JPH04238813A - Production of rare earth element ammonium oxalate double salt and production of rare earth element oxide - Google Patents
Production of rare earth element ammonium oxalate double salt and production of rare earth element oxideInfo
- Publication number
- JPH04238813A JPH04238813A JP2416594A JP41659490A JPH04238813A JP H04238813 A JPH04238813 A JP H04238813A JP 2416594 A JP2416594 A JP 2416594A JP 41659490 A JP41659490 A JP 41659490A JP H04238813 A JPH04238813 A JP H04238813A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth element
- salt
- double salt
- oxalic acid
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 53
- 150000003839 salts Chemical class 0.000 title claims abstract description 25
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 53
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 7
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 150000003891 oxalate salts Chemical class 0.000 abstract 2
- -1 rare earth nitrates Chemical class 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HUUNYHBLBOEOGQ-UHFFFAOYSA-K azanium oxalate yttrium(3+) Chemical class [NH4+].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O HUUNYHBLBOEOGQ-UHFFFAOYSA-K 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- DAHVGXJQRTYNST-UHFFFAOYSA-N nitric acid;yttrium Chemical compound [Y].O[N+]([O-])=O DAHVGXJQRTYNST-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は蛍光灯用赤色蛍光体原料
、セラミックス原料として有用な希土類元素酸化物およ
びその前駆体としての希土類元素蓚酸アンモニウム複塩
の製造方法の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a method for producing a rare earth element oxide useful as a red phosphor raw material for fluorescent lamps and a ceramic raw material, and a rare earth element ammonium oxalate double salt as a precursor thereof.
【０００２】0002
【従来の技術】希土類元素酸化物の製造方法としては、
希土類硝酸塩の硝酸溶液中に蓚酸と引き続いてアンモニ
アを加えるか、あるいは蓚酸とアンモニアを同時に加え
て反応させた後、これを焼成する方法（Ｍ．Ｆ．Ｂａｒ
ｅｔｔ，ｅｔ ａｌ；Ｊ．Ｉｎｏｒｇ．Ｎｕｃｌ．Ｃｈ
ｅｍ．，１９６４ ｖｏｌ．２６，ｐ．９３１ 〜９３
６ ）、および希土類鉱酸塩溶液とアルカリとを反応さ
せて得られる希土類水酸化物スラリーに蓚酸を加えて希
土類蓚酸塩を生成させた後、これを焼成する方法（特公
昭５７−３５８５３号公報）等が知られていた。[Prior Art] As a method for producing rare earth element oxides,
A method of adding oxalic acid and then ammonia to a nitric acid solution of rare earth nitrates, or adding oxalic acid and ammonia at the same time to cause a reaction, and then firing this (M.F.Bar
ett, et al; J. et al. Inorg. Nucl. Ch
em. , 1964 vol. 26, p. 931-93
6), and a method in which oxalic acid is added to a rare earth hydroxide slurry obtained by reacting a rare earth mineral salt solution with an alkali to produce rare earth oxalate, and then this is calcined (Japanese Patent Publication No. 57-35853) ) etc. were known.
【０００３】0003
【発明が解決しようとする課題】しかしながら、これら
の製造方法では生成過程において一般重金属例えば鉄等
の混入が避け難いという問題点を有している。この理由
は鉄等の金属は難溶性の水酸化物を生成し易く、避け難
いことであった。一般に、前述した用途に使用する場合
には、上記不純物の混入は望ましくなく、高純度の希土
類酸化物の開発が要望されている。本発明はかかる問題
点を解決し、高純度の希土類元素酸化物の製造方法およ
びその前駆体である希土類元素蓚酸アンモニウム複塩の
製造方法を提供するものである。However, these manufacturing methods have a problem in that common heavy metals such as iron are unavoidably mixed in during the production process. The reason for this is that metals such as iron tend to generate poorly soluble hydroxides, which is difficult to avoid. Generally, when used for the above-mentioned purposes, the contamination of the above impurities is undesirable, and there is a demand for the development of highly pure rare earth oxides. The present invention solves these problems and provides a method for producing a highly pure rare earth element oxide and a rare earth element ammonium oxalate double salt, which is a precursor thereof.
【０００４】0004
【課題を解決するための手段】本発明者等はかかる問題
点を解決するために、鋭意研究した結果、本発明に到達
したもので、その要旨とするところは、第１の発明とし
て水素イオン濃度が０．３モル／リットル以下の希土類
元素鉱酸塩の鉱酸溶液に蓚酸を添加して希土類元素蓚酸
塩を生成させ濾別した後、該蓚酸塩と蓚酸およびアンモ
ニアとを反応させることを特徴とする希土類元素蓚酸ア
ンモニウム複塩の製造方法、ならびに第２の発明として
第１の発明の製造方法により得た希土類元素蓚酸アンモ
ニウム複塩を焼成することを特徴とする希土類元素酸化
物の製造方法にある。[Means for Solving the Problems] In order to solve the problems, the present inventors have arrived at the present invention as a result of intensive research. Adding oxalic acid to a mineral acid solution of a rare earth mineral salt having a concentration of 0.3 mol/liter or less to produce a rare earth element oxalate and filtering it, and then reacting the oxalate with oxalic acid and ammonia. A method for producing a rare earth element ammonium oxalate double salt, characterized by a second invention, and a method for producing a rare earth element oxide, characterized by firing the rare earth element ammonium oxalate double salt obtained by the production method of the first invention. It is in.
【０００５】以下、本発明を詳細に説明する。まず、本
発明で使用される希土類元素鉱酸塩としては希土類元素
塩化物、希土類元素硝酸塩、希土類元素硫酸塩などであ
り、鉱酸溶液としては希土類元素塩に対応する塩酸、硝
酸、硫酸などの溶液を用いて蓚酸と反応させるものであ
る。希土類元素としてはＹを含むＬａ、Ｃｅ、Ｐｒ、Ｎ
ｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ
、ＹｂおよびＬｕなどから選ばれる１種もしくは２種以
上であってもよい。希土類元素鉱酸塩の鉱酸溶液中にお
ける希土類元素イオン濃度としては０．０１〜 １．５
モル／リットル の範囲が望ましい。[0005] The present invention will be explained in detail below. First, the rare earth element mineral salts used in the present invention include rare earth element chlorides, rare earth element nitrates, rare earth element sulfates, etc., and the mineral acid solutions include hydrochloric acid, nitric acid, sulfuric acid, etc. corresponding to the rare earth element salts. A solution is used to react with oxalic acid. Rare earth elements include La, Ce, Pr, and N, including Y.
d, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm
, Yb, Lu, and the like. The rare earth element ion concentration in the mineral acid solution of rare earth element mineral salt is 0.01 to 1.5.
A range of moles/liter is desirable.
【０００６】蓚酸との反応に際して例えば１〜３０重量
％の蓚酸二水和物水溶液を用いて撹拌しながら添加・混
合することにより希土類元素蓚酸塩が得られる。この場
合、反応温度としては１０〜６０℃の範囲、所要時間と
しては１分間〜３時間程度、使用される蓚酸量としては
希土類イオンに対し １．５〜２倍量の範囲が望ましい
。なお、上記した反応に際して水素イオン濃度が０．３
モル／リットルを超えると不純物の混入が生ずるため不
都合である。以上のように処理することにより希土類元
素蓚酸塩が結晶として得られ、これを濾別・分離し、適
宜水洗すれば不純物の少ないものが得られる。[0006] In the reaction with oxalic acid, for example, a rare earth element oxalate can be obtained by adding and mixing with stirring an aqueous solution of 1 to 30% by weight of oxalic acid dihydrate. In this case, the reaction temperature is preferably in the range of 10 to 60°C, the required time is about 1 minute to 3 hours, and the amount of oxalic acid used is preferably in the range of 1.5 to 2 times the amount of rare earth ions. Note that during the above reaction, the hydrogen ion concentration is 0.3
Exceeding mol/liter is disadvantageous because impurities may be mixed in. By the above treatment, rare earth element oxalate is obtained as a crystal, which is filtered and separated, and washed with water as appropriate to obtain a product containing few impurities.
【０００７】つぎに、上記で得た希土類元素蓚酸塩の結
晶を５〜３０倍量の水に懸濁させ、撹拌しながら、蓚酸
およびアンモニアを添加し、反応させて希土類元素蓚酸
アンモニウム複塩を晶出させる。使用する蓚酸としては
例えば蓚酸二水和物を希土類元素蓚酸塩に対して ０．
５〜 ０．６倍量とすれば良く、また使用するアンモニ
アとしては例えば２８重量％のアンモニア水を希土類元
素蓚酸塩に対して １．０〜 １．５倍量とすれば良い
。また反応温度としては１０〜６０℃の範囲、反応時間
は３０分間〜５時間の範囲とすれば良い。このように処
理することにより希土類元素蓚酸アンモニウム複塩 （
ＮＨ４）Ｒ（Ｃ２Ｏ４）２ （ここにＲは希土類元素を
表す）が得られ、濾別・分離し適宜水洗することにより
不純物の少ないものとなる。Next, the rare earth element oxalate crystals obtained above are suspended in 5 to 30 times the amount of water, and while stirring, oxalic acid and ammonia are added and reacted to form the rare earth element ammonium oxalate double salt. Let it crystallize. As the oxalic acid to be used, for example, oxalic acid dihydrate is used at a ratio of 0.0% to the rare earth element oxalate.
The ammonia used may be, for example, 28% by weight ammonia water in an amount of 1.0 to 1.5 times the amount of rare earth element oxalate. Further, the reaction temperature may be in the range of 10 to 60°C, and the reaction time may be in the range of 30 minutes to 5 hours. By treating in this way, the rare earth element ammonium oxalate double salt (
NH4)R(C2O4)2 (R represents a rare earth element) is obtained, and by filtering, separating and washing with water as appropriate, it becomes a product with less impurities.
【０００８】さらに上記で得た希土類元素蓚酸アンモニ
ウム複塩を室温〜 １００℃程度に加熱し乾燥すれば角
状の複塩が得られる。次いで焼成することにより角状の
希土類元素酸化物が容易に得られる。焼成温度としては
希土類の種類により異なるが、蓚酸塩の分解温度以上に
加熱すれば良く、 ６００〜 １，２００℃の範囲、好
ましくは ７００〜 １，０００℃の範囲とすれば良い
。 焼成時間としては所定温度に加熱して３０分間〜
３時間の範囲とすれば良い。なお、上記の乾燥工程を省
略して直接焼成処理を行うこともできる。[0008] Furthermore, if the rare earth element ammonium oxalate double salt obtained above is heated to about room temperature to 100°C and dried, a prismatic double salt can be obtained. Then, by firing, a angular rare earth element oxide can be easily obtained. The firing temperature varies depending on the type of rare earth, but it may be heated to a temperature higher than the decomposition temperature of oxalate, and may be in the range of 600 to 1,200°C, preferably in the range of 700 to 1,000°C. The baking time is 30 minutes after heating to the specified temperature.
It may be within a range of 3 hours. Note that the above drying step can be omitted and the firing treatment can be performed directly.
【０００９】以上詳述したように本発明によれば不純物
の混入がなく、蛍光体用原料に適した、粒子形状の揃っ
た角状物として高純度の希土類元素酸化物が得られる。As described in detail above, according to the present invention, a highly pure rare earth element oxide can be obtained in the form of angular particles with uniform particle shapes, which are free from contamination with impurities and are suitable as raw materials for phosphors.
【００１０】0010
【実施例】以下、本発明の実施態様を実施例を挙げて説
明するが、本発明はこれらに限定されるものではない。
（実施例）イットリウム濃度 ０．７ｍｏｌ／ｌ，遊離
酸濃度 １．２ｍｏｌ／ｌであり、不純物として鉄イオ
ンを１リットルあたり ０．１ｍｇ含む硝酸溶液５リッ
トルに蓚酸二水和物７０５ｇを５０℃の温水３リットル
に溶かした溶液を、撹拌しながら１０分かけて加えた。
さらに１０分間撹拌した後、生じたイットリウム蓚酸の
沈殿を、ブフナー漏斗で濾別し、６リットルの水で洗浄
した。 一方、水６リットルに、蓚酸二水和物２２０
ｇ、２８％アンモニア水 ２６５ｍｌを加え充分撹拌し
、これに先に晶出した蓚酸塩を投入し２時間撹拌した後
、ブフナー漏斗で濾別し、６リットルの水で洗浄した。
得られた塩を５０℃で１２時間乾燥した。元素分析した
ところ、組成式 ＮＨ４Ｙ（Ｃ２Ｏ４）２・Ｈ２Ｏであ
り、粒形は角状で良く揃っていた。 この蓚酸イット
リウムアンモニウム複塩を ９００℃で２時間焼成して
得たイットリウム酸化物Ｙ２Ｏ３中の Ｆｅ２Ｏ３含有
量は０．５ｐｐｍであった。[Examples] Hereinafter, embodiments of the present invention will be explained with reference to Examples, but the present invention is not limited thereto. (Example) 705 g of oxalic acid dihydrate was added to 5 liters of nitric acid solution containing 0.7 mol/l of yttrium concentration, 1.2 mol/l of free acid concentration, and 0.1 mg of iron ion per liter as an impurity at 50°C. A solution in 3 liters of warm water was added over 10 minutes with stirring. After stirring for an additional 10 minutes, the resulting yttrium oxalate precipitate was filtered off on a Buchner funnel and washed with 6 liters of water. Meanwhile, add 220 oxalic acid dihydrate to 6 liters of water.
g, 265 ml of 28% aqueous ammonia were added and thoroughly stirred, and the oxalate crystallized earlier was added thereto and stirred for 2 hours, then filtered through a Buchner funnel and washed with 6 liters of water. The resulting salt was dried at 50°C for 12 hours. Elemental analysis revealed that the composition was NH4Y(C2O4)2.H2O, and the grain shape was angular and well-aligned. The Fe2O3 content in the yttrium oxide Y2O3 obtained by firing this yttrium ammonium oxalate double salt at 900° C. for 2 hours was 0.5 ppm.
【００１１】（比較例１）実施例と同一のイットリウム
硝酸溶液５リットルに、蓚酸二水和物９２７ｇを５０℃
の温水３．２リットル に溶かした溶液を、撹拌しなが
ら１０分間かけて加えた。生じたスラリーに、２８％ア
ンモニア水を加えて、液のｐＨ値を ２．０に調整した
。さらに１０分間撹拌した後、生じた沈殿をブフナー漏
斗で濾別し、６リットルの水で洗浄した。得られた塩を
５０℃で１２時間乾燥した。元素分析したところ、組成
式 ＮＨ４Ｙ（Ｃ２Ｏ４）２・Ｈ２Ｏであり、粒形は角
状で良く揃っていた。この蓚酸イットリウムアンモニウ
ムを、９００ ℃で２時間焼成して得た酸化物中の Ｆ
ｅ２Ｏ３含有量は、３．７ｐｐｍであった。(Comparative Example 1) 927 g of oxalic acid dihydrate was added to 5 liters of the same yttrium nitric acid solution as in Example at 50°C.
The solution in 3.2 liters of warm water was added over 10 minutes with stirring. 28% aqueous ammonia was added to the resulting slurry to adjust the pH value of the liquid to 2.0. After stirring for an additional 10 minutes, the resulting precipitate was filtered off on a Buchner funnel and washed with 6 liters of water. The resulting salt was dried at 50°C for 12 hours. Elemental analysis revealed that the composition was NH4Y(C2O4)2.H2O, and the grain shape was angular and well-aligned. F in the oxide obtained by calcining this yttrium ammonium oxalate at 900 °C for 2 hours.
The e2O3 content was 3.7 ppm.
【００１２】（比較例２）実施例と同一のイットリウム
硝酸溶液５リットルに、２８％アンモニア水を加えてｐ
Ｈ７に調整した。生じた水酸化物スラリーに蓚酸二水和
物９２７ｇと２８％アンモニア水８００ｍｌを １０リ
ットル の水に溶かした溶液を、撹拌しながら２０分間
かけて加えた。さらに１０分間撹拌した後、生じた沈殿
をブフナー濾斗で濾別し、２０リットルの水で洗浄した
。得られた塩を５０℃で１２時間乾燥した。
元素分析をしたところ、組成式 ＮＨ４Ｙ（Ｃ２Ｏ４）
２・Ｈ２Ｏであり、粒形は角状で良く揃っていた。この
蓚酸イットリウムアンモニウムを、 ９００℃で２時間
焼成して得られた酸化物中のＦｅ２Ｏ３ 含有量は３．
４ｐｐｍであった。(Comparative Example 2) 28% ammonia water was added to 5 liters of the same yttrium nitric acid solution as in the example.
Adjusted to H7. A solution of 927 g of oxalic acid dihydrate and 800 ml of 28% aqueous ammonia dissolved in 10 liters of water was added to the resulting hydroxide slurry over 20 minutes with stirring. After stirring for a further 10 minutes, the resulting precipitate was filtered off on a Buchner funnel and washed with 20 liters of water. The resulting salt was dried at 50°C for 12 hours. Elemental analysis revealed the composition formula: NH4Y(C2O4)
2.H2O, and the grain shape was angular and well-aligned. The Fe2O3 content in the oxide obtained by firing this yttrium ammonium oxalate at 900°C for 2 hours was 3.
It was 4 ppm.
【００１３】[0013]
【発明の効果】本発明は希土類元素酸化物の製造方法お
よびその前駆体である希土類元素蓚酸アンモニウム複塩
の製造方法に関し、従来法より不純物の混入がなく、粒
子形状の揃った角状物である高純度の希土類元素酸化物
が得られ、蛍光体用原料、セラミックス用原料として有
用であり、産業上その利用価値は極めて高いものである
。[Effects of the Invention] The present invention relates to a method for producing rare earth element oxides and a rare earth element ammonium oxalate double salt, which is a precursor thereof. A certain high purity rare earth element oxide is obtained, which is useful as a raw material for phosphors and a raw material for ceramics, and has extremely high industrial utility value.
Claims (2)
下の希土類元素鉱酸塩の鉱酸溶液に蓚酸を添加して希土
類元素蓚酸塩を生成させ濾別した後、該蓚酸塩と蓚酸お
よびアンモニアとを反応させることを特徴とする希土類
元素蓚酸アンモニウム複塩の製造方法。Claim 1: Oxalic acid is added to a mineral acid solution of a rare earth mineral salt having a hydrogen ion concentration of 0.3 mol/liter or less to produce a rare earth element oxalate, which is filtered, and then the oxalate, oxalic acid and A method for producing a rare earth element ammonium oxalate double salt, which comprises reacting with ammonia.
類元素蓚酸アンモニウム複塩を焼成することを特徴とす
る希土類元素酸化物の製造方法。2. A method for producing a rare earth element oxide, which comprises firing the rare earth element ammonium oxalate double salt obtained by the production method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2416594A JPH04238813A (en) | 1990-12-28 | 1990-12-28 | Production of rare earth element ammonium oxalate double salt and production of rare earth element oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2416594A JPH04238813A (en) | 1990-12-28 | 1990-12-28 | Production of rare earth element ammonium oxalate double salt and production of rare earth element oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04238813A true JPH04238813A (en) | 1992-08-26 |
Family
ID=18524809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2416594A Pending JPH04238813A (en) | 1990-12-28 | 1990-12-28 | Production of rare earth element ammonium oxalate double salt and production of rare earth element oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04238813A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003063883A (en) * | 2001-08-29 | 2003-03-05 | Shin Etsu Chem Co Ltd | Oxide member containing rare earths |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05262518A (en) * | 1990-11-13 | 1993-10-12 | Rhone Poulenc Chim | Preparation of ammonium pare earth double oxalate, use thereof for production of rare earth oxide, and obtained rare earth oxide |
-
1990
- 1990-12-28 JP JP2416594A patent/JPH04238813A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05262518A (en) * | 1990-11-13 | 1993-10-12 | Rhone Poulenc Chim | Preparation of ammonium pare earth double oxalate, use thereof for production of rare earth oxide, and obtained rare earth oxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003063883A (en) * | 2001-08-29 | 2003-03-05 | Shin Etsu Chem Co Ltd | Oxide member containing rare earths |
| JP4663927B2 (en) * | 2001-08-29 | 2011-04-06 | 信越化学工業株式会社 | Rare earth-containing oxide member |
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