WO2020003925A1 - 三塩化ホウ素の製造方法 - Google Patents
三塩化ホウ素の製造方法 Download PDFInfo
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- WO2020003925A1 WO2020003925A1 PCT/JP2019/022195 JP2019022195W WO2020003925A1 WO 2020003925 A1 WO2020003925 A1 WO 2020003925A1 JP 2019022195 W JP2019022195 W JP 2019022195W WO 2020003925 A1 WO2020003925 A1 WO 2020003925A1
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- boron carbide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/061—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/991—Boron carbide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- the present invention relates to a method for producing boron trichloride.
- Patent Document 1 discloses a method in which boron carbide having an average particle size of 1 to 4 mm is put in a reaction vessel, heated to 600 to 1200 ° C., and then chlorine gas is introduced to synthesize boron trichloride.
- An object of the present invention is to provide a method for producing boron trichloride that is less likely to damage a reaction vessel.
- one embodiment of the present invention is as described in the following [1] to [7].
- the reaction vessel is hardly damaged.
- boron trichloride can be produced at low cost.
- the method for producing boron trichloride of the present embodiment is a step of performing a reaction between chlorine gas in chlorine gas-containing gas and boron carbide in a state in which particulate boron carbide is flowing in chlorine gas-containing gas. Having. If the reaction of chlorine gas in the chlorine gas-containing gas with boron carbide is performed while the boron carbide is flowing in the chlorine gas-containing gas in the reaction vessel, the boron carbide is fixed at a predetermined position in the reaction vessel. The reaction vessel moves during the reaction without heat, so that heat storage by the reaction heat in the reaction vessel hardly occurs. Therefore, the temperature inside the reaction vessel does not become locally high, and the reaction vessel is hardly damaged.
- the method for bringing boron carbide into a state of flowing in the chlorine gas-containing gas in the reaction vessel is not particularly limited.
- the boron carbide may be blown up and caused to flow.
- the boron carbide may be caused to flow by simultaneously supplying the boron carbide and the chlorine gas-containing gas into the reaction vessel.
- boron carbide may be caused to flow by supplying boron carbide into a reaction vessel filled with a chlorine gas-containing gas.
- boron carbide is supplied from the top of a reaction vessel filled with a chlorine gas-containing gas and the boron carbide is dropped from the top to the bottom of the reaction vessel, the boron carbide flows in the chlorine gas-containing gas. State.
- the introduction form of the boron carbide into the reaction vessel may be a vertical introduction form or a horizontal introduction form.
- the method of supplying boron carbide to the reaction vessel is not particularly limited as long as the powdery boron carbide can be supplied stably. For example, a method of naturally dropping from a hopper, a screw feeder, a vibration feeder And a method using a feeder such as a circle feeder.
- the introduction direction of the chlorine gas-containing gas (that is, the direction in which the chlorine gas-containing gas flows) is not particularly limited, but is opposite to the moving direction of the boron carbide ( That is, it is preferable to introduce in the opposite direction).
- the residence time of boron carbide can be lengthened, and the boron carbide reacts easily.
- the method for producing boron trichloride of the present embodiment can be applied to a batch-type (batch-type) reaction or a continuous-type reaction.
- a chlorine gas-containing gas and boron carbide are charged into a reaction vessel, and when the reaction between the chlorine gas in the chlorine gas-containing gas and boron carbide is completed, the reaction product containing boron trichloride is removed.
- the operation of discharging from the reaction vessel, newly charging a gas containing chlorine gas and boron carbide into the reaction vessel, and performing the reaction again is repeated.
- the size of the particulate boron carbide particles is not particularly limited, but the volume-based average particle size D50 is preferably less than 500 ⁇ m, more preferably less than 100 ⁇ m, and more preferably less than 50 ⁇ m. Is more preferable. Since the smaller the size of the boron carbide particles, the easier it is to flow, heat storage is less likely to occur in the reaction vessel, and damage to the reaction vessel is less likely to occur.
- the volume-based average particle diameter D50 of the boron carbide particles is preferably 10 nm or more, more preferably 100 nm or more, and even more preferably 500 nm or more.
- the volume-based average particle diameter D50 of the boron carbide particles is within the above range, the influence of static electricity is small, and the boron carbide is unlikely to adhere to the reaction vessel. Boron carbide having a volume-based average particle size D50 of less than 100 nm may be difficult to handle.
- the average particle diameter D50 in the present invention means a particle diameter at which the cumulative frequency from the small particle diameter side becomes 50% in the volume-based cumulative particle diameter distribution.
- D50 can be measured by a laser diffraction method or the like. For example, it can be measured using a laser diffraction / scattering type particle size distribution measuring device Microtrac MT3300EX manufactured by Microtrac Bell Co., Ltd.
- ethanol can be used as a dispersion solvent for dispersing powdery and granular boron carbide at the time of measurement.
- inexpensive boron carbide fine powder for abrasives can be used in the method for producing boron trichloride of the present embodiment.
- the boron carbide used in the method for producing boron trichloride of the present embodiment preferably has a low water content. Water contained in boron carbide reacts with boron trichloride to produce boric acid.
- the generated boric acid may block lines such as pipes of the boron trichloride production device.
- the water content of boron carbide is preferably less than 1% by mass, more preferably less than 0.2% by mass. Since the water content of the powdered boron carbide is usually 1% by mass or more, it is preferable to dry the powder before the reaction to reduce the water content.
- the method for drying the boron carbide is not particularly limited, and a general drying method such as heat drying can be employed.
- the reaction temperature of chlorine gas and boron carbide in the chlorine gas-containing gas is not particularly limited as long as the reaction proceeds, but in order to sufficiently increase the reaction rate of boron carbide, 600 ° C.
- the temperature is preferably at least 800 ° C.
- the reaction temperature between chlorine gas and boron carbide in the chlorine gas-containing gas is preferably 1200 ° C. or lower, more preferably 1100 ° C. or lower. Is more preferred.
- the method of setting the temperature of the chlorine gas-containing gas and the boron carbide to the reaction temperature is not particularly limited.
- the chlorine gas-containing gas is introduced.
- the gas and boron carbide may be heated by conventional heating means, or after the normal temperature boron carbide is placed in the reaction vessel, a high-temperature (for example, 600 ° C. or more and 1200 ° C. or less) chlorine gas-containing gas is supplied into the reaction vessel. May be introduced.
- the reaction pressure between chlorine gas and boron carbide in the chlorine gas-containing gas is not particularly limited, but is preferably 0.500 MPaG or less in order to sufficiently maintain the airtightness of the reaction vessel. Further, in order to sufficiently increase the reaction rate of boron carbide, it is preferable to be -0.050 MPaG or more.
- a mixed gas composed of 50% by volume or more and less than 100% by volume of chlorine gas and the remaining inert gas can be used. It is preferable to use a mixed gas consisting of chlorine gas of not less than 100% by volume and less than 100% by volume, and it is more preferable to use 100% by volume of chlorine gas containing no inert gas.
- a mixed gas composed of chlorine gas and inert gas is used as the chlorine gas-containing gas, the produced boron trichloride and inert gas are mixed, and these must be separated.
- the type of inert gas that can be used for the mixed gas is not particularly limited, and examples thereof include nitrogen gas, argon, and helium.
- the chlorine-containing gas used in the method for producing boron trichloride of the present embodiment preferably has a low water vapor content for the same reason as in the case of boron carbide.
- the water vapor content of the chlorine gas-containing gas is preferably less than 1% by volume, and more preferably less than 100 ppm by volume.
- the chlorine gas-containing gas is dried before being subjected to the reaction to reduce the water vapor content.
- the method for drying the chlorine gas-containing gas is not particularly limited.
- the chlorine gas-containing gas can be dried by contact with a desiccant.
- the desiccant include zeolite, and specific examples include molecular sieves 3A, molecular sieves 4A, high silica zeolite AW300, and high silica zeolite AW500.
- One type of zeolite may be used alone, or two or more types may be used in combination.
- the desiccant may contain components other than zeolite.
- the amount of the chlorine gas-containing gas used is not particularly limited, but can be appropriately selected depending on the shape of the reaction vessel.
- a tubular reaction vessel having an inner diameter of 10 to 100 mm and a length (length of a portion where the reaction is performed) of 200 to 2000 mm can be used.
- the amount of the chlorine gas-containing gas used per kg of boron carbide is preferably 100 L or more, more preferably 2000 L or more.
- the boron carbide supplied to the reaction vessel does not completely react, and unreacted boron carbide may remain. .
- the material of the reaction vessel is not particularly limited as long as it is not corroded by chlorine gas, boron trichloride, hydrogen chloride or the like, and examples thereof include quartz, graphite, metal, and ceramic.
- Boron trichloride produced by the method for producing boron trichloride of the present embodiment contains chlorine gas, oxygen gas, nitrogen gas, carbon dioxide, carbon monoxide, methane, hydrogen gas, helium, hydrogen chloride, tetrachloride as impurities. It may contain silicon or the like. These impurities can be removed from boron trichloride by common distillation.
- FIG. 1 showing an example of a boron trichloride production apparatus.
- the main parts may be illustrated in an enlarged manner in order to make the features of the present invention easy to understand, and the dimensional ratios and the like of the components shown in FIG. It is not always the same as the actual boron trichloride production equipment.
- the apparatus for producing boron trichloride shown in FIG. 1 includes a chlorine gas container 1 (for example, a cylinder) filled with chlorine gas, a nitrogen gas container 2 (for example, a cylinder) filled with nitrogen gas, which is an inert gas, and a chlorine gas container.
- a drying apparatus 3 for drying an inert gas a tubular reaction vessel 5 made of quartz in which a reaction between the chlorine gas-containing gas and the particulate boron carbide 4 is performed, and a particulate boron carbide 4.
- a supply device 6 for example, a feeder for supplying to the tubular reaction vessel 5
- a temperature sensor 7 for example, a thermocouple
- a heating device 8 for heating the tubular reaction vessel 5
- a Fourier-transform infrared spectrometer 9 capable of analyzing boron trichloride, water vapor, hydrogen chloride, and the like.
- the tubular reaction vessel 5 is installed so that the central axis thereof is along the vertical direction, and a pipe 10 extending from the drying device 3 is connected to a lower end of the tubular reaction vessel 5 via a connection flange 11.
- a pipe 20 extending to the Fourier transform infrared spectrometer 9 is connected to an upper end of the tubular reaction vessel 5 via a connection flange 21.
- the Fourier transform infrared spectrometer 9 for example, an infrared spectrometer Nicolet @ iS5 manufactured by Thermo Fisher Scientific Inc. can be used.
- connection flanges 11 and 21 can be cooled by the cooling device 23. That is, the cooling pipe 24 provided in the cooling device 23 is disposed so as to be in contact with the connection flanges 11 and 21, and the cooling device 23 circulates a coolant such as cooling water through the cooling pipe 24, thereby forming a connection pipe. The flanges 11 and 21 are cooled.
- the drying device 3 includes a tubular drying container 32 containing a desiccant 31 such as zeolite, and a heating device 33 for heating the drying container 32.
- the material of the drying container 32 is, for example, a metal such as SUS316.
- chlorine gas is introduced from the chlorine gas container 1 into the tubular reaction container 5 via the pipes 12 and 10.
- a mixed gas obtained by diluting chlorine gas with an inert gas into the tubular reaction vessel 5
- chlorine gas and nitrogen gas are mixed in an intermediate portion of the pipe 12 (that is, upstream of the tubular reaction vessel 5)
- the mixed gas prepared in the pipe 12 is introduced into the tubular reaction vessel 5 through the pipe 10. That is, a pipe 13 that communicates the nitrogen gas container 2 with an intermediate portion of the pipe 12 is provided. Nitrogen gas is introduced from the nitrogen gas container 2 to the intermediate portion of the pipe 12 via the pipe 13, and chlorine gas and Nitrogen gas is mixed.
- chlorine gas-containing gas Since the drying device 3 is disposed between the pipe 10 and the pipe 12, the chlorine gas or the mixed gas (hereinafter, these two gases are collectively referred to as “chlorine gas-containing gas”) is supplied to the drying container of the drying device 3. After passing through the inside 32, it is introduced into the tubular reaction vessel 5. Accordingly, the chlorine gas-containing gas is introduced into the tubular reaction vessel 5 after being dried while being in contact with the desiccant 31 in the drying vessel 32.
- the granular boron carbide 4 is supplied to the tubular reaction vessel 5 by the supply device 6 and comes into contact with the chlorine gas-containing gas in the tubular reaction vessel 5. Since the inside of the tubular reaction vessel 5 is heated to a desired temperature (for example, a temperature of 600 ° C. or more) by the heating device 8, the chlorine gas in the chlorine gas-containing gas and the boron carbide 4 come into contact in the tubular reaction vessel 5. To form boron trichloride. The produced boron trichloride is sent out by the gas containing chlorine gas and discharged from the upper end of the tubular reaction vessel 5.
- the temperature in the tubular reaction vessel 5 (that is, the reaction temperature) can be controlled by adjusting the output of the heating device 8 based on the temperature measured by the temperature sensor 7.
- the temperature sensor 7 may be installed, for example, so as to measure the temperature at the central portion in the axial direction inside the tubular reaction vessel 5.
- the temperature measuring contact of the thermocouple may be arranged at the center in the axial direction inside the tubular reaction vessel 5.
- the pressure in the tubular reaction vessel 5 (that is, the reaction pressure) can be adjusted based on the pressure measured by the pressure sensors 15 and 26.
- the pressure sensors 15 and 26 may be installed, for example, at a portion of the pipe 10 near the lower end of the tubular reaction vessel 5 and at a portion of the pipe 20 near the upper end of the tubular reaction vessel 5.
- the boron carbide 4 is supplied from the upper end to the tubular reaction vessel 5 by the supply device 6. Since the tubular reaction vessel 5 is installed so that the central axis thereof extends along the vertical direction, the boron carbide 4 supplied from the upper end portion falls inside the tubular reaction vessel 5 from above to below. On the other hand, since the chlorine gas-containing gas is introduced from the lower end portion of the tubular reaction vessel 5, the chlorine gas-containing gas flows in a direction opposite to the moving direction of the boron carbide. 4 is in a flowing state.
- the flow rate of the chlorine gas-containing gas is set in the range of 500 to 10000 ccm (cm 3 / min). It can be selected as appropriate.
- the moving speed of the boron carbide 4 is reduced and the residence time in the reaction vessel is increased, so that the reaction rate of the boron carbide 4 is increased. Is higher.
- the chlorine gas-containing gas is also introduced from the upper end of the tubular reaction vessel 5 similarly to the boron carbide 4. May be. In this case, the generated chlorine gas-containing gas containing boron trichloride is discharged from the lower end of the tubular reaction vessel 5.
- the entire amount of boron carbide 4 supplied to the tubular reaction vessel 5 reacts, and the entire amount cannot react and unreacted boron carbide 4 remains. There is. The particles of the remaining boron carbide 4 fall to the lower end of the tubular reaction vessel 5 and are collected below the tubular reaction vessel 5 and are received in the receiving vessel 28 continuous with the lower end of the tubular reaction vessel 5. You.
- the boron trichloride discharged from the upper end of the tubular reaction vessel 5 is sent to the outside of the boron trichloride manufacturing apparatus via the pipe 20 after passing through the Fourier transform infrared spectrometer 9 together with the chlorine gas-containing gas, It is subjected to a post-treatment step such as a purification step.
- a post-treatment step such as a purification step.
- the analysis of boron trichloride and the like can be performed, so that the purity, yield, yield, and the like of boron trichloride can be calculated.
- the boron carbide 4 may contain moisture, it is preferable that the boron carbide 4 be dried before being subjected to the reaction.
- the drying of the boron carbide 4 can be performed by, for example, a drying facility shown in FIG.
- the drying equipment shown in FIG. 2 includes a metal container 41 having airtightness, and a heater 43 for heating the metal container 41.
- the metal container 41 is filled with powdered boron carbide 4 and the metal container 41 is heated by the heater 43 while the nitrogen gas is flowing through the metal container 41 and the temperature is raised to, for example, 200 ° C., for 4 hours, for example. Keep warm.
- the drying is completed, the mixture is cooled to room temperature, and the boron carbide 4 in the metal container 41 is moved to the supply device 6 of the boron trichloride production device, and is subjected to the reaction.
- Example 1 Using a boron trichloride production apparatus having the same configuration as that of the boron trichloride production apparatus of FIG. 1, the same operation as in the above-described embodiment is performed to cause the reaction between the particulate boron carbide and the chlorine gas-containing gas. Boron was produced.
- the diameter of the tubular reaction vessel is 38 mm, the length is 1400 mm, and the material is quartz. The details will be described below.
- the chlorine gas-containing gas a commercially available high-purity chlorine gas having a purity of 99.999% by volume and a water vapor content of 0.9% by volume was used.
- the boron carbide powdery boron carbide having a D50 of 20.88 ⁇ m measured by a laser diffraction method (manufacturer: Riken Corundum Co., Ltd.) was used. And this boron carbide was dried using the drying equipment shown in FIG. The drying conditions are the same as those described above, and the temperature is kept at 200 ° C. for 4 hours under a flow of nitrogen gas.
- the desiccant 31 contained in the drying container 32 is Hi-Silica Zeolite AW500 (manufacturer: Union Showa Co., Ltd.) and is calcined at 200 ° C. for 10 hours under a nitrogen gas flow.
- nitrogen gas was flowed from the nitrogen gas container 2 to the entire boron trichloride producing apparatus at a flow rate of 1500 ccm, and purged for 1 hour or more.
- the tubular reaction vessel 5 was heated to 800 ° C. (set temperature) by the heating device 8 while cooling the connection flanges 11 and 21 by the cooling device 23.
- the flow of nitrogen gas was stopped, and chlorine gas was introduced from the chlorine gas container 1 into the tubular reaction container 5.
- the flow rate of chlorine gas is set to 1800 ccm (cm 3 / min)
- boron carbide is supplied from the supply device 6 to the tubular reaction vessel 5 at a rate of 1 g / min.
- chlorine gas and boron carbide were reacted for 2 hours.
- the flow rate of chlorine gas of 1800 ccm is 4.42 mol / h in terms of mol
- the supply rate of boron carbide of 1 g / min is 1.085 mol / h in terms of mol.
- Example 1 the reaction is performed in a state in which the particulate boron carbide is flowing in the chlorine gas-containing gas, so that heat is hardly generated in the tubular reaction vessel 5, and The temperature did not rise to a high temperature that deviated from the set temperature. As a result, in Example 1, the tubular reaction vessel 5 was not damaged by high temperature.
- the generated chlorine gas containing boron trichloride was sent to a Fourier transform infrared spectrometer 9 (manufacturer: Thermo Fisher Scientific) to analyze and calculate the content of boron trichloride in the chlorine gas. .
- the analysis conditions are as follows.
- the material of the window plate of the Fourier transform infrared spectrometer 9 is silver chloride (AgCl)
- the cell length is 1 cm
- the data interval is 0.964 cm ⁇ 1
- the number of scans is 16.
- the wave number used for the analysis is 1908 cm -1 .
- the chlorine gas concentration was determined by titration with sodium thiosulfate.
- the formation rate of boron trichloride was 273 g / h (2.33 mol / h). Therefore, the yield based on chlorine gas is 79%.
- Example 9 the pressure of the tubular reaction vessel was changed in the range of -0.06 to 0.05 MPaG, but the tubular reaction vessel was not damaged, and boron trichloride could be produced satisfactorily.
- Example 11 although the chlorine gas content of the chlorine gas-containing gas was set to 50% by volume, boron trichloride was successfully produced without any damage to the tubular reaction vessel.
- reference numeral 101 denotes a chlorine gas container
- reference numeral 102 denotes a nitrogen gas container
- reference numeral 103 denotes a drying device
- reference numeral 107 denotes a temperature sensor
- reference numeral 109 denotes a Fourier transform infrared spectrometer
- reference numerals 110, 112, 113, and 120 Is a pipe
- reference numerals 111 and 121 are connection flanges
- reference numerals 115 and 126 are pressure sensors
- reference numeral 123 is a cooling device
- reference numeral 124 is a cooling pipe
- reference numeral 131 is a desiccant
- reference numeral 132 is a drying container
- reference numeral 133 is a heating device. Is shown.
- the reaction between boron carbide and chlorine gas proceeded from the lower part to the upper part of the tubular reaction vessel 105 at a speed of about 1 cm / h.
- the temperature of the reaction point (hot spot) measured by the temperature sensor 107 during the reaction was 1210 ° C., which was a large difference from the set temperature. That is, in Comparative Example 1, the reaction is performed in a state where the position of the boron carbide is fixed without moving, so that heat is easily generated in the tubular reaction vessel 105, and the temperature in the tubular reaction vessel 105 deviates from the set temperature. It is thought that the temperature rose to high temperature. As a result, in Comparative Example 1, the tubular reaction vessel 105 was damaged by high temperature.
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Description
B4C + 6Cl2 → 4BCl3 + C
例えば特許文献1には、平均粒径1~4mmの炭化ホウ素を反応容器に入れ、600~1200℃に加熱した後に塩素ガスを導入して三塩化ホウ素を合成する方法が開示されている。
本発明は、反応容器に損傷が生じにくい三塩化ホウ素の製造方法を提供することを課題とする。
[1] 塩素ガス含有ガス中で粉粒体状の炭化ホウ素が流動している状態で、前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を行う工程を有する三塩化ホウ素の製造方法。
[2] 反応容器内に前記塩素ガス含有ガス及び前記炭化ホウ素を連続的に供給するとともに前記反応容器からその反応生成物を連続的に排出しながら、前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を連続的に行う[1]に記載の三塩化ホウ素の製造方法。
[4] 前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を600℃以上の温度で行う[1]~[3]のいずれか一項に記載の三塩化ホウ素の製造方法。
[5] 前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を-0.050MPaG以上0.500MPaG以下の圧力下で行う[1]~[4]のいずれか一項に記載の三塩化ホウ素の製造方法。
[7] 前記塩素ガス含有ガスの水蒸気含有量が1体積%未満である[1]~[6]のいずれか一項に記載の三塩化ホウ素の製造方法。
反応容器内において炭化ホウ素が塩素ガス含有ガス中で流動している状態で塩素ガス含有ガス中の塩素ガスと炭化ホウ素との反応を行えば、炭化ホウ素は反応容器内の決まった位置に固定されることがなく、反応中に移動するので、反応容器に反応熱による蓄熱が生じにくい。そのため、反応容器内が局所的に高温になることがなく、反応容器の損傷が生じにくい。
反応容器へ炭化ホウ素を供給する方法は、粉粒体状の炭化ホウ素を安定的に供給できるならば特に限定されるものではないが、例えば、ホッパーから自然落下させる方法や、スクリューフィーダー、振動フィーダー、サークルフィーダー等のフィーダーを用いる方法が挙げられる。
粉粒体状の炭化ホウ素の粒子のサイズは特に限定されるものではないが、体積基準の平均粒径D50を500μm未満とすることが好ましく、100μm未満とすることがより好ましく、50μm未満とすることがさらに好ましい。炭化ホウ素の粒子のサイズが小さい方が、流動させることが容易であるので、反応容器に蓄熱が生じにくく、反応容器に損傷が生じにくい。また、炭化ホウ素と塩素ガス含有ガスとの接触時間が短い場合には、炭化ホウ素の粒子のサイズが小さい方が、炭化ホウ素の粒子の中心部にまで反応が及びやすく、炭化ホウ素の反応率が高くなりやすい。
また、本実施形態の三塩化ホウ素の製造方法において使用する炭化ホウ素は、水分含有量が低いことが好ましい。炭化ホウ素が含有する水は、三塩化ホウ素と反応し、ホウ酸を生成する。生成したホウ酸は、三塩化ホウ素製造装置の配管等のラインを閉塞させるおそれがある。
本実施形態の三塩化ホウ素の製造方法によって製造された三塩化ホウ素は、不純物として、塩素ガス、酸素ガス、窒素ガス、二酸化炭素、一酸化炭素、メタン、水素ガス、ヘリウム、塩化水素、四塩化ケイ素等を含有している場合がある。これらの不純物は、一般的な蒸留によって三塩化ホウ素から除去することができる。
〔実施例1〕
図1の三塩化ホウ素製造装置と同様の構成の三塩化ホウ素製造装置を用い、上記実施形態と同様の操作を行って粉粒体状の炭化ホウ素と塩素ガス含有ガスとを反応させ、三塩化ホウ素を製造した。管状反応容器の径は38mm、長さは1400mm、材質は石英である。以下に詳細を説明する。
炭化ホウ素としては、レーザー回折法により測定したD50が20.88μmである粉粒体状の炭化ホウ素(製造会社名:理研コランダム株式会社)を用いた。そして、この炭化ホウ素は、図2に示す乾燥設備を用いて乾燥したものである。乾燥条件は、上記と同様の条件であり、窒素ガス流通下で200℃で4時間保温するというものである。
反応を開始する前に、窒素ガス容器2から三塩化ホウ素製造装置の全体に窒素ガスを1500ccmの流量で流通し、1時間以上パージした。パージ時は、冷却装置23で接続用フランジ11、21を冷却しながら、加熱装置8で管状反応容器5を800℃(設定温度)に加熱した。
加熱装置8の設定温度は800℃であったが、反応中に温度センサー7により測定された管状反応容器5内の温度は807℃であり、設定温度との差はほとんど無かった。
原料の炭化ホウ素として粒径1~3mmの粒状の炭化ホウ素を使用し、塩素ガス含有ガス中で炭化ホウ素が流動していない状態で反応を行う点と、管状反応容器105を加熱する加熱装置108の設定温度が850℃である点と、塩素ガスの流量が567ccmである点以外は、実施例1と同様にして反応と分析を行った。
すなわち、炭化ホウ素104を落下させながら反応を行うのではなく、図3に示す三塩化ホウ素製造装置を用い、反応開始前に炭化ホウ素104を管状反応容器105に充填し、炭化ホウ素104の位置が移動せず固定された状態で反応を行った。
2 窒素ガス容器
4 炭化ホウ素
5 管状反応容器
6 供給装置
8 加熱装置
9 フーリエ変換赤外分光装置
Claims (7)
- 塩素ガス含有ガス中で粉粒体状の炭化ホウ素が流動している状態で、前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を行う工程を有する三塩化ホウ素の製造方法。
- 反応容器内に前記塩素ガス含有ガス及び前記炭化ホウ素を連続的に供給するとともに前記反応容器からその反応生成物を連続的に排出しながら、前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を連続的に行う請求項1に記載の三塩化ホウ素の製造方法。
- 前記炭化ホウ素の体積基準の平均粒径D50が500μm未満である請求項1又は請求項2に記載の三塩化ホウ素の製造方法。
- 前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を600℃以上の温度で行う請求項1~3のいずれか一項に記載の三塩化ホウ素の製造方法。
- 前記塩素ガス含有ガス中の塩素ガスと前記炭化ホウ素との反応を-0.050MPaG以上0.500MPaG以下の圧力下で行う請求項1~4のいずれか一項に記載の三塩化ホウ素の製造方法。
- 前記塩素ガス含有ガスは50体積%以上100体積%以下の塩素ガスと残部の不活性ガスとからなる請求項1~5のいずれか一項に記載の三塩化ホウ素の製造方法。
- 前記塩素ガス含有ガスの水蒸気含有量が1体積%未満である請求項1~6のいずれか一項に記載の三塩化ホウ素の製造方法。
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