WO2010055768A1 - Method for producing germanium tetrafluoride - Google Patents
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- WO2010055768A1 WO2010055768A1 PCT/JP2009/068372 JP2009068372W WO2010055768A1 WO 2010055768 A1 WO2010055768 A1 WO 2010055768A1 JP 2009068372 W JP2009068372 W JP 2009068372W WO 2010055768 A1 WO2010055768 A1 WO 2010055768A1
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- C01G17/00—Compounds of germanium
- C01G17/04—Halides of germanium
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- the present invention relates to a method for producing germanium tetrafluoride.
- germanium tetrafluoride As a method for producing germanium tetrafluoride, (a) a halogen exchange method in which germanium tetrachloride is reacted with antimony fluoride (for example, Non-Patent Document 1), and (b) a method of thermally decomposing hexafluorogermanate ( For example, Non-Patent Document 2), (c) a method by reaction of germanium oxide and bromine trifluoride (for example, Non-Patent Document 3), (d) a direct fluorination method using metal germanium and fluorine gas, etc. are well known. ing.
- a halogen exchange method in which germanium tetrachloride is reacted with antimony fluoride for example, Non-Patent Document 1
- a method of thermally decomposing hexafluorogermanate For example, Non-Patent Document 2
- a method by reaction of germanium oxide and bromine trifluoride for example,
- germanium tetrafluoride obtained by the above methods (a), (b) and (c), various gases such as fluorinated germanium, HF, CO 2 , CF 4 , N 2 and O 2 are used. Is contained as an impurity.
- An object of the present invention is to provide a method of producing germanium tetrafluoride by performing a direct reaction between metal germanium and fluorine gas safely and efficiently.
- the present inventors have found that the above object can be achieved by synthesizing and cooling and collecting germanium tetrafluoride in a closed system, and have reached the present invention.
- the present invention includes a step of supplying a fluorine gas to a reactor filled with metal germanium and a diluent gas, and a gas discharged from the reactor through a cooling collector so that the reaction product is a four-fluid product.
- a method for producing germanium tetrafluoride comprising a step of collecting germanium iodide and a step of returning and circulating the gas passing through the cold collector again to the reactor.
- the temperature of the metal germanium in the reactor is preferably in the range of 100 ° C to 400 ° C. Further, the fluorine concentration in the gas released from the reactor is preferably less than 10.0 vol%.
- germanium tetrafluoride is synthesized and cooled and collected in a closed system. Specifically, fluorine gas is supplied to a reactor filled with metal germanium and a diluent gas, and the fluorine gas and metal germanium are directly reacted. The gas released from the reactor is passed through a cold collector to collect germanium tetrafluoride which is a reaction product. The gas that passes through the cold collector is circulated back to the reactor again by a circulator such as a pump.
- a circulator such as a pump.
- the shape of metal germanium charged in the reactor is not particularly limited, and a lump or rod can be used. Since its purity directly affects the purity of germanium tetrafluoride as a reaction product, it is desired to have a purity of 99.99% or more.
- the diluent gas charged in the reactor is not particularly limited as long as it has low reactivity with fluorine gas, and for example, nitrogen gas, helium gas, neon gas, argon gas, or the like can be used.
- the filling amount of the diluent gas in the reactor is not particularly limited as long as the diluent gas exists in the reactor.
- the purity of the fluorine gas used as a raw material gas for fluorinating metal germanium directly affects the purity of germanium tetrafluoride, a purity of 99% or more is desired.
- the material used for the reactor must exhibit corrosion resistance to fluorine gas at least at the reaction temperature between metal germanium and fluorine gas, such as nickel or monel.
- the reaction temperature is preferably such that the temperature of the metal germanium in the reactor is in the range of 100 ° C. to 400 ° C., more preferably 200 ° C. to 300 ° C. If it exceeds 400 ° C., the reaction between the material of the reactor and the fluorine gas may be accelerated, which is not preferable.
- the fluorine concentration in the gas released from the reactor can be adjusted as appropriate by adjusting the amount of dilution gas charged into the reactor, the circulation flow rate of the circulator, or the supply flow rate of the fluorine gas.
- the fluorine concentration in the gas released from the reactor is preferably less than 10.0 vol%. If it is 10.0 vol% or more, there is a possibility that the reaction between metal germanium and fluorine gas may run away in the reactor, and the material of the reactor may be damaged.
- the temperature of the cooling collector when collecting germanium tetrafluoride produced in the reactor can be arbitrarily selected as long as it is below the dew point of germanium tetrafluoride, but the nitrogen gas which is a fluorine gas and a dilution gas It is desirable that the temperature be ⁇ 180 ° C. or higher which is higher than the boiling point of helium gas, neon gas, or argon gas. If the temperature is lower than -180 ° C, the utilization efficiency of fluorine gas may be lowered.
- germanium tetrafluoride was produced using the system shown in FIG.
- the generation system was configured as a closed system by arranging the F 2 mass flow controller 1, the pump 2, the reactor 4, and the cooling collector 5 in this order.
- the flow rate of the fluorine gas was controlled by the F 2 mass flow controller 1, introduced into the system between the pump 2 and the cooling collector 5, and supplied to the reactor 4.
- Metal germanium 3 was filled in the central portion of the reactor 4.
- the heater 6 was installed in the reactor 4 and the reactor 4 was heated to predetermined temperature.
- the gas in the reactor 4 was introduced into the cold collector 5 to collect the reaction product (germanium tetrafluoride) by cooling.
- the gas passed without being collected by the cold collector 5 was returned to the reactor 4 by the pump 2 and circulated.
- a vacuum line for evacuating the inside of the system and a gas supply line for supplying dilution gas (helium gas) into the system and filling the reactor 4 are cooled with the reactor 4 respectively.
- the collector 5 was connected via a leak valve.
- Example 1 1000 g of a metal germanium 3 powder having a purity of 99.99% was filled in the center of a tubular reactor 4 made of nickel and having an inner diameter of 80 mm and a length of 1000 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 200 ° C., and helium gas was introduced into the system to 80 kPa. The cold collector 5 was cooled to ⁇ 60 ° C. Next, the circulation flow rate of the pump 2 was set to 6 L / min, and fluorine was supplied at a flow rate of 400 cc / min by the F 2 mass flow controller 1 to react for 10 hours.
- the product gas collected in the cooled collector 5 was analyzed with FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and ultraviolet spectrophotometer (U-2810 manufactured by Hitachi). It was confirmed. Further, the fluorine gas concentration in the reactor 4 outlet gas was analyzed by an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), and the concentration of germanium tetrafluoride was determined as FT-IR (IG-IG manufactured by Otsuka Electronics Co., Ltd.). 1000), it was 14 vol%, and the other component was helium gas.
- the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 98% based on germanium.
- Example 2 500 g of a metal germanium 3 powder having a purity of 99.99% was charged in the center of a tubular reactor 4 made of nickel and having an inner diameter of 80 mm and a length of 1000 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 150 ° C., and helium gas was introduced into the system to 120 kPa. The cold collector 5 was cooled to ⁇ 60 ° C. Next, the circulation flow rate of the pump 2 was set to 10 L / min, and fluorine was supplied at a flow rate of 300 cc / min by the F 2 mass flow controller 1 to react for 10 hours.
- the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 99% based on germanium.
- Example 3 2000 g of metal germanium 3 powder having a purity of 99.99% was filled in the center of the reactor 4 made of nickel and having an inner diameter of 130 mm and a length of 700 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 250 ° C., and helium gas was introduced into the system to 101 kPa. The cold collector 5 was cooled to ⁇ 60 ° C. Next, the circulation flow rate of the pump 2 was set to 15 L / min, and fluorine was supplied at a flow rate of 700 cc / min by the F 2 mass flow controller 1 to react for 10 hours.
- the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 99% based on germanium.
- Example 4 2000 g of metal germanium 3 powder having a purity of 99.99% was filled in the center of the reactor 4 made of nickel and having an inner diameter of 130 mm and a length of 700 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 250 ° C., and helium gas was introduced into the system to 101 kPa. The cold collector 5 was cooled to ⁇ 60 ° C. Next, the circulation flow rate of the pump 2 was set to 15 L / min, and fluorine was supplied at a flow rate of 50 cc / min by the F 2 mass flow controller 1 to react for 10 hours.
- the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 99% based on germanium.
- Germanium tetrafluoride was produced using the system shown in FIG.
- the generation system was configured as an open system by the mass flow controller 11 for F 2 , the reactor 14, and the cooling collector 15.
- the flow rate of the fluorine gas was controlled by the F 2 mass flow controller 11 and supplied to the reactor 14.
- Metal germanium 13 was filled into the reactor 14.
- a heater 16 for heating the reactor 14 to a predetermined temperature was installed in the reactor 14.
- the gas discharged from the reactor 14 was introduced into the cold collector 15 and the reaction product (germanium tetrafluoride) was cooled and collected.
- the gas that passed without being collected by the cooling collector 15 was sent as exhaust gas to an abatement apparatus outside the system.
- a vacuum line for evacuating the inside of the system, and a diluent gas (helium gas) is supplied into the system to fill the reactor 14.
- a diluent gas helium gas
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Abstract
A method for producing germanium tetrafluoride, which comprises a step of supplying a fluorine gas into a reactor which is filled with germanium metal and a diluent gas; a step of collecting germanium tetrafluoride, which is a reaction product, by passing the gas discharged from the reactor through a cooling collection unit, and a step of circulating the gas passed through the cooling collection unit back to the reactor. By circulating the gas in the closed system as described above, germanium tetrafluoride can be produced safely and efficiently.
Description
本発明は、四フッ化ゲルマニウムの製造方法に関する。
The present invention relates to a method for producing germanium tetrafluoride.
四フッ化ゲルマニウムの製造方法としては、（ａ）四塩化ゲルマニウムにフッ化アンチモンを反応させるハロゲン交換法（例えば、非特許文献１）、（ｂ）六フッ化ゲルマニウム酸塩を熱分解する方法（例えば、非特許文献２）、（ｃ）酸化ゲルマニウムと三フッ化臭素との反応による方法（例えば、非特許文献３）、（ｄ）金属ゲルマニウムとフッ素ガスによる直接フッ素化法等がよく知られている。
As a method for producing germanium tetrafluoride, (a) a halogen exchange method in which germanium tetrachloride is reacted with antimony fluoride (for example, Non-Patent Document 1), and (b) a method of thermally decomposing hexafluorogermanate ( For example, Non-Patent Document 2), (c) a method by reaction of germanium oxide and bromine trifluoride (for example, Non-Patent Document 3), (d) a direct fluorination method using metal germanium and fluorine gas, etc. are well known. ing.
しかしながら、上記（ａ）、（ｂ）及び（ｃ）の方法で得られる四フッ化ゲルマニウム中には、フッ化塩化ゲルマニウム、ＨＦ，ＣＯ2，ＣＦ4，Ｎ2，Ｏ2など多種類のガスを不純物として含有する。
However, in the germanium tetrafluoride obtained by the above methods (a), (b) and (c), various gases such as fluorinated germanium, HF, CO 2 , CF 4 , N 2 and O 2 are used. Is contained as an impurity.
一方、上記（ｄ）の方法では、高純度の金属ゲルマニウムやフッ素ガスが入手可能なことから、高純度の四フッ化ゲルマニウムを得ることができる。しかしながら、下記反応式（１）に示すように、金属ゲルマニウムとフッ素ガスとの反応による発熱量が大きいため、フッ素ガスを希釈導入しなければ反応が暴走する。
Ｇｅ＋２Ｆ2→ＧｅＦ4 （ΔＨ273＝－２８４．４ｋｃａｌ） （１）
また、生成した四フッ化ゲルマニウムを冷却捕集する際に、四フッ化ゲルマニウムの蒸気圧が－８０℃においても２．６ｋＰａ以上であるため、捕集効率を向上させるためには極低温の冷媒を使用する必要がある。よって、上記（ｄ）の方法のように、金属ゲルマニウムのフッ素化反応を開放系で行った場合、反応の制御や製造効率の向上が難しい。 On the other hand, in the method (d), since high-purity metal germanium and fluorine gas are available, high-purity germanium tetrafluoride can be obtained. However, as shown in the following reaction formula (1), since the calorific value due to the reaction between metal germanium and fluorine gas is large, the reaction runs away unless fluorine gas is diluted.
Ge + 2F 2 → GeF 4 (ΔH 273 = −284.4 kcal) (1)
In addition, when the produced germanium tetrafluoride is cooled and collected, the vapor pressure of germanium tetrafluoride is 2.6 kPa or more even at −80 ° C. Therefore, in order to improve the collection efficiency, a cryogenic refrigerant is used. Need to use. Therefore, when the metal germanium fluorination reaction is performed in an open system as in the method (d), it is difficult to control the reaction and improve the production efficiency.
Ｇｅ＋２Ｆ2→ＧｅＦ4 （ΔＨ273＝－２８４．４ｋｃａｌ） （１）
また、生成した四フッ化ゲルマニウムを冷却捕集する際に、四フッ化ゲルマニウムの蒸気圧が－８０℃においても２．６ｋＰａ以上であるため、捕集効率を向上させるためには極低温の冷媒を使用する必要がある。よって、上記（ｄ）の方法のように、金属ゲルマニウムのフッ素化反応を開放系で行った場合、反応の制御や製造効率の向上が難しい。 On the other hand, in the method (d), since high-purity metal germanium and fluorine gas are available, high-purity germanium tetrafluoride can be obtained. However, as shown in the following reaction formula (1), since the calorific value due to the reaction between metal germanium and fluorine gas is large, the reaction runs away unless fluorine gas is diluted.
Ge + 2F 2 → GeF 4 (ΔH 273 = −284.4 kcal) (1)
In addition, when the produced germanium tetrafluoride is cooled and collected, the vapor pressure of germanium tetrafluoride is 2.6 kPa or more even at −80 ° C. Therefore, in order to improve the collection efficiency, a cryogenic refrigerant is used. Need to use. Therefore, when the metal germanium fluorination reaction is performed in an open system as in the method (d), it is difficult to control the reaction and improve the production efficiency.
本発明の目的は、安全に且つ高効率に、金属ゲルマニウムとフッ素ガスの直接反応を行い、四フッ化ゲルマニウムを製造する方法を提供することにある。
An object of the present invention is to provide a method of producing germanium tetrafluoride by performing a direct reaction between metal germanium and fluorine gas safely and efficiently.
本発明者等は、鋭意検討の結果、閉鎖系内で四フッ化ゲルマニウムの合成及び冷却捕集を行うことにより、上記目的が達成できることを見出し、本発明に至った。
As a result of intensive studies, the present inventors have found that the above object can be achieved by synthesizing and cooling and collecting germanium tetrafluoride in a closed system, and have reached the present invention.
すなわち、本発明は、金属ゲルマニウムと希釈ガスが充填されている反応器にフッ素ガスを供給する工程と、反応器より放出される気体を冷却捕集器に通過させて反応生成物である四フッ化ゲルマニウムを捕集する工程と、冷却捕集器を通過するガスを再び反応器へ戻し循環させる工程と、を含む四フッ化ゲルマニウムの製造方法が提供される。
That is, the present invention includes a step of supplying a fluorine gas to a reactor filled with metal germanium and a diluent gas, and a gas discharged from the reactor through a cooling collector so that the reaction product is a four-fluid product. There is provided a method for producing germanium tetrafluoride comprising a step of collecting germanium iodide and a step of returning and circulating the gas passing through the cold collector again to the reactor.
反応器内の金属ゲルマニウムの温度は１００℃～４００℃の範囲にあることが好ましい。また、反応器より放出される気体中のフッ素濃度は１０．０ｖｏｌ％未満であることが好ましい。
The temperature of the metal germanium in the reactor is preferably in the range of 100 ° C to 400 ° C. Further, the fluorine concentration in the gas released from the reactor is preferably less than 10.0 vol%.
以下、本発明について詳細に述べる。
Hereinafter, the present invention will be described in detail.
本発明では、閉鎖系内で四フッ化ゲルマニウムの合成及び冷却捕集を行う。具体的には、金属ゲルマニウムと希釈ガスが充填されている反応器にフッ素ガスを供給して、フッ素ガスと金属ゲルマニウムの直接反応を行う。反応器より放出される気体を冷却捕集器に通過させて、反応生成物である四フッ化ゲルマニウムを捕集する。冷却捕集器を通過するガスは、ポンプ等の循環器により再び反応器へ戻し循環させる。
In the present invention, germanium tetrafluoride is synthesized and cooled and collected in a closed system. Specifically, fluorine gas is supplied to a reactor filled with metal germanium and a diluent gas, and the fluorine gas and metal germanium are directly reacted. The gas released from the reactor is passed through a cold collector to collect germanium tetrafluoride which is a reaction product. The gas that passes through the cold collector is circulated back to the reactor again by a circulator such as a pump.
反応器に充填される金属ゲルマニウムは、その形状を特に限定するものではなく、塊状又はロッド状のものが使用できる。その純度は反応生成物である四フッ化ゲルマニウムの純度に直接影響を及ぼすことから９９．９９％以上のものが望まれる。
The shape of metal germanium charged in the reactor is not particularly limited, and a lump or rod can be used. Since its purity directly affects the purity of germanium tetrafluoride as a reaction product, it is desired to have a purity of 99.99% or more.
反応器に充填される希釈ガスは、フッ素ガスとの反応性の低いものであれば特に限定されず、例えば、窒素ガス、ヘリウムガス、ネオンガス、アルゴンガス等を用いることができる。
The diluent gas charged in the reactor is not particularly limited as long as it has low reactivity with fluorine gas, and for example, nitrogen gas, helium gas, neon gas, argon gas, or the like can be used.
反応器内の希釈ガスの充填量は、反応器内に希釈ガスが存在していればよく、特に限定するものではない。
The filling amount of the diluent gas in the reactor is not particularly limited as long as the diluent gas exists in the reactor.
また、金属ゲルマニウムをフッ素化する原料ガスとして用いられるフッ素ガスの純度も四フッ化ゲルマニウムの純度に直接影響を及ぼすことから９９％以上のものが望まれる。
Also, since the purity of the fluorine gas used as a raw material gas for fluorinating metal germanium directly affects the purity of germanium tetrafluoride, a purity of 99% or more is desired.
反応器に用いる材質は、ニッケルあるいはモネルのような、少なくとも、金属ゲルマニウムとフッ素ガスとの反応温度において、フッ素ガスに対する耐食性を示すものでなければならない。
The material used for the reactor must exhibit corrosion resistance to fluorine gas at least at the reaction temperature between metal germanium and fluorine gas, such as nickel or monel.
反応温度は、反応器内の金属ゲルマニウムの温度が１００℃～４００℃の範囲であることが好ましく、更に好ましくは２００℃～３００℃が好適である。４００℃を超えると反応器の材質とフッ素ガスとの反応が促進される可能性があるため好ましくない。
The reaction temperature is preferably such that the temperature of the metal germanium in the reactor is in the range of 100 ° C. to 400 ° C., more preferably 200 ° C. to 300 ° C. If it exceeds 400 ° C., the reaction between the material of the reactor and the fluorine gas may be accelerated, which is not preferable.
反応器より放出される気体中のフッ素濃度は、反応器への希釈ガスの充填量、循環器の循環流量、またはフッ素ガスの供給流量を調節することで、適宜、調整できる。反応器より放出される気体中のフッ素濃度は１０．０ｖｏｌ％未満であることが好ましい。１０．０ｖｏｌ％以上では反応器内で金属ゲルマニウムとフッ素ガスとの反応が暴走している可能性があり、反応器の材質を損傷する恐れがあるため好ましくない。
The fluorine concentration in the gas released from the reactor can be adjusted as appropriate by adjusting the amount of dilution gas charged into the reactor, the circulation flow rate of the circulator, or the supply flow rate of the fluorine gas. The fluorine concentration in the gas released from the reactor is preferably less than 10.0 vol%. If it is 10.0 vol% or more, there is a possibility that the reaction between metal germanium and fluorine gas may run away in the reactor, and the material of the reactor may be damaged.
反応器で生成した四フッ化ゲルマニウムを捕集する際の冷却捕集器の温度は、四フッ化ゲルマニウムの露点以下であれば任意に選択可能であるが、フッ素ガス及び希釈ガスである窒素ガス、ヘリウムガス、ネオンガス、アルゴンガスの沸点以上となる－１８０℃以上であることが望ましい。－１８０℃未満ではフッ素ガスの利用効率が下がる可能性がある。
The temperature of the cooling collector when collecting germanium tetrafluoride produced in the reactor can be arbitrarily selected as long as it is below the dew point of germanium tetrafluoride, but the nitrogen gas which is a fluorine gas and a dilution gas It is desirable that the temperature be −180 ° C. or higher which is higher than the boiling point of helium gas, neon gas, or argon gas. If the temperature is lower than -180 ° C, the utilization efficiency of fluorine gas may be lowered.
上述の通り、閉鎖系でガスを循環させることにより任意の希釈濃度での金属ゲルマニウムのフッ素化反応が可能となり、反応を容易に制御することができ、高収率で四フッ化ゲルマニウムを得ることができる。
As described above, by circulating gas in a closed system, fluorination reaction of metal germanium at any dilution concentration is possible, the reaction can be easily controlled, and germanium tetrafluoride can be obtained in high yield. Can do.
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
各実施例では、図１に示すシステムを用いて四フッ化ゲルマニウムを生成した。生成システムは、Ｆ2用マスフローコントローラ１と、ポンプ２と、反応器４と、冷却捕集器５をこの順序で配置して閉鎖系として構成した。フッ素ガスは、Ｆ2用マスフローコントローラ１により流量を制御し、ポンプ２と冷却捕集器５の間で系内に導入して、反応器４に供給した。金属ゲルマニウム３は、反応器４内の中央部に充填した。また、ヒーター６を反応器４内にヒーター６を設置し、反応器４を所定の温度に加熱した。反応器４内ガスは、冷却捕集器５に導入され、反応生成物（四フッ化ゲルマニウム）を冷却捕集した。冷却捕集器５で捕集されず通過したガスは、ポンプ２により反応器４内に戻して循環した。さらに、生成システムには、系内を真空置換するための真空ライン、及び希釈ガス（ヘリウムガス）を系内に供給して反応器４に充填するためのガス供給ラインをそれぞれ反応器４と冷却捕集器５の間においてれ開閉弁を介して接続した。
In each example, germanium tetrafluoride was produced using the system shown in FIG. The generation system was configured as a closed system by arranging the F 2 mass flow controller 1, the pump 2, the reactor 4, and the cooling collector 5 in this order. The flow rate of the fluorine gas was controlled by the F 2 mass flow controller 1, introduced into the system between the pump 2 and the cooling collector 5, and supplied to the reactor 4. Metal germanium 3 was filled in the central portion of the reactor 4. Moreover, the heater 6 was installed in the reactor 4 and the reactor 4 was heated to predetermined temperature. The gas in the reactor 4 was introduced into the cold collector 5 to collect the reaction product (germanium tetrafluoride) by cooling. The gas passed without being collected by the cold collector 5 was returned to the reactor 4 by the pump 2 and circulated. Further, in the production system, a vacuum line for evacuating the inside of the system and a gas supply line for supplying dilution gas (helium gas) into the system and filling the reactor 4 are cooled with the reactor 4 respectively. The collector 5 was connected via a leak valve.
［実施例１］
純度９９．９９％の金属ゲルマニウム３の粉末１０００ｇを、ニッケル製で内径８０ｍｍ、長さ１０００ｍｍの管状反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を２００℃に設定し、系内にヘリウムガスを導入し８０ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を６Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により４００ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ、四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ２ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１４ｖｏｌ％であり、他の成分はヘリウムガスであった。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９８％であった。 [Example 1]
1000 g of ametal germanium 3 powder having a purity of 99.99% was filled in the center of a tubular reactor 4 made of nickel and having an inner diameter of 80 mm and a length of 1000 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 200 ° C., and helium gas was introduced into the system to 80 kPa. The cold collector 5 was cooled to −60 ° C. Next, the circulation flow rate of the pump 2 was set to 6 L / min, and fluorine was supplied at a flow rate of 400 cc / min by the F 2 mass flow controller 1 to react for 10 hours. Thereafter, the product gas collected in the cooled collector 5 was analyzed with FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and ultraviolet spectrophotometer (U-2810 manufactured by Hitachi). It was confirmed. Further, the fluorine gas concentration in the reactor 4 outlet gas was analyzed by an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), and the concentration of germanium tetrafluoride was determined as FT-IR (IG-IG manufactured by Otsuka Electronics Co., Ltd.). 1000), it was 14 vol%, and the other component was helium gas. After completion of the reaction, the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 98% based on germanium.
純度９９．９９％の金属ゲルマニウム３の粉末１０００ｇを、ニッケル製で内径８０ｍｍ、長さ１０００ｍｍの管状反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を２００℃に設定し、系内にヘリウムガスを導入し８０ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を６Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により４００ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ、四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ２ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１４ｖｏｌ％であり、他の成分はヘリウムガスであった。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９８％であった。 [Example 1]
1000 g of a
［実施例２］
純度９９．９９％の金属ゲルマニウム３の粉末５００ｇを、ニッケル製で内径８０ｍｍ、長さ１０００ｍｍの管状反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を１５０℃に設定し、系内にヘリウムガスを導入し１２０ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を１０Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により３００ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ１．５ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１１ｖｏｌ％であり、他の成分はヘリウムガスである。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９９％であった。 [Example 2]
500 g of ametal germanium 3 powder having a purity of 99.99% was charged in the center of a tubular reactor 4 made of nickel and having an inner diameter of 80 mm and a length of 1000 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 150 ° C., and helium gas was introduced into the system to 120 kPa. The cold collector 5 was cooled to −60 ° C. Next, the circulation flow rate of the pump 2 was set to 10 L / min, and fluorine was supplied at a flow rate of 300 cc / min by the F 2 mass flow controller 1 to react for 10 hours. After that, when the product gas collected in the cooled collector 5 was analyzed with FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), the production of germanium tetrafluoride was found. confirmed. In addition, the fluorine gas concentration in the reactor 4 outlet gas was analyzed by an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), and the concentration of germanium tetrafluoride was FT-IR (manufactured by Otsuka Electronics Co., Ltd.). IG-1000) is 11 vol%, and the other component is helium gas. After completion of the reaction, the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 99% based on germanium.
純度９９．９９％の金属ゲルマニウム３の粉末５００ｇを、ニッケル製で内径８０ｍｍ、長さ１０００ｍｍの管状反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を１５０℃に設定し、系内にヘリウムガスを導入し１２０ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を１０Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により３００ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ１．５ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１１ｖｏｌ％であり、他の成分はヘリウムガスである。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９９％であった。 [Example 2]
500 g of a
［実施例３］
純度９９．９９％の金属ゲルマニウム３の粉末２０００ｇを、ニッケル製で内径１３０ｍｍ、長さ７００ｍｍの反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を２５０℃に設定し、系内にヘリウムガスを導入し１０１ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を１５Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により７００ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ１．８ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１３ｖｏｌ％であり、他の成分はヘリウムガスである。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９９％であった。 [Example 3]
2000 g ofmetal germanium 3 powder having a purity of 99.99% was filled in the center of the reactor 4 made of nickel and having an inner diameter of 130 mm and a length of 700 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 250 ° C., and helium gas was introduced into the system to 101 kPa. The cold collector 5 was cooled to −60 ° C. Next, the circulation flow rate of the pump 2 was set to 15 L / min, and fluorine was supplied at a flow rate of 700 cc / min by the F 2 mass flow controller 1 to react for 10 hours. After that, when the product gas collected in the cooled collector 5 was analyzed with FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), the production of germanium tetrafluoride was found. confirmed. Further, the fluorine gas concentration in the reactor 4 outlet gas was analyzed by an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), and the concentration of germanium tetrafluoride was FT-IR (manufactured by Otsuka Electronics Co., Ltd.). IG-1000) is 13 vol%, and the other component is helium gas. After completion of the reaction, the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 99% based on germanium.
純度９９．９９％の金属ゲルマニウム３の粉末２０００ｇを、ニッケル製で内径１３０ｍｍ、長さ７００ｍｍの反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を２５０℃に設定し、系内にヘリウムガスを導入し１０１ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を１５Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により７００ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ１．８ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１３ｖｏｌ％であり、他の成分はヘリウムガスである。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９９％であった。 [Example 3]
2000 g of
［実施例４］
純度９９．９９％の金属ゲルマニウム３の粉末２０００ｇを、ニッケル製で内径１３０ｍｍ、長さ７００ｍｍの反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を２５０℃に設定し、系内にヘリウムガスを導入し１０１ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を１５Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により５０ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ０．６ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１３ｖｏｌ％であり、他の成分はヘリウムガスである。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９９％であった。 [Example 4]
2000 g ofmetal germanium 3 powder having a purity of 99.99% was filled in the center of the reactor 4 made of nickel and having an inner diameter of 130 mm and a length of 700 mm. After the system was evacuated, the outer wall temperature of the reactor 4 was set to 250 ° C., and helium gas was introduced into the system to 101 kPa. The cold collector 5 was cooled to −60 ° C. Next, the circulation flow rate of the pump 2 was set to 15 L / min, and fluorine was supplied at a flow rate of 50 cc / min by the F 2 mass flow controller 1 to react for 10 hours. After that, when the product gas collected in the cooled collector 5 was analyzed with FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), the production of germanium tetrafluoride was found. confirmed. Further, the fluorine gas concentration in the reactor 4 outlet gas was analyzed by an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), and the concentration of germanium tetrafluoride was FT-IR (manufactured by Otsuka Electronics Co., Ltd.). IG-1000) is 13 vol%, and the other component is helium gas. After completion of the reaction, the inside of the cooling collector 5 is vacuum-replaced, and helium gas and fluorine gas as dilution gases are removed, and the amount of germanium tetrafluoride is determined by the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. When the yield was determined, it was 99% based on germanium.
純度９９．９９％の金属ゲルマニウム３の粉末２０００ｇを、ニッケル製で内径１３０ｍｍ、長さ７００ｍｍの反応器４内の中央部に充填した。系内を真空置換した後、反応器４の外壁温度を２５０℃に設定し、系内にヘリウムガスを導入し１０１ｋＰａとした。冷却捕集器５は－６０℃に冷却した。次に、ポンプ２の循環流量を１５Ｌ／ｍｉｎに設定し、Ｆ2用マスフローコントローラ１により５０ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ四フッ化ゲルマニウムの生成を確認した。また、反応器４出口ガス中のフッ素ガス濃度は、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ０．６ｖｏｌ％、四フッ化ゲルマニウムの濃度は、ＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）で分析したところ１３ｖｏｌ％であり、他の成分はヘリウムガスである。反応終了後、冷却捕集器５内を真空置換し、希釈ガスであるヘリウムガス及びフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で９９％であった。 [Example 4]
2000 g of
［比較例１］
図２に示すシステムを用いて四フッ化ゲルマニウムを生成した。生成システムは、Ｆ2用マスフローコントローラ１１と、反応器１４と、冷却捕集器１５により開放系で構成した。フッ素ガスは、Ｆ2用マスフローコントローラ１１により流量を制御して、反応器１４に供給した。金属ゲルマニウム１３は、反応器１４の内部に充填した。また、反応器１４を所定の温度に加熱するためのヒーター１６を反応器１４内に設置した。反応器１４より排出されるガスは、冷却捕集器１５に導入され、反応生成物（四フッ化ゲルマニウム）が冷却捕集された。冷却捕集器１５で捕集されず通過するガスは、排出ガスとして系外の除害装置に送られた。生成システムの反応器１４と冷却捕集器１５の間には、系内を真空置換するための真空ライン、及び希釈ガス（ヘリウムガス）を系内に供給して反応器１４に充填するためのガス供給ラインをそれぞれ開閉弁を介して接続した。 [Comparative Example 1]
Germanium tetrafluoride was produced using the system shown in FIG. The generation system was configured as an open system by themass flow controller 11 for F 2 , the reactor 14, and the cooling collector 15. The flow rate of the fluorine gas was controlled by the F 2 mass flow controller 11 and supplied to the reactor 14. Metal germanium 13 was filled into the reactor 14. In addition, a heater 16 for heating the reactor 14 to a predetermined temperature was installed in the reactor 14. The gas discharged from the reactor 14 was introduced into the cold collector 15 and the reaction product (germanium tetrafluoride) was cooled and collected. The gas that passed without being collected by the cooling collector 15 was sent as exhaust gas to an abatement apparatus outside the system. Between the reactor 14 and the cold collector 15 of the production system, a vacuum line for evacuating the inside of the system, and a diluent gas (helium gas) is supplied into the system to fill the reactor 14. Each gas supply line was connected via an on-off valve.
図２に示すシステムを用いて四フッ化ゲルマニウムを生成した。生成システムは、Ｆ2用マスフローコントローラ１１と、反応器１４と、冷却捕集器１５により開放系で構成した。フッ素ガスは、Ｆ2用マスフローコントローラ１１により流量を制御して、反応器１４に供給した。金属ゲルマニウム１３は、反応器１４の内部に充填した。また、反応器１４を所定の温度に加熱するためのヒーター１６を反応器１４内に設置した。反応器１４より排出されるガスは、冷却捕集器１５に導入され、反応生成物（四フッ化ゲルマニウム）が冷却捕集された。冷却捕集器１５で捕集されず通過するガスは、排出ガスとして系外の除害装置に送られた。生成システムの反応器１４と冷却捕集器１５の間には、系内を真空置換するための真空ライン、及び希釈ガス（ヘリウムガス）を系内に供給して反応器１４に充填するためのガス供給ラインをそれぞれ開閉弁を介して接続した。 [Comparative Example 1]
Germanium tetrafluoride was produced using the system shown in FIG. The generation system was configured as an open system by the
純度９９．９９％の金属ゲルマニウム１３の粉末１０００ｇを、ニッケル製で内径２００ｍｍ、長さ７００ｍｍの反応器１４内に充填した。系内を真空置換した後、反応器の外壁温度を２００℃に設定し、系内にヘリウムガスを導入し８０ｋＰａとした。冷却捕集器１５は－６０℃に冷却した。次に、フッ素ガスをＦ2用マスフローコントローラ１１により４００ｃｃ／ｍｉｎの流量でフッ素を供給して１０時間反応を行った。その後、冷却捕集器５に捕集された生成ガスをＦＴ－ＩＲ（大塚電子社製 ＩＧ－１０００）、紫外分光光度計（日立製 Ｕ－２８１０）で分析したところ四フッ化ゲルマニウムの生成を確認した。反応終了後、冷却捕集器１５内を真空置換することによりフッ素ガスを除去し、導入したフッ素ガス量と捕集された四フッ化ゲルマニウムの質量により四フッ化ゲルマニウムの収率を求めたところ、ゲルマニウム基準で８７％であった。また、反応器１４の内面に損傷が生じているのが確認された。損傷の原因は１００％濃度のフッ素ガスを導入したため、局所的に大きな発熱が生じたためであると推測される。
1000 g of metal germanium 13 powder having a purity of 99.99% was charged into a reactor 14 made of nickel and having an inner diameter of 200 mm and a length of 700 mm. After evacuating the system, the outer wall temperature of the reactor was set to 200 ° C., and helium gas was introduced into the system to 80 kPa. The cold collector 15 was cooled to −60 ° C. Next, the fluorine gas was supplied at a flow rate of 400 cc / min by the F 2 mass flow controller 11 and reacted for 10 hours. After that, when the product gas collected in the cooled collector 5 was analyzed with FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and ultraviolet spectrophotometer (U-2810 manufactured by Hitachi), the production of germanium tetrafluoride was found. confirmed. After completion of the reaction, the inside of the cooling collector 15 is vacuum-substituted to remove fluorine gas, and the yield of germanium tetrafluoride is determined from the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. And 87% based on germanium. Moreover, it was confirmed that the inner surface of the reactor 14 was damaged. The cause of the damage is presumed to be that a large amount of heat was generated locally because 100% concentration of fluorine gas was introduced.
本発明を具体的な実施例に基づいて説明してきたが、本発明は上記実施例に限定されるものではなく、その趣旨を逸脱しない範囲で種々の変形・変更を含むものである。
Although the present invention has been described based on specific embodiments, the present invention is not limited to the above embodiments, and includes various modifications and changes without departing from the spirit of the present invention.
Claims (3)
- 金属ゲルマニウムと希釈ガスが充填されている反応器にフッ素ガスを供給する工程と、反応器より放出される気体を冷却捕集器に通過させて反応生成物である四フッ化ゲルマニウムを捕集する工程と、冷却捕集器を通過するガスを再び反応器へ戻し循環させる工程と、を含む四フッ化ゲルマニウムの製造方法。 Supplying fluorine gas to a reactor filled with metal germanium and a diluent gas, and passing the gas released from the reactor through a cooling collector to collect germanium tetrafluoride as a reaction product A method for producing germanium tetrafluoride, comprising: a step; and a step of circulating the gas passing through the cold collector back to the reactor again.
- 反応器内の金属ゲルマニウムの温度が１００℃～４００℃の範囲にあることを特徴とする、請求項１に記載の四フッ化ゲルマニウムの製造方法。 The method for producing germanium tetrafluoride according to claim 1, wherein the temperature of the metal germanium in the reactor is in the range of 100 ° C to 400 ° C.
- 反応器より放出される気体中のフッ素濃度が１０．０ｖｏｌ％未満であることを特徴とする、請求項１に記載の四フッ化ゲルマニウムの製造方法。 The method for producing germanium tetrafluoride according to claim 1, wherein the fluorine concentration in the gas released from the reactor is less than 10.0 vol%.
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| CN115231609A (en) * | 2022-08-24 | 2022-10-25 | 和远潜江电子特种气体有限公司 | Synthesis and purification method and system of high-purity germanium tetrafluoride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01234301A (en) * | 1988-03-16 | 1989-09-19 | Mitsui Toatsu Chem Inc | Production of gaseous metal fluoride |
| JPH02172806A (en) * | 1988-12-23 | 1990-07-04 | Mitsubishi Electric Corp | Device for producing hydrogen peroxide solution |
| JP2004131370A (en) * | 2002-08-14 | 2004-04-30 | Advance Research Chemicals Inc | Method of manufacturing high purity germanium tetrafluoride |
| JP2006265057A (en) * | 2005-03-25 | 2006-10-05 | Japan Nuclear Cycle Development Inst States Of Projects | Method for preparing iodine heptafluoride by fluorine circulation system |
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| EP0333084B1 (en) * | 1988-03-16 | 1994-07-27 | MITSUI TOATSU CHEMICALS, Inc. | Method for preparing gaseous fluorides |
| JP3258413B2 (en) * | 1993-02-12 | 2002-02-18 | 三井化学株式会社 | Method for producing germanium tetrafluoride |
| JP2000072438A (en) * | 1998-08-25 | 2000-03-07 | Mitsui Chemicals Inc | Purifying method of germanium tetrafluoride |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01234301A (en) * | 1988-03-16 | 1989-09-19 | Mitsui Toatsu Chem Inc | Production of gaseous metal fluoride |
| JPH02172806A (en) * | 1988-12-23 | 1990-07-04 | Mitsubishi Electric Corp | Device for producing hydrogen peroxide solution |
| JP2004131370A (en) * | 2002-08-14 | 2004-04-30 | Advance Research Chemicals Inc | Method of manufacturing high purity germanium tetrafluoride |
| JP2006265057A (en) * | 2005-03-25 | 2006-10-05 | Japan Nuclear Cycle Development Inst States Of Projects | Method for preparing iodine heptafluoride by fluorine circulation system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115231609A (en) * | 2022-08-24 | 2022-10-25 | 和远潜江电子特种气体有限公司 | Synthesis and purification method and system of high-purity germanium tetrafluoride |
| CN115231609B (en) * | 2022-08-24 | 2024-05-10 | 和远潜江电子特种气体有限公司 | Synthetic purification method and system for high-purity germanium tetrafluoride |
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| KR20110051289A (en) | 2011-05-17 |
| CN102164857A (en) | 2011-08-24 |
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