JP2966724B2 - Method for producing rare earth hydroxide and spherical particles of rare earth oxide - Google Patents
Method for producing rare earth hydroxide and spherical particles of rare earth oxideInfo
- Publication number
- JP2966724B2 JP2966724B2 JP6103639A JP10363994A JP2966724B2 JP 2966724 B2 JP2966724 B2 JP 2966724B2 JP 6103639 A JP6103639 A JP 6103639A JP 10363994 A JP10363994 A JP 10363994A JP 2966724 B2 JP2966724 B2 JP 2966724B2
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth element
- hydroxide
- spherical particles
- oxide
- Prior art date
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】主に各種蛍光体の原料、セラミッ
クス焼結助剤等の幅広い用途を持つ希土類元素水酸化物
および希土類元素酸化物の製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rare earth element hydroxide and a rare earth element oxide having a wide variety of uses, mainly as a raw material for various phosphors, a ceramic sintering aid and the like.
【０００２】[0002]
【従来の技術】従来水溶性希土類元素化合物の水溶液に
無機塩基を加えて希土類元素水酸化物を沈殿させ、これ
を焼成して希土類元素酸化物を得ていた。2. Description of the Related Art Conventionally, an inorganic base has been added to an aqueous solution of a water-soluble rare earth element compound to precipitate a rare earth element hydroxide, which has been calcined to obtain a rare earth element oxide.
【０００３】[0003]
【発明が解決しようとする課題】希土類元素を水酸化物
として沈殿させるのに沈殿剤として無機塩基である水酸
化アルカリ或はアンモニアを用いた場合、生じる沈殿は
多くの場合ゲル状で濾過性が悪く、これを乾燥或は焼成
したものは数mm以上の固い凝集物になり、用途によって
は粉砕、篩分を必要とする。蛍光体原料としてはその取
扱、処理上、粒径が２〜10μｍの粒子で、さらに形状は
球状に近い方が望ましいとされており、また、蛍光体原
料として希土類元素の酸化物あるいは水酸化物を用いる
場合、通常アルカリ金属の混入を嫌うので沈殿剤として
の水酸化アルカリの使用はこの面からも好ましくない。
本発明は、このような不利を解決し、球状微粒子からな
り、アルカリ金属を含有しない希土類元素水酸化物およ
び酸化物を提供しようとするものである。When a rare earth element is precipitated as hydroxide using an inorganic base, such as alkali hydroxide or ammonia, as a precipitant, the resulting precipitate is often gel-like and has poor filterability. It is bad, and the dried or calcined one forms hard aggregates of several mm or more, and requires pulverization and sieving depending on the application. It is said that it is desirable that the phosphor raw material be particles having a particle size of 2 to 10 μm in terms of handling and processing, and that the shape be closer to a sphere, and that an oxide or hydroxide of a rare earth element be used as the phosphor raw material In the case where is used, the use of an alkali hydroxide as a precipitant is not preferable from this point of view, since it is generally reluctant to mix an alkali metal.
An object of the present invention is to solve such disadvantages and to provide a rare earth element hydroxide and an oxide composed of spherical fine particles and containing no alkali metal.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、かかる課
題を解決するために、希土類元素水酸化物の沈殿工程に
於て、沈殿剤としてエタノールアミン類が有効であるこ
とを見出し、諸条件を確立して本発明を完成したもの
で、その要旨は、水溶性希土類元素化合物の水溶液にエ
タノールアミン類を添加し、反応させることを特徴とす
る希土類元素水酸化物の球状粒子の製造方法、並びにこ
こで得られた球状希土類元素水酸化物を大気中 600℃以
上1500℃以下で焼成することを特徴とする希土類元素酸
化物の球状粒子の製造方法にあり、更に詳しくは、エタ
ノールアミン類が一般式HnN(CH2-CH2-OH)3-n（式中ｎは
０、１、２である）で表されるものであることからな
る。Means for Solving the Problems In order to solve such problems, the present inventors have found that ethanolamines are effective as a precipitant in the step of precipitating a rare earth element hydroxide. The present invention has been completed by establishing conditions, and the gist of the present invention is to provide a method for producing spherical particles of a rare earth element hydroxide, wherein ethanolamines are added to an aqueous solution of a water-soluble rare earth element compound and reacted. And a method for producing spherical particles of a rare earth element oxide, characterized in that the spherical rare earth element hydroxide obtained here is calcined in the air at a temperature of 600 ° C or more and 1500 ° C or less. Is represented by the general formula H n N (CH 2 —CH 2 —OH) 3-n (where n is 0, 1, 2).
【０００５】以下、本発明を詳細に説明する。希土類元
素水酸化物の沈殿工程に於て、沈殿剤として各種の有機
塩基を用いることを検討した。その中でエタノールアミ
ン類を用いた場合に、微粒子が球状に凝集した粒径２〜
10μｍでかつ濾過性、水切り性の良い希土類元素水酸化
物の球状粒子が得られることを見出したもので、以下工
程順に説明する。塩化物、硝酸塩等の水溶性希土類元素
化合物の0.01〜0.5mol/Lの水溶液に、希土類元素１モル
あたり３〜４モルのエタノールアミン類を必要ならば水
で希釈して加える。ここに、エタノールアミン類とは、
モノエタノールアミン：NH2CH2CH2OH 、ジエタノールア
ミン：NH(CH2CH2OH)2 、トリエタノールアミン：N(CH2C
H2OH)3の総称であり、これらの中から選ばれる１種の化
合物または２種以上の混合物を使用できる。中でもトリ
エタノールアミンが最も有効である。加えるエタノール
アミン類の量は、希土類元素１モルあたり３モルに満た
ないと収率が悪くなり、４モルを超えて増やしても利点
は無く不経済となる。希土類元素とエタノールアミン類
を混合する順序は任意で良いが、希土類元素の溶液に撹
拌下エタノールアミン類を注ぎ込む方がより望ましい。
また、混合時の温度は高いほうが収率が良く、得られる
製品の粒径が大きい傾向があるが、60℃を超えて高くし
ても効果は薄い。以上によって得られた沈殿を濾別し、
必要に応じて水洗し、また風乾あるいは加熱乾燥して、
希土類元素水酸化物を得る。得られた水酸化物は球状凝
集粒子からなり、レーザー回折法による平均粒径は２〜
10μｍであり、濾過性、水洗性とも良好であった。酸化
物に変換したい場合は、さらに電気炉中で大気雰囲気下
600 ℃以上1500℃以下で焼成すれば良く、焼成前と後と
で粒子の形状、粒径はほぼ同じに保たれる。本発明の適
用範囲は、Ｙを含むＬa、Ｃe、Ｐr、Ｎd、Ｓm、Ｅu、Ｇd、Ｔb、
Ｄy、Ｈo、Ｅr、Ｔm、Ｙb およびＬu から成る群から選択さ
れる１種の元素、または２種以上の元素混合物である。Hereinafter, the present invention will be described in detail. The use of various organic bases as precipitants in the precipitation process of rare earth element hydroxides was studied. When ethanolamines are used among them, the particle diameter is 2
It has been found that spherical particles of a rare earth element hydroxide having a diameter of 10 μm and having good filterability and drainage properties can be obtained. To a 0.01 to 0.5 mol / L aqueous solution of a water-soluble rare earth element compound such as chloride or nitrate, 3 to 4 mol of ethanolamines per 1 mol of rare earth element is diluted with water if necessary, and then added. Here, ethanolamines are
Monoethanolamine: NH 2 CH 2 CH 2 OH, diethanolamine: NH (CH 2 CH 2 OH) 2 , triethanolamine: N (CH 2 C
H 2 OH) 3 , and one compound selected from these compounds or a mixture of two or more compounds can be used. Among them, triethanolamine is most effective. If the amount of ethanolamines to be added is less than 3 moles per mole of the rare earth element, the yield will be poor, and if it exceeds 4 moles, there is no advantage and uneconomical. The order of mixing the rare earth element and the ethanolamine may be arbitrary, but it is more desirable to pour the ethanolamine into the rare earth element solution with stirring.
Also, the higher the temperature during mixing, the better the yield and the particle size of the obtained product tends to be large. However, if the temperature is higher than 60 ° C, the effect is weak. The precipitate obtained by the above is filtered off,
If necessary, wash with water, air-dry or heat dry,
Obtain rare earth element hydroxide. The obtained hydroxide is composed of spherical aggregated particles, and the average particle size by laser diffraction method is 2 to 2.
It was 10 μm, and both the filterability and the washability were good. If you want to convert to oxides, further in an electric furnace under air atmosphere
The sintering may be performed at a temperature of 600 ° C. or more and 1500 ° C. or less, and the shape and the particle size of the particles before and after the sintering are kept substantially the same. The applicable range of the present invention is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, including Y.
One element selected from the group consisting of Dy, Ho, Er, Tm, Yb and Lu, or a mixture of two or more elements.
【０００６】以下、本発明の実施様態を実施例を挙げて
具体的に説明するが、本発明はこれらに限定されるもの
ではない。Hereinafter, embodiments of the present invention will be specifically described with reference to examples, but the present invention is not limited to these.
（実施例１）濃度0.3mol/L、pH 2.0の硝酸イットリウム
水溶液 700mlを1Lビーカーにいれ、約200rpmで撹拌しな
がら水浴で50℃に加熱した。これに予めトリエタノール
アミン100gと水100ml を混合しておいた溶液を撹拌を続
けながら５分間かけて注加した。さらに10分間撹拌を続
けた後ブフナー漏斗で濾別し、1200mlの水をふりかけ洗
浄した。得られた水酸化物のケーキは、66.8g であり、
濾過性、水洗性とも良好で濾過水洗を通じた所要時間は
約５分であった。このケーキを少量とって電子顕微鏡で
観察すると２〜６μｍ程度の直径の球状粒子からなり、
さらに倍率を上げていくと、その球状粒子は、0.1 μｍ
程度の微粒子からなる凝集体であった。ケーキを磁製坩
堝に入れ、電気炉中で大気中 800℃で１時間焼成した。
23.2g の酸化イットリウムを得た。この酸化物を電子顕
微鏡で観察した結果、ケーキの時とほぼ同様であり、ま
たレーザー回折法によって測定した平均粒径は 4.6μｍ
であった。Example 1 700 ml of an aqueous solution of yttrium nitrate having a concentration of 0.3 mol / L and a pH of 2.0 was placed in a 1 L beaker, and heated to 50 ° C. in a water bath while stirring at about 200 rpm. A solution in which 100 g of triethanolamine and 100 ml of water had been previously mixed was added thereto over 5 minutes while stirring was continued. After stirring was continued for another 10 minutes, the mixture was filtered off with a Buchner funnel and sprinkled with 1200 ml of water to wash. The resulting hydroxide cake weighs 66.8 g,
Both the filterability and the water washability were good, and the required time through the filter waterwash was about 5 minutes. When a small amount of this cake is taken and observed with an electron microscope, it consists of spherical particles having a diameter of about 2 to 6 μm,
As the magnification is further increased, the spherical particles become 0.1 μm
It was an agglomerate composed of fine particles. The cake was placed in a porcelain crucible and fired in an electric furnace at 800 ° C. for 1 hour in the atmosphere.
23.2 g of yttrium oxide were obtained. Observation of this oxide with an electron microscope revealed that the result was almost the same as that of the cake. The average particle size measured by a laser diffraction method was 4.6 μm.
Met.
【０００７】（比較例）トリエタノールアミン水溶液の
代わりに、0.32mol/L のアンモニア水溶液200ml を加え
ることの他は実施例１と同様に処理して水酸化イットリ
ウムを沈殿させた。沈殿はゲル状であり、実施例と同じ
方法で濾別水洗したがケーキの重量は167gであり、濾過
性、水洗性ともに悪く、濾過水洗を通じた所要時間は約
90分であった。ケーキを磁製坩堝に入れ、電気炉中で大
気中 800℃で１時間焼成し、23.3g の酸化イットリウム
を得た。この酸化物は数mm程度の固い凝集体からなり、
乳鉢で粉砕したものを電子顕微鏡で観察したところ数10
μｍの不定形粒子からなり、さらに倍率を上げていく
と、その粒子は極めて細かい粒子が密に凝集したもので
あった。Comparative Example A yttrium hydroxide was precipitated in the same manner as in Example 1, except that 200 ml of a 0.32 mol / L aqueous ammonia solution was added instead of the aqueous triethanolamine solution. The precipitate was in the form of a gel and was filtered and washed with water in the same manner as in the example, but the weight of the cake was 167 g, and both the filterability and the washability were poor.
90 minutes. The cake was placed in a porcelain crucible and fired in an electric furnace at 800 ° C. for 1 hour in the atmosphere to obtain 23.3 g of yttrium oxide. This oxide consists of hard aggregates of about several mm,
When crushed in a mortar and observed with an electron microscope, several tens
The particles consisted of irregular particles of μm, and when the magnification was further increased, the particles were very fine particles aggregated densely.
【０００８】[0008]
【発明の効果】本発明によれば、希土類元素水酸化物お
よび酸化物共に球状微粒子からなり、流動性に優れ、粒
度分布が狭いものが得られ、蛍光体原料、セラミックス
焼結助剤等として有用である。According to the present invention, both rare earth element hydroxides and oxides are composed of spherical fine particles, and have excellent fluidity and a narrow particle size distribution. Useful.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01F 1/00 - 17/00 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) C01F 1/00-17/00
Claims (3)
ールアミン類を添加し、反応させることを特徴とする希
土類元素水酸化物の球状粒子の製造方法。1. A method for producing spherical particles of a rare earth element hydroxide, comprising adding an ethanolamine to an aqueous solution of a water-soluble rare earth element compound and reacting the resulting mixture.
OH)3-n（式中ｎは０、１、２である）で表されるもので
ある請求項１に記載の希土類元素水酸化物の球状粒子の
製造方法。2. An ethanolamine represented by the general formula H n N (CH 2 -CH 2-
The method for producing spherical particles of a rare earth element hydroxide according to claim 1, wherein the compound is represented by OH) 3-n (where n is 0, 1, or 2).
水酸化物を大気中 600℃以上1500℃以下で焼成すること
を特徴とする希土類元素酸化物の球状粒子の製造方法。3. A method for producing spherical particles of rare earth element oxide, characterized by firing the spherical rare earth element hydroxide according to claim 1 or 2 in the atmosphere at a temperature of 600 ° C. to 1500 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6103639A JP2966724B2 (en) | 1994-05-18 | 1994-05-18 | Method for producing rare earth hydroxide and spherical particles of rare earth oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6103639A JP2966724B2 (en) | 1994-05-18 | 1994-05-18 | Method for producing rare earth hydroxide and spherical particles of rare earth oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07309621A JPH07309621A (en) | 1995-11-28 |
| JP2966724B2 true JP2966724B2 (en) | 1999-10-25 |
Family
ID=14359345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6103639A Expired - Fee Related JP2966724B2 (en) | 1994-05-18 | 1994-05-18 | Method for producing rare earth hydroxide and spherical particles of rare earth oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2966724B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4765801B2 (en) * | 2006-07-11 | 2011-09-07 | 株式会社デンソー | Method for producing metal oxide particles |
-
1994
- 1994-05-18 JP JP6103639A patent/JP2966724B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07309621A (en) | 1995-11-28 |
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