JP3557867B2 - Method for producing low α-ray barium hydroxide and barium carbonate - Google Patents
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Description
【０００１】
【発明の属する技術分野】
この発明は、α線量が０．０１ｃｐｈ／ｃｍ2 以下の低α線水酸化バリウム（以下、低α線水酸化バリウム）およびα線量が０．０１ｃｐｈ／ｃｍ2 以下の低α線炭酸バリウム（以下、低α線炭酸バリウムという）の製造方法に関するものである。
【０００２】
【従来の技術】
一般に、水酸化バリウムおよび炭酸バリウムは、ＢａＴｉＯ3 、（Ｂａ、Ｓｒ）ＴｉＯ3 など高誘電体の原料として使用されており、特に、ＢａＴｉＯ3 、（Ｂａ、Ｓｒ）ＴｉＯ3 など高誘電体の薄膜は半導体メモリーにおけるキャパシター膜として使用されている。しかし、近年、半導体装置の高集積化にともない、ＢａＴｉＯ3 、（Ｂａ、Ｓｒ）ＴｉＯ3 など高誘電体薄膜から放射されるα線によるエラーが問題となっている。この高誘電体薄膜から放射されるα線は、主としてＢａＴｉＯ3 、（Ｂａ、Ｓｒ）ＴｉＯ3 など高誘電体薄膜のＢａの不純物から放出されていることも知られている。
【０００３】
前記ＢａＴｉＯ3 、（Ｂａ、Ｓｒ）ＴｉＯ3 など高誘電体薄膜の原料となる水酸化バリウムおよび炭酸バリウムは、重晶石原料鉱石または毒重石原料鉱石を塊状に破砕して塊状破砕鉱を製造し、この塊状破砕鉱をさらに粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して重晶石精鉱または毒重石精鉱とし、重晶石原料鉱石精鉱の場合はこれをカーボンで還元して硫化バリウムを製造し、この硫化バリウムを塩酸に溶解して塩化物とし、また毒重石精鉱の場合はそのまま塩酸に溶解して塩化物とし、これら塩化物を塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムのの水に対する溶解度が違う性質を利用して再結晶を繰り返すことにより微量に含まれているストロンチュウムおよびカルシウムを除去し、ついで苛性化して水酸化バリウムを製造し、この水酸化バリウムを一旦溶液にした後、再結晶して不純物除去後、溶液に炭酸塩または炭酸ガスと反応させることにより炭酸バリウムを製造している。
【０００４】
【発明が解決しようとする課題】
従って、ＢａＴｉＯ3 、（Ｂａ、Ｓｒ）ＴｉＯ3 など高誘電体薄膜から放射されるα線量を少なくするには、高誘電体薄膜の原料であるα線放出量の少ない水酸化バリウムまたは炭酸バリウムを使用する必要がある。しかし、α線放出量の少ない（０．０１ｃｐｈ／ｃｍ2 以下）水酸化バリウムまたは炭酸バリウムを製造することはできない。
【０００５】
【課題を解決するための手段】
そこで、本発明者らは、低α線水酸化バリウムおよび低α線炭酸バリウムを提供するべく研究を行った結果、
（ａ）重晶石原料鉱石または毒重石原料鉱石は、同じ鉱脈から採掘された重晶石原料鉱石または毒重石原料鉱石であっても、α線放出量の多い部分とα線放出量の少ない部分があるところから、重晶石原料鉱石または毒重石原料鉱石を破砕して得られた塊状破砕鉱のα線量を測定し、α線量の少ない塊状破砕鉱を選別して採取し、このα線量の少ない塊状破砕鉱を通常の粉砕、浮遊選鉱、還元、塩化、晶析を行うことにより水酸化バリウムおよび炭酸バリウムを製造すると、得られた水酸化バリウムおよび炭酸バリウムはα線放射量が従来よりも少ない、
（ｂ）高誘電体薄膜の原料として使用することのできるα線量：０．０１ｃｐｈ／ｃｍ2 以下の水酸化バリウムまたは炭酸バリウムを得るには、α線放出量が１ｃｐｈ／ｃｍ2 以下の重晶石原料鉱石または毒重石原料鉱石を使用する必要がある、
などの研究結果が得られたのである。
【０００６】
この発明は、かかる研究結果に基づいて成されたものであって、
（１）重晶石原料鉱石を破砕して塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱をカーボンで還元して硫化バリウムを製造し、この硫化バリウムを塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化後再結晶により精製して水酸化バリウムを製造する方法において、
前記塊状破砕鉱のα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線放出量の少ない塊状破砕鉱を粉砕して粉鉱とする低α線水酸化バリウムの製造方法、
（２）重晶石原料鉱石を破砕して塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱をカーボンで還元して硫化バリウムを製造し、この硫化バリウムを塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化して水酸化バリウムを製造し、再結晶による精製後、この水酸化バリウムを一旦溶液にし、ついで炭酸塩または炭酸ガスと反応させることにより炭酸バリウムを製造する方法において、
前記塊状破砕鉱から放出されるα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線量の少ない塊状破砕鉱を粉砕して粉鉱とする低α線炭酸バリウムの製造方法、
（３）毒重石原料鉱石を破砕して塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱を塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化後、再結晶により精製して水酸化バリウムを製造する方法において、
前記塊状破砕鉱のα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線放出量の少ない塊状破砕鉱を粉砕して粉鉱とする低α線水酸化バリウムの製造方法、
（４）毒重石原料鉱石を破砕して塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱を塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化して水酸化バリウムを製造し、この水酸化バリウムを一旦溶液にし、再結晶によって精製後、炭酸塩または炭酸ガスと反応させることにより炭酸バリウムを製造する方法において、
前記塊状破砕鉱から放出されるα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線量の少ない塊状破砕鉱を粉砕して粉鉱とする低α線炭酸バリウムの製造方法、
に特徴を有するものである。
【０００７】
高誘電体薄膜の原料として使用することのできるα線量：０．０１ｃｐｈ／ｃｍ2 以下の水酸化バリウムまたは炭酸バリウムを得るには、α線放出量が１ｃｐｈ／ｃｍ2 以下の重晶石原料鉱石または毒重石原料鉱石の塊状破砕鉱を使用する必要がある。従って、塊状破砕鉱から放出されるα線量を測定し、α線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を選別して粉砕し粉鉱とする必要がある。重晶石原料鉱石または毒重石原料鉱石を破砕して得られた塊状破砕鉱は、最大粒径が０．０５〜０．５ｍｍの範囲内の大きさに破砕する。塊状破砕鉱の最大粒径が０．５ｍｍより大きい塊状破砕鉱ではα線量の測定を正確に行うことができず、一方、塊状破砕鉱の最大粒径が０．０５ｍｍより小さい塊状破砕鉱ではα線量の測定を正確に行うことができるが、選別に多大の労力がかかってコストが高くなるので好ましくない。
【０００８】
従って、この発明は、
（５）重晶石原料鉱石を破砕して最大粒径：０．０５〜０．５ｍｍの範囲内の大きさの塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱をカーボンで還元して硫化バリウムを製造し、この硫化バリウムを塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化した後、再結晶による精製を行って水酸化バリウムを製造する方法において、
前記塊状破砕鉱のα線量を測定してα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を選別し、この選別されたα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を粉砕して粉鉱とする低α線水酸化バリウムの製造方法、
（６）重晶石原料鉱石を破砕して最大粒径：０．０５〜０．５ｍｍの範囲内の大きさの塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱をカーボンで還元して硫化バリウムを製造し、この硫化バリウムを塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化して水酸化バリウムを製造し、この水酸化バリウムを一旦溶液にした後、さらに再結晶によって精製し、ついで炭酸塩または炭酸ガスと反応させることにより炭酸バリウムを製造する方法において、
前記塊状破砕鉱から放出されるα線量を測定してα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を選別し、この選別されたα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を粉砕して粉鉱とする低α線炭酸バリウムの製造方法、
（７）毒重石原料鉱石を破砕して最大粒径：０．０５〜０．５ｍｍの範囲内の大きさの塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱を塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化し、ついで再結晶による精製を行って水酸化バリウムを製造する方法において、
前記塊状破砕鉱のα線量を測定してα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を選別し、この選別されたα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を粉砕して粉鉱とする低α線水酸化バリウムの製造方法、
（８）毒重石原料鉱石を破砕して最大粒径：０．０５〜０．５ｍｍの範囲内の大きさの塊状破砕鉱とし、この塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱を塩酸に溶解して塩化物とし、再結晶を繰り返すことにより塩化バリウム、塩化ストロンチュウムおよび塩化カルシウムの水に対する溶解度が違う性質を利用してストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化して水酸化バリウムを製造し、この水酸化バリウムを一旦溶液にした後、再結晶による精製を行い、ついで炭酸塩または炭酸ガスと反応させることにより炭酸バリウムを製造する方法において、
前記塊状破砕鉱から放出されるα線量を測定してα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を選別し、この選別されたα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を粉砕して粉鉱とする低α線炭酸バリウムの製造方法、
に特徴を有するものである。
【０００９】
【発明の実施の形態】
実施例１〜３
重晶石原料鉱石を用意し、この重晶石原料鉱石を破砕して最大粒径：０．０５〜０．５ｍｍの範囲内の大きさの塊状破砕鉱とし、この塊状破砕鉱のα線をガスフロータイプのα線測定器を用いて測定し、α線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を選別し、この選別されたα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱をコークス（α線量の低いものを選択した）で還元して硫化バリウムを製造し、この硫化バリウムに塩酸を加えて塩化バリウムを作り、この塩化バリウムを用いて温度：６０℃の塩化バリウム飽和溶液を作り、この飽和溶液の温度を３０℃まで下げて再結晶させることによりストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化して水酸化バリウムを製造し、この水酸化バリウムのα線量をガスフロータイプのα線測定器を用いて測定し、その結果を表１に示た。さらに、得られた水酸化バリウムを水溶液とし、この水溶液に炭酸ガスを吹き込んで炭酸バリウムを製造し、得られた炭酸バリウムのα線量をガスフロータイプのα線測定器を用いて測定し、その結果を表１に示た。
【００１０】
従来例１
実施例１〜３で用意した重晶石原料鉱石を選別することなくそのまま破砕し粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱をコークスで還元して硫化バリウムを製造し、この硫化バリウムに塩酸を加えて塩化バリウムを作り、この塩化バリウムを用いて温度：６０℃の塩化バリウム飽和溶液を作り、この飽和溶液の温度を３０℃まで下げて再結晶させることによりストロンチュウムおよびカルシウムを除去する晶析を行って塩化バリウムを精製し、精製した塩化バリウムを苛性化して水酸化バリウムを製造し、この水酸化バリウムのα線量をガスフロータイプのα線測定器を用いて測定し、その結果を表１に示た。さらに得られた水酸化バリウムを水溶液とし、この水溶液に炭酸ガスを吹き込んで炭酸バリウムを製造し、得られた炭酸バリウムのα線量をガスフロータイプのα線測定器を用いて測定し、その結果を表１に示た。
【００１１】
【表１】
表１に示される結果から、同じ重晶石原料鉱石を使用しても、α線量による選別を行わない従来例１で製造した水酸化バリウムおよび炭酸バリウムは、α線量は多いのに対し、重晶石塊状破砕鉱のα線量による選別を行った実施例１〜３で製造した水酸化バリウムおよび炭酸バリウムは、α線量の極めて少ない水酸化バリウムおよび炭酸バリウムが得られることが分かる。
【００１３】
実施例４〜６
毒重石原料鉱石を用意し、この毒重石原料鉱石のα線をガスフロータイプのα線測定器を用いて測定したところα線量は１．５ｃｐｈ／ｃｍ2 であった。この毒重石原料鉱石を破砕して最大粒径：０．０５〜０．５ｍｍの範囲内の大きさの塊状破砕鉱とし、この塊状破砕鉱のα線をガスフロータイプのα線測定器を用いて測定し、α線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を選別し、この選別されたα線量が１ｃｐｈ／ｃｍ2 以下の塊状破砕鉱を粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱に塩酸を加えて６０℃に保持することにより塩化バリウム飽和溶液とし、以下実施例１〜３と同様にして水酸化バリウムおよび炭酸バリウムを製造し、得られた水酸化バリウムおよび炭酸バリウムのα線量をガスフロータイプのα線測定器を用いて測定し、その結果を表２に示た。
【００１４】
従来例２
実施例４〜６で用意した毒重石原料鉱石を選別することなくそのまま破砕し粉砕して粉鉱とし、この粉鉱を浮遊選鉱して母岩および脈石を除去して精鉱とし、この精鉱を用いる以外は、実施例４〜６と同様にして水酸化バリウムおよび炭酸バリウムを製造し、得られた水酸化バリウムおよび炭酸バリウムのα線量をガスフロータイプのα線測定器を用いて測定し、その結果を表２に示た。
【００１５】
【表２】
表２に示される結果から、同じ毒重石原料鉱石を使用しても、α線量による選別を行わない従来例２で製造した水酸化バリウムおよび炭酸バリウムは、晶析回数を格段に多くしてもα線量は多いのに対し、毒重石塊状破砕鉱のα線量による選別を行った実施例４〜６で製造した水酸化バリウムおよび炭酸バリウムは晶析回数が少ないにもかかわらず、α線量の極めて少ない水酸化バリウムおよび炭酸バリウムが得られることが分かる。
【００１７】
【発明の効果】
上述のように、この発明の方法によると、α線量の極めて少ない水酸化バリウムおよび炭酸バリウムを低コストで製造することができ、産業上優れた効果を奏するものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a low α-ray barium hydroxide having an α dose of 0.01 cph / cm 2 or less (hereinafter referred to as “low α-ray barium hydroxide”) and a low α-ray barium carbonate having an α dose of 0.01 cph / cm 2 or less (hereinafter referred to as “low barium hydroxide”). α-barium carbonate).
[0002]
[Prior art]
In general, barium hydroxide and barium carbonate are used as raw materials for high dielectric materials such as BaTiO3 and (Ba, Sr) TiO3. In particular, thin films of high dielectric materials such as BaTiO3 and (Ba, Sr) TiO3 are used in semiconductor memories. Used as a capacitor film. However, in recent years, with the increase in the degree of integration of semiconductor devices, errors due to α rays radiated from high dielectric thin films such as BaTiO3 and (Ba, Sr) TiO3 have become a problem. It is also known that α rays emitted from the high dielectric thin film are mainly emitted from Ba impurities of the high dielectric thin film, such as BaTiO3 and (Ba, Sr) TiO3.
[0003]
Barium hydroxide and barium carbonate, which are the raw materials of the high dielectric thin film such as BaTiO3 and (Ba, Sr) TiO3, crush the barite raw material ore or the poisonite raw material ore into blocks to produce massive crushed ore. The lump crushed ore is further pulverized into fine ore, and the fine ore is flotated to remove the host rock and gangue to obtain barite concentrate or poisonite concentrate. Reduces barium sulfide with carbon to produce barium sulfide, and this barium sulfide is dissolved in hydrochloric acid to form chlorides.In the case of poisonite concentrate, it is dissolved directly in hydrochloric acid to form chlorides. Trace amounts of strontium and calcium are removed by repeated recrystallization using the different solubility of barium, strontium chloride and calcium chloride in water. Then, barium hydroxide is produced, and after the barium hydroxide is once converted into a solution, recrystallized to remove impurities, and then the solution is reacted with carbonate or carbon dioxide gas to produce barium carbonate.
[0004]
[Problems to be solved by the invention]
Therefore, in order to reduce the α dose emitted from a high dielectric thin film such as BaTiO3 or (Ba, Sr) TiO3, barium hydroxide or barium carbonate which emits a small amount of α rays, which is a raw material of the high dielectric thin film, is used. There is a need. However, it is not possible to produce barium hydroxide or barium carbonate having a small α-ray emission amount (0.01 cph / cm 2 or less).
[0005]
[Means for Solving the Problems]
Thus, the present inventors have conducted research to provide low α-ray barium hydroxide and low α-ray barium carbonate,
(A) The barite ore or poisonous ore mined from the same ore vein is a portion having a high α-ray emission amount and a low α-ray emission amount even if it is a barite ore or poisonite raw material ore. From where there is, measure the alpha dose of massive crushed ore obtained by crushing barite raw material ore or poisonite raw material ore, sort and collect massive crushed ore with small alpha dose, and collect this alpha dose When barium hydroxide and barium carbonate are produced by performing ordinary pulverization, flotation, reduction, salinization, and crystallization of massive crushed ore, barium hydroxide and barium carbonate have a higher α-ray emission than before. Less,
(B) To obtain barium hydroxide or barium carbonate of 0.01 cph / cm 2 or less, which can be used as a raw material of the high dielectric thin film, a barite raw material having an α-ray emission of 1 cph / cm 2 or less. Need to use ore or poisonous raw material ore,
Such research results were obtained.
[0006]
The present invention has been made based on such research results,
(1) Crushing barite raw material ore into massive crushed ore, crushing this massive crushed ore to fine ore, flotation of this fine ore to remove host rock and gangue to concentrate This concentrate is reduced with carbon to produce barium sulfide, and this barium sulfide is dissolved in hydrochloric acid to form a chloride, and by repeating recrystallization, the solubility of barium chloride, strontium chloride and calcium chloride in water is different. A method for producing barium hydroxide by purifying barium chloride by performing crystallization to remove strontium and calcium by utilizing properties, and purifying the purified barium chloride by recrystallization after causticizing,
The α-dose of the massive crushed ore is measured to sort out the massive crushed ore with a small α-dose, and the thus-selected massive crushed ore with a small amount of α-ray emission is pulverized into low α-ray barium hydroxide as fine ore. Production method,
(2) crushing the barite raw material ore into a massive crushed ore, crushing the massive crushed ore into a fine ore, flotating the fine ore to remove a host rock and gangue and forming a concentrate; This concentrate is reduced with carbon to produce barium sulfide, and this barium sulfide is dissolved in hydrochloric acid to form a chloride, and by repeating recrystallization, the solubility of barium chloride, strontium chloride and calcium chloride in water is different. Purification of barium chloride by crystallization to remove strontium and calcium by utilizing the properties, causticization of the purified barium chloride to produce barium hydroxide, after purification by recrystallization, this barium hydroxide In a method for producing barium carbonate by once making a solution and then reacting with carbonate or carbon dioxide gas,
The α-dose released from the massive crushed ore is measured to sort out the massive crushed ore with a small α-dose, and the thus-selected massive crushed ore with a small α-dose is pulverized to obtain a fine α-barium carbonate as fine ore. Production method,
(3) Pulverized ore raw material ore is crushed into massive crushed ore, and this massive crushed ore is crushed into fine ore, and this fine ore is subjected to flotation to remove host rock and gangue to concentrate. The concentrate is dissolved in hydrochloric acid to form chloride, and recrystallization is repeated to remove strontium and calcium by utilizing the different solubility of barium chloride, strontium chloride and calcium chloride in water. In a method of producing barium hydroxide by purifying and purifying barium chloride, causticizing the purified barium chloride, and then purifying by recrystallization,
The α-dose of the massive crushed ore is measured to sort out the massive crushed ore with a small α-dose, and the thus-selected massive crushed ore with a small amount of α-ray emission is pulverized into low α-ray barium hydroxide as fine ore. Production method,
(4) Poisonous stone raw material ore is crushed to form massive crushed ore, and this massive crushed ore is crushed to form fine ore. This fine ore is subjected to flotation to remove host rock and gangue to concentrate. The concentrate is dissolved in hydrochloric acid to form chloride, and recrystallization is repeated to remove strontium and calcium by utilizing the different solubility of barium chloride, strontium chloride and calcium chloride in water. To purify the barium chloride, causticize the refined barium chloride to produce barium hydroxide, once convert this barium hydroxide into a solution, purify by recrystallization, and react with carbonate or carbon dioxide gas to obtain barium carbonate. In the method for producing
The α-dose released from the massive crushed ore is measured to sort out the massive crushed ore with a small α-dose, and the thus-selected massive crushed ore with a small α-dose is pulverized to obtain a fine α-barium carbonate as fine ore. Production method,
It is characterized by the following.
[0007]
In order to obtain barium hydroxide or barium carbonate having an α dose of 0.01 cph / cm 2 or less, which can be used as a raw material of the high dielectric thin film, a barite raw material ore or a poison having an α-ray emission of 1 cph / cm 2 or less is obtained. It is necessary to use massive crushed ore of heavy ore. Therefore, it is necessary to measure the α dose emitted from the lump crushed ore, and to sort and pulverize the lump crushed ore having the α dose of 1 cph / cm 2 or less to obtain fine ore. The massive crushed ore obtained by crushing barite raw material ore or poisonite raw material ore is crushed to a size having a maximum particle size in the range of 0.05 to 0.5 mm. In the case of a massive crushed ore in which the maximum particle size of the crushed ore is larger than 0.5 mm, the measurement of the α dose cannot be performed accurately, while in the case of the crushed ore in which the maximum particle size of the crushed ore is smaller than 0.05 mm, Although the measurement of the dose can be performed accurately, it is not preferable because a great deal of labor is required for sorting and the cost is increased.
[0008]
Therefore, the present invention
(5) Crushing the barite raw material ore into a massive crushed ore having a maximum particle size within a range of 0.05 to 0.5 mm; crushing the massive crushed ore into a fine ore; Flotation to remove the host rock and gangue to concentrate, reduce this concentrate with carbon to produce barium sulfide, dissolve this barium sulfide in hydrochloric acid to chloride, and repeat recrystallization Barium chloride, strontium chloride, and calcium chloride were used to remove strontium and calcium by using the different properties of water in water to purify barium chloride and to purify the purified barium chloride. Thereafter, in a method of producing barium hydroxide by performing purification by recrystallization,
The α-dose of the massive crushed ore is measured, and the crushed ore having an α-dose of 1 cph / cm 2 or less is selected. α-ray barium hydroxide production method,
(6) The barite raw material ore is crushed to form a lump crushed ore having a maximum particle size within a range of 0.05 to 0.5 mm. Flotation to remove the host rock and gangue to concentrate, reduce this concentrate with carbon to produce barium sulfide, dissolve this barium sulfide in hydrochloric acid to chloride, and repeat recrystallization The barium chloride, strontium chloride and calcium chloride are differently soluble in water, and the crystallization of strontium and calcium is removed by utilizing crystallization.Purification of barium chloride is carried out, and the purified barium chloride is causticized. A method in which barium hydroxide is produced, and once this barium hydroxide is made into a solution, it is purified by recrystallization and then reacted with carbonate or carbon dioxide gas to produce barium carbonate. In,
The α-dose emitted from the massive crushed ore is measured, and the crushed ore having an α-dose of 1 cph / cm 2 or less is selected. A method for producing low α-ray barium carbonate,
(7) Pulverized ore raw material ore is crushed into a massive crushed ore having a maximum particle size of 0.05 to 0.5 mm, and the crushed ore is crushed into fine ore. Flotation removes host rock and gangue to concentrate, and this concentrate is dissolved in hydrochloric acid to form chloride, and the recrystallization is repeated, so that barium chloride, strontium chloride, and calcium chloride are soluble in water. In a method for producing barium hydroxide by performing crystallization to remove strontium and calcium by utilizing different properties, purifying barium chloride, causticizing the purified barium chloride, and then purifying by recrystallization. ,
The α-dose of the massive crushed ore is measured, and the crushed ore having an α-dose of 1 cph / cm 2 or less is selected. α-ray barium hydroxide production method,
(8) The poisonous stone raw material ore is crushed into a massive crushed ore having a maximum particle size of 0.05 to 0.5 mm, and the massive crushed ore is crushed into a fine ore. Flotation removes host rock and gangue to concentrate, and this concentrate is dissolved in hydrochloric acid to form chloride, and the recrystallization is repeated to obtain water solubility of barium chloride, strontium chloride, and calcium chloride. However, crystallization was performed to remove strontium and calcium by utilizing a different property, and barium chloride was purified.The purified barium chloride was causticized to produce barium hydroxide, and the barium hydroxide was once made into a solution. Thereafter, in a method of producing barium carbonate by performing purification by recrystallization and then reacting with carbonate or carbon dioxide gas,
The α-dose emitted from the massive crushed ore is measured, and the crushed ore having an α-dose of 1 cph / cm 2 or less is selected. A method for producing low α-ray barium carbonate,
It is characterized by the following.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Examples 1-3
A barite raw material ore is prepared, and the barite raw material ore is crushed to form a massive crushed ore having a maximum particle size within a range of 0.05 to 0.5 mm. It is measured using a gas flow type α-ray measuring instrument, and the crushed ore having an α dose of 1 cph / cm 2 or less is selected, and the selected crushed ore having an α dose of 1 cph / cm 2 or less is pulverized to This fine ore is flotated to remove the host rock and gangue to concentrate, and this concentrate is reduced with coke (low alpha dose was selected) to produce barium sulfide. Barium chloride is prepared by adding hydrochloric acid to barium, a barium chloride saturated solution having a temperature of 60 ° C. is prepared using the barium chloride, and the temperature of the saturated solution is lowered to 30 ° C. to recrystallize strontium and calcium. Crystallization to remove Barium chloride was purified, the purified barium chloride was causticized to produce barium hydroxide, and the α-dose of this barium hydroxide was measured using a gas flow type α-ray measuring instrument. The results are shown in Table 1. Was. Further, the obtained barium hydroxide was used as an aqueous solution, carbon dioxide gas was blown into the aqueous solution to produce barium carbonate, and the α-ray dose of the obtained barium carbonate was measured using a gas flow type α-ray measuring instrument. The results are shown in Table 1.
[0010]
Conventional example 1
The barite raw material ore prepared in Examples 1 to 3 was crushed and pulverized as it was without being sorted without separating, and this fine ore was subjected to flotation to remove the host rock and gangue to form a concentrate. The concentrate is reduced with coke to produce barium sulfide, and hydrochloric acid is added to the barium sulfide to form barium chloride. Using this barium chloride, a barium chloride saturated solution is prepared at a temperature of 60 ° C. Was cooled to 30 ° C. and recrystallized to remove strontium and calcium, thereby purifying barium chloride, and causticizing the purified barium chloride to produce barium hydroxide. The α dose was measured using a gas flow type α-ray measuring instrument, and the results are shown in Table 1. Further, the obtained barium hydroxide was used as an aqueous solution, carbon dioxide gas was blown into the aqueous solution to produce barium carbonate, and the α dose of the obtained barium carbonate was measured using a gas flow type α-ray measuring instrument. Are shown in Table 1.
[0011]
[Table 1]
From the results shown in Table 1, the barium hydroxide and barium carbonate produced in Conventional Example 1 in which the same barite raw material ore is used but is not sorted by α-dose has a large α-dose, It can be seen that barium hydroxide and barium carbonate produced in Examples 1 to 3 in which the crushed ore crushed ore was sorted by α-dose yielded barium hydroxide and barium carbonate with extremely small α-dose.
[0013]
Examples 4 to 6
An ore raw material ore was prepared, and the α-ray of the raw ore heavy stone ore was measured using a gas flow type α-ray measuring instrument. The α dose was 1.5 cph / cm 2. This poisonous ore raw material ore is crushed into a massive crushed ore having a maximum particle size of 0.05 to 0.5 mm, and the α-ray of the massive crushed ore is measured using a gas flow type α-ray measuring instrument. Crushed ore having an α dose of 1 cph / cm 2 or less is screened, and the selected crushed ore having an α dose of 1 cph / cm 2 or less is pulverized into fine ore. The host rock and gangue were removed to form a concentrate. Hydrochloric acid was added to the concentrate to maintain a saturated solution of barium chloride at 60 ° C. Barium hydroxide and barium carbonate were prepared in the same manner as in Examples 1-3. Was produced, and the α doses of the obtained barium hydroxide and barium carbonate were measured using a gas flow type α-ray measuring instrument. The results are shown in Table 2.
[0014]
Conventional example 2
The ore weight ore raw materials prepared in Examples 4 to 6 were crushed and pulverized as they were without sorting, and the ores were separated by flotation to remove the host rock and gangue to concentrate. Barium hydroxide and barium carbonate were produced in the same manner as in Examples 4 to 6, except that ore was used, and the α-ray dose of the obtained barium hydroxide and barium carbonate was measured using a gas flow type α-ray measuring instrument. The results are shown in Table 2.
[0015]
[Table 2]
From the results shown in Table 2, the barium hydroxide and barium carbonate produced in Conventional Example 2 in which the same poisonous weight raw material ore is used and the α-dose is not used, the crystallization frequency is significantly increased. Although the α dose is large, the barium hydroxide and barium carbonate produced in Examples 4 to 6 in which the poisonous massive crushed ore is sorted by the α dose are extremely low in the α dose despite the small number of crystallizations. It can be seen that less barium hydroxide and barium carbonate are obtained.
[0017]
【The invention's effect】
As described above, according to the method of the present invention, barium hydroxide and barium carbonate having extremely small α dose can be produced at low cost, and have excellent industrial effects.
Claims (8)
前記塊状破砕鉱のα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線放出量の少ない塊状破砕鉱を粉砕して粉鉱とすることを特徴とする低α線水酸化バリウムの製造方法。The barite raw material ore is crushed into lump crushed ore, and the lump crushed ore is crushed into fine ore, and the fine ore is flotated to remove the host rock and gangue to concentrate, and this concentrate is removed. Is reduced with carbon to produce barium sulfide, this barium sulfide is dissolved in hydrochloric acid to form a chloride, crystallization is performed to purify barium chloride, and the purified barium chloride is causticized to produce barium hydroxide. In the method,
The α-dose of the massive crushed ore is measured to sort out the massive crushed ore with a small α-dose, and the thus-selected massive crushed ore with a small amount of α-ray emission is pulverized into a fine ore to reduce the α. A method for producing barium hydroxide linear.
前記塊状破砕鉱から放出されるα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線量の少ない塊状破砕鉱を粉砕して粉鉱とすることを特徴とする低α線炭酸バリウムの製造方法。The barite raw material ore is crushed into lump crushed ore, and the lump crushed ore is crushed into fine ore, and the fine ore is flotated to remove the host rock and gangue to concentrate, and this concentrate is removed. Is reduced with carbon to produce barium sulfide, this barium sulfide is dissolved in hydrochloric acid to form chloride, crystallization is performed to purify barium chloride, and the purified barium chloride is causticized to produce barium hydroxide. In a method for producing barium carbonate by once converting this barium hydroxide into a solution and reacting it with a carbonate or carbon dioxide gas,
Measuring the α-dose released from the massive crushed ore to sort out the massive crushed ore with a small α-dose, and pulverizing the selected massive crushed ore with a small α-dose into fine ore; Method for producing α-ray barium carbonate.
前記塊状破砕鉱のα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線放出量の少ない塊状破砕鉱を粉砕して粉鉱とすることを特徴とする低α線水酸化バリウムの製造方法。The ore raw material ore is crushed into a massive crushed ore, the crushed ore is crushed into a fine ore, and this fine ore is flotated to remove the host rock and gangue to a concentrate, which is then concentrated. In a method of producing barium hydroxide by dissolving in hydrochloric acid to form a chloride, performing crystallization to purify barium chloride, and causticizing the purified barium chloride,
The α-dose of the massive crushed ore is measured to sort out the massive crushed ore with a small α-dose, and the thus-selected massive crushed ore with a small amount of α-ray emission is pulverized into a fine ore to reduce the α. A method for producing barium hydroxide linear.
前記塊状破砕鉱から放出されるα線量を測定してα線量の少ない塊状破砕鉱を選別し、この選別されたα線量の少ない塊状破砕鉱を粉砕して粉鉱とすることを特徴とする低α線炭酸バリウムの製造方法。The ore raw material ore is crushed into a massive crushed ore, the crushed ore is crushed into a fine ore, and this fine ore is flotated to remove the host rock and gangue to a concentrate, which is then concentrated. Barium chloride is purified by dissolving it in hydrochloric acid, crystallizing to purify barium chloride, causticizing the purified barium chloride to produce barium hydroxide, and once converting this barium hydroxide into a solution, carbonate or carbonate. In a method for producing barium carbonate by reacting with a gas,
Measuring the α-dose released from the massive crushed ore to sort out the massive crushed ore with a small α-dose, and pulverizing the selected massive crushed ore with a small α-dose into fine ore; Method for producing α-ray barium carbonate.
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| CN107662937A (en) * | 2016-07-29 | 2018-02-06 | 中国科学院大连化学物理研究所 | A kind of order mesoporous barium hydroxide catalyst and its application in the preparation of the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 |
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| CN102583488B (en) * | 2012-03-30 | 2014-04-09 | 贵州红星发展股份有限公司 | Method for producing low-strontium high-purity barium chloride and low-strontium high-purity barium chloride |
| WO2017111145A1 (en) | 2015-12-25 | 2017-06-29 | 堺化学工業株式会社 | LOW α-RAY BARIUM SULFATE PARTICLES, USE METHOD THEREFOR, AND PRODUCTION METHOD THEREFOR |
| KR102571368B1 (en) | 2015-12-25 | 2023-08-25 | 사까이가가꾸고오교가부시끼가이샤 | Low α-dose barium sulfate particles and their use and manufacturing method |
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| CN107662937A (en) * | 2016-07-29 | 2018-02-06 | 中国科学院大连化学物理研究所 | A kind of order mesoporous barium hydroxide catalyst and its application in the preparation of the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 |
| CN107662937B (en) * | 2016-07-29 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of order mesoporous barium hydroxide catalyst and its application in the preparation of 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate |
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