KR20110051289A - Method for producing germanium tetrafluoride - Google Patents

Abstract

According to the present invention, a process of supplying fluorine gas to a reactor filled with metal germanium and a diluent gas, passing a gas discharged from the reactor through a cooling collector and collecting germanium tetrafluoride as a reaction product, and a cooling collector Provided is a method for producing germanium tetrafluoride including a step of returning a gas to be returned to the reactor for circulating. By circulating the gas in a closed system in this manner, germanium tetrafluoride can be produced safely and with high efficiency.

Description

Method for producing germanium tetrafluoride {METHOD FOR PRODUCING GERMANIUM TETRAFLUORIDE}

The present invention relates to a method for producing germanium tetrafluoride.

As a manufacturing method of germanium tetrafluoride, (a) halogen-exchange method (for example, nonpatent literature 1) which makes antimony fluoride react with germanium tetrachloride, and (b) the method of thermally decomposing germanium hexafluoride (for example, Nonpatent literature 2), (c) The method by reaction of germanium oxide and bromine trifluoride (for example, nonpatent literature 3), (d) direct fluorination method by metal germanium and fluorine gas, etc. are well known.

However, in the germanium tetrafluoride obtained by the method of the above (a), (b) and (c), various kinds of gases such as germanium fluoride, HF, CO ₂ , CF ₄ , N ₂ and O ₂ are contained as impurities. .

On the other hand, in the method of (d), since high-purity metal germanium and fluorine gas can be obtained, high-purity germanium tetrafluoride can be obtained. However, as shown in the following reaction formula (1), since the calorific value due to the reaction of the metal germanium and the fluorine gas is large, the reaction is congested unless the fluorine gas is diluted and introduced.

Ge + 2F ₂ → GeF ₄ (ΔH ₂₇₃ = -284.4 kcal) (1)

In addition, since the vapor pressure of germanium tetrafluoride is 2.6 kPa or more even at -80 degreeC, when cold-collecting the produced germanium tetrafluoride, it is necessary to use a cryogenic refrigerant | coolant to improve collection efficiency. Therefore, when the fluorination of the metal germanium is carried out in an open system as in the method of (d) above, it is difficult to control the reaction and improve the production efficiency.

 H. S. Booth et al. J. Am. Chem. Soc. 58,90 (1936)  Inorganic Syntheses IV 147  H. J., J. Chem. Soc. 164 (1950)

An object of the present invention is to provide a method for producing germanium tetrafluoride by directly reacting metal germanium with fluorine gas safely and with high efficiency.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, it discovered that the said objective can be achieved by carrying out synthesis | combination and cooling collection of germanium tetrafluoride in a closed system, and came to this invention.

That is, the present invention provides a process of supplying fluorine gas to a reactor filled with a metal germanium and a diluent gas, passing the gas discharged from the reactor through a cold collector, and collecting germanium tetrafluoride as a reaction product, and a cold collector. Provided is a method for producing germanium tetrafluoride comprising a step of circulating a gas passing through the gas back to the reactor.

It is preferable that the temperature of the metal germanium in a reactor exists in the range of 100 degreeC-400 degreeC. In addition, the fluorine concentration in the gas discharged from the reactor is preferably less than 10.0 vol%.

1 is a schematic diagram of a germanium tetrafluoride production system according to an embodiment of the present invention.
2 is a schematic diagram of a conventional germanium tetrafluoride production system.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is described in detail.

In the present invention, germanium tetrafluoride is synthesized and cooled in a closed system. Specifically, fluorine gas is supplied to the reactor filled with the metal germanium and the dilution gas to directly react the fluorine gas with the metal germanium. The gas discharged from the reactor is passed through a cold collector to collect the reaction product germanium tetrafluoride. The gas passing through the cooling collector is circulated back to the reactor by a circulator such as a pump.

The shape of the metal germanium to be filled in the reactor is not particularly limited, and a bulk or rod shape can be used. Since the purity directly affects the purity of the reaction product germanium tetrafluoride, it is desired to be 99.99% or more.

The diluent gas charged in the reactor is not particularly limited as long as it is low in reactivity with fluorine gas. For example, nitrogen gas, helium gas, neon gas, argon gas, or the like can be used.

The filling amount of the dilution gas in the reactor should just be present in the reactor, and is not particularly limited.

In addition, since the purity of the fluorine gas used as the source gas for fluorinating metal germanium also directly affects the purity of germanium tetrafluoride, it is desired to be 99% or more.

The material used for the reactor should exhibit corrosion resistance to fluorine gas at least at the reaction temperature of metal germanium and fluorine gas, such as nickel or monel.

It is preferable that reaction temperature is the range of 100-400 degreeC of metal germanium in a reactor, More preferably, 200-300 degreeC is preferable. If the temperature exceeds 400 ° C, the reaction between the material of the reactor and the fluorine gas may be promoted, which is not preferable.

The fluorine concentration in the gas discharged from the reactor can be appropriately adjusted by adjusting the filling amount of the diluent gas to the reactor, the circulation flow rate of the circulator, or the supply flow rate of the fluorine gas. The fluorine concentration in the gas discharged from the reactor is preferably less than 10.0 vol%. At 10.0 vol% or more, the reaction between the metal germanium and the fluorine gas may be congested in the reactor, which may damage the material of the reactor.

When collecting the germanium tetrafluoride generated in the reactor, the temperature of the cold collector can be arbitrarily selected if it is below the dew point of germanium tetrafluoride. It is preferable that it becomes -180 degreeC or more which becomes. Below -180 ° C, the utilization efficiency of fluorine gas may decrease.

As described above, by circulating the gas in a closed system, the fluorination reaction of the metal germanium at an arbitrary dilution concentration becomes possible, the reaction can be easily controlled, and germanium tetrafluoride can be obtained in high yield.

Example

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

In each Example, germanium tetrafluoride was produced using the system shown in FIG. Generating system, by placing the mass flow controller (1) F _2, the pump 2, a reactor 4, a cooling collector (5) in this order was constructed as a closed system. The fluorine gas was controlled by the mass flow controller 1 for F ₂ , introduced into the system between the pump 2 and the cooling collector 5, and supplied to the reactor 4. The metal germanium 3 was charged to the center portion in the reactor 4. Moreover, the heater 6 was installed in the reactor 4, and the heater 6 was heated to the predetermined temperature. The gas in the reactor 4 was introduced into the cooling collector 5 to collect and collect the reaction product (germanium tetrafluoride). The gas which has passed through the cold collector 5 without being collected is returned to the reactor 4 by the pump 2 and circulated. In addition, the production system includes a vacuum line for vacuum-substituting the system and a gas supply line for supplying diluent gas (helium gas) into the system and filling the reactor 4, respectively, with the reactor 4 and the cooling collector 5, respectively. It connected through the on-off valve between.

Example 1

1000 g of the powder of the metal germanium (3) having a purity of 99.99% was packed into a central portion in the tubular reactor 4 made of nickel and having an inner diameter of 80 mm and a length of 1000 mm. After vacuum-substituting the system, the outer wall temperature of the reactor 4 was set to 200 ° C, and helium gas was introduced into the system to make 80 kPa. The cooling collector 5 was cooled to -60 degreeC. Next, setting the circulation rate of the pump (2) with 6ℓ / min, and the supply of fluorine at a flow rate of 400cc / min by the mass flow controller for F ₂ (1) was subjected to 10 hours of reaction. Thereafter, the produced gas collected in the cooling collector 5 was analyzed by FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi) to confirm the formation of germanium tetrafluoride. . The concentration of fluorine gas in the outlet gas of the reactor 4 was analyzed by an ultraviolet spectrophotometer (Hitachi U-2810). As a result, the concentration of 2 vol% and germanium tetrafluoride was FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.). As a result, it was 14 vol% and the other component was helium gas. After completion of the reaction, the inside of the cooling collector 5 was vacuum-substituted to remove helium gas and fluorine gas, which are dilution gases, and the yield of germanium tetrafluoride was determined based on the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. It was 98% on the germanium basis.

[Example 2]

500 g of powder of the metal germanium (3) having a purity of 99.99% was filled in a central portion in the tubular reactor 4 made of nickel and having an inner diameter of 80 mm and a length of 1000 mm. After vacuum-substituting a system, the outer wall temperature of the reactor 4 was set to 150 degreeC, and helium gas was introduce | transduced into the system, and it was 120 kPa. The cooling collector 5 was cooled to -60 degreeC. Next, the circulation flow rate of the pump 2 was set to 10 l / min, fluorine was supplied at a flow rate of 300 cc / min by the mass flow controller 1 for F ₂ , and reaction was performed for 10 hours. Thereafter, the produced gas collected in the cooling collector 5 was analyzed by FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi) to confirm the formation of germanium tetrafluoride. The concentration of fluorine gas in the outlet gas of the reactor 4 was analyzed by an ultraviolet spectrophotometer (Hitachi U-2810). As a result, the concentration of 1.5 vol% and germanium tetrafluoride was FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.). 11vol%, and the other component is helium gas. After completion of the reaction, the inside of the cooling collector 5 was vacuum-substituted to remove helium gas and fluorine gas, which are dilution gases, and the yield of germanium tetrafluoride was determined based on the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. It was 99% on the basis of germanium.

Example 3

2000 g of the powder of the metal germanium (3) having a purity of 99.99% was packed in a central portion in the reactor 4 made of nickel and having an inner diameter of 130 mm and a length of 700 mm. After vacuum-substituting the system, the outer wall temperature of the reactor 4 was set at 250 ° C, and helium gas was introduced into the system to set 101 kPa. The cooling collector 5 was cooled to -60 degreeC. Next, the circulation flow rate of the pump 2 was set to 15 l / min, fluorine was supplied at a flow rate of 700 cc / min by the F ₂ mass flow controller 1, and the reaction was carried out for 10 hours. Thereafter, the produced gas collected in the cooling collector 5 was analyzed by FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi) to confirm the formation of germanium tetrafluoride. In addition, the fluorine gas concentration in the outlet gas of the reactor 4 was analyzed by an ultraviolet spectrophotometer (Hitachi U-2810). As a result, the concentration of 1.8 vol% and germanium tetrafluoride was FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.). 13vol%, and the other component is helium gas. After completion of the reaction, the inside of the cooling collector 5 was vacuum-substituted to remove helium gas and fluorine gas, which are dilution gases, and the yield of germanium tetrafluoride was determined based on the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. It was 99% on the basis of germanium.

Example 4

2000 g of the powder of the metal germanium (3) having a purity of 99.99% was packed in a central portion in the reactor 4 made of nickel and having an inner diameter of 130 mm and a length of 700 mm. After vacuum-substituting the system, the outer wall temperature of the reactor 4 was set at 250 ° C, and helium gas was introduced into the system to set 101 kPa. The cooling collector 5 was cooled to -60 degreeC. Next, the circulation flow rate of the pump 2 was set to 15 l / min, fluorine was supplied at a flow rate of 50 cc / min by the mass flow controller 1 for F ₂ , and the reaction was carried out for 10 hours. Thereafter, the produced gas collected in the cooling collector 5 was analyzed by FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi) to confirm the formation of germanium tetrafluoride. In addition, the fluorine gas concentration in the outlet gas of the reactor 4 was analyzed by an ultraviolet spectrophotometer (Hitachi U-2810), and as a result, 0.6 vol% and the concentration of germanium tetrafluoride were FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.). 13vol%, and the other component is helium gas. After completion of the reaction, the inside of the cooling collector 5 was vacuum-substituted to remove helium gas and fluorine gas, which are dilution gases, and the yield of germanium tetrafluoride was determined based on the amount of fluorine gas introduced and the mass of germanium tetrafluoride collected. It was 99% on the basis of germanium.

Comparative Example 1

Germanium tetrafluoride was produced using the system shown in FIG. The production system was configured in an open system by the mass flow controller 11 for F ₂ , the reactor 14, and the cooling collector 15. The fluorine gas was controlled by the mass flow controller 11 for F ₂ and supplied to the reactor 14. The metal germanium 13 was charged inside 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 | emitted from the reactor 14 was introduce | transduced into the cooling collector 15, and the reaction product (germanium tetrafluoride) was collected by cooling. The gas which passes through without being collected by the cooling collector 15 is sent to a decontamination apparatus outside the system as discharge gas. Between the reactor 14 and the cooling collector 15 of the production system, a vacuum line for vacuum replacing the system and a gas supply line for supplying diluent gas (helium gas) into the system and filling the reactor 14 are respectively. Connection was made via an on / off valve.

1000 g of a powder of metal germanium 13 having a purity of 99.99% was packed into a reactor 14 made of nickel and having an inner diameter of 200 mm and a length of 700 mm. After vacuum-substituting the system, the outer wall temperature of the reactor was set to 200 ° C, and helium gas was introduced into the system to make 80 kPa. The cooling collector 15 was cooled to -60 degreeC. Next, fluorine was supplied to the fluorine gas at a flow rate of 400 cc / min by the mass flow controller 11 for F _2, and the reaction was performed for 10 hours. Thereafter, the produced gas collected in the cooling collector 5 was analyzed by FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and an ultraviolet spectrophotometer (U-2810 manufactured by Hitachi) to confirm the formation of germanium tetrafluoride. After completion | finish of reaction, the inside of the cooling collector 15 was vacuum-substituted, fluorine gas was removed, and the yield of germanium tetrafluoride was calculated | required by the amount of the introduced fluorine gas and the mass of the collected germanium tetrafluoride, and it was 87% on the basis of germanium. In addition, it was confirmed that damage occurred on the inner surface of the reactor 14. It is assumed that the cause of damage is due to the introduction of fluorine gas at a concentration of 100% and a large amount of heat generated locally.

Although this invention was demonstrated based on the specific Example, this invention is not limited to the said Example, Comprising: Various deformation | transformation and a change are included in the range which does not deviate from the meaning.

Claims (3)

Supplying fluorine gas to the reactor filled with the metal germanium and the diluent gas; passing the gas discharged from the reactor through a cold collector; collecting germanium tetrafluoride as a reaction product; and passing the gas through the cold collector. A method for producing germanium tetrafluoride, including the step of returning to a reactor and circulating it. The method of claim 1,
A method for producing germanium tetrafluoride, wherein the temperature of the metal germanium in the reactor is in the range of 100 ° C to 400 ° C. The method of claim 1,
A method for producing germanium tetrafluoride, wherein the concentration of fluorine in the gas discharged from the reactor is less than 10.0 vol%.

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