JP3591756B2 - Production method of metal fluoride - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、金属フッ化物、特に高純度金属フッ化物の製造方法、更に詳細には光増幅器用高純度フッ化物原料の製造方法に関する。
【０００２】
【従来の技術】
ＺｒＦ４ 、ＨｆＦ４ 、ＬａＦ３ 、ＹＦ３ 、ＺｎＦ２ 、ＣｄＦ２ 、ＩｎＦ３ は光増幅器用フッ化物光ファイバの構成原料である。フッ化物光ファイバによる光増幅を阻害する要因として光ファイバ中に混入しているＦｅ、Ｃｕ、Ｎｉなどの遷移金属の不純物及び酸素不純物が挙げられる。これらの遷移金属及び酸素は構成原料中に不純物として存在しており、フッ化物光ファイバの光増幅には遷移金属の不純物濃度が１ｐｐｂ以下、酸素の不純物濃度が１ｐｐｍ以下の高純度金属フッ化物の作製が不可欠である。
従来、これらのフッ化物光ファイバ原料の製造方法については、金属、酸化物、炭酸塩などを出発物質とし、金属や酸化物については、該金属や該酸化物をＦ２ ガスあるいはＨＦガスと直接反応させ、金属フッ化物とする製造方法、炭酸塩については、該炭酸塩にフッ化水素酸を添加し、金属フッ化物の水和物を製造する方法などがある。例えば、金属、酸化物を出発物質とする例としては、ＺｒにＦ２ ガスを１９０℃で反応させ、ＺｒＦ４ を製造する方法、ＺｒＯ２ にＦ２ ガスを５２５℃で反応させ、ＺｒＦ４ を製造する方法、ＺｒＯ２ にＨＦガスを５５０℃で反応させ、ＺｒＦ４ を製造する方法、又は、Ｉｎを容器に入れた後、減圧し、ＨＦガスを容器に送入し、２００℃で反応させ、ＩｎＦ３ を製造する方法などがある。これらの方法で製造したＺｒＦ４ 又はＩｎＦ３ については、Ｆ２ ガス又はＨＦガスを高温で取り扱う危険が伴うことが欠点である。次に、炭酸塩を出発物質とする例としては、試薬特級品のＺｎＣＯ３ に熱フッ化水素酸を添加し、蒸発、濃縮後、ＺｎＦ２ ・４Ｈ２ Ｏとし、乾燥フッ化水素ガスにより、３００℃で加熱脱水し、ＺｎＦ２ とする製造方法がある。この方法で作製したＺｎＦ２ については、出発物質のＺｎＣＯ３ が未溶解のためにＣＯ２ が残留したり、３００℃で脱水・乾燥することによって酸化物が発生し、ＣＯ２ や酸化物がフッ化物光ファイバの損失増の要因となり、更には光増幅を阻害する欠点がある。
また、出発物質の炭酸塩の純度については、せいぜい５Ｎ（９９．９９９％）程度であり、フッ化水素酸との反応工程では精製は行われないため、製造したＺｎＦ２ 中の遷移金属の不純物濃度は１ｐｐｍ以上、酸素の不純物濃度は１０ｐｐｍ以上と推定され、これについてもフッ化物光ファイバの損失増となる。更に、高純度フッ化亜鉛の製造方法として、亜鉛の水溶性塩を出発物質としてｐＨを調整した後、金属不純物の抽出有機試薬としてβ−ジケトンを使用して金属不純物を除去する精製法が提案されている（特願平５−４９８９９号）が、この方法では酸素不純物の除去ができないことに問題がある。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、出発物質にＦｅ、Ｎｉ、Ｃｕなどの遷移金属の不純物及び酸素不純物を除去した金属を使用することにより、上述の欠点を解決し、金属フッ化物、特に高純度の金属フッ化物を製造する方法を提供することにある。
【０００４】
【課題を解決するための手段】
本発明を概説すれば、本発明は金属フッ化物の製造方法に関する発明であって、金属フッ化物を製造する方法において、出発物質として高純度の金属を使用し、β−ジケトン処理をすることなく、該高純度金属を、酸化剤を含むフッ化水素酸溶液内で加熱し、該高純度金属を、溶解させ、その後、該酸化剤を含むフッ化水素酸溶液を冷却し、金属フッ化物沈殿を作製し、更に該沈殿物を脱水、乾燥処理することを特徴とする。
【０００５】
本発明は、従来技術のＺｒにＦ２ ガスを１９０℃で反応させＺｒＦ４ を製造する方法、ＺｒＯ２ にＦ２ ガスを５２５℃で反応させＺｒＦ４ を製造する方法、ＺｒＯ２ にＨＦガスを５５０℃で反応させＺｒＦ４ を製造する方法、Ｉｎを容器に入れた後、ＨＦガスで反応させ、ＩｎＦ３ を製造する方法、ＺｎＣＯ３ に熱フッ化水素酸を添加し、ＺｎＦ２ ・４Ｈ２ Ｏとし、乾燥ＨＦガスにより、ＺｎＦ２ とする製造方法、亜鉛塩の水溶液にＮａＦ水溶液を添加し、ＺｎＦ２ ・４Ｈ２ Ｏを生成後、脱水・加熱乾燥後、フッ化亜鉛を製造する方法、抽出有機試薬としてβ−ジケトンを添加して亜鉛を含む水溶液中の遷移金属不純物を抽出除去する精製法などの問題点を解決するために、Ｆｅ、Ｎｉ、Ｃｕなどの遷移金属不純物、及び酸素不純物の少ない高純度金属を出発物質に使用し、酸化剤を含むフッ化水素酸で溶解後、金属フッ化物の沈殿を作製し、沈殿物の脱水・乾燥を行い、遷移金属不純物及び酸素不純物の少ない金属フッ化物、特に高純度の金属フッ化物を製造するものである。
【０００６】
【発明の実施の形態】
以下、本発明を具体的に説明する。
本発明方法において原料として使用する金属の例としては、Ｚｒ、Ｈｆ、Ｌａ、Ｙ、Ｚｎ、Ｃｄ、Ｉｎ等が挙げられるが、中でもその用途上、高純度のＺｒ、Ｈｆ、又はＬａが有用である。高純度の程度は、６Ｎ〜７Ｎが好ましい。
【０００７】
次に、本発明方法において、フッ化水素酸に含有させる酸化剤の例としては通常の各種の酸化剤が挙げられるが、中でも、過酸化水素水、硝酸、又は過塩素酸が好適なものである。
加熱溶解は特殊な条件を必要とせず、当該金属を加熱により溶液中に溶解できる条件であればよい。したがって、従来法におけるような高温加熱を必要としない。
次に、脱水も常用の方法でよく、操作上、吸引ろ過が好適である。
最後に、乾燥も常用の方法でよく、操作上、真空乾燥が好適である。
【０００８】
以上具体的に説明したように、本発明方法において、特に高純度の金属フッ化物を製造する方法の場合には、従来技術の金属の酸化物、炭酸塩、金属塩の水溶液などを出発物質とする高純度フッ化物の製造方法とは、高純度金属を出発物質とし、酸化剤とフッ素化剤を加え、高純度の金属フッ化物を製造する点で異なる。また、抽出有機試薬としてβ−ジケトンを添加して金属不純物を除去する精製法とは製造方法に精製工程がない点が異なる。
【０００９】
【実施例】
以下、本発明を実施例により更に具体的に説明するが、本発明はこれら実施例に限定されない。
【００１０】
実施例１
純度：７Ｎ（９９．９９９９９％）の金属亜鉛を出発物質とする高純度無水フッ化亜鉛の製造方法について、図１に示す工程図によって説明する。高純度金属亜鉛５０ｇを秤量し、電子工業用の３０％過酸化水素水５０ｍｌとフッ化水素酸２００ｍｌと超純水２００ｍｌを加え、加熱し、溶解する。溶解後、冷却し、フッ化亜鉛沈殿物を得る。フッ化亜鉛沈殿物は、吸引ろ過で脱水し、真空乾燥を行う。図２は、フッ化亜鉛沈殿物を脱水・乾燥した物質、すなわち、ＺｎＦ２ のＴＧ（熱重量分析）−ＤＴＡ（示差熱分析）曲線である。また、図３は、市販品の純度９９．９％のＺｎＦ２ ・４Ｈ２ ＯのＴＧ−ＤＴＡ曲線である。
なお、図２及び図３において、横軸は温度（℃）、左縦軸はＴＧにおける重量減少率（％）、右縦軸はＤＴＡにおける熱容量（μＶ）を意味する。
図３から、１１０℃付近の脱水による吸熱ピーク、８７２℃のＺｎＦ２ の融点による吸熱ピークは観察されたが、図２には、８７２℃のＺｎＦ２ の融点による吸熱ピーク以外に吸熱ピークは観察されかった。すなわち、Ｘ線回折（ＸＲＤ）及び熱分析（ＴＧ−ＤＴＡ）での解析結果より、作製した物質は、無水のＺｎＦ２ である。
【００１１】
また、作製した無水のフッ化亜鉛のＦｅ、Ｎｉ、Ｃｕ、酸素の放射化分析を行い、Ｆｅ、Ｎｉ、Ｃｕについて１ｐｐｂ、酸素について１ｐｐｍの分析結果が得られ、従来、行われていたフッ化亜鉛についてのＦｅ、Ｎｉ、Ｃｕ不純物濃度の定量値よりも３桁、酸素不純物濃度の定量値よりも１桁ほど高純度の無水のフッ化亜鉛が作製できた。
【００１２】
実施例２
純度：７Ｎ（９９．９９９９９％）の金属亜鉛を出発物質とする高純度の無水フッ化亜鉛の製造方法について、図４に示す工程図によって説明する。高純度金属亜鉛５０ｇを秤量し、電子工業用の６１％硝酸１００ｍｌとフッ化水素酸２００ｍｌと超純水２００ｍｌを加え、加熱し、溶解する。溶解後、冷却し、フッ化亜鉛沈殿物を得る。フッ化亜鉛沈殿物は、吸引ろ過で脱水し、真空乾燥を行う。乾燥後のフッ化亜鉛沈殿物のＴＧ−ＤＴＡ曲線及び赤外吸収（ＩＲ）スペクトルの解析結果には、何ら、ＮＯｘに相当するピークは観察されなかった。ＺｎＦ２ 作製物のＴＧ−ＤＴＡ曲線は図２に示すものと同じであり、ＸＲＤの結果から、無水のＺｎＦ２ が作製できていることが明らかになった。
また、作製した無水のフッ化亜鉛中のＦｅ、Ｎｉ、Ｃｕ、酸素の放射化分析を行い、Ｆｅ、Ｎｉ、Ｃｕについて１ｐｐｂ、酸素について１ｐｐｍの分析結果が得られ、従来、行われていたフッ化亜鉛についてのＦｅ、Ｎｉ、Ｃｕ不純物濃度の定量値よりも３桁、酸素不純物濃度の定量値よりも１桁ほど高純度の無水のフッ化亜鉛が作製できた。
【００１３】
実施例３
純度：７Ｎ（９９．９９９９９％）の金属亜鉛を出発物質とする高純度の無水フッ化亜鉛の製造方法について、図５に示す工程図によって説明する。高純度金属亜鉛５０ｇを秤量し、高純度の精密分析用の６０％過塩素酸（ＨＣｌＯ４ ）２００ｍｌとフッ化水素酸２００ｍｌと超純水２００ｍｌを加え、加熱し、溶解する。溶解後、冷却し、フッ化亜鉛沈殿物を得る。フッ化亜鉛沈殿物は、吸引ろ過で脱水し、真空乾燥を行う。乾燥後のフッ化亜鉛沈殿物のＴＧ−ＤＴＡ曲線及びＩＲスペクトルの解析結果には、何ら、Ｈ２ Ｏ、ＣｌあるいはＣｌＯ４ に相当するピークは観察されなかった。また、ＸＲＤによる解析より、乾燥後のフッ化亜鉛沈殿物はＺｎＦ２ であることがわかった。また、ＺｎＦ２ 作製物のＴＧ−ＤＴＡ曲線は図２に示すものと同じである。
作製した無水のフッ化亜鉛中のＦｅ、Ｎｉ、Ｃｕ、酸素の放射化分析を行い、Ｆｅ、Ｎｉ、Ｃｕについて１ｐｐｂ、酸素について１ｐｐｍの分析結果が得られ、従来、行われていたフッ化亜鉛についてのＦｅ、Ｎｉ、Ｃｕ不純物濃度の定量値よりも３桁、酸素不純物濃度の定量値よりも１桁ほど高純度の無水のフッ化亜鉛が作製できた。
【００１４】
実施例４
純度：６Ｎ（９９．９９９９％）の金属ジルコニウム（以下Ｚｒと記す）を出発物質とする高純度の無水フッ化ジルコニウム（ＺｒＦ４ ）の製造方法について、図６に示す工程図によって説明する。高純度Ｚｒ５０ｇを秤量し、高純度の精密分析用の６０％過塩素酸（ＨＣｌＯ４ ）２００ｍｌとフッ化水素酸２００ｍｌと超純水２００ｍｌを加え、加熱し、溶解する。溶解後、冷却し、フッ化ジルコニウム沈殿物を得る。フッ化ジルコニウム沈殿物は、吸引ろ過で脱水後、高真空で乾燥を行う。また、ＸＲＤによる解析より、乾燥後のフッ化ジルコニウム沈殿物は無水のＺｒＦ４ であることがわかった。
また、６Ｎ（９９．９９９９％）の金属ハフニウム（Ｈｆ）を出発物質とする高純度の無水のフッ化ハフニウム（ＨｆＦ４ ）の製造方法についても無水のＺｒＦ４ 製造と同じ方法で作製できる。更に、酸化剤として硝酸又は過酸化水素水を用いても同一の無水ＺｒＦ４ 又は無水ＨｆＦ４ が作製できる。
作製したＺｒＦ４ 及びＨｆＦ４ 中のＦｅ、Ｎｉ、Ｃｕ、酸素の放射化分析を行い、Ｆｅ、Ｎｉ、Ｃｕについて１ｐｐｂ、酸素について１ｐｐｍの分析結果が得られ、従来、行われていたＺｒＦ４ 及びＨｆＦ４ についてのＦｅ、Ｎｉ、Ｃｕ不純物濃度の定量値よりも３桁、酸素不純物濃度の定量値よりも１桁ほど高純度の無水ＺｒＦ４ 及び無水ＨｆＦ４ が作製できた。
【００１５】
実施例５
純度：６Ｎ（９９．９９９９％）の金属ランタン（Ｌａ）を出発物質とする高純度の無水フッ化ランタンの製造方法について、図７に示す工程図によって説明する。高純度金属ランタン５０ｇを秤量し、電子工業用の３０％過酸化水素水（Ｈ２ Ｏ２ ）５０ｍｌとフッ化水素酸２００ｍｌと超純水２００ｍｌを加え、加熱し、溶解する。溶解後、冷却した後、フッ化ランタン沈殿物は吸引ろ過で脱水し、真空乾燥を行う。また、ＬａＦ３ のＴＧ−ＤＴＡ曲線からは、何ら、Ｈ２ Ｏに相当するピークは観察されなかった。また、ＸＲＤでの解析結果より、真空乾燥後に作製した物質は無水のＬａＦ３ であることがわかった。
また、６Ｎ（９９．９９９９％）の金属イットリウム（Ｙ）を出発物質とする高純度の無水フッ化イットリウム（ＹＦ３ ）の製造方法についてもＬａＦ３ 製造と同じ方法で作製できる。更に、酸化剤として硝酸又は過塩素酸を用いても同一の無水ＬａＦ３ 又は無水ＹＦ３ が作製できる。
作製したフッ化ランタン（ＬａＦ３ ）とフッ化イットリウム（ＹＦ３ ）中のＦｅ、Ｎｉ、Ｃｕ、酸素の放射化分析を行い、Ｆｅ、Ｎｉ、Ｃｕについて１ｐｐｂ、酸素について１ｐｐｍの分析結果が得られ、従来、行われていたＬａＦ３ 、ＹＦ３ についてのＦｅ、Ｎｉ、Ｃｕ不純物濃度の定量値よりも３桁、酸素不純物濃度の定量値よりも１桁ほど高純度の無水ＬａＦ３ 、無水ＹＦ３ が作製できた。
【００１６】
実施例６
純度：７Ｎ（９９．９９９９９％）の金属インジウムを出発物質とする高純度のフッ化インジウム（ＩｎＦ３ ・３Ｈ２ Ｏ）の製造方法について、図８に示す工程図によって説明する。高純度金属インジウム５０ｇを秤量し、高純度の電子工業用の６１％硝酸（ＨＮＯ３ ）１００ｍｌとフッ化水素酸２００ｍｌと超純水２００ｍｌを加え、加熱し、溶解する。溶解後、冷却し、フッ化インジウム沈殿物を得る。沈殿物は、吸引ろ過で脱水し、真空乾燥を行う。乾燥後に作製した物質、すなわち、ＩｎＦ３ ・３Ｈ２ ＯのＴＧ−ＤＴＡ曲線には、何ら、ＮＯｘに相当するピークは観察されなかった。また、ＸＲＤによる解析より、再結晶後に作製した物質はＩｎＦ３ ・３Ｈ２ Ｏであることがわかった。更に、酸化剤として過酸化水素水又は過塩素酸を用いても同一のＩｎＦ３ ・３Ｈ２ Ｏが作製できる。
作製したＩｎＦ３ ・３Ｈ２ Ｏ中のＦｅ、Ｎｉ、Ｃｕ、酸素の放射化分析を行い、Ｆｅ、Ｎｉ、Ｃｕについて１ｐｐｂ、酸素について１ｐｐｍの分析結果が得られ、従来、行われていたＩｎＦ３ ・３Ｈ２ ＯのＦｅ、Ｎｉ、Ｃｕ不純物濃度の定量値よりも３桁、酸素不純物濃度の定量値よりも１桁ほど高純度のＩｎＦ３ ・３Ｈ２ Ｏが作製できた。
【００１７】
実施例７
純度：６Ｎ（９９．９９９９％）の金属カドミウムを出発物質とする高純度の無水フッ化カドミウムの製造方法について、図９に示す工程図によって説明する。高純度金属カドミウム５０ｇを秤量し、高純度の精密分析用の６０％過塩素酸（ＨＣｌＯ４ ）２００ｍｌとフッ化水素酸２００ｍｌと超純水２００ｍｌを加え、加熱し、溶解する。溶解後、冷却し、フッ化カドミウム沈殿物を得る。フッ化カドミウム沈殿物は、吸引ろ過で脱水し、真空乾燥を行う。乾燥後に作製した物質、すなわち、ＣｄＦ２ のＴＧ−ＤＴＡ曲線及びＩＲスペクトルには、何ら、Ｈ２ Ｏ、ＣｌあるいはＣｌＯ４ に相当するピークは観察されなかった。また、ＸＲＤによる解析より、乾燥後に作製した物質はＣｄＦ２ であることがわかった。
更に、酸化剤として硝酸又は過酸化水素水を用いても同一のＣｄＦ２ が製造できる。
作製したフッ化カドミウム中のＦｅ、Ｎｉ、Ｃｕ、酸素の放射化分析を行い、Ｆｅ、Ｎｉ、Ｃｕについて１ｐｐｂ、酸素について１ｐｐｍの分析結果が得られ、従来、行われていたフッ化カドミウムについてのＦｅ、Ｎｉ、Ｃｕ不純物濃度の定量値よりも３桁、酸素不純物濃度の定量値よりも１桁ほど高純度の無水ＣｄＦ２ が作製できた。
【００１８】
【発明の効果】
以上説明したように、本発明の製造方法によれば、無水あるいは水和物を含む金属フッ化物を作製できる。特に、無水のＺｎＦ２ 、ＺｒＦ４ 、ＨｆＦ４ 、ＬａＦ３ 、ＹＦ３ 、ＣｄＦ２ は、従来の３００℃〜６００℃でＨＦガスにより脱水・乾燥し、無水の金属フッ化物とするものに比べ、極めて簡便に無水の金属フッ化物を作製するものであるから、高温で熱処理することによって発生する酸化物を抑え、しかも、遷移金属を極低濃度にした高純度の無水フッ化物を製造することができるものである。更に、これをフッ化物光ファイバアンプの出発物質として用いることにより、増幅度の高い光ファイバアンプを製造できる利点がある。
【図面の簡単な説明】
【図１】本発明の実施例１における高純度の無水フッ化亜鉛の製造方法を示す工程図でである。
【図２】本発明の実施例１により作製したＺｎＦ２ のＴＧ−ＤＴＡ曲線を示すグラフである。
【図３】市販品のＺｎＦ２ ・４Ｈ２ ＯのＴＧ−ＤＴＡ曲線を示すグラフである。
【図４】本発明の実施例２における高純度の無水フッ化亜鉛の製造方法を示す工程図である。
【図５】本発明の実施例３における高純度の無水フッ化亜鉛の製造方法を示す工程図である。
【図６】本発明の実施例４における高純度の無水フッ化ジルコニウム（ＺｒＦ４ ）の製造方法を示す工程図である。
【図７】本発明の実施例５における高純度の無水フッ化ランタン（ＬａＦ３ ）の製造方法を示す工程図である。
【図８】本発明の実施例６における高純度のフッ化インジウム（ＩｎＦ３ ・３Ｈ２ Ｏ）の製造方法を示す工程図である。
【図９】本発明の実施例７における高純度の無水フッ化カドミウムの製造方法を示す工程図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a metal fluoride, particularly a high-purity metal fluoride, and more particularly to a method for producing a high-purity fluoride raw material for an optical amplifier.
[0002]
[Prior art]
ZrF 4 , HfF 4 , LaF 3 , YF 3 , ZnF 2 , CdF 2 , and InF 3 are constituent materials of a fluoride optical fiber for an optical amplifier. Factors inhibiting optical amplification by the fluoride optical fiber include impurities of transition metals such as Fe, Cu, and Ni and oxygen impurities mixed in the optical fiber. These transition metals and oxygen are present as impurities in the constituent materials. For optical amplification of the fluoride optical fiber, high-purity metal fluoride having a transition metal impurity concentration of 1 ppb or less and an oxygen impurity concentration of 1 ppm or less is used. Fabrication is essential.
Conventionally, in the production method of these fluoride optical fiber raw materials, metals, oxides, carbonates, and the like are used as starting materials. For metals and oxides, the metals and the oxides are directly mixed with F 2 gas or HF gas. Regarding a production method and a carbonate which are reacted to form a metal fluoride, there is a method in which hydrofluoric acid is added to the carbonate to produce a hydrate of the metal fluoride. For example, a metal, examples of the starting material an oxide, an F 2 gas is reacted at 190 ° C. to Zr, a method of manufacturing a ZrF 4, reacted at 525 ° C. The F 2 gas to ZrO 2, the ZrF 4 A method of producing, a method of reacting HF gas with ZrO 2 at 550 ° C., or a method of producing ZrF 4 , or putting In into a container, reducing the pressure, sending HF gas into the container, and reacting at 200 ° C. , InF 3 and the like. A disadvantage of ZrF 4 or InF 3 produced by these methods is that there is a danger of handling F 2 gas or HF gas at a high temperature. Next, examples of the starting material carbonate, heat hydrofluoric acid was added to ZnCO 3 reagent special grade, evaporated, concentrated, and ZnF 2 · 4H 2 O, drying hydrogen fluoride gas, There is a production method of heating and dehydrating at 300 ° C. to obtain ZnF 2 . For ZnF 2 produced by this method, an oxide is generated by the ZnCO 3 starting materials CO 2 is or remains for undissolved, dehydrated and dried at 300 ° C., CO 2 and oxides fluoride This has the disadvantage of increasing the loss of the compound optical fiber, and further impeding the optical amplification.
As for the purity of the carbonate of the starting material is at most 5N (99.999%) or so, since the purification is in the step of the reaction with hydrofluoric acid is not performed, the impurity of the transition metal in ZnF 2 produced The concentration is estimated to be 1 ppm or more, and the impurity concentration of oxygen is estimated to be 10 ppm or more, which also increases the loss of the fluoride optical fiber. Furthermore, as a method for producing high-purity zinc fluoride, a purification method in which a pH is adjusted using a water-soluble salt of zinc as a starting material, and metal impurities are removed using β-diketone as an organic reagent for extracting metal impurities is proposed. However, this method has a problem in that oxygen impurities cannot be removed by this method.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned disadvantages by using a metal from which impurities of transition metals such as Fe, Ni, and Cu and oxygen impurities have been removed as a starting material, and to solve the above-mentioned metal fluorides, particularly high-purity metal fluorides. It is an object of the present invention to provide a method for producing a compound.
[0004]
[Means for Solving the Problems]
To summarize the present invention, the present invention relates to a method for producing a metal fluoride, and in a method for producing a metal fluoride, a high-purity metal is used as a starting material , without performing a β-diketone treatment. , the high-purity metal, and heated in a hydrofluoric acid solution containing an oxidizing agent, the high-purity metal, lysed, then cooled hydrofluoric acid solution containing the oxidizing agent, metal fluoride It is characterized in that a precipitate is produced, and the precipitate is subjected to a dehydration and drying treatment.
[0005]
The present invention relates to a method for producing a ZrF 4 by reacting F 2 gas at 190 ° C. to Zr in the prior art, a method of manufacturing a ZrF 4 was reacted at 525 ° C. The F 2 gas to ZrO 2, the HF gas into ZrO 2 method of making a ZrF 4 was reacted at 550 ° C., after putting the in the vessel, is reacted with HF gas, a method of manufacturing a InF 3, heat hydrofluoric acid was added to ZnCO 3, ZnF 2 · 4H 2 O, and a method of producing ZnF 2 by dry HF gas, a method of adding a NaF aqueous solution to an aqueous solution of a zinc salt, generating ZnF 2 .4H 2 O, dehydrating and heating and drying, and then producing zinc fluoride. In order to solve problems such as a purification method of extracting and removing transition metal impurities in an aqueous solution containing zinc by adding β-diketone as an extraction organic reagent, transition metal impurities such as Fe, Ni, and Cu, and oxygen impurities Low-purity metal is used as a starting material, dissolved in hydrofluoric acid containing an oxidizing agent, and then a precipitate of metal fluoride is prepared, and the precipitate is dehydrated and dried to reduce transition metal impurities and oxygen impurities. It is for producing metal fluorides, especially high-purity metal fluorides.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically.
Examples of the metal used as a raw material in the method of the present invention include Zr, Hf, La, Y, Zn, Cd, In, and the like. Among them, high-purity Zr, Hf, or La is useful. is there. The degree of high purity is preferably 6N to 7N.
[0007]
Next, in the method of the present invention, examples of the oxidizing agent to be contained in hydrofluoric acid include various various oxidizing agents. Among them, aqueous hydrogen peroxide, nitric acid, or perchloric acid is preferable. is there.
Heating dissolution does not require special conditions, and may be any condition that allows the metal to be dissolved in the solution by heating. Therefore, high-temperature heating as in the conventional method is not required.
Next, dehydration may be performed by a conventional method, and suction filtration is preferable in operation.
Lastly, drying may be performed by a conventional method, and vacuum drying is preferable in operation.
[0008]
As specifically described above, in the method of the present invention, particularly in the case of a method for producing a high-purity metal fluoride, a metal oxide, a carbonate, and an aqueous solution of a metal salt of the related art are used as starting materials. This is different from the method of producing a high-purity fluoride in that a high-purity metal is used as a starting material, and an oxidizing agent and a fluorinating agent are added to produce a high-purity metal fluoride. Further, it differs from the purification method in which β-diketone is added as an extraction organic reagent to remove metal impurities in that the production method has no purification step.
[0009]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0010]
Example 1
A method for producing high-purity anhydrous zinc fluoride using 7N (99.999999%) metallic zinc as a starting material will be described with reference to the process chart shown in FIG. 50 g of high-purity metallic zinc is weighed, and 50 ml of 30% hydrogen peroxide solution for electronic industry, 200 ml of hydrofluoric acid and 200 ml of ultrapure water are added, heated and dissolved. After dissolution, the mixture is cooled to obtain a zinc fluoride precipitate. The zinc fluoride precipitate is dehydrated by suction filtration and dried under vacuum. 2, zinc fluoride precipitate material was dehydrated and dried, i.e., ZnF 2 of TG (thermogravimetric analysis) -DTA (differential thermal analysis) is a curve. FIG. 3 is a TG-DTA curve of a commercially available ZnF 2 .4H 2 O having a purity of 99.9%.
In FIGS. 2 and 3, the horizontal axis represents temperature (° C.), the left vertical axis represents weight loss rate (%) in TG, and the right vertical axis represents heat capacity (μV) in DTA.
From FIG. 3, an endothermic peak due to dehydration around 110 ° C. and an endothermic peak due to the melting point of ZnF 2 at 872 ° C. were observed, but in FIG. 2, an endothermic peak other than the endothermic peak due to the melting point of ZnF 2 at 872 ° C. was observed. It was not done. That is, from the results of analysis by X-ray diffraction (XRD) and thermal analysis (TG-DTA), the produced substance is anhydrous ZnF 2 .
[0011]
Further, activation analysis of Fe, Ni, Cu, and oxygen of the produced anhydrous zinc fluoride was performed, and analysis results of 1 ppb for Fe, Ni, and Cu and 1 ppm for oxygen were obtained. Anhydrous zinc fluoride with a high purity of about three orders of magnitude more than the quantitative value of the impurity concentration of Fe, Ni, and Cu and about one digit than the quantitative value of the oxygen impurity concentration of zinc could be produced.
[0012]
Example 2
A method for producing high-purity anhydrous zinc fluoride using 7N (99.999999%) metallic zinc as a starting material will be described with reference to the process chart shown in FIG. 50 g of high-purity metallic zinc is weighed, 100 ml of 61% nitric acid for electronic industry, 200 ml of hydrofluoric acid and 200 ml of ultrapure water are added, heated and dissolved. After dissolution, the mixture is cooled to obtain a zinc fluoride precipitate. The zinc fluoride precipitate is dehydrated by suction filtration and dried under vacuum. In the analysis results of the TG-DTA curve and the infrared absorption (IR) spectrum of the dried zinc fluoride precipitate, no peak corresponding to NOx was observed. The TG-DTA curve of the ZnF 2 preparation was the same as that shown in FIG. 2, and the result of XRD revealed that anhydrous ZnF 2 could be prepared.
Activation analysis of Fe, Ni, Cu, and oxygen in the produced anhydrous zinc fluoride was performed, and an analysis result of 1 ppb for Fe, Ni, and Cu and 1 ppm for oxygen was obtained. Anhydrous zinc fluoride having a purity of about three orders of magnitude higher than the quantitative value of the Fe, Ni, and Cu impurity concentrations and approximately one order of magnitude higher than the quantitative value of the oxygen impurity concentration of zinc oxide was produced.
[0013]
Example 3
A method for producing high-purity anhydrous zinc fluoride using 7N (99.999999%) metallic zinc as a starting material will be described with reference to the process chart shown in FIG. 50 g of high-purity metallic zinc is weighed, and 200 ml of 60% perchloric acid (HClO 4 ), 200 ml of hydrofluoric acid, and 200 ml of ultrapure water for precision analysis of high purity are added, and heated to dissolve. After dissolution, the mixture is cooled to obtain a zinc fluoride precipitate. The zinc fluoride precipitate is dehydrated by suction filtration and dried under vacuum. In the analysis results of the TG-DTA curve and the IR spectrum of the dried zinc fluoride precipitate, no peak corresponding to H 2 O, Cl or ClO 4 was observed. XRD analysis also showed that the zinc fluoride precipitate after drying was ZnF 2 . In addition, the TG-DTA curve of the ZnF 2 product is the same as that shown in FIG.
Activation analysis of Fe, Ni, Cu, and oxygen in the produced anhydrous zinc fluoride was performed, and analysis results of 1 ppb for Fe, Ni, and Cu and 1 ppm for oxygen were obtained. Thus, anhydrous zinc fluoride having a purity of about three orders of magnitude higher than the quantitative values of the Fe, Ni, and Cu impurity concentrations and one order of magnitude higher than the quantitative values of the oxygen impurity concentrations was obtained.
[0014]
Example 4
A method for producing high-purity anhydrous zirconium fluoride (ZrF 4 ) starting from metal zirconium having a purity of 6N (99.9999%) (hereinafter referred to as Zr) will be described with reference to the process chart shown in FIG. 50 g of high-purity Zr is weighed, and 200 ml of 60% perchloric acid (HClO 4 ), 200 ml of hydrofluoric acid, and 200 ml of ultrapure water for high-purity precision analysis are added, heated and dissolved. After dissolution, the mixture is cooled to obtain a zirconium fluoride precipitate. The zirconium fluoride precipitate is dried under a high vacuum after dehydration by suction filtration. Further, analysis by XRD showed that the dried zirconium fluoride precipitate was anhydrous ZrF 4 .
Also, a method for producing high-purity anhydrous hafnium fluoride (HfF 4 ) using 6N (99.9999%) metal hafnium (Hf) as a starting material can be produced by the same method as that for producing anhydrous ZrF 4 . Furthermore, the same anhydrous ZrF 4 or anhydrous HfF 4 can be produced even if nitric acid or aqueous hydrogen peroxide is used as the oxidizing agent.
Performs Fe of ZrF 4 and HfF 4 produced, Ni, Cu, oxygen activation analysis, Fe, Ni, Cu for 1 ppb, 1 ppm results of analyzes oxygen is obtained, conventionally, ZrF 4 and has been carried out With respect to HfF 4 , anhydrous ZrF 4 and anhydrous HfF 4 having a purity higher by about three orders of magnitude than the quantitative values of the Fe, Ni, and Cu impurity concentrations and by approximately one digit than the quantitative values of the oxygen impurity concentrations were produced.
[0015]
Example 5
A method for producing high-purity anhydrous lanthanum fluoride starting from metal lanthanum (La) having a purity of 6N (99.9999%) will be described with reference to the process chart shown in FIG. 50 g of high-purity metal lanthanum is weighed, and 50 ml of 30% aqueous hydrogen peroxide (H 2 O 2 ), 200 ml of hydrofluoric acid, and 200 ml of ultrapure water for electronic industry are added, heated and dissolved. After dissolving and cooling, the lanthanum fluoride precipitate is dehydrated by suction filtration and vacuum dried. No peak corresponding to H 2 O was observed from the TG-DTA curve of LaF 3 . In addition, the result of XRD analysis revealed that the substance prepared after vacuum drying was anhydrous LaF 3 .
A method for producing high-purity anhydrous yttrium fluoride (YF 3 ) using 6N (99.9999%) metal yttrium (Y) as a starting material can be produced by the same method as that for producing LaF 3 . Further, even when nitric acid or perchloric acid is used as an oxidizing agent, the same anhydrous LaF 3 or anhydrous YF 3 can be produced.
Activation analysis of Fe, Ni, Cu, and oxygen in the produced lanthanum fluoride (LaF 3 ) and yttrium fluoride (YF 3 ) was performed, and analysis results of 1 ppb for Fe, Ni, and Cu and 1 ppm for oxygen were obtained. Conventionally, LaF 3 and YF 3 have high purity of anhydrous LaF 3 and anhydrous YF 3 which are three orders of magnitude higher than the quantitative values of Fe, Ni and Cu impurity concentrations and approximately one order of magnitude higher than the quantitative values of oxygen impurity concentrations for LaF 3 and YF 3. Was produced.
[0016]
Example 6
A method for producing high-purity indium fluoride (InF 3 .3H 2 O) starting from metal indium having a purity of 7N (99.999999%) will be described with reference to the process chart shown in FIG. 50 g of high-purity metal indium is weighed, and 100 ml of high-
Performs Fe of InF 3 · 3H 2 in O produced, Ni, Cu, oxygen activation analysis, Fe, Ni, Cu for 1 ppb, 1 ppm results of analyzes oxygen is obtained, conventionally, InF 3 which has performed with · 3H 2 O of Fe, Ni, 3 orders of magnitude than the quantitative value of Cu impurity concentration, InF 3 · 3H 2 O as 1 digit higher purity than quantitative value of the oxygen impurity concentration could be produced.
[0017]
Example 7
A method for producing high-purity anhydrous cadmium fluoride starting from cadmium metal having a purity of 6N (99.9999%) will be described with reference to the process chart shown in FIG. 50 g of high-purity metal cadmium is weighed, and 200 ml of 60% perchloric acid (HClO 4 ), 200 ml of hydrofluoric acid, and 200 ml of ultrapure water for precision analysis of high purity are added, and heated to dissolve. After dissolution, the mixture is cooled to obtain a cadmium fluoride precipitate. The cadmium fluoride precipitate is dehydrated by suction filtration and vacuum dried. No peak corresponding to H 2 O, Cl or ClO 4 was observed in the TG-DTA curve and IR spectrum of the substance prepared after drying, ie, CdF 2 . In addition, XRD analysis revealed that the substance prepared after drying was CdF 2 .
Furthermore, the same CdF 2 can be produced even if nitric acid or aqueous hydrogen peroxide is used as the oxidizing agent.
Activation analysis of Fe, Ni, Cu, and oxygen in the produced cadmium fluoride was performed, and an analysis result of 1 ppb for Fe, Ni, and Cu and 1 ppm for oxygen was obtained. Anhydrous CdF 2 having a purity of about three orders of magnitude higher than the quantitative values of the Fe, Ni, and Cu impurity concentrations and one order of magnitude higher than the quantitative values of the oxygen impurity concentrations was produced.
[0018]
【The invention's effect】
As described above, according to the production method of the present invention, a metal fluoride containing anhydrous or hydrate can be produced. In particular, anhydrous ZnF 2 , ZrF 4 , HfF 4 , LaF 3 , YF 3 , and CdF 2 are dehydrated and dried with conventional HF gas at 300 ° C. to 600 ° C. to obtain anhydrous metal fluoride. Since it is very easy to produce anhydrous metal fluoride, it is necessary to suppress oxides generated by heat treatment at high temperature and to produce high-purity anhydrous fluoride with an extremely low concentration of transition metal. You can do it. Further, by using this as a starting material of a fluoride optical fiber amplifier, there is an advantage that an optical fiber amplifier having a high amplification degree can be manufactured.
[Brief description of the drawings]
FIG. 1 is a process chart showing a method for producing high-purity anhydrous zinc fluoride in Example 1 of the present invention.
FIG. 2 is a graph showing a TG-DTA curve of ZnF 2 produced according to Example 1 of the present invention.
FIG. 3 is a graph showing a TG-DTA curve of a commercially available ZnF 2 .4H 2 O.
FIG. 4 is a process chart showing a method for producing high-purity anhydrous zinc fluoride in Example 2 of the present invention.
FIG. 5 is a process chart showing a method for producing high-purity anhydrous zinc fluoride in Example 3 of the present invention.
FIG. 6 is a process chart showing a method for producing high-purity anhydrous zirconium fluoride (ZrF 4 ) in Example 4 of the present invention.
FIG. 7 is a process chart showing a method for producing high-purity anhydrous lanthanum fluoride (LaF 3 ) in Example 5 of the present invention.
FIG. 8 is a process chart showing a method for producing high-purity indium fluoride (InF 3 .3H 2 O) in Example 6 of the present invention.
FIG. 9 is a process chart showing a method for producing high-purity anhydrous cadmium fluoride in Example 7 of the present invention.
Claims (2)
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| JP10082097A JP3591756B2 (en) | 1997-04-04 | 1997-04-04 | Production method of metal fluoride |
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| JP10082097A JP3591756B2 (en) | 1997-04-04 | 1997-04-04 | Production method of metal fluoride |
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-
1997
- 1997-04-04 JP JP10082097A patent/JP3591756B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103221560A (en) * | 2010-11-19 | 2013-07-24 | 吉坤日矿日石金属株式会社 | Production method for high-purity lanthanum, high-purity lanthanum, sputtering target composed of high-purity lanthanum, and metal gate film containing high-purity lanthanum as main component |
| CN103221560B (en) * | 2010-11-19 | 2014-09-24 | 吉坤日矿日石金属株式会社 | Production method for high-purity lanthanum, high-purity lanthanum, sputtering target composed of high-purity lanthanum, and metal gate film containing high-purity lanthanum as main component |
| CN103328663A (en) * | 2011-01-21 | 2013-09-25 | 吉坤日矿日石金属株式会社 | Method for producing high-purity lanthanum, high-purity lanthanum, sputtering target formed from high-purity lanthanum, and metal gate film having high-purity lanthanum as main component |
| CN103328663B (en) * | 2011-01-21 | 2015-11-25 | 吉坤日矿日石金属株式会社 | The manufacture method of highly pure lanthanum, highly pure lanthanum, comprise highly pure lanthanum sputtering target and take highly pure lanthanum as the metal gate film of main component |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10287402A (en) | 1998-10-27 |
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