JP6039474B2 - Method for producing alkaline earth metal imide - Google Patents
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Description
本発明は、アルカリ土類金属イミドの製造方法に関する。 The present invention relates to a method for producing an alkaline earth metal imide.
近年、アルカリ土類金属窒化物を用いた蛍光体も多数見出されており、その原料の一つとして、アルカリ土類金属イミドの需要も高まってきている（特許文献１）。 In recent years, many phosphors using alkaline earth metal nitrides have been found, and the demand for alkaline earth metal imides is increasing as one of the raw materials (Patent Document 1).
従来のアルカリ土類金属イミドの製造方法としては、カルシウム等のアルカリ土類金属をアンモニア雰囲気で加熱する方法が知られている（特許文献１）。また、アルカリ土類金属アミド（ＡＥ（ＮＨ2）2）をアンモニア雰囲気中や減圧下で加熱することにより、アルカリ土類金属イミドを得ることが出来る（特許文献２、非特許文献１）。 As a conventional method for producing an alkaline earth metal imide, a method of heating an alkaline earth metal such as calcium in an ammonia atmosphere is known (Patent Document 1). Moreover, an alkaline earth metal imide can be obtained by heating an alkaline earth metal amide (AE (NH 2 ) 2 ) in an ammonia atmosphere or under reduced pressure (Patent Document 2, Non-Patent Document 1).
しかしながら、特許文献１記載の方法では、発熱により溶融し、強固に凝集する場合があり、回収が困難であった。さらに、凝集物を粉砕すると、過度の粉砕により、微量成分が混入するおそれがある。また、特許文献２記載の方法で得られたアルカリ土類金属イミドは、酸素含有量が高く、この方法では高純度なアルカリ土類金属イミドを合成することはできなかった。かように、これらの方法で得られたアルカリ土類金属イミドは、前記蛍光体等の高純度品が要求される用途には使用できなかった。また、アンモニアガスを用いる場合には、装置の腐食が懸念されるとともに、不要となったアンモニアガスは廃棄のための処理が必要であった。さらに、液体アンモニアと反応させる場合には、前述アンモニアガスを用いる場合への対処に加えて、高圧に耐え得る耐圧容器等を用いる必要があるため、多大な手間とコストを要した。
従って、本発明は、上記の問題点が無く、アルカリ土類金属イミドを容易な方法で収率良く、安定的に製造する方法を提供することを課題とする。
However, in the method described in Patent Document 1, it may be melted due to heat generation and strongly agglomerated, which makes recovery difficult. Furthermore, when the aggregate is pulverized, trace components may be mixed due to excessive pulverization. Moreover, the alkaline earth metal imide obtained by the method described in Patent Document 2 has a high oxygen content, and it was not possible to synthesize a high purity alkaline earth metal imide by this method. Thus, the alkaline earth metal imide obtained by these methods could not be used for applications requiring high purity products such as the phosphors. Further, when ammonia gas is used, there is a concern about the corrosion of the apparatus, and the unnecessary ammonia gas needs to be disposed of for disposal. Furthermore, in the case of reacting with liquid ammonia, in addition to dealing with the case of using the ammonia gas, it is necessary to use a pressure-resistant container that can withstand high pressure, which requires a lot of labor and cost.
Accordingly, an object of the present invention is to provide a method for stably producing an alkaline earth metal imide by a simple method with good yield without the above-mentioned problems.
斯かる実情に鑑み、本発明者は鋭意研究を行った結果、アルカリ土類金属水素化物を原料として用い、これを窒素ガス下、加熱するのみで、全く意外にも、高純度のアルカリ土類金属イミドを容易な方法で収率良く得られることを見出し、本発明を完成した。 In view of such circumstances, the present inventor has conducted intensive research, and as a result, the alkaline earth metal hydride was used as a raw material and was heated under nitrogen gas. The present inventors have found that a metal imide can be obtained in a good yield with an easy method and completed the present invention.
すなわち、本発明は、次の〔１〕〜〔３〕を提供するものである。 That is, the present invention provides the following [1] to [3].
〔１〕アルカリ土類金属水素化物を窒素ガス下、加熱することを特徴とするアルカリ土類金属イミドの製造方法。
〔２〕アルカリ土類金属水素化物が、水素化カルシウム、水素化ストロンチウム及び水素化バリウムから選ばれる１種又は２種以上である〔１〕記載の製造方法。
〔３〕加熱の温度が３００〜１０００℃である〔１〕又は〔２〕記載の製造方法。
[1] A method for producing an alkaline earth metal imide, comprising heating an alkaline earth metal hydride under nitrogen gas.
[2] The production method according to [1], wherein the alkaline earth metal hydride is one or more selected from calcium hydride, strontium hydride, and barium hydride.
[3] The production method according to [1] or [2], wherein the heating temperature is 300 to 1000 ° C.
本発明によれば、容易な方法で収率良く、蛍光体等への使用が可能な、高純度のアルカリ土類金属イミドを製造することができる。 According to the present invention, it is possible to produce a high-purity alkaline earth metal imide that can be used for a phosphor or the like with a simple method and with a high yield.
本発明に用いられるアルカリ土類金属水素化物としては、ＭｇＨ2、ＣａＨ2、ＳｒＨ2、ＢａＨ2が挙げられ、これら水素化物から選ばれる１種又は２種以上である。 Examples of the alkaline earth metal hydride used in the present invention include MgH 2 , CaH 2 , SrH 2 , and BaH 2 , and one or more selected from these hydrides.
本発明の原料であるアルカリ土類金属水素化物は、例えば、アルカリ土類金属に高温で水素を作用させる方法（「化学大辞典」縮刷版、共立出版（株）水素化カルシウム、水素化バリウムの項）等により製造することができる。 The alkaline earth metal hydride that is a raw material of the present invention is, for example, a method in which hydrogen is allowed to act on an alkaline earth metal at a high temperature (“Chemical Dictionary”), Kyoritsu Publishing Co., Ltd., calcium hydride, barium hydride Etc.).
本発明に用いるアルカリ土類金属水素化物は、粒度は問わないが、未反応のアルカリ土類金属水素化物の残存を防止する点から、１０ｃｍ以下が好ましく、５ｃｍ以下がより好ましく、１ｃｍ以下がさらに好ましい。また、粒度の下限も問わないが、１μｍ以上が好ましく、１０μｍ以上がより好ましい。具体的には、１μｍ〜１０ｃｍが好ましく、１０μｍ〜５ｃｍがより好ましく、１０μｍ〜１ｃｍがさらに好ましい。
また、アルカリ土類金属水素化物粒子の形状は特に問わず、針状、柱状、塊状、球状等のいずれでもよい。
The alkaline earth metal hydride used in the present invention is not limited in particle size, but is preferably 10 cm or less, more preferably 5 cm or less, and further preferably 1 cm or less from the viewpoint of preventing the remaining unreacted alkaline earth metal hydride. preferable. Moreover, although the minimum of a particle size is not ask | required, 1 micrometer or more is preferable and 10 micrometers or more are more preferable. Specifically, 1 μm to 10 cm is preferable, 10 μm to 5 cm is more preferable, and 10 μm to 1 cm is more preferable.
The shape of the alkaline earth metal hydride particles is not particularly limited, and may be any of acicular, columnar, massive, spherical and the like.
本発明において、アルカリ土類金属イミドの製造は、アルカリ土類金属水素化物を、窒素ガス雰囲気下で加熱することにより行う。また、窒素ガス雰囲気下で反応を行う圧力は特に制限はないが、常圧で行うのが経済的で好ましい。また、反応は、バッチ式でも連続式でも良いが、量産する場合は、連続式が有利である。
窒素ガス雰囲気とするには、反応装置に窒素ガスを満たせばよく、通常の窒素ガスボンベから反応装置中に窒素ガスを供給すればよい。
In the present invention, the alkaline earth metal imide is produced by heating an alkaline earth metal hydride in a nitrogen gas atmosphere. The pressure at which the reaction is performed in a nitrogen gas atmosphere is not particularly limited, but it is economical and preferable to carry out the reaction at normal pressure. The reaction may be a batch type or a continuous type, but the continuous type is advantageous for mass production.
In order to obtain a nitrogen gas atmosphere, the reactor may be filled with nitrogen gas, and nitrogen gas may be supplied into the reactor from a normal nitrogen gas cylinder.
本発明において、加熱温度は、完全にアルカリ土類金属イミドにするために３００℃以上が好ましく、４００℃以上がより好ましく、５００℃以上がさらに好ましい。温度の上限は、生成するアルカリ土類金属イミドが分解しない温度であり、１０００℃以下とすることが好ましい。従って、加熱温度は、３００〜１０００℃が好ましく、さらに４００〜９００℃、特に５００〜７５０℃が好ましい。
より具体的には、カルシウムイミドを得る場合には、４００〜１０００℃が好ましく、５００〜９００℃がより好ましい。ストロンチウムイミドを得る場合には、３００〜７５０℃が好ましく、４００〜７００℃がより好ましい。またバリウムイミドを得る場合には、３００〜７５０℃が好ましく、５００〜７００℃がより好ましい。
In the present invention, the heating temperature is preferably 300 ° C. or higher, more preferably 400 ° C. or higher, and further preferably 500 ° C. or higher in order to make the alkaline earth metal imide completely. The upper limit of the temperature is a temperature at which the generated alkaline earth metal imide does not decompose, and is preferably 1000 ° C. or lower. Accordingly, the heating temperature is preferably 300 to 1000 ° C, more preferably 400 to 900 ° C, and particularly preferably 500 to 750 ° C.
More specifically, when obtaining calcium imide, 400-1000 degreeC is preferable and 500-900 degreeC is more preferable. When obtaining strontium imide, 300-750 degreeC is preferable and 400-700 degreeC is more preferable. Moreover, when obtaining barium imide, 300-750 degreeC is preferable and 500-700 degreeC is more preferable.
反応時間は、装置、反応温度、原料量により適宜決定すればよいが、通常１０分〜４８時間とすることが好ましく、１時間〜２４時間がさらに好ましく、特に３時間〜１２時間が好ましい。 The reaction time may be appropriately determined depending on the apparatus, reaction temperature, and amount of raw material, but is usually preferably 10 minutes to 48 hours, more preferably 1 hour to 24 hours, and particularly preferably 3 hours to 12 hours.
反応装置は、１０００℃程度の熱に耐えられる装置であればよく、例えば、管状炉、電気炉、バッチ式キルン、ロータリーキルンを用いればよい。 The reaction apparatus may be an apparatus that can withstand heat of about 1000 ° C., and for example, a tubular furnace, an electric furnace, a batch kiln, or a rotary kiln may be used.
反応終了後は、例えばバッチ式の場合には、反応装置内には目的とするアルカリ土類金属イミドのみが粉体状で残存するので、回収は極めて容易である。
一方、連続式の場合には、例えば、窒素で内部が満たされたロータリーキルンを用いれば、容易にアルカリ土類金属イミドが連続的に回収される。
After completion of the reaction, for example, in the case of a batch type, since only the target alkaline earth metal imide remains in a powder form in the reaction apparatus, the recovery is extremely easy.
On the other hand, in the case of a continuous type, for example, if a rotary kiln filled with nitrogen is used, the alkaline earth metal imide is easily recovered continuously.
本発明で得られるアルカリ土類金属イミドは、ＭｇＮＨ、ＣａＮＨ、ＳｒＮＨ、ＢａＮＨ、Ｂａ2ＮＨ及びβ−ＳｒＮＨから選ばれる１種又は２種以上が好ましい。本発明によれば、前記のように容易な手段により、高純度で蛍光体等の原料にも使用可能なアルカリ土類金属イミドが収率良く得られる。 The alkaline earth metal imide obtained in the present invention is preferably one or more selected from MgNH, CaNH, SrNH, BaNH, Ba 2 NH and β-SrNH. According to the present invention, an alkaline earth metal imide that can be used as a raw material such as a phosphor with high purity can be obtained in a high yield by an easy means as described above.
以下実施例を挙げて、本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
参考例
（１）出発原料である水素化ストロンチウムは、２００ｃｃ耐圧容器に金属ストロンチウム４０ｇを仕込み、真空排気した後、水素０．９ＭＰａを充填し、反応温度１５０℃で１２時間反応を行って製造した。得られた水素化ストロンチウムは遊星ボールミルで粉砕し、目開き１ｍｍの篩い分けを行い、１ｍｍ以下のものを用いた。
Reference Example (1) Strontium hydride as a starting material was prepared by charging 40 g of metal strontium into a 200 cc pressure vessel, evacuating, filling with 0.9 MPa of hydrogen, and reacting at a reaction temperature of 150 ° C. for 12 hours. . The obtained strontium hydride was pulverized with a planetary ball mill, sieved with an opening of 1 mm, and one having a size of 1 mm or less was used.
（２）出発原料である水素化バリウムは、２００ｃｃ耐圧容器に金属バリウム４０ｇを仕込み、真空排気した後、水素０．９ＭＰａを充填し、反応温度１５０℃で１２時間反応を行って製造した。得られた水素化バリウムは遊星ボールミルで粉砕し、目開き１ｍｍの篩い分けを行い、１ｍｍ以下のものを用いた。 (2) Barium hydride as a starting material was prepared by charging 40 g of metal barium into a 200 cc pressure vessel, evacuating, filling with 0.9 MPa of hydrogen, and reacting at a reaction temperature of 150 ° C. for 12 hours. The obtained barium hydride was pulverized with a planetary ball mill, sieved with an opening of 1 mm, and one having a size of 1 mm or less was used.
実施例１
水素化ストロンチウム５０ｇを窒素フロー下（３０００ｃｃ／分）最高温度５５０℃で１２時間保持した。加熱処理は、グローブボックス内設置した炉心管（内径５０ｍｍ、長さ６００ｍｍ）のアルミナボードに載せ、炉心管をシリコンキャップで密閉、グローブボックスから取り出した炉心管を管状炉にセットし、最高温度まで３００℃／時間で昇温して行った。
得られた薄黄色の反応物の粉末ＸＲＤ解析を行ったところ全相ストロンチウムイミド（ＳｒＮＨ）であった（図１）。このストロンチウムイミドを窒素酸素水素同時分析計で定量したところ、Ｏ2量は０．７ｍａｓｓ％であった。また、窒素酸素水素同時分析計で水素量を測定したところ、Ｈ2量は１．１ｍａｓｓ％であった。
Example 1
50 g of strontium hydride was held at a maximum temperature of 550 ° C. for 12 hours under a nitrogen flow (3000 cc / min). The heat treatment is carried on an alumina board with a core tube (inner diameter: 50 mm, length: 600 mm) installed in the glove box, the core tube is sealed with a silicon cap, and the core tube taken out from the glove box is set in a tubular furnace until the maximum temperature is reached. The temperature was raised at 300 ° C./hour.
When the powder XRD analysis of the obtained light yellow reaction material was conducted, it was all phase strontium imide (SrNH) (FIG. 1). When this strontium imide was quantified with a nitrogen-oxygen-hydrogen simultaneous analyzer, the amount of O 2 was 0.7 mass%. Moreover, when the amount of hydrogen was measured with a nitrogen-oxygen-hydrogen simultaneous analyzer, the amount of H 2 was 1.1 mass%.
実施例２
水素化ストロンチウム５０ｇを窒素フロー下（３０００ｃｃ／分）最高温度６００℃で１２時間保持した。加熱処理は実施例１と同様に行った。得られた黄色の反応物の粉末ＸＲＤ解析を行ったところ全相ストロンチウムイミド（β−ＳｒＮＨ）であった（図２）。このストロンチウムイミドを窒素酸素水素同時分析計で定量したところ、Ｏ2量は０．７ｍａｓｓ％であった。
Example 2
50 g of strontium hydride was held at a maximum temperature of 600 ° C. for 12 hours under a nitrogen flow (3000 cc / min). The heat treatment was performed in the same manner as in Example 1. When the powder XRD analysis of the obtained yellow reaction material was conducted, it was all phase strontium imide ((beta) -SrNH) (FIG. 2). When this strontium imide was quantified with a nitrogen-oxygen-hydrogen simultaneous analyzer, the amount of O 2 was 0.7 mass%.
実施例３
水素化ストロンチウム５０ｇを窒素フロー下（３０００ｃｃ／分）最高温度７００℃で１２時間保持した。加熱処理は実施例１と同様に行った。得られた淡緑色の反応物の粉末ＸＲＤ解析を行ったところ全相ストロンチウムイミド（β−ＳｒＮＨ）であった（図３）。このストロンチウムイミドを窒素酸素水素同時分析計で定量したところ、Ｏ2量は０．８ｍａｓｓ％であった。
Example 3
50 g of strontium hydride was held at a maximum temperature of 700 ° C. for 12 hours under a nitrogen flow (3000 cc / min). The heat treatment was performed in the same manner as in Example 1. When the powder XRD analysis of the obtained light green reaction material was conducted, it was all phase strontium imide ((beta) -SrNH) (FIG. 3). When this strontium imide was quantified with a nitrogen-oxygen-hydrogen simultaneous analyzer, the amount of O 2 was 0.8 mass%.
実施例４
水素化バリウム１０ｇを窒素フロー下（１０００ｃｃ／分）最高温度６５０℃で４時間保持した。加熱処理は実施例１と同様に行った。得られた紫色の反応物の粉末ＸＲＤ解析を行ったところ全相バリウムイミド（Ｂａ2ＮＨ）であった（図４）。
Example 4
10 g of barium hydride was held at a maximum temperature of 650 ° C. for 4 hours under nitrogen flow (1000 cc / min). The heat treatment was performed in the same manner as in Example 1. The resulting purple reaction product of a powder XRD analysis of all phases barium imide was performed was (Ba 2 NH) (Figure 4).
比較例１
水素化バリウム１０ｇを窒素フロー下（１０００ｃｃ／分）最高温度８００℃で４時間保持した。加熱処理は実施例１と同様に行った。得られた黒色の反応物の粉末ＸＲＤ解析を行ったところ全相窒化バリウム（Ｂａ2Ｎ）であった（図５）。
Comparative Example 1
10 g of barium hydride was held at a maximum temperature of 800 ° C. for 4 hours under nitrogen flow (1000 cc / min). The heat treatment was performed in the same manner as in Example 1. When the powder XRD analysis of the obtained black reactant was conducted, it was all-phase barium nitride (Ba 2 N) (FIG. 5).
比較例２及び３
ストロンチウムアミドを原料としてストロンチウムイミドを合成した。
出発原料であるストロンチウムアミドは、５００ｃｃ耐圧容器に金属ストロンチウム８５ｇを仕込み、真空排気した後、系内に液体アンモニアを１７０ｇ充填し、反応温度１００℃で３時間反応を行った。得られたストロンチウムアミド５０ｇをグローブボックス内にて炉心管（内径５０ｍｍ、長さ６００ｍｍ）に入れ、シリコンキャップで密閉した。グローブボックスから取り出した炉心管を管状炉にセットし、窒素フロー下（３０００ｃｃ／分）で加熱した。３００℃／時間で昇温し、６５０℃と７００℃で１２時間保持した。
得られた反応物の粉末ＸＲＤ解析を行ったところ全相ストロンチウムイミド（β−ＳｒＮＨ）であった。このストロンチウムイミドを窒素酸素水素同時分析計で定量したところ、Ｏ2量は６５０℃の場合は２．０ｍａｓｓ％、７００℃の場合は１．９ｍａｓｓ％であった。
Comparative Examples 2 and 3
Strontium imide was synthesized from strontium amide as a raw material.
Strontium amide as a starting material was charged with 85 g of metal strontium in a 500 cc pressure vessel, evacuated, filled with 170 g of liquid ammonia, and reacted at a reaction temperature of 100 ° C. for 3 hours. 50 g of the obtained strontium amide was placed in a core tube (inner diameter: 50 mm, length: 600 mm) in a glove box and sealed with a silicon cap. The furnace core tube taken out from the glove box was set in a tubular furnace and heated under a nitrogen flow (3000 cc / min). The temperature was raised at 300 ° C./hour and held at 650 ° C. and 700 ° C. for 12 hours.
When the powder XRD analysis of the obtained reaction material was conducted, it was all phase strontium imide ((beta) -SrNH). When this strontium imide was quantified with a nitrogen-oxygen-hydrogen simultaneous analyzer, the O 2 content was 2.0 mass% at 650 ° C. and 1.9 mass% at 700 ° C.
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