WO2024070744A1 - Méthode de production de sulfure de carbonyle - Google Patents

Méthode de production de sulfure de carbonyle Download PDF

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Publication number
WO2024070744A1
WO2024070744A1 PCT/JP2023/033606 JP2023033606W WO2024070744A1 WO 2024070744 A1 WO2024070744 A1 WO 2024070744A1 JP 2023033606 W JP2023033606 W JP 2023033606W WO 2024070744 A1 WO2024070744 A1 WO 2024070744A1
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WIPO (PCT)
Prior art keywords
gas
plasma
carbonyl sulfide
raw material
starting material
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PCT/JP2023/033606
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English (en)
Japanese (ja)
Inventor
啓太 稲田
豪 松浦
隆行 渡辺
学 田中
和希 松井
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日本ゼオン株式会社
国立大学法人九州大学
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Application filed by 日本ゼオン株式会社, 国立大学法人九州大学 filed Critical 日本ゼオン株式会社
Publication of WO2024070744A1 publication Critical patent/WO2024070744A1/fr

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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
    • C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
    • C01B32/77—Carbon oxysulfide

Definitions

  • the present invention relates to a method for producing carbonyl sulfide.
  • Carbonyl sulfide is known as a useful gas for etching carbon hard masks and other materials in the semiconductor manufacturing process.
  • Patent Documents 1 and 2 Known methods for producing carbonyl sulfide in the gas phase include reacting carbon dioxide with carbon disulfide in the presence of a catalyst (Patent Documents 1 and 2) and reacting sulfur with carbon monoxide in the presence of a catalyst (Patent Document 3).
  • Patent Document 4 a method that does not use a catalyst has also been proposed for producing carbonyl sulfide (Patent Document 4), which involves discharging a raw material gas containing starting materials consisting of CS2 and at least one selected from the group consisting of CO2 , CO, O2 and O3 while it is continuously flowing, and then continuously releasing the gas outside the discharge region.
  • Patent Documents 1 to 3 all use catalysts, and as the activity of the catalyst decreases, the yield decreases, making continuous production difficult.
  • the manufacturing method of Patent Document 4 does not use a catalyst, so this problem does not occur, but it is desirable to achieve a higher level of carbonyl sulfide yield.
  • the present invention aims to provide a method for producing carbonyl sulfide in a high yield using a gas-phase flow method without using a catalyst.
  • thermal plasma is plasma generated under a pressure of 0.03 MPa or more (e.g., atmospheric pressure), in which electrons, gas molecules, and radicals are all at high temperatures, and is distinguished from vacuum plasma, which is generated under a pressure of 0.0001 MPa or less, in which only the electrons are at high temperatures.
  • the present invention aims to advantageously solve the above problems, and relates to a method for producing carbonyl sulfide, which includes a step of exciting a raw material gas containing a starting material containing carbon atoms, sulfur atoms, and oxygen atoms with thermal plasma, and a step of cooling the plasma-excited raw material gas.
  • the raw material gas is excited by thermal plasma, converting the starting material containing carbon atoms, sulfur atoms, and oxygen atoms in the raw material gas into active species that can be precursors of COS, and then cooling the gas causes the active species to recombine and produce carbonyl sulfide.
  • COS carbonyl sulfide
  • slm Standard Liter per Minute
  • the measurement conditions are a temperature of 0°C and a pressure of 1 atm (1013 hPa).
  • the starting material may consist of CS2 and at least one selected from the group consisting of CO2 , CO, O2 and O3 . These combinations are advantageous in that they can suitably generate CS active species, CO active species and active species consisting of simple oxygen, which can be precursors of COS.
  • carbonyl sulfide can be produced in a high yield using a gas-phase flow method without using a catalyst.
  • 1 is an example of an apparatus for generating thermal plasma that can be used in the method for producing carbonyl sulfide of the present invention.
  • the starting material contains carbon, sulfur and oxygen atoms.
  • the starting material can be composed of these three elements (carbon, sulfur and oxygen).
  • the starting material can be either an element or a compound, and usually consists of two or more kinds. It is not intended that the starting material contain only carbonyl sulfide.
  • the starting material is preferably a combination of CS2 and at least one selected from the group consisting of CO2 , CO, O2 , and O3 .
  • CS active species CO active species, active species consisting of simple oxygen, active species consisting of simple sulfur, etc.
  • the combination of CS2 and CO2 is more preferable in terms of efficiently obtaining COS.
  • the ratio of the volume of CS2 to the total volume of at least one selected from the group consisting of CO2 , CO, O2 , and O3 is preferably 0.05 or more. From the viewpoint of the selectivity of COS, it is more preferably 0.10 or more. Moreover, the volume ratio can be, for example, 2.00 or less, and from the viewpoint of obtaining good selectivity while maintaining the raw material conversion rate, it is preferably 0.70 or less.
  • the raw material gas may contain an inert gas.
  • the inert gas include N2 , He, Ne, Ar, Xe, and Kr, and N2 , Ar, and He are preferred, and N2 and Ar are more preferred.
  • the inert gas may be used alone or in combination of two or more kinds.
  • the content of the inert gas in the raw material gas can be 60% by volume or less, and preferably 30% by volume or less.
  • the content of the inert gas may be 0% by volume.
  • the raw material gas may contain impurities that are inevitably mixed in from the surrounding environment, in addition to the starting materials and any inert gas. Impurities include moisture.
  • the raw material gas may consist of the starting materials and the inevitable impurities.
  • the volume ratio of CS2 in the raw material gas is preferably 2 volume % or more. Also, the volume ratio is preferably 70 volume % or less. If it is within this range, COS can be obtained sufficiently.
  • the raw material gas may contain the starting material and any inert gas when energy is applied to excite the plasma.
  • the starting material and any inert gas may be supplied separately as gases to a plasma device (hereinafter simply referred to as a "plasma device") that generates thermal plasma to be used as the raw material gas, or all of them may be supplied as a premixed gas to be used as the raw material gas, or a portion of them may be supplied as a premixed gas separately from the remaining gas to be used as the raw material gas.
  • a plasma device hereinafter simply referred to as a "plasma device”
  • the flow rate of the raw material gas when it is supplied to the device for generating thermal plasma is preferably 15 slm or more, more preferably 20 slm or more, from the viewpoint of stabilizing the plasma.
  • the upper limit of the flow rate is not particularly limited, and can be set according to the device to be used.
  • the flow rate can be 5000 slm or less, but is not limited thereto.
  • the flow rate of CS2 can be, for example, 0.3 slm or more and 200 slm or less, but is not limited thereto.
  • the flow rates of starting materials other than CS2 and optional inert gases can be adjusted according to the flow rate of CS2 .
  • the flow rate is the total amount of starting materials and optional inert gases supplied to the plasma device.
  • a liquid that is either a gas under standard conditions or has a sufficiently high vapor pressure that it can be easily vaporized by heating, etc.
  • Such starting materials can be supplied to the plasma device as a gas without providing a separate vaporization chamber, etc., but it is preferable to vaporize a liquid in a separately provided vaporization chamber before supplying it to the plasma device.
  • Supply can be continuous.
  • the supply flow rate can be controlled using a mass flow controller, etc.
  • the starting material When the starting material is a liquid or solid with a low vapor pressure under standard conditions, the starting material can be vaporized in a separately provided vaporization chamber and then supplied to the plasma device.
  • CS2 roofing point 46°C
  • the starting material When the starting material is a solid, it can be heated to a liquid state and then introduced into the vaporization chamber, or it can be directly sublimated in the vaporization chamber.
  • the starting material can be vaporized by introducing it in a liquid state into a vaporization chamber that is maintained at a temperature and pressure at which the starting material is sufficiently vaporized.
  • the temperature and pressure of the vaporization chamber are preferably maintained at a temperature and pressure at which the starting material can be vaporized instantaneously.
  • the starting material can be continuously introduced into the vaporization chamber as a liquid, instantly vaporized in the vaporization chamber, and continuously supplied to the plasma device as a gas. If the starting material is in a solid state, it can be heated to a liquid state and then introduced into the vaporization chamber, or it can be directly sublimated in the vaporization chamber and continuously supplied to the plasma device as a gas.
  • the supply flow rate can be controlled by controlling the gas vaporized in the vaporization chamber with a mass flow controller or the like, or by controlling the starting material in liquid form when it is continuously introduced into the vaporization chamber with a liquid mass flow controller or the like.
  • the vaporized starting material may be diluted with an inert gas or the like when it is introduced into the plasma device.
  • the vaporization chamber may be filled with a filler to adjust the flow rate.
  • the filler include Helipak, glass beads, and SUS mesh.
  • CS2 when used as the starting material, it is advantageous to increase the supply amount by heating in a vaporization chamber filled with the filler.
  • the manufacturing method of the present invention utilizes a reaction field created by thermal plasma.
  • a plasma device that generates thermal plasma is used to generate active species that can be precursors of COS from a raw material gas in the thermal plasma region.
  • Thermal plasma can be formed using electrical methods, such as arc discharge, high-frequency discharge, pulse discharge, and multi-phase AC discharge.
  • the arc discharge may be a DC arc or an AC arc.
  • a multi-phase AC arc is preferred because it can be used to treat a large flow rate.
  • an inductively coupled high-frequency discharge plasma is advantageous in terms of efficient treatment.
  • [Plasma device] 1 shows an example of an apparatus for generating thermal plasma that can be used in the manufacturing method of the present invention. This plasma apparatus utilizes arc discharge.
  • the plasma device 1 has a combustion tube 10 inside a cooling jacket 30, and the cooling jacket 30 is designed so that cooling water flows through it.
  • the combustion tube 10 is preferably made of ceramic from the viewpoint of heat resistance.
  • a cathode 11 is installed above the combustion tube 10, and an anode 12 is installed inside the combustion tube 10.
  • An ignition wire 34 is placed on the cathode side.
  • a voltage is applied between the cathode 11 and anode 12 to cause a discharge.
  • the discharge conditions are not particularly limited, but can be, for example, a voltage of 300 to 600 V and a current of 1 to 20 A.
  • the size of the combustion tube 10 and the distance between the electrodes can be set appropriately.
  • the plasma generated by the discharge is downstream of the anode 12 side.
  • a gas supply pipe 21 is connected to the plasma device 1 on the cathode 11 side.
  • Raw material gas is supplied from this gas supply pipe 21, and a plasma state is created within the device, generating active species that can serve as precursors of COS.
  • the installation position of the gas supply pipe 21 is not limited to the position shown in FIG. 1.
  • a pipe may be inserted from the gas recovery port 22, and the raw material gas may be supplied from the pipe.
  • the bottom of the plasma device 1 is provided with a gas recovery port 22.
  • the raw material gas excited within the plasma device 1 is recovered from the gas recovery port 22 to the outside of the plasma device 1.
  • the activated species generated by cooling during this process combine to produce carbonyl sulfide. Recovery can be performed by connecting a vacuum pump, for example, to the gas recovery port 23.
  • Cooling can be performed by continuously releasing the plasma-excited source gas from the plasma device.
  • the continuous release can be performed at a space velocity that corresponds to the continuous flow of the source gas.
  • the plasma-excited raw gas After the plasma-excited raw gas is discharged from the plasma device, it may be further introduced into a heat exchanger for cooling.
  • the type of heat exchanger is not particularly limited, and examples include air-cooling and water-cooling. Since the product after cooling may contain substances other than carbonyl sulfide, carbonyl sulfide may be separated and purified by an optional separation and purification process. Separation and purification methods include distillation, absorption by a solution, membrane separation, etc.
  • Example 1 A long DC arc plasma device (volume: 6.5 L, electrode distance: 300 mm) made of Hastelloy was used as the plasma device 1.
  • a cylindrical mullite ceramic tube (inner diameter 42 mm, length 600 mm) was installed inside the plasma device 1 as the combustion tube 10.
  • CO2 which is the parent gas of the plasma, was introduced at 20 slm from a gas supply pipe 21 attached to the ceramic tube, and the plasma was ignited at a current value of 10 A.
  • CO2 was introduced into the plasma device 1 at 20 slm from the gas supply pipe 21 and CS2 vaporized through a vaporizer heated to 75°C was introduced into the plasma device 1 at 2 slm from the gas supply pipe 21.
  • the gas in the plasma device was discharged from the system through the gas recovery port 22, and the recovered gas discharged from the system was collected in an aluminum bag and detoxified with an aqueous KOH solution.
  • the gas was discharged out of the system at a space velocity equivalent to the space velocity of the raw material gas introduction.
  • GC-MS gas chromatography-mass spectrometry
  • Example 2 (Examples 2 and 3) The procedure was the same as in Example 1, except that the flow rate of CS2 was changed to the amount shown in Table 1. The results are shown in Table 1.
  • Example 4 The procedure was the same as in Example 2, except that N2 , which serves as a plasma parent gas, was further introduced through the gas supply pipe 21 at a flow rate shown in Table 1. The results are shown in Table 1.
  • Table 1 shows that in the examples, carbonyl sulfide can be produced in good yield without using a catalyst.
  • carbonyl sulfide can be produced in a high yield using a gas-phase flow method without using a catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une méthode de production de sulfure de carbonyle qui peut produire du sulfure de carbonyle avec un bon rendement à l'aide d'une méthode d'écoulement en phase gazeuse et sans utiliser de catalyseur. Cette méthode de production de sulfure de carbonyle comprend : une étape consistant à exciter, dans un plasma chaud, un gaz brut comprenant une substance de départ contenant des atomes de carbone, des atomes de soufre et des atomes d'oxygène ; et une étape consistant à refroidir le gaz brut excité par le plasma.
PCT/JP2023/033606 2022-09-28 2023-09-14 Méthode de production de sulfure de carbonyle WO2024070744A1 (fr)

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JP2022-155589 2022-09-28

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5659614A (en) * 1979-08-22 1981-05-23 Ihara Chem Ind Co Ltd Manufacture of carbonyl sulfide
WO2012144441A1 (fr) * 2011-04-18 2012-10-26 昭和電工株式会社 Procédé de production de sulfure de carbonyle
JP2012224494A (ja) * 2011-04-18 2012-11-15 Showa Denko Kk 硫化カルボニルの製造方法
WO2020262319A1 (fr) * 2019-06-27 2020-12-30 日本ゼオン株式会社 Procédé de production de sulfure de carbonyle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5659614A (en) * 1979-08-22 1981-05-23 Ihara Chem Ind Co Ltd Manufacture of carbonyl sulfide
WO2012144441A1 (fr) * 2011-04-18 2012-10-26 昭和電工株式会社 Procédé de production de sulfure de carbonyle
JP2012224494A (ja) * 2011-04-18 2012-11-15 Showa Denko Kk 硫化カルボニルの製造方法
WO2020262319A1 (fr) * 2019-06-27 2020-12-30 日本ゼオン株式会社 Procédé de production de sulfure de carbonyle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BEZUK STEVE J., MILLER LARRY L., PLATZNER I.: "Reactions of carbonyl sulfide in a radio-frequency plasma", THE JOURNAL OF PHYSICAL CHEMISTRY, AMERICAN CHEMICAL SOCIETY, vol. 87, no. 1, 1 January 1983 (1983-01-01), pages 131 - 136, XP055780958, ISSN: 0022-3654, DOI: 10.1021/j100224a030 *

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