があった。There are the following methods for separating rare earth impurities from each other. Ion exchange separation of rare earths of fission products with α-hydroxyisobutyric acid [MM Zeligman, Anal.Chem., 37 (1965)
pp524-525] Y, Tb, Gd, Eu, Sm, Pm, Nd, Pr, C
e and La are separated from each other by using a cation exchange resin Dowex 50W-X8 100-200 mesh in an exchange column (inner diameter 7 mm, length 30 inches) and α-hydroxyisobutyric acid as eluent. The way to do it. However, in such a method, the capacity of the exchange column is small, and the rare earth which can be separated is about several mg, and 10 g
There is a disadvantage that rare earths cannot be separated to a certain extent.
【０００７】[0007]
【発明が解決しようとする課題】よって、本発明におけ
る課題は、高純度のＬａＦ3 あるいはＹＦ3 の製造にお
いて、陽イオン交換樹脂カラムによりＬａあるいはＹの
水溶液に含まれているＦｅ，Ｃｏ，Ｎｉ，Ｃｕなどの遷
移金属不純物およびＮｄ，Ｐｒなどの希土類不純物を低
減し、純度が優れたＬａＦ3 あるいはＹＦ3 が容易に得
られる方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high-purity LaF 3 or YF 3 for producing Fe, Co, Ni contained in an aqueous solution of La or Y by a cation exchange resin column. It is an object of the present invention to provide a method by which transition metal impurities such as Cu, Cu and rare earth impurities such as Nd and Pr can be reduced and LaF 3 or YF 3 having excellent purity can be easily obtained.
【０００８】[0008]
【課題を解決するための手段】かかる課題は、Ｌａある
いはＹの水溶液を陽イオン交換樹脂カラムを用いて湿式
精製を行った後、ＬａあるいはＹの溶出液にフッ素化剤
を加え、ＬａあるいはＹのフッ化物沈殿を生成し、この
フッ化物沈殿を脱水、乾燥、焼成後、ＬａＦ3あるいは
ＹＦ3 とする方法で解決される。The object of the present invention is to solve the problem by performing a wet purification of an aqueous solution of La or Y using a cation exchange resin column, and then adding a fluorinating agent to the eluate of La or Y to obtain La or Y. This is solved by a method in which a fluoride precipitate is formed, and the fluoride precipitate is dehydrated, dried, calcined, and then converted to LaF 3 or YF 3 .
【０００９】以下、本発明を詳細に説明する。本発明の
高純度希土類フッ化物の製造方法は、ＬａあるいはＹの
水溶液を陽イオン交換樹脂カラムを用いて湿式精製を行
った後、ＬａあるいはＹの溶出液にフッ素化剤を加え、
ＬａあるいはＹのフッ化物沈殿を生成し、このフッ化物
沈殿を脱水、乾燥、焼成後、ＬａＦ3 あるいはＹＦ3 と
する方法である。Hereinafter, the present invention will be described in detail. The method for producing a high-purity rare earth fluoride according to the present invention comprises the steps of wet-purifying an aqueous solution of La or Y using a cation exchange resin column, and then adding a fluorinating agent to the eluate of La or Y;
This is a method in which a fluoride precipitate of La or Y is generated, and the fluoride precipitate is dehydrated, dried, and calcined to obtain LaF 3 or YF 3 .
【００１０】陽イオン交換樹脂カラムとしては、スチレ
ンジビニルベンゼン共重合体にスルホン酸基を導入して
なる強酸性陽イオン交換樹脂を充填したカラムを用いる
ことが好ましい。As the cation exchange resin column, it is preferable to use a column filled with a strongly acidic cation exchange resin obtained by introducing a sulfonic acid group into a styrene divinylbenzene copolymer.
【００１１】湿式精製は、ＬａあるいはＹの水溶液を陽
イオン交換樹脂カラムに通し、陽イオン交換樹脂がＬａ
あるいはＹを吸着した後、pHが３．５〜４．５である
０．２〜１．０Ｍのα−ヒドロキシイソ酪酸溶液を溶離
剤として用いるのが好ましい。In the wet purification, an aqueous solution of La or Y is passed through a cation exchange resin column,
Alternatively, it is preferable to use a 0.2-1.0 M α-hydroxyisobutyric acid solution having a pH of 3.5 to 4.5 after adsorbing Y as an eluent.
【００１２】フッ素化剤としては、フッ化水素酸、酸性
フッ化アンモニウム、フッ化水素ガスのいづれか１つを
用いることが好ましい。As the fluorinating agent, it is preferable to use any one of hydrofluoric acid, ammonium acid fluoride and hydrogen fluoride gas.
【００１３】ＬａあるいはＹのフッ化物沈澱の焼成は、
酸性フッ化アンモニウムを添加し、６００〜８００℃に
おいて行なうのが好ましい。The calcination of the La or Y fluoride precipitate is
It is preferable to add ammonium ammonium fluoride and carry out at 600 to 800 ° C.
【００１４】本発明の高純度希土類フッ化物の製造方法
は、陽イオン交換樹脂カラムによる希土類元素の相互分
離の長所を活かし、かつ、ＬａあるいはＹの水溶液を陽
イオン交換樹脂カラムに通し、陽イオン交換樹脂がＬａ
あるいはＹを吸着した後、これに溶離剤を加えＣｒ（II
I), Ｆｅ（III), Ｃｏ(II)，Ｎｉ(II)，Ｃｕ(II)の遷移
金属不純物を溶離させ、Ｌａの水溶液の場合は、Ｌａ以
外のＮｄ，Ｐｒを含むランタノイドを溶離させた後、Ｌ
ａを溶出させ、一方、Ｙの水溶液の場合はＹを溶出し、
ランタノイドは陽イオン交換樹脂カラムに残留させるこ
とを最も主要な特徴とする。The method for producing a high-purity rare earth fluoride according to the present invention takes advantage of the mutual separation of rare earth elements by a cation exchange resin column and passes an aqueous solution of La or Y through a cation exchange resin column to form a cation exchange resin. Replacement resin is La
Alternatively, after adsorbing Y, an eluent is added thereto and Cr (II
Transition metal impurities of I), Fe (III), Co (II), Ni (II) and Cu (II) were eluted, and in the case of La aqueous solution, lanthanoids other than La and containing Nd and Pr were eluted. Later, L
e, while in the case of an aqueous solution of Y, elute Y
The main feature of the lanthanoid is that it remains on the cation exchange resin column.
【００１５】このような高純度希土類フッ化物の製造方
法は、従来の技術ではＣｕ以外の遷移金属不純物だけの
除去、１ppm レベルの希土類不純物の低減化だけが実施
されているのに対して、１種の精製法で遷移金属不純物
と希土類不純物の両者が容易に除去できるものである。
従って、本発明の高純度希土類フッ化物の製造方法によ
って得られる希土類フッ化物は、遷移金属不純物、Ｌａ
あるいはＹ以外の希土類不純物の両者が大幅に低減し、
純度が向上する。In such a method for producing a high-purity rare earth fluoride, in the prior art, only the removal of transition metal impurities other than Cu was performed, and only the reduction of rare earth impurities at the level of 1 ppm was performed. Both kinds of transition metal impurities and rare earth impurities can be easily removed by various kinds of purification methods.
Therefore, the rare earth fluoride obtained by the method for producing a high-purity rare earth fluoride of the present invention contains a transition metal impurity, La
Alternatively, both rare earth impurities other than Y are significantly reduced,
Purity is improved.
【００１６】[0016]
【実施例】以下、実施例をあげて本発明を具体的に説明
する。 （実施例１）Ｌａ2 Ｏ3 を出発とするＬａＦ3 の製造方
法を図面を用いて説明する。図１は本発明の高純度希土
類フッ化物の製造方法の実施に好適に用いられる陽イオ
ン交換樹脂カラムによるＬａあるいはＹの精製を説明す
るための図である。図１中符号１は陽イオン交換樹脂、
２は陽イオン交換樹脂１が充填されたカラム、３はフィ
ルタ、４はチューブ、５はペリスタポンプ、６は溶離
液、７は溶出液である。The present invention will be described below in detail with reference to examples. (Example 1) the La 2 O 3 will be described with reference to the accompanying drawings the manufacturing method of LaF 3 to start. FIG. 1 is a diagram for explaining the purification of La or Y by a cation exchange resin column suitably used for carrying out the method for producing a high-purity rare earth fluoride of the present invention. 1 is a cation exchange resin,
2 is a column filled with the cation exchange resin 1, 3 is a filter, 4 is a tube, 5 is a peristaltic pump, 6 is an eluent, and 7 is an eluent.
【００１７】まず、Ｌａ2 Ｏ3 ２５ｇを秤量後、硝酸４
０ｍｌに溶解し、酢酸アンモニウムを添加し、pHを４．
５とした後、分析グレードの陽イオン交換樹脂１（５０
Ｗ−Ｘ８）６００ｇを充填したカラム２（内径７０ｍ／
ｍ，長さ６００ｍ／ｍ）にＬａの水溶液を流し、上記陽
イオン交換樹脂１にＬａを吸着させた。ついで、カラム
２に０．４Ｍのα−ヒドロキシイソ酪酸溶離液６を３０
００ｍｌ流入し、遷移金属不純物およびＬａ以外の希土
類不純物を溶離して除去した。さらに、上記カラム２に
１．０Ｍのα−ヒドロキシイソ酪酸溶離液６を１０００
ｍｌ流入させＬａを溶出させた。ついで、Ｌａの溶出液
７をフッ素化剤のフッ化水素酸に入れＬａのフッ化物沈
殿を生成した。そして、Ｌａのフッ化物沈殿を脱水、乾
燥させた後、酸性フッ化アンモニウムを添加し、６００
℃で焼成しＬａＦ3 を得た。このＬａＦ3 の同定はＸ線
回折で行った。表１にこの実施例１で製造したＬａＦ3
の中性子放射化分析による遷移金属不純物、Ｎｄ，Ｐｒ
の分析値を示す。First, after weighing 25 g of La 2 O 3 ,
Dissolve in 0 ml, add ammonium acetate and adjust pH to 4.
5, and then the analytical grade cation exchange resin 1 (50
W-X8) column 2 packed with 600 g (inner diameter 70 m /
(m, 600 m / m in length), an aqueous solution of La was allowed to flow, and La was adsorbed on the cation exchange resin 1. Then, 30 ml of 0.4 M α-hydroxyisobutyric acid eluent 6 was added to column 2 for 30 minutes.
00 ml was introduced, and transition metal impurities and rare earth impurities other than La were eluted and removed. In addition, 1.0 M of α-hydroxyisobutyric acid eluent 6
ml was introduced to elute La. Next, the La eluate 7 was placed in hydrofluoric acid as a fluorinating agent to produce a La fluoride precipitate. Then, after dehydrating and drying the fluoride precipitate of La, ammonium acid fluoride is added, and
Calcination was carried out at ℃ to obtain LaF 3 . This LaF 3 was identified by X-ray diffraction. Table 1 shows that LaF 3 produced in Example 1 was used.
Metal impurities, Nd, Pr by neutron activation analysis
Shows the analytical value of.
【００１８】[0018]
【表１】 [Table 1]
【００１９】上記表１においてＣｏ，Ｃｕは各々０．１
ｐｐｂ、Ｃｒ，Ｆｅ，Ｎｄ，Ｐｒは各々１ｐｐｂ未満、
Ｎｉは１０ｐｐｂ未満であり、いずれも検出下限に近い
値まで高純度化できていることが確認できる。In Table 1 above, Co and Cu are each 0.1%.
ppb, Cr, Fe, Nd and Pr are each less than 1 ppb,
Ni is less than 10 ppb, and it can be confirmed that all of them have been highly purified to a value close to the lower detection limit.
【００２０】ついで、この実施例１で製造したＬａＦ3
をフッ化物ガラス光ファイバ原料成分として使用した。
その結果、吸収損失の小さい良好なフッ化ガラス光ファ
イバが得られた。また、フッ素化剤として酸性フッ化ア
ンモニウムあるいはフッ化水素ガスを用いてＬａのフッ
化物沈殿を生成しても上記と同様に高純度のＬａＦ3が
得られた。Next, the LaF 3 produced in Example 1 was used.
Was used as a raw material component of a fluoride glass optical fiber.
As a result, a good fluorinated glass optical fiber having a small absorption loss was obtained. Further, even when La fluoride precipitates were formed using acidic ammonium fluoride or hydrogen fluoride gas as a fluorinating agent, high-purity LaF 3 was obtained in the same manner as described above.
【００２１】（実施例２）Ｙ2 Ｏ3 を出発とするＹＦ3
の製造方法を図１を用いて以下に説明する。Ｙ2 Ｏ3 ２
０ｇを秤量後、硝酸４０ｍｌに溶解し、酢酸アンモニウ
ムを添加しpHを３．５とした。溶解したＹの水溶液を分
析グレードの陽イオン交換樹脂１（５０Ｗ−Ｘ８）６０
０ｇを充填したカラム２に流し、Ｙを吸着させた。つい
で、カラム２に０．２Ｍのα−ヒドロキシイソ酪酸溶離
液６の２００ｍｌをペリスタポンプ５を使用し流入さ
せ、遷移金属不純物を溶離し廃棄した。さらに上記カラ
ム２に、０．４Ｍのα−ヒドロキシイソ酪酸溶離液６を
１８００ｍｌ流入し、Ｙを溶出させた。ついで、Ｙの溶
出液７をフッ素化剤のフッ化水素酸に入れ、Ｙのフッ化
物沈殿を生成した。そして、Ｙのフッ化物沈殿を脱水、
乾燥し、酸性フッ化アンモニウムを添加し、８００℃で
焼成し、ＹＦ3 を得た。このＹＦ3 について遷移金属お
よび希土類不純物分析を行った結果、上記表１に示した
分析値とほぼ同様、Ｃｒ，Ｆｅ，Ｎｄ，Ｐｒは各々１ｐ
ｐｂ以下、Ｃｏ，Ｃｕは０．１ｐｐｂ以下となり、いず
れも検出下限値まで高純度化できていることを確認し
た。[0021] (Example 2) Y 2 O 3 and a starting YF 3
The manufacturing method will be described below with reference to FIG. Y 2 O 3 2
After weighing 0 g, it was dissolved in 40 ml of nitric acid, and the pH was adjusted to 3.5 by adding ammonium acetate. The dissolved aqueous solution of Y was converted to a cation exchange resin 1 (50W-X8) 60 of analytical grade.
The solution was passed through a column 2 packed with 0 g to adsorb Y. Then, 200 ml of 0.2M α-hydroxyisobutyric acid eluent 6 was introduced into the column 2 using the peristaltic pump 5, and transition metal impurities were eluted and discarded. Further, 1800 ml of 0.4 M α-hydroxyisobutyric acid eluent 6 was introduced into the column 2 to elute Y. Next, the eluate 7 of Y was put into hydrofluoric acid as a fluorinating agent to generate a precipitate of Y fluoride. And dehydrate the fluoride precipitate of Y,
Dried, adding an acidic ammonium fluoride, and calcined at 800 ° C., to obtain a YF 3. As a result of conducting a transition metal and rare earth impurity analysis on this YF 3 , Cr, Fe, Nd, and Pr were 1 p each, almost in the same manner as the analysis values shown in Table 1 above.
pb or less and Co and Cu were 0.1 ppb or less, and it was confirmed that all of them could be highly purified to the detection lower limit.
【００２２】ついで、この実施例２で製造したＹＦ3 を
フッ化物ガラス光ファイバ原料成分として使用した。そ
の結果、吸収損失の小さい良好なフッ化ガラス光ファイ
バが得られた。また、フッ素化剤としてフッ化水素ガス
を用いてフッ化物沈殿を生成しても上記と同様に高純度
のＹＦ3 が得られた。Then, YF 3 produced in Example 2 was used as a raw material component of a fluoride glass optical fiber. As a result, a good fluorinated glass optical fiber having a small absorption loss was obtained. Even when a fluoride precipitate was formed using hydrogen fluoride gas as a fluorinating agent, high-purity YF 3 was obtained in the same manner as described above.
【００２３】[0023]
【発明の効果】以上説明したように、本発明の高純度希
土類フッ化物の製造方法は、ＬａあるいはＹの水溶液を
陽イオン交換樹脂カラムを用いて湿式精製を行った後、
ＬａあるいはＹの溶出液にフッ素化剤を加え、Ｌａある
いはＹのフッ化物沈殿を生成し、このフッ化物沈殿を脱
水、乾燥、焼成してＬａＦ3 あるいはＹＦ3 とするの
で、陽イオン交換樹脂カラムと溶離剤とによって、遷移
金属不純物およびＬａあるいはＹ以外の希土類不純物の
除去が行えるため、遷移金属不純物、希土類不純物の両
者が極めて少ない高純度希土類フッ化物が容易に得られ
る。従って、本発明の高純度希土類フッ化物の製造方法
によって得られる高純度希土類フッ化物をフッ化物ガラ
ス光ファイバ原料として用いることによって、超低損失
のフッ化物ガラス光ファイバを製造できるという利点が
ある。As described above, the method for producing a high-purity rare earth fluoride according to the present invention comprises the steps of: wet-purifying an aqueous solution of La or Y using a cation exchange resin column;
A fluorinating agent is added to the La or Y eluate to produce a La or Y fluoride precipitate, and the fluoride precipitate is dehydrated, dried, and calcined into LaF 3 or YF 3 , so that a cation exchange resin column is used. The transition metal impurities and the rare earth impurities other than La or Y can be removed by using the eluent and the eluent, so that a high-purity rare earth fluoride containing both very little transition metal impurities and rare earth impurities can be easily obtained. Therefore, there is an advantage that an ultra-low loss fluoride glass optical fiber can be manufactured by using the high purity rare earth fluoride obtained by the method for manufacturing a high purity rare earth fluoride of the present invention as a raw material of a fluoride glass optical fiber.
【図１】本発明の高純度希土類フッ化物の製造方法の実
施に好適に用いられる陽イオン交換樹脂カラムによるＬ
ａあるいはＹの精製を説明するための図である。FIG. 1 shows a cation exchange resin column preferably used for carrying out the method for producing a high-purity rare earth fluoride of the present invention.
It is a figure for demonstrating refinement | purification of a or Y.
１ 陽イオン交換樹脂 ２ カラム ６ 溶離液 ７ 溶出液 1 Cation exchange resin 2 Column 6 Eluent 7 Eluate
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C01F 17/00 C22B 59/00 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C01F 17/00 C22B 59/00 CA (STN)
Claims (5)
樹脂カラムを用いて湿式精製を行った後、Ｌａあるいは
Ｙの溶出液にフッ素化剤を加え、ＬａあるいはＹのフッ
化物沈殿を生成し、このフッ化物沈殿を脱水、乾燥、焼
成してＬａＦ3 あるいはＹＦ3 とすることを特徴とする
高純度希土類フッ化物の製造方法。An aqueous solution of La or Y is subjected to wet purification using a cation exchange resin column, and then a fluorinating agent is added to the eluate of La or Y to produce a La or Y fluoride precipitate. A method for producing a high-purity rare earth fluoride, wherein the fluoride precipitate is dehydrated, dried and fired to obtain LaF 3 or YF 3 .
ビニルベンゼン共重合体にスルホン酸基を導入してなる
強酸性陽イオン交換樹脂を充填したカラムであることを
特徴とする請求項１記載の高純度希土類フッ化物の製造
方法。2. The column according to claim 1, wherein the cation exchange resin column is a column packed with a strongly acidic cation exchange resin obtained by introducing a sulfonic acid group into a styrene divinylbenzene copolymer. A method for producing a rare earth fluoride having a high purity.
陽イオン交換樹脂カラムに通し、陽イオン交換樹脂がＬ
ａあるいはＹを吸着した後、pHが３．５〜４．５である
０．２〜１．０Ｍのα−ヒドロキシイソ酪酸溶液を溶離
剤として用いるものであることを特徴とする請求項１記
載の高純度希土類フッ化物の製造方法。3. In the wet purification, an aqueous solution of La or Y is passed through a cation exchange resin column, and
2. The method according to claim 1, wherein after adsorbing a or Y, a 0.2-1.0 M α-hydroxyisobutyric acid solution having a pH of 3.5 to 4.5 is used as an eluent. Production method of high purity rare earth fluoride.
アンモニウム、フッ化水素ガスのいづれか１つであるこ
とを特徴とする請求項１記載の高純度希土類フッ化物の
製造方法。4. The method for producing a high-purity rare earth fluoride according to claim 1, wherein the fluorinating agent is any one of hydrofluoric acid, ammonium acid fluoride, and hydrogen fluoride gas.
が、酸性フッ化アンモニウムを添加し、６００〜８００
℃において行なうことを特徴とする請求項１記載の高純
度希土類フッ化物の製造方法。5. The calcination of the La or Y fluoride precipitate is carried out by adding ammonium acid fluoride,
2. The method for producing a high-purity rare-earth fluoride according to claim 1, wherein the method is carried out at a temperature of ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04053905A JP3134896B2 (en) | 1992-03-12 | 1992-03-12 | Production method of high purity rare earth fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04053905A JP3134896B2 (en) | 1992-03-12 | 1992-03-12 | Production method of high purity rare earth fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05254831A JPH05254831A (en) | 1993-10-05 |
| JP3134896B2 true JP3134896B2 (en) | 2001-02-13 |
Family
ID=12955732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04053905A Expired - Lifetime JP3134896B2 (en) | 1992-03-12 | 1992-03-12 | Production method of high purity rare earth fluoride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3134896B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264078B (en) * | 2016-12-30 | 2020-03-27 | 有研稀土新材料股份有限公司 | Hydrogen-containing rare earth fluoride, preparation method and application thereof |
| CN109694100B (en) * | 2019-02-01 | 2021-04-02 | 渤海大学 | Preparation of LaF by self-sacrifice template method3Method (2) |
-
1992
- 1992-03-12 JP JP04053905A patent/JP3134896B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ａｎａｌ．Ｃｈｅｍ．３７（１９６５）ｐ．５２４−５２５ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05254831A (en) | 1993-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Moeller | The chemistry of the lanthanides: Pergamon texts in inorganic chemistry | |
| US4514367A (en) | Method for separating rare earth metals | |
| US4738834A (en) | Treatment of technetium containing solutions | |
| CN109416952B (en) | Method for producing fractions of iodine radioisotopes, in particular I-131, fractions of iodine radioisotopes, in particular I-131 | |
| JP2003529517A (en) | Inorganic adsorbent for extracting molybdenum-99 from irradiated uranium solution and method of using the same | |
| JP3134896B2 (en) | Production method of high purity rare earth fluoride | |
| US2796320A (en) | Solvent extraction process for purification of thorium | |
| JP3303066B2 (en) | How to purify scandium | |
| CA2681180A1 (en) | Production of thorium 228 starting from a natural thorium salt | |
| CN115404342B (en) | Carrier-free body 161 Tb preparation method | |
| CN108423708B (en) | Method for preparing thallium bromide and thallium bromide | |
| JPS6157900B2 (en) | ||
| US2759793A (en) | Separating hafnium from zirconium | |
| US3173757A (en) | Purification of strontium solutions by ion exchange | |
| Cheng et al. | Study on the separation of molybdenum-99 and recycling of uranium to water boiler reactor | |
| JPS6158533B2 (en) | ||
| Gongyi et al. | Application of extraction chromatography to the preparation of high-purity scandium oxide | |
| JPH0617207B2 (en) | Method for producing high-purity metal fluoride | |
| US3687641A (en) | Separation and recovery of americium from curium and other elements | |
| JPH01258737A (en) | Adsorbent for recovery of rare earth element in aqueous solution | |
| CN111785407B (en) | Treatment method of molybdenum-containing substance | |
| CN117737427A (en) | Method for preparing high-purity rare earth by mixed leaching ion exchange method | |
| Arnfelt et al. | Spectrophotometric determination of thorium in low-grade minerals and ores | |
| SU1057061A1 (en) | Method of chromatographic separation of yttrium from solutions containing compounds of heavy rare-earthed elements | |
| US2901313A (en) | Separation of plutonium from water insoluble fluorides derived from nitrate solutions of plutonium, uranium and fission products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071201 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081201 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091201 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101201 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101201 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111201 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111201 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121201 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121201 Year of fee payment: 12 |