JPH07309621A - Production of spherical particles of hydroxide of rare earth element and oxide of rare earth element - Google Patents
Production of spherical particles of hydroxide of rare earth element and oxide of rare earth elementInfo
- Publication number
- JPH07309621A JPH07309621A JP6103639A JP10363994A JPH07309621A JP H07309621 A JPH07309621 A JP H07309621A JP 6103639 A JP6103639 A JP 6103639A JP 10363994 A JP10363994 A JP 10363994A JP H07309621 A JPH07309621 A JP H07309621A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth element
- hydroxide
- spherical particles
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
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 The present invention mainly relates to a method for producing rare earth element hydroxides and rare earth element oxides, which have a wide range of uses such as raw materials for various phosphors and ceramics sintering aids.
【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 is added to an aqueous solution of a water-soluble rare earth element compound to precipitate a rare earth element hydroxide, which is then 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 alkaline earth hydroxide or ammonia, which is an inorganic base, is used as a precipitant for precipitating a rare earth element as a hydroxide, the resulting precipitate is often gel-like and has poor filterability. It is bad, and if dried or fired, it becomes a hard agglomerate of several mm or more, and crushing and sieving are required depending on the application. From the viewpoint of handling and processing, it is said that it is desirable that the phosphor raw material be particles having a particle size of 2 to 10 μm, and that it is desirable that the shape is closer to a spherical shape, and that the phosphor raw material is an oxide or hydroxide of a rare earth element. In the case of using, the use of alkali hydroxide as a precipitant is not preferable from this aspect as well since it is generally disliked to mix alkali metals.
The present invention is intended to solve such disadvantages and provide a rare earth element hydroxide and an oxide which are composed of spherical fine particles and do not contain an 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。In order to solve such a problem, the present inventors have found that ethanolamines are effective as a precipitating agent in the step of precipitating a rare earth hydroxide. The present invention has been completed by establishing the conditions, and the gist thereof is to add ethanolamines to an aqueous solution of a water-soluble rare earth element compound, and to react them, and a method for producing spherical particles of a rare earth element hydroxide. , 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 fired in the atmosphere at 600 ° C. or higher and 1500 ° C. or lower, more specifically, ethanolamines 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。The present invention will be described in detail below. We investigated the use of various organic bases as precipitants in the precipitation process of rare earth hydroxides. When ethanolamines are used among them, the particle size of the spherical particles is 2 to 2
It has been found that spherical particles of a rare earth element hydroxide having a particle size of 10 μm and excellent in filterability and drainability can be obtained. The steps will be described below in order. 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 moles of ethanolamines per mole of the rare earth element are diluted with water if necessary and 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 is a general term, and one compound or a mixture of two or more selected from these can be used. Of these, triethanolamine is most effective. If the amount of ethanolamines to be added is less than 3 mol per 1 mol of the rare earth element, the yield will be poor, and even if it exceeds 4 mol, there is no advantage and it is uneconomical. The order of mixing the rare earth element and the ethanolamines may be arbitrary, but it is more preferable to pour the ethanolamines into the solution of the rare earth element with stirring.
Further, the higher the mixing temperature is, the better the yield is, and the particle size of the obtained product tends to be large. However, even if the temperature is higher than 60 ° C, the effect is small. The precipitate obtained by the above is filtered off,
If necessary, wash with water, air dry or heat dry,
Obtain rare earth hydroxide. The hydroxide obtained was composed of spherical agglomerated particles, and the average particle size by laser diffraction method was 2 to
The thickness was 10 μm, and the filterability and the water washability were good. If you want to convert to oxide, further in an electric furnace in the atmosphere.
It suffices to perform firing at 600 ° C. or higher and 1500 ° C. or lower, and the shape and the particle size of the particles are kept substantially the same before and after firing. The applicable range of the present invention includes La, Ce, Pr, Nd, Sm, Eu, Gd, Tb containing Y,
It is 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, the embodiments of the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
（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 pH 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 prepared by previously mixing 100 g of triethanolamine and 100 ml of water was added over 5 minutes while continuing stirring. After stirring was continued for further 10 minutes, the mixture was filtered with a Buchner funnel and sprinkled with 1200 ml of water for washing. The cake of hydroxide obtained is 66.8 g,
Both the filterability and the water washability were good, and the time required for the filter water wash was about 5 minutes. Taking a small amount of this cake and observing with an electron microscope, it consists of spherical particles with a diameter of about 2 to 6 μm,
When 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 baked in an electric furnace at 800 ° C. in the atmosphere for 1 hour.
23.2 g of yttrium oxide was obtained. As a result of observing this oxide with an electron microscope, it was almost the same as that of the cake, and the average particle size measured by the 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) 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 triethanolamine aqueous solution. The precipitate was in the form of gel, and was filtered and washed by the same method as in Example, but the weight of the cake was 167 g, and both filterability and water washability were poor, and the time required for filtration and water washing was about
It was 90 minutes. The cake was put into a porcelain crucible and baked 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, the number is 10
The particles consisted of irregularly shaped particles of μm, and when the magnification was further increased, the particles were extremely fine particles densely aggregated.
【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。EFFECTS OF THE INVENTION According to the present invention, both rare earth element hydroxides and oxides are composed of spherical fine particles, which are excellent in fluidity and have a narrow particle size distribution. It is useful.
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, which comprises adding ethanolamines to an aqueous solution of a water-soluble rare earth element compound and reacting them.
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. Ethanolamines having 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, which is represented by OH) 3-n (wherein n is 0, 1, 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 a rare earth element oxide, which comprises firing the spherical rare earth element hydroxide according to claim 1 or 2 in the atmosphere at 600 ° C. or more and 1500 ° C. or less.
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 true JPH07309621A (en) | 1995-11-28 |
| JP2966724B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019106A (en) * | 2006-07-11 | 2008-01-31 | Denso Corp | Method for producing metal oxide particle |
-
1994
- 1994-05-18 JP JP6103639A patent/JP2966724B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019106A (en) * | 2006-07-11 | 2008-01-31 | Denso Corp | Method for producing metal oxide particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2966724B2 (en) | 1999-10-25 |
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