JP2980504B2 - Cerium carbonate and cerium carbonate having novel morphology and method for producing cerium oxide - Google Patents
Cerium carbonate and cerium carbonate having novel morphology and method for producing cerium oxideInfo
- Publication number
- JP2980504B2 JP2980504B2 JP5345144A JP34514493A JP2980504B2 JP 2980504 B2 JP2980504 B2 JP 2980504B2 JP 5345144 A JP5345144 A JP 5345144A JP 34514493 A JP34514493 A JP 34514493A JP 2980504 B2 JP2980504 B2 JP 2980504B2
- Authority
- JP
- Japan
- Prior art keywords
- cerium
- carbonate
- aqueous solution
- cerium carbonate
- mol
- 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.)
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、顔料、触媒等に有用な
板状の新規な形態を有する炭酸セリウムおよび炭酸セリ
ウム並びに酸化セリウム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 novel plate-like cerium carbonate, cerium carbonate and cerium oxide which are useful for pigments, catalysts and the like.
【０００２】[0002]
【従来の技術】炭酸セリウムの製造法は種々知られてお
り、希土類イオンに対し当量以上の炭酸根を投入し、微
細な炭酸塩粉末を得る方法（特開昭５３−９５９００号
公報参照）等が一般的であるが、これは、反応中に炭酸
根がＣＯ2ガスとして反応系外に逸散し、炭酸根の不足
が生ずるのを防ぐためである。しかしこの方法では、得
られた炭酸塩の沈殿は鱗片状であり、濾過、水洗効率が
悪く、結果として生産性が低いという欠点がある。ま
た、この炭酸セリウムを焼成して酸化セリウムとして
も、鱗片状で流動性の悪いものしか得られず、用途によ
っては取扱上不利である。2. Description of the Related Art Various methods for producing cerium carbonate are known, such as a method in which a carbonate is added in an equivalent amount or more with respect to rare earth ions to obtain a fine carbonate powder (see JP-A-53-95900). This is generally to prevent carbonate groups from escaping out of the reaction system as CO 2 gas during the reaction and causing a shortage of carbonate groups. However, this method has a disadvantage that the obtained carbonate precipitate is scaly, and the filtration and washing efficiency is poor, resulting in low productivity. Further, even if this cerium carbonate is calcined to obtain cerium oxide, only scaly and poorly fluid ones can be obtained, which is disadvantageous in handling depending on the use.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、濾過、水洗
効率が良く、生産性の高い新規な形態を有する炭酸セリ
ウム及び流動性の良い炭酸セリウム並びに酸化セリウム
の製造方法を提供しようとするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel form of cerium carbonate, cerium carbonate and cerium oxide having a high efficiency in filtration and washing, and having high productivity. It is.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に本発明では、アスペクト比（長軸と短軸の長さの比）
が１．０〜１０．０の範囲に有り、平均粒径が０．５〜
５０μｍである板状の形態を有する炭酸セリウムであ
り、セリウム鉱酸塩水溶液と炭酸根を反応させ、反応終
了後セリウムイオン存在下で熟成し、炭酸セリウムを得
る。熟成時に溶液中に存在するセリウムイオン量が沈殿
状態のセリウム量の５〜２５モル％であることが好まし
い。熟成時間は少なくとも５分間であり、生成した炭酸
セリウムの沈殿を分離後、必要に応じて通常の乾燥操作
を行い、ここで得られた炭酸セリウムを３００℃以上の
温度で焼成して、アスペクト比が１．０〜１０．０の範
囲に有り、平均粒径が０．５〜５０μｍである板状の形
態を有する酸化セリウムを製造するものである。In order to solve the above-mentioned problems, the present invention provides an aspect ratio (the ratio of the length of the major axis to the minor axis).
Is in the range of 1.0 to 10.0, and the average particle size is 0.5 to
Cerium carbonate having a plate shape of 50 μm. A cerium mineral salt aqueous solution is allowed to react with a carbonate group. After the reaction, the mixture is aged in the presence of cerium ions to obtain cerium carbonate. It is preferable that the amount of cerium ions present in the solution at the time of aging is 5 to 25 mol% of the amount of cerium in the precipitated state. The aging time is at least 5 minutes. After separating the formed cerium carbonate precipitate, if necessary, a normal drying operation is performed, and the obtained cerium carbonate is calcined at a temperature of 300 ° C. or higher to obtain an aspect ratio. Is in the range of 1.0 to 10.0 and has an average particle size of 0.5 to 50 μm in the form of a plate-like cerium oxide.
【０００５】[0005]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明者は、沈殿の生成機構、並びに生成方法の検討を
重ねた結果、炭酸セリウムをセリウムイオン存在下で熟
成すれば良いとの知見を得て、諸条件を確立して本発明
を完成させたものである。本発明の最大の特徴は、炭酸
セリウムをセリウムイオンの存在下に熟成することによ
り、アスペクト比が１．０〜１０．０の範囲に有り、平
均粒径が０．５〜５０μｍである、板状の形態を有し、
かつ濾過性、水洗性の良い炭酸セリウムの沈殿が得られ
ることである。この新規な板状形態を有する炭酸セリウ
ムを得るには、沈殿熟成時にセリウムイオンが存在して
いる必要があり、この条件を満たす製造方法としては、 １）セリウム鉱酸塩水溶液に炭酸根を有する化合物を、
炭酸塩生成に必要な当量以下の量、投入し、炭酸塩の沈
殿をセリウムイオン存在下で熟成する方法。 ２）セリウム鉱酸塩水溶液と炭酸根を有する化合物を当
量反応させ、生成した炭酸セリウムスラリーにセリウム
鉱酸塩水溶液を添加し、熟成する方法。 ３）セリウム鉱酸塩水溶液と炭酸根を有する化合物を当
量反応させ、生成した炭酸セリウムスラリーをセリウム
鉱酸塩水溶液に添加し、熟成する方法、等が挙げられ、
いずれの方法によっても目的は達成される。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The present inventor has repeatedly studied the generation mechanism of the precipitate and the generation method, and as a result, obtained the knowledge that cerium carbonate may be aged in the presence of cerium ions, established various conditions, and completed the present invention. It is a thing. The most important feature of the present invention is that the cerium carbonate is aged in the presence of cerium ions to have an aspect ratio in the range of 1.0 to 10.0 and an average particle size of 0.5 to 50 μm. Having a shape of
In addition, a cerium carbonate precipitate having good filterability and water washability can be obtained. In order to obtain cerium carbonate having this novel plate-like morphology, cerium ions must be present at the time of precipitation and ripening. The production method satisfying this condition is as follows: 1) A cerium mineral salt aqueous solution has a carbonate group The compound
A method in which an amount equal to or less than the equivalent required for carbonate formation is added, and the carbonate precipitate is aged in the presence of cerium ions. 2) A method in which an equivalent amount of a cerium mineral salt aqueous solution is reacted with a compound having a carbonate group, and a cerium mineral salt aqueous solution is added to the resulting cerium carbonate slurry to ripen. 3) A method of reacting an equivalent amount of a cerium mineral salt aqueous solution with a compound having a carbonate group, adding the resulting cerium carbonate slurry to the cerium mineral salt aqueous solution, and ripening, and the like.
The objective is achieved by either method.
【０００６】１）の方法において、セリウム鉱酸塩水溶
液としては、炭酸セリウムや水酸化セリウムを硝酸、塩
酸等で分解した硝酸セリウム、塩酸セリウム等を使用す
るが、これらに限定されるものではない。セリウム濃度
は０．０１〜２．０モル／リットル、Ｈ+は０．００１
〜１．０モル／リットルに調整しておく。また炭酸根と
しては炭酸アンモニウム、炭酸水素アンモニウムが挙げ
られるが、他に炭酸ガスとアンモニア水の混合物、また
は、アルカリ金属が不純物として混入しても問題となら
ない場合においては、炭酸ナトリウム、炭酸水素ナトリ
ウム等のアルカリ金属塩も使用可能である。その使用量
は、熟成時に溶液中のセリウムイオンが沈殿状態のセリ
ウムに対して５〜２５モル％、好ましくは１０〜１５モ
ル％残存するように調整する。残存量が５モル％未満で
はゲル状の沈殿状態を維持し、２５モル％を越えると炭
酸セリウムの歩留まりが悪くなるので、５〜２５モル％
が良い。炭酸塩は粉末ではなく、濃度０．１〜１０モル
／リットルの水溶液を調整しておくのが良い。In the method 1), cerium carbonate or cerium hydroxide obtained by decomposing cerium carbonate or cerium hydroxide with nitric acid, hydrochloric acid or the like is used as the cerium mineral salt aqueous solution, but is not limited thereto. . The cerium concentration is 0.01 to 2.0 mol / l, and H + is 0.001.
Adjust to ~ 1.0 mol / l. Examples of the carbonate group include ammonium carbonate and ammonium hydrogencarbonate. In addition, a mixture of carbon dioxide gas and aqueous ammonia, or sodium carbonate and sodium hydrogencarbonate when there is no problem even if an alkali metal is mixed as an impurity. And the like can also be used. The amount used is adjusted so that the cerium ions in the solution at the time of aging remain in 5 to 25 mol%, preferably 10 to 15 mol%, based on the precipitated cerium. If the remaining amount is less than 5 mol%, a gel-like precipitation state is maintained, and if it exceeds 25 mol%, the yield of cerium carbonate deteriorates.
Is good. It is preferable that the carbonate is not a powder but an aqueous solution having a concentration of 0.1 to 10 mol / liter is prepared.
【０００７】反応は、撹拌中のセリウム鉱酸塩水溶液に
温度０〜６０℃下に炭酸塩水溶液を注入し、引き続き熟
成に入る。熟成時間は炭酸塩注入後５〜１８０分、好ま
しくは５〜１００分で、５分未満ではゲル状から板状に
変化せず、１８０分を越えると板状成長には無駄な時間
となる。温度は１０〜３０℃が良く、熟成中のセリウム
イオン量は、沈殿状態のセリウム量の５〜２５モル％が
好ましく、５モル％未満ではゲル状の沈殿のままで濾過
性が悪く、２５モル％を越える場合は歩留まりが悪くな
り好ましくない。セリウムイオンの無い状態、即ち、炭
酸根を当量以上添加、もしくは炭酸塩生成に過剰の炭酸
根を有する水溶液にセリウム鉱酸塩水溶液を添加した場
合は、ゲル状のスラリーが生成し、熟成を行っても板状
に変化せず、生成した炭酸塩を分離するため濾過を行う
が、濾過性が非常に悪く、たとえ濾過できたとしても含
水量が非常に多いものとなり、生産性が悪いものとな
る。In the reaction, an aqueous carbonate solution is injected into the stirred aqueous cerium mineral salt solution at a temperature of 0 to 60 ° C., and then ripening starts. The ripening time is 5 to 180 minutes, preferably 5 to 100 minutes after injection of the carbonate. If it is less than 5 minutes, it does not change from a gel to a plate, and if it exceeds 180 minutes, it takes time to grow the plate. The temperature is preferably 10 to 30 ° C., and the amount of cerium ions during aging is preferably 5 to 25 mol% of the amount of cerium in the precipitated state, and if it is less than 5 mol%, it remains gel-like precipitate and has poor filterability. %, The yield is unfavorably decreased. When there is no cerium ion, that is, when the carbonate is added in an equivalent amount or more, or when the cerium mineral salt aqueous solution is added to an aqueous solution having an excess of carbonate for carbonate formation, a gel-like slurry is formed and aging is performed. Even though it does not change to a plate shape, filtration is performed to separate the generated carbonate, but the filterability is very poor, even if it can be filtered, the water content becomes very large, and the productivity is poor. Become.
【０００８】２）の方法は、セリウム鉱酸塩水溶液と炭
酸根を有する化合物を当量反応させ、生成した炭酸セリ
ウムスラリーにセリウム鉱酸塩水溶液を添加し熟成する
方法であり、その条件は、セリウム鉱酸塩水溶液として
は、炭酸セリウムや水酸化セリウムを硝酸、塩酸等で分
解した硝酸セリウム、塩酸セリウム等を使用するが、こ
れらに限定されるものではない。セリウム濃度は０．０
１〜２．０モル／リットル、Ｈ+は０．００１〜１．０
モル／リットルに調整しておく。また炭酸根としては炭
酸アンモニウム、炭酸水素アンモニウムが挙げられる
が、他に炭酸ガスとアンモニア水の混合物、または、ア
ルカリ金属が不純物として混入しても問題とならない場
合においては、炭酸ナトリウム、炭酸水素ナトリウム等
のアルカリ金属塩も使用可能である。反応は、撹拌中の
セリウム鉱酸塩水溶液に温度０〜６０℃下に炭酸塩水溶
液を注入、もしくは炭酸塩水溶液にセリウム鉱酸塩水溶
液を注入し、セリウム炭酸塩の沈殿を生成させる。注入
後スラリーにセリウム鉱酸塩水溶液を添加し、引き続き
熟成に入る。添加するセリウム量は、沈殿状態のセリウ
ム量の５〜２５モル％が好ましく、５モル％未満ではゲ
ル状の沈殿のままで濾過性が悪く、２０モル％を越える
場合は歩留まりが悪くなり、好ましくない。熟成時間
は、炭酸塩注入後５〜１８０分、好ましくは５〜１００
分で、５分未満ではゲル状から板状に変化せず、１８０
分を越えると板状成長には無駄な時間となる。このよう
にして得られた炭酸セリウムを濾過、水洗等の通常の固
液分離の操作を行い炭酸セリウムを得る。必要に応じて
１００℃以下で乾燥を行い炭酸塩粉末を得る。The method 2) is a method in which an aqueous solution of cerium mineral salt is reacted with a compound having a carbonate group in an equivalent amount, and an aqueous solution of cerium mineral salt is added to the produced cerium carbonate slurry to ripen it. As the mineral salt aqueous solution, cerium nitrate, cerium hydrochloride, or the like obtained by decomposing cerium carbonate or cerium hydroxide with nitric acid, hydrochloric acid, or the like is used, but is not limited thereto. Cerium concentration is 0.0
1 to 2.0 mol / liter, H + is 0.001 to 1.0
Adjust to mol / l. Examples of the carbonate group include ammonium carbonate and ammonium hydrogencarbonate. In addition, a mixture of carbon dioxide gas and aqueous ammonia, or sodium carbonate and sodium hydrogencarbonate when there is no problem even if an alkali metal is mixed as an impurity. And the like can also be used. In the reaction, a carbonate aqueous solution is injected into the stirring cerium mineral aqueous solution at a temperature of 0 to 60 ° C., or a cerium mineral aqueous solution is injected into the carbonate aqueous solution to generate cerium carbonate precipitate. After the pouring, an aqueous solution of cerium mineral salt is added to the slurry, and then aging is started. The amount of cerium to be added is preferably 5 to 25 mol% of the amount of cerium in the precipitated state, and if it is less than 5 mol%, the gel-like precipitate remains poor in filterability. Absent. The aging time is 5 to 180 minutes after injection of the carbonate, preferably 5 to 100 minutes.
In less than 5 minutes, the gel does not change from a gel to a plate,
Beyond this, it is wasted time for plate growth. The thus obtained cerium carbonate is subjected to ordinary solid-liquid separation operations such as filtration and washing with water to obtain cerium carbonate. If necessary, drying is performed at 100 ° C. or lower to obtain a carbonate powder.
【０００９】３）の方法は、セリウム鉱酸塩水溶液と炭
酸根を有する化合物を当量反応させ、生成した炭酸セリ
ウムスラリーをセリウム鉱酸塩水溶液に添加し熟成する
方法であり、その条件は、セリウム鉱酸塩水溶液として
は、炭酸セリウムや水酸化セリウムを硝酸、塩酸等で分
解した硝酸セリウム、塩酸セリウム等を使用するが、こ
れらに限定されるものではない。セリウム濃度は０．０
１〜２．０モル／リットル、Ｈ+は０．００１〜１．０
モル／リットルに調整しておく。また炭酸根としては炭
酸アンモニウム、炭酸水素アンモニウムが挙げられる
が、他に炭酸ガスとアンモニア水の混合物、または、ア
ルカリ金属が不純物として混入しても問題とならない場
合においては、炭酸ナトリウム、炭酸水素ナトリウム等
のアルカリ金属塩も使用可能である。反応は、撹拌中の
セリウム鉱酸塩水溶液に温度０〜６０℃下に炭酸塩水溶
液を注入、もしくは炭酸塩水溶液にセリウム鉱酸塩水溶
液を注入し、セリウム炭酸塩の沈殿を生成させる。注入
後炭酸塩スラリーを別のセリウム鉱酸塩水溶液に添加
し、引き続き熟成に入る。別のセリウム鉱酸塩水溶液の
セリウム量は、沈殿状態のセリウム量の５〜２５モル％
が好ましく、５モル％未満ではゲル状の沈殿のままで濾
過性が悪く、２５モル％を越える場合は歩留まりが悪く
なり、好ましくない。熟成時間は、炭酸塩注入後５〜１
８０分、好ましくは５〜１００分で、５分未満ではゲル
状から板状に変化せず、１８０分を越えると板状成長に
は無駄な時間となる。このようにして得られた炭酸セリ
ウムを濾過、水洗等の通常の固液分離の操作を行い、炭
酸セリウムを得る。必要に応じて１００℃以下で乾燥を
行い、炭酸塩粉末を得る。乾燥は、通常の真空乾燥、温
風乾燥、凍結乾燥、流動乾燥等で行えば良い。The method 3) is a method in which an aqueous solution of cerium mineral salt is reacted with a compound having a carbonate group in an equivalent amount, and the resulting cerium carbonate slurry is added to the aqueous solution of cerium mineral salt to ripen it. As the mineral salt aqueous solution, cerium nitrate, cerium hydrochloride, or the like obtained by decomposing cerium carbonate or cerium hydroxide with nitric acid, hydrochloric acid, or the like is used, but is not limited thereto. Cerium concentration is 0.0
1 to 2.0 mol / liter, H + is 0.001 to 1.0
Adjust to mol / l. Examples of the carbonate group include ammonium carbonate and ammonium hydrogencarbonate. In addition, a mixture of carbon dioxide gas and aqueous ammonia, or sodium carbonate and sodium hydrogencarbonate when there is no problem even if an alkali metal is mixed as an impurity. And the like can also be used. In the reaction, a carbonate aqueous solution is injected into the stirring cerium mineral aqueous solution at a temperature of 0 to 60 ° C., or a cerium mineral aqueous solution is injected into the carbonate aqueous solution to generate cerium carbonate precipitate. After the injection, the carbonate slurry is added to another cerium mineral salt aqueous solution, and then aging is started. The cerium content of another cerium mineral salt aqueous solution is 5 to 25 mol% of the cerium content in the precipitated state.
If it is less than 5 mol%, the filtration property is poor with the gel-like precipitate remaining, and if it exceeds 25 mol%, the yield becomes poor, which is not preferable. Aging time is 5-1 after injection of carbonate.
It is 80 minutes, preferably 5 to 100 minutes. If it is less than 5 minutes, it does not change from a gel state to a plate form, and if it exceeds 180 minutes, it takes time to grow the plate form. The thus obtained cerium carbonate is subjected to ordinary solid-liquid separation operations such as filtration and washing with water to obtain cerium carbonate. If necessary, drying is performed at 100 ° C. or lower to obtain a carbonate powder. Drying may be performed by ordinary vacuum drying, warm air drying, freeze drying, fluidized drying, or the like.
【００１０】上記３種類の製造方法で得られた炭酸セリ
ウムはいずれもその形態が板状で、アスペクト比が１．
０〜１０．０の範囲に有り、平均粒径が０．５〜５０μ
ｍであり、流動性がよく、取扱が容易な粉末である。こ
れを３００℃以上で焼成して得られる酸化セリウムもそ
の形態は炭酸セリウムと相似しており、アスペクト比が
１．０〜１０．０の範囲に有り、平均粒径が０．５〜５
０μｍである板状の流動性の良いものが得られる。[0010] The cerium carbonate obtained by any of the above three production methods has a plate-like form and an aspect ratio of 1.
It is in the range of 0 to 10.0, and the average particle size is 0.5 to 50 μm.
m, a powder with good fluidity and easy handling. The form of cerium oxide obtained by firing this at 300 ° C. or more is similar to cerium carbonate, the aspect ratio is in the range of 1.0 to 10.0, and the average particle size is 0.5 to 5
A plate-like material having a good fluidity of 0 μm is obtained.
【００１１】[0011]
【実施例】以下、本発明の実施態様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。 （実施例１） セリウム鉱酸塩水溶液として硝酸第一セリウム水溶液
（Ｃｅ濃度０．６モル／リットル、［Ｈ+］＝０．１モ
ル／リットル）を１リットル、炭酸根として炭酸水素ア
ンモニウム水溶液を用いた。熟成時の未反応残留セリウ
ムイオン濃度が仕込量の１０％になるように、炭酸水素
アンモニウムの量は、 遊離酸の中和：ＨＮＯ3＋ＮＨ4ＨＣＯ3＝ＮＨ4ＮＯ3＋Ｈ2Ｏ＋ＣＯ2↑ 晶出反応：２Ｃｅ（ＮＯ3）3＋６ＮＨ4ＨＣＯ3＝Ｃｅ2（ＣＯ3）3＋６ＮＨ4Ｎ Ｏ3＋３Ｈ2Ｏ＋３ＣＯ2↑ の二つの反応から計算して、１．７２モルを１リットル
の純水に溶解し、水溶液とした。３リットルのガラスビ
ーカーに上記硝酸セリウムを入れ、撹拌しながら炭酸水
素アンモニウム水溶液を３０分で添加し、炭酸セリウム
の沈殿を生成させた。添加終了後３０分間熟成を行い、
ブフナー漏斗で濾過を行った後、１リットルの純水で洗
浄した。濾過性、水洗性とも良好であった。得られた沈
殿を５０℃で乾燥し、炭酸セリウムを得た。粒子の形状
を電子顕微鏡で観察したところ、アスペクト比１〜５の
板状粒子であった（図１参照）。平均粒径は、レーザ回
折法で測定した結果、１４μｍであった。ここで得られ
た炭酸セリウムをアルミナ坩堝に充填し、大気雰囲気下
５００℃で焼成し、酸化セリウムを得た。得られた酸化
セリウムは炭酸セリウムの形状を維持しており（図２参
照）、アスペクト比１〜５の板状であり、平均粒径はレ
ーザ回折法で１０μｍであった。EXAMPLES Hereinafter, embodiments of the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. (Example 1) 1 liter of cerous nitrate aqueous solution (Ce concentration 0.6 mol / L, [H + ] = 0.1 mol / L) as cerium mineral salt aqueous solution, and ammonium bicarbonate aqueous solution as carbonate group Using. The amount of ammonium bicarbonate is adjusted to neutralize the free acid: HNO 3 + NH 4 HCO 3 = NH 4 NO 3 + H 2 O + CO 2晶 crystal so that the unreacted residual cerium ion concentration during aging becomes 10% of the charged amount. Out reaction: Calculated from two reactions of 2 Ce (NO 3 ) 3 + 6NH 4 HCO 3 ＣCe 2 (CO 3 ) 3 + 6NH 4 NO 3 + 3H 2 O + 3CO 2 、 １, 1.72 mol was calculated as 1 liter of pure water. To give an aqueous solution. The above-mentioned cerium nitrate was placed in a 3 liter glass beaker, and an aqueous solution of ammonium hydrogen carbonate was added thereto with stirring for 30 minutes to produce a precipitate of cerium carbonate. After completion of addition, ripen for 30 minutes,
After filtration with a Buchner funnel, the mixture was washed with 1 liter of pure water. Both filterability and washability were good. The obtained precipitate was dried at 50 ° C. to obtain cerium carbonate. When the shape of the particles was observed with an electron microscope, the particles were plate-like particles having an aspect ratio of 1 to 5 (see FIG. 1). The average particle size was 14 μm as measured by a laser diffraction method. The cerium carbonate obtained here was filled in an alumina crucible and fired at 500 ° C. in the atmosphere to obtain cerium oxide. The obtained cerium oxide maintained the shape of cerium carbonate (see FIG. 2), had a plate shape with an aspect ratio of 1 to 5, and had an average particle diameter of 10 μm by a laser diffraction method.
【００１２】（実施例２） 実施例１と同じ硝酸セリウム水溶液および炭酸水素アン
モニウム水溶液を用い、投入法を変えて行った。まず３
リットルのガラスビーカーに上記炭酸水素アンモニウム
水溶液を１．０リットル入れ、撹拌機で撹拌しながら硝
酸セリウム溶液を３０分で添加し、炭酸セリウムの沈殿
を生成させた。得られた炭酸セリウムスラリーを３０分
間熟成後、ブフナー漏斗で濾過を行った後、１リットル
の純水で洗浄した。濾過性、水洗性ともに良好であっ
た。得られた沈殿を５０℃で乾燥し、炭酸セリウムを得
た。粒子の形状を電子顕微鏡で観察したところ、アスペ
クト比１〜５の板状粒子であった。ここで得られた炭酸
セリウムをアルミナ坩堝に充填し、大気雰囲気下５００
℃で焼成し酸化セリウムを得た。得られた酸化セリウム
は、炭酸セリウムの形状を維持していた。(Example 2) [0012] Using the same cerium nitrate aqueous solution and ammonium hydrogen carbonate aqueous solution as in Example 1, the charging method was changed. First 3
1.0 liter of the above aqueous solution of ammonium hydrogen carbonate was placed in a liter glass beaker, and a cerium nitrate solution was added over 30 minutes while stirring with a stirrer to form a precipitate of cerium carbonate. The obtained cerium carbonate slurry was aged for 30 minutes, filtered with a Buchner funnel, and washed with 1 liter of pure water. Both filterability and washability were good. The obtained precipitate was dried at 50 ° C. to obtain cerium carbonate. When the shape of the particles was observed with an electron microscope, the particles were plate-like particles having an aspect ratio of 1 to 5. The obtained cerium carbonate was filled in an alumina crucible and placed in an air atmosphere for 500 minutes.
C. to obtain cerium oxide. The obtained cerium oxide maintained the shape of cerium carbonate.
【００１３】（比較例１） 実施例１と同じ硝酸セリウム水溶液（Ｃｅ濃度０．６モ
ル／リットル、［Ｈ+］＝０．１モル／リットル）１リ
ットルを３リットルのガラスビーカに仕込んだ。炭酸根
として炭酸水素アンモニウムを、未反応残留セリウムイ
オンが０％、即ち仕込んだセリウムが全て炭酸セリウム
として沈殿するように、炭酸水素アンモニウム１．９０
モル相当量を１リットルの純水に溶解し、水溶液とし
た。これを先の硝酸セリウム溶液に撹拌しながら３０分
で添加し、炭酸セリウムの沈殿を生成させた。添加終了
後３０分間熟成を行い、ブフナー漏斗で濾過を行った
が、濾過性が悪かった。その後１リットルの純水で洗浄
したが、同様に濾過性は悪いものであった。得られた炭
酸セリウムを電子顕微鏡で観察すると、鱗片状の粒であ
った（図３参照）。ここで得られた炭酸セリウムを５０
０℃で焼成し酸化セリウムとした。得られたものは、矢
張り鱗片状で、流動性の悪いものであった。Comparative Example 1 One liter of the same cerium nitrate aqueous solution as in Example 1 (Ce concentration: 0.6 mol / l, [H + ] = 0.1 mol / l) was charged into a 3 liter glass beaker. Ammonium hydrogen carbonate is used as a carbonate group, and ammonium hydrogen carbonate 1.90 is used so that unreacted residual cerium ions are 0%, that is, all the charged cerium precipitates as cerium carbonate.
An equivalent molar amount was dissolved in 1 liter of pure water to obtain an aqueous solution. This was added to the cerium nitrate solution with stirring for 30 minutes to produce a precipitate of cerium carbonate. After completion of the addition, the mixture was aged for 30 minutes and filtered with a Buchner funnel, but the filterability was poor. Thereafter, washing was performed with 1 liter of pure water, but the filterability was similarly poor. When the obtained cerium carbonate was observed with an electron microscope, it was found to be scale-like particles (see FIG. 3). 50% of the cerium carbonate obtained here
It was calcined at 0 ° C. to obtain cerium oxide. The resulting product was in the form of arrow scales and had poor fluidity.
【００１４】[0014]
【発明の効果】本発明によれば、濾過性、水洗性の良い
アスペクト比が１．０〜１０．０の範囲に有り、平均粒
径が０．５〜５０μｍである板状炭酸セリウムが得ら
れ、これを焼成して得た酸化セリウムもまた同様の物性
を有し、流動性の高いものであり、産業上その利用価値
は極めて高い。According to the present invention, plate-like cerium carbonate having an aspect ratio in the range of 1.0 to 10.0 and an average particle size of 0.5 to 50 μm having good filterability and washability is obtained. The cerium oxide obtained by calcining the cerium oxide also has similar physical properties and high fluidity, and its industrial value is extremely high.
【図１】実施例１で得られた炭酸セリウムの粒子構造を
示す写真である。FIG. 1 is a photograph showing the particle structure of cerium carbonate obtained in Example 1.
【図２】実施例１で得られた酸化セリウムの粒子構造を
示す写真である。FIG. 2 is a photograph showing the particle structure of cerium oxide obtained in Example 1.
【図３】比較例１で得られた炭酸セリウムの粒子構造を
示す写真である。FIG. 3 is a photograph showing the particle structure of cerium carbonate obtained in Comparative Example 1.
Claims (5)
平均粒径が0.5〜50μｍである板状の形態を有する炭酸
セリウム。(1) an aspect ratio in a range of 1.0 to 10.0;
Cerium carbonate having a plate-like shape having an average particle size of 0.5 to 50 μm.
溶液とを反応させ、セリウムイオンが存在する状態で生
成した沈殿を熟成して得られる請求項１に記載の炭酸セ
リウムの製造方法。2. A cerium mineral is reacted with an aqueous solution and the aqueous solution having a carbonate groups, method for producing a cerium carbonate according to 請 Motomeko 1 obtained form mature the precipitate formed in a state in which cerium ions are present .
量が沈殿状態のセリウム量の５〜２５モル％である請求
項２に記載の炭酸セリウムの製造方法。3. The amount of cerium ions present in the solution during aging is 5 to 25 mol% of the amount of cerium in the precipitated state.
Item 3. The method for producing cerium carbonate according to Item 2 .
求項２又は３に記載の炭酸セリウムの製造方法。4. The method for producing cerium carbonate according to claim 2 , wherein the aging time is at least 5 minutes or more.
で得られた炭酸セリウムを少なくとも３００℃以上の温
度で焼成して得られる、アスペクト比が１．０〜１０．
０かつ平均粒径が０．５〜５０μｍである板状の形態を
有する酸化セリウムの製造方法。5. An aspect ratio obtained by calcining cerium carbonate obtained by the production method according to any one of claims 2 to 4 at a temperature of at least 300 ° C. or higher .
0 and an average particle size of 0.5 to 50 μm
Method for producing oxidation cerium with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5345144A JP2980504B2 (en) | 1993-12-21 | 1993-12-21 | Cerium carbonate and cerium carbonate having novel morphology and method for producing cerium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5345144A JP2980504B2 (en) | 1993-12-21 | 1993-12-21 | Cerium carbonate and cerium carbonate having novel morphology and method for producing cerium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07172826A JPH07172826A (en) | 1995-07-11 |
| JP2980504B2 true JP2980504B2 (en) | 1999-11-22 |
Family
ID=18374584
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5345144A Expired - Lifetime JP2980504B2 (en) | 1993-12-21 | 1993-12-21 | Cerium carbonate and cerium carbonate having novel morphology and method for producing cerium oxide |
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| Country | Link |
|---|---|
| JP (1) | JP2980504B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110200504A1 (en) * | 2008-10-17 | 2011-08-18 | Ono Mariko | Exhaust gas purifying catalyst and method for purifying exhaust gas using the catalyst |
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|---|---|---|---|---|
| JPH11181403A (en) | 1997-12-18 | 1999-07-06 | Hitachi Chem Co Ltd | Cerium oxide abrasive and grinding of substrate |
| JP4776519B2 (en) * | 1997-12-18 | 2011-09-21 | 日立化成工業株式会社 | Abrasive and slurry |
| JP4776518B2 (en) * | 1997-12-18 | 2011-09-21 | 日立化成工業株式会社 | Abrasive and slurry |
| KR100463799B1 (en) * | 2001-12-26 | 2004-12-29 | 한국지질자원연구원 | A method for manufacturing of cerium carbonate from the cerium hydroxide |
| JP4445820B2 (en) * | 2004-08-30 | 2010-04-07 | 日立化成工業株式会社 | Cerium oxide abrasive and substrate polishing method |
| EP1756244B1 (en) * | 2005-01-26 | 2011-07-27 | LG Chem, Ltd. | Cerium oxide abrasive and slurry containing the same |
| JP4917098B2 (en) * | 2005-09-20 | 2012-04-18 | エルジー・ケム・リミテッド | Cerium carbonate powder and production method, cerium oxide powder produced therefrom and production method, and CMP slurry containing the same |
| US8361419B2 (en) | 2005-09-20 | 2013-01-29 | Lg Chem, Ltd. | Cerium carbonate powder, method for preparing the same, cerium oxide powder made therefrom, method for preparing the same, and CMP slurry comprising the same |
| KR100812052B1 (en) * | 2005-11-14 | 2008-03-10 | 주식회사 엘지화학 | Cerium carbonate powder, cerium oxide powder, method for preparing the same, and cmp slurry comprising the same |
| CN101641289B (en) * | 2007-03-16 | 2012-11-21 | 株式会社Lg化学 | Method for preparing cerium carbonate powder using urea |
| KR100986881B1 (en) * | 2007-03-16 | 2010-10-08 | 주식회사 엘지화학 | Method for preparing cerium carbonate powder |
| JP5406555B2 (en) * | 2009-02-23 | 2014-02-05 | 国立大学法人東北大学 | Method for producing plate-like ceria particles |
| JP2010030041A (en) * | 2009-11-04 | 2010-02-12 | Hitachi Chem Co Ltd | Cerium oxide abrasive and method of polishing substrate |
| JP5843431B2 (en) * | 2010-08-12 | 2016-01-13 | 株式会社 東北テクノアーチ | Petal-like cerium oxide powder, method for producing the same, and cosmetics |
-
1993
- 1993-12-21 JP JP5345144A patent/JP2980504B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110200504A1 (en) * | 2008-10-17 | 2011-08-18 | Ono Mariko | Exhaust gas purifying catalyst and method for purifying exhaust gas using the catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07172826A (en) | 1995-07-11 |
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