WO2015072224A1 - 水素ガス製造用シリコン原料ａ、水素ガス製造用シリコン原料ｂ、水素ガス製造用シリコン原料ａの製造方法、水素ガス製造用シリコン原料ｂの製造方法、水素ガス製造方法および水素ガス製造装置 - Google Patents

水素ガス製造用シリコン原料ａ、水素ガス製造用シリコン原料ｂ、水素ガス製造用シリコン原料ａの製造方法、水素ガス製造用シリコン原料ｂの製造方法、水素ガス製造方法および水素ガス製造装置 Download PDF

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WO2015072224A1
WO2015072224A1 PCT/JP2014/074516 JP2014074516W WO2015072224A1 WO 2015072224 A1 WO2015072224 A1 WO 2015072224A1 JP 2014074516 W JP2014074516 W JP 2014074516W WO 2015072224 A1 WO2015072224 A1 WO 2015072224A1
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hydrogen gas
silicon
acid
raw material
producing
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PCT/JP2014/074516
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English (en)
French (fr)
Japanese (ja)
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辰郎 下司
正彦 池内
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株式会社Tkx
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Priority to KR1020167010627A priority Critical patent/KR101726983B1/ko
Priority to CN201480062004.0A priority patent/CN105722785A/zh
Priority to MYPI2016000885A priority patent/MY176196A/en
Publication of WO2015072224A1 publication Critical patent/WO2015072224A1/ja

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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
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a silicon raw material A for hydrogen gas production, a silicon raw material B for hydrogen gas production, a method for producing silicon raw material A for hydrogen gas production, a method for producing silicon raw material B for hydrogen gas production, a hydrogen gas production method, and hydrogen gas production. Relates to the device.
  • a silicon wafer is manufactured as follows. First, a cylindrical silicon ingot is manufactured by crystal growth from molten silicon. Next, an orientation flat or notch indicating the direction of the crystal axis is formed in the silicon ingot. Next, the silicon ingot is sliced to a predetermined thickness to produce a silicon wafer. Slicing is done with a dicer or multi-wire saw. Next, lapping processing for cutting to a predetermined thickness, etching processing for removing processing distortion, beveling processing for preventing peripheral chipping, mirror polishing processing for making the surface a mirror surface, and the like are performed on the silicon wafer. In the manufacturing process of such a silicon wafer, a large amount of silicon waste is generated. Conventionally, silicon scraps are discarded, but the cost burden and environmental burden due to disposal cannot be ignored.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2000-191303
  • silicon waste and an aqueous alkali solution are placed in a reaction vessel that can be sealed, the reaction vessel is heated to react the silicon waste with the aqueous alkali solution, and the generated hydrogen gas is collected.
  • the reaction proceeds abruptly immediately after the start of the reaction, but the reaction stops thereafter. Therefore, it is difficult to control the generation of hydrogen gas.
  • silicate ions (SiO 3 2 ⁇ ) are generated in the reaction between silicon and the aqueous alkali solution. If the aqueous alkali solution or silicon is excessive, the silicate ions form a gel and cover the unreacted silicon, thereby inhibiting the reaction, that is, the generation of hydrogen gas.
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-213609
  • silicon powder is mixed with water and supplied as sludge.
  • the intense reaction immediately after the contact between the silicon and the aqueous alkali solution is suppressed, and the generation of gel-like silicate ions is also suppressed.
  • hydrogen gas can be continuously obtained by taking out hydrogen gas from the reaction vessel and adding silicon sludge or an aqueous alkali solution so that the pressure in the reaction vessel is maintained within a predetermined range. .
  • the inventor of the present application conducted an experiment of mixing silicon powder with water and supplying it with sludge, as in Patent Document 2. Although the content will be described later as an explanation of the comparative example of FIG. 3 of the present application, as a result, even if silicon powder is mixed with water and supplied as sludge, the intense reaction immediately after the contact between silicon and the aqueous alkali solution cannot be suppressed. It was.
  • silicon powder is mixed with water, but in an actual multi-wire saw, the silicon ingot and the wire are cut while being cooled with a coolant.
  • the coolant is not mere water, but a liquid obtained by mixing water with, for example, propylene glycol (PG).
  • PG propylene glycol
  • Propylene glycol reduces the surface tension of water and improves the wettability of the wire and the penetration of the silicon ingot into the slicing grooves.
  • Propylene glycol or a material having a similar function is called oil in the coolant.
  • silicon particles generated from the multi-wire saw contain silicon particles and coolant (water and oil).
  • coolant water and oil
  • the silicon scrap generated from the multi-wire saw contains a coolant
  • the oil in the coolant covers the surface of the silicon particles, preventing the contact between the silicon particles and the alkaline aqueous solution, thereby inhibiting the reaction. Therefore, the amount of hydrogen gas generation is less than the theoretical value.
  • the first object of the present invention is to prevent the oil in the coolant from inhibiting the generation of hydrogen gas.
  • 1 mole of silicon particles reacts with 2 moles of alkali and 2 moles of water, reacting with 2 moles of SiO 2 (OH) 2 2 ⁇ (hydrate of metasilicate ion and water-soluble) and 2 Molar hydrogen gas is generated.
  • the alkali aqueous solution in the reaction tank consumes twice the number of moles of silicon particles, and then comes out of the reaction tank as alkali mist together with the generated hydrogen gas and water vapor.
  • the alkaline aqueous solution deficient in the reaction tank is immediately replenished with a pump from the alkaline aqueous solution tank. Not only is water consumed in the above reaction, but the water corresponding to the saturated water vapor pressure at the reaction vessel temperature evaporates with hydrogen gas, so the shortage is replenished from the water in the sludge tank and the water in the alkaline aqueous solution tank. Is done.
  • the second object of the present invention is to moderately suppress the reaction between silicon particles and an aqueous alkali solution so that hydrogen gas can be obtained constantly.
  • a third problem of the present invention is to realize a hydrogen gas production method and a hydrogen gas production apparatus with little pressure fluctuation in the reaction tank.
  • the third problem (method and apparatus for producing hydrogen gas with little pressure fluctuation) is closely related to the second problem (moderately suppresses the reaction between silicon particles and an aqueous alkali solution).
  • the third problem (hydrogen gas production device with little pressure fluctuation) cannot be solved unless the reaction between the aqueous solution and the alkaline aqueous solution is moderately suppressed.
  • the capacity of the reaction tank is 0.2 liter.
  • the capacity of the reaction tank is not described in the example of Patent Document 2, since the alkaline aqueous solution (NaOH aqueous solution) is 1 liter, the capacity of the reaction tank is estimated to be several liters. According to the research of the present inventor, this scale does not cause a problem in a laboratory hydrogen gas production apparatus, but the following problems occur in a mass production hydrogen production apparatus having a scale of 10 to 100 times.
  • a condenser is coupled to the reaction tank.
  • the condenser is a device that cools the gas mixture of hydrogen gas and water vapor to lower the dew point of the gas mixture, condenses the water vapor into water, and removes water vapor from the gas mixture.
  • alkaline aqueous solution mist manganesy alkaline aqueous solution
  • metasilicate hydrate mist silicon particles
  • a fourth problem of the present invention is to prevent corrosion and clogging due to alkaline aqueous solution mist, metasilicate hydrate mist, and silicon particles.
  • the silicon raw material A for producing hydrogen gas according to the present invention does not completely remove the oil in the coolant, but leaves an appropriate amount when the silicon particles are refined. Since the oil component inhibits the reaction between the silicon particles and the aqueous alkali solution, hydrogen gas is not generated if the oil component is excessive. Conversely, if the oil content is too small, hydrogen gas is explosively generated and cannot be controlled. Therefore, an appropriate amount of coolant remains. Since silicon particles and oil alone are solid, continuous supply by a pump is difficult. Therefore, add water to make sludge. (1)
  • the silicon raw material A for producing hydrogen gas of the present invention contains silicon particles, 0.1 to 10% by weight of oil content of the silicon particles, and water.
  • the oil content is Isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethyl-1-hexanol, Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, Or a mixture thereof. These substances may be contained as oils in the coolant.
  • the average particle size of the silicon particles is 0.1 ⁇ m to 30 ⁇ m.
  • the oil reaction suppression effect may be insufficient.
  • the average particle diameter of the silicon particles exceeds 30 ⁇ m, the surface area of the silicon particles may be insufficient and the reaction may be insufficient.
  • silicon particles are likely to precipitate and may not be uniformly dispersed in the aqueous alkali solution.
  • the weight of water is 1 to 10 times the weight of silicon particles.
  • the viscosity of the sludge may be too high, making it difficult to supply with a sludge pump. If the weight of water exceeds 10 times the weight of silicon particles, the balance between the silicon particles and the aqueous alkali solution will be lost (the concentration of the aqueous alkali solution will be too thin), or the liquid temperature of the liquid mixture in the reaction tank will decrease. As a result, the generation rate of hydrogen gas may decrease.
  • the silicon raw material B for producing hydrogen gas of the present invention is obtained by removing most of the oil in the coolant that inhibits the hydrogen gas generation reaction when refining silicon particles, and newly adding a reaction inhibitor.
  • the reaction-suppressing substance is a substance having a function of suppressing the reaction between the silicon particles and the alkaline aqueous solution, like the oil.
  • the reaction-suppressing substance used for the silicon raw material B for producing hydrogen gas of the present invention usually includes a substance not included in the coolant. The reaction-suppressing substance is added after removing oil in the coolant that inhibits the hydrogen gas generation reaction.
  • the silicon raw material B for producing hydrogen gas of the present invention contains silicon particles, 0.1 to 10% by weight of the reaction inhibitory substance of the silicon particles, and water.
  • the reaction inhibitor is Formic acid, lactic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, acrylic acid, oleic acid , Malic acid, citric acid, oxalic acid, maleic acid, fumaric acid, Vinyl pyrrolidone, polyvinyl pyrrolidone, sodium polyacrylate, polyethylene oxide, polyethylene imide, polyvinyl alcohol, polyacrylamide, polyethylene glycol, Or a mixture thereof.
  • the average particle size of the silicon particles is 0.1 ⁇ m to 30 ⁇ m.
  • the weight of water is 1 to 10 times the weight of silicon particles.
  • the method for producing silicon raw material A for producing hydrogen gas according to the present invention is characterized in that an appropriate amount of coolant oil (0.1 to 10% by weight of silicon particles) is left when refining silicon particles.
  • the method for producing the silicon raw material A for producing hydrogen gas according to the present invention comprises: Preparing silicon scraps containing oil and water derived from silicon particles and coolant, Centrifuging or filtering silicon debris to produce a solid A containing silicon particles, 0.1 wt% to 10 wt% oil content of silicon particles, and a small amount of water; Drying the solid A to produce a solid B containing silicon particles and an oil content of 0.1% to 10% by weight of the silicon particles; A step of producing sludge A by adding water to the solid B; (10)
  • the oil content is Isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethyl-1-hexanol, Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,2-propanediol, 1,4
  • Method for producing silicon raw material B for hydrogen gas production In the method for producing silicon raw material B for hydrogen gas production of the present invention, when refining silicon particles, oil that inhibits the hydrogen gas generation reaction in the coolant is almost removed in the high-temperature drying step, and then a new reaction is performed. It is characterized by adding inhibitory substances.
  • the method for producing the silicon raw material B for producing hydrogen gas of the present invention comprises: Preparing silicon scraps containing oil and water derived from silicon particles and coolant, Centrifuge or filter silicon waste to produce a solid A containing silicon particles, oil and a small amount of water, Drying the solid A to produce a solid B containing silicon particles and oil; A step of producing a solid C composed of silicon particles by drying the solid B at a high temperature to evaporate the oil; A step of producing sludge B by adding 0.1 wt% to 10 wt% of a reaction inhibiting substance of silicon particles and water to solid C is included.
  • the reaction inhibitor is Isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethyl-1-hexanol, Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol,
  • Formic acid lactic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexa
  • the drying temperature of the solid A is 100 ° C. to 120 ° C. This drying temperature is a temperature at which water evaporates but oil does not evaporate.
  • the high temperature drying temperature of the solid B is 500 ° C. to 700 ° C. This high temperature drying temperature is a temperature at which the oil contained in the solid B is almost evaporated.
  • the hydrogen gas production method of the present invention uses the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production of the present invention, and the injection rate of the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production is increased.
  • Feedback control based on the temperature of the liquid mixture in the reaction tank, feedback control of the injection rate of the alkaline aqueous solution based on the alkali concentration in the reaction tank, hydrogen gas, water vapor, alkaline aqueous solution mist, metasilicate hydrate
  • the gas P containing mist and silicon particles is treated with a scrubber to remove alkaline aqueous solution mist, metasilicate hydrate mist, and silicon particles from the gas P.
  • the hydrogen gas production method of the present invention comprises: Preparing a silicon raw material A for hydrogen gas production or a silicon raw material B for hydrogen gas production; Preparing an alkaline aqueous solution, A step of injecting the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production into the reaction tank while feedback control of the injection speed based on the temperature of the mixed liquid in the reaction tank; A step of injecting an aqueous alkali solution into the reaction vessel while controlling the injection rate based on the alkali concentration in the reaction vessel, Maintaining the mixed liquid of the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production and the alkaline aqueous solution in the reaction tank at a predetermined temperature;
  • the gas P containing hydrogen gas, water vapor, alkaline aqueous solution mist, metasilicate hydrate mist, and silicon particles taken out from the reaction tank is treated with a scrubber, and the alkaline aqueous solution mist, metasilicate hydrate mist from the
  • the alkaline aqueous solution is a NaOH aqueous solution or a KOH aqueous solution.
  • the concentration of the NaOH aqueous solution or the KOH aqueous solution is 1 mol / L to 8 mol / L.
  • the predetermined temperature is 50 ° C. to 90 ° C.
  • the hydrogen gas production apparatus of the present invention comprises: A sealable reaction vessel; Means for supplying the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production to the reaction vessel; Means for supplying an aqueous alkaline solution to the reaction vessel; A thermometer, heater and cooler provided in the reaction vessel; A scrubber, a condenser, and a regulator are provided in this order on the hydrogen gas extraction side of the reaction tank. (21) In the hydrogen gas production apparatus of the present invention, the scrubber removes the alkaline aqueous solution mist, metasilicate hydrate mist, and silicon particles generated from the reaction vessel.
  • the means for supplying the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production is preferably a Mono pump or a gear pump. Mono pumps and gear pumps can stably discharge sludge material.
  • the reaction tank includes means for mixing the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production with an alkaline aqueous solution.
  • the silicon raw material A for producing hydrogen gas of the present invention contains an appropriate amount of oil that moderately suppresses the reaction between the silicon particles and the aqueous alkali solution.
  • the oil comes from the coolant.
  • the silicon scrap obtained by separating the regenerated coolant from the waste coolant of the multi-wire saw contains more than 10% of the weight of silicon particles.
  • silicone waste when there is too much oil content contained in silicon
  • silicone waste reaction of a silicon particle and aqueous alkali solution is inhibited. Therefore, even when an alkaline aqueous solution is added to silicon scrap, the hydrogen gas obtained is less than the theoretical value.
  • Such silicon scrap cannot be used as it is as a silicon raw material for producing hydrogen gas.
  • the silicon raw material for producing hydrogen gas of the present invention contains less oil than silicon scrap, the hydrogen gas as theoretical value can be obtained by adding an alkaline aqueous solution. Moreover, since the silicon raw material for producing hydrogen gas of the present invention contains an appropriate amount of oil (0.1% to 10% by weight of the silicon particles) that suppresses the reaction between the silicon particles and the aqueous alkali solution, Does not become explosive. Thereby, reaction of silicon particles and aqueous alkali solution is moderately suppressed, and hydrogen gas can be generated constantly over a long period of time. As a result, the first problem (oil inhibits the generation of hydrogen gas) and the second problem (moderately suppresses the reaction between the silicon particles and the aqueous alkali solution) are solved simultaneously.
  • the silicon raw material B for producing hydrogen gas of the present invention is obtained by evaporating and removing the oil component derived from the coolant by high-temperature drying, and then mixing a desired amount of reaction inhibitor with a desired amount of silicon particles.
  • the reaction-suppressing substance is a substance having a function of appropriately suppressing the reaction between the silicon particles and the alkaline aqueous solution, like the oil.
  • the mechanism by which the reaction inhibitor moderately suppresses the reaction between the silicon particles and the aqueous alkali solution is the same as the mechanism by the oil component derived from the coolant.
  • the reaction suppressing substance contained in the silicon raw material B for hydrogen gas production a substance different from the oil content of the coolant is usually used, but the same material as the oil content of the coolant may be used. Even when the silicon raw material B for producing hydrogen gas is used, the reaction between the silicon particles and the aqueous alkali solution is moderately suppressed, and hydrogen gas can be generated constantly over a long period of time.
  • the silicon raw material for producing hydrogen gas of the present invention is added with water having a weight of 1 to 10 times, preferably 1 to 5 times, more preferably 2 to 4 times the weight of silicon particles to form sludge. is there. Thereby, it can inject
  • the method for producing the silicon raw material A for producing hydrogen gas according to the present invention uses an oil contained in the coolant, and thus the production process is short.
  • any reaction suppressing substance can be mixed with high accuracy.
  • the injection rate of the silicon raw material for hydrogen gas production and the aqueous alkali solution is continuously injected while feedback control is performed based on the temperature and alkali concentration of the mixture in the reaction tank, a certain amount of hydrogen Gas is obtained continuously.
  • the reason why the alkaline aqueous solution and the silicon raw material can be continuously injected is that the second problem (moderately suppressing the reaction between the silicon particles and the alkaline aqueous solution) has been solved. Thereby, the 3rd subject (pressure fluctuation of a reaction tank) is solved.
  • a scrubber is provided between the reaction tank and the condenser. Hydrogen gas generated in the reaction vessel is led to a scrubber.
  • the scrubber removes the aqueous alkali mist, metasilicate hydrate, and silicon particles scattered from the reaction vessel before entering the condenser. This solves the fourth problem (corrosion and clogging with alkaline aqueous solution mist, metasilicate hydrate, silicon particles).
  • Production flow chart of silicon raw material for producing hydrogen gas of the present invention Configuration diagram of the hydrogen gas production apparatus of the present invention Graph of hydrogen gas production experiment (effect of reaction inhibitor) Graph of hydrogen gas production experiment (Example 1) Graph of hydrogen gas production experiment (Example 2)
  • the silicon raw material for producing hydrogen gas of the present invention A and silicon raw material B for hydrogen gas production are produced according to the flowchart of FIG.
  • a silicon ingot 102 is installed on a multi-wire saw 101, and the silicon ingot 102 is cut while being cooled with a coolant 103 (mixed liquid of water and oil) to manufacture a silicon wafer 104.
  • the portion cut by the wire becomes amorphous silicon particles having a size of about 0.1 ⁇ m to 30 ⁇ m.
  • the average particle size of the silicon particles is preferably about 1 ⁇ m.
  • Waste coolant 105 generated in the multi-wire saw 101 includes silicon particles and coolant 103.
  • the oil component contained in the coolant 103 is, for example, propylene glycol.
  • the waste coolant 105 is first subjected to a centrifuge A106 to be separated into a supernatant and a precipitate.
  • the supernatant contains water and oil and is used again in the multi-wire saw 101 as the regenerated coolant 107.
  • the precipitate is called silicon scrap 108, and contains water, oil, and silicon particles. Since the silicon scrap 108 contains an oil component that exceeds 10% of the weight of the silicon particles, the reaction with the alkaline aqueous solution tends to be hindered.
  • the silicon waste 108 is again applied to the centrifuge B109 or passed through the filter 110.
  • the supernatant 111 contains water and oil. This supernatant 111 is discarded.
  • the precipitate obtained by centrifugation is a solid A112 mainly composed of silicon particles, and contains oil (0.1 to 10% by weight of silicon particles) and a small amount of water.
  • the solid material A112 mainly composed of silicon particles obtained by filtration contains an oil (0.1% to 10% by weight of silicon particles) and a small amount of water.
  • the solid matter A112 obtained by centrifugation and the solid matter A112 obtained by filtration can proceed in the same way to the next step (drying) as shown in the flowchart of FIG. .
  • the solid material A 112 is dried in a drying furnace 114.
  • the purpose of drying is to remove a small amount of water contained in the solid material A112. Therefore, the temperature of the drying furnace 114 is preferably 100 ° C. to 120 ° C. At this temperature, water evaporates but oil does not evaporate.
  • the components of the solid B115 after drying are silicon particles and oil (0.1% to 10% by weight of silicon particles).
  • the solid B115 has 0.1% by weight to 10% by weight (typically 3% by weight) of the silicon particles. %) Oil can be included.
  • the solid B115 contains 0.1 wt% to 10 wt% (typically 3 wt%) of oil. be able to.
  • the surface of the silicon particles in the solid material B115 is considered to include a portion where silicon is exposed and a portion where silicon is covered with oil. It is considered that the portion where the silicon is exposed reacts with the alkaline aqueous solution, and the portion where the silicon is covered with oil does not react with the alkaline aqueous solution. If the entire surface of the silicon particles is covered with oil, it is considered that the reaction between the silicon particles and the aqueous alkali solution does not occur. When the silicon exposed surface and the part covered with oil are mixed in an appropriate ratio on the surface of the silicon particle, the silicon particle and the alkaline aqueous solution react slowly, and the silicon particle and the alkaline aqueous solution stay for a long time. It is believed that the reaction can continue and hydrogen gas can be generated constantly.
  • Water 116 is added to the solid material B115 obtained by drying in the drying furnace 114 to obtain sludge A117.
  • water is added to solid B115.
  • the sludge obtained by adding 116 is named sludge A117
  • the sludge obtained by adding the reaction inhibitor 121 and water 123 to the solid C is named sludge B124.
  • Sludge A117 is the silicon raw material A for hydrogen gas production of the present invention. The reason why water 116 is added to the solid material B115 to make the sludge A117 is to first make it suitable for pumping with a sludge pump.
  • the amount of water 116 added is preferably 1 to 10 times the weight of the silicon particles contained in the solid B115, more preferably 1 to 5 times, and even more preferably 2 to 4 times. When the water 116 is added 1 to 10 times, the silicon particles are uniformly dispersed in the water 116, so that clogging of pipes and pumps is difficult to occur.
  • the silicon raw material A for hydrogen gas production contains 0.1 wt% to 10 wt%, preferably 0.5 wt% to 5 wt%, more preferably 2 wt% of silicon particles.
  • the oil content of 4% by weight to 4% by weight, typically 3% by weight is mixed, the silicon particles and the alkaline aqueous solution continue to react for a long time, and hydrogen gas can be generated constantly.
  • the silicon raw material A sludge A117
  • the silicon particles may settle if left standing for a long time. Therefore, it is preferable to redisperse the silicon particles with a dispersing device immediately before injection into the reaction vessel.
  • the next step of the flowchart of FIG. 1 is further performed.
  • the solid B115 containing oil is fired in a high-temperature furnace 118, and the oil 119 derived from the coolant is evaporated to obtain a solid C120 made of only silicon particles.
  • the temperature of the high temperature furnace 118 is preferably 500 ° C. to 700 ° C., more preferably 600 ° C.
  • the oil component 119 evaporates at this temperature. Nitrogen gas is passed through the high temperature furnace 118 to prevent surface oxidation of the silicon particles and oxidation and combustion of the oil component 119.
  • the solid C120 baked in the high temperature furnace 118 contains almost no oil. Therefore, the solid substance C120 is mixed with the reaction inhibitor 121 and water 123 to obtain sludge B122.
  • the amount of the reaction inhibitor 121 is 0.1% to 10% by weight of the silicon particles, preferably 0.5% to 5% by weight, more preferably 2% to 4% by weight, typically 3%. %.
  • the reaction inhibiting substance 121 may be the same substance as the oil component 119 or a different substance.
  • reaction inhibitor substances to be mixed will be described later, but reaction inhibitor substances such as carboxylic acids, water-soluble polymers, and monomers are hardly contained in the coolant. Therefore, in particular, when a reaction inhibitor such as a carboxylic acid, a water-soluble polymer, or a monomer is used, a process after firing in the high temperature furnace 118 is necessary.
  • Sludge B124 is the silicon raw material B for hydrogen gas production of the present invention.
  • the reason for adding the water 123 is to first mix the silicon particles and the reaction-suppressing substance uniformly and to make it suitable for pumping with a sludge pump. Secondly, the reaction heat between the silicon particles and the aqueous alkali solution is cooled with water. Third, to replenish water consumed by the reaction.
  • the amount (weight) of water 123 added is preferably 1 to 10 times, more preferably 1 to 5 times, and further preferably 2 to 4 times the weight of the solid C120 (silicon particles).
  • the sludge A117 containing 3% by weight of oil (propylene glycol) derived from the coolant and 3% by weight of a reaction inhibitor (propylene glycol) of the same kind as the oil are mixed after firing in a high temperature furnace.
  • oil propylene glycol
  • a reaction inhibitor propylene glycol
  • the reaction inhibitor the following water-soluble organic substances or mixtures thereof are preferred.
  • (1) and (2) may be contained in the coolant as oil.
  • (3) and (4) are usually not included in the coolant, and even if included, the amount is small.
  • Polyhydric alcohol ethylene glycol, diethylene glycol, propylene Glycol, dipropylene glycol, glycerin, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, (The above monohydric alcohol and polyhydric alcohol can be collectively represented as X- (OH) n, where X is a saturated or unsaturated hydrocarbon group having 3 to 7 carbon atoms, and
  • Carboxylic acid / saturated fatty acid formic acid, lactic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid , Heptadecanoic acid / unsaturated aliphatic carboxylic acid: acrylic acid, oleic acid / hyroxylic acid: malic acid, citric acid / dicarboxylic acid: oxalic acid, maleic acid, fumaric acid (4) water-soluble polymer, monomer vinylpyrrolidone, polyvinylpyrrolidone , Sodium polyacrylate, polyethylene oxide, polyethylene imide, polyvinyl alcohol, polyacrylamide, polyethylene glycol stearic acid, stearic acid,
  • FIG. 2 is a block diagram of the hydrogen gas production apparatus 200 of the present invention.
  • a silicon raw material 202 for producing hydrogen gas is injected into a sealed reaction tank 201 by a sludge pump 203.
  • the silicon raw material 202 for producing hydrogen gas is the sludge A117 (silicon raw material A for producing hydrogen gas) or sludge B122 (silicon raw material B for producing hydrogen gas) in the flowchart of FIG. Therefore, as the sludge pump 203, a Mono pump or a gear pump capable of pumping sludge is suitable.
  • An alkaline aqueous solution 204 (for example, NaOH aqueous solution) is injected into the reaction tank 201 by an alkaline aqueous solution pump 205.
  • an alkaline aqueous solution pump 205 for example, an alkali-resistant pump made of fluororesin or polyethylene is suitable.
  • the reaction tank 201 needs to have pressure resistance because hydrogen gas is generated and is in a pressurized state. Further, the reaction vessel 201 needs to be resistant to alkali. Therefore, the reaction vessel 201 is preferably a stainless steel pressure vessel.
  • the alkaline aqueous solution 204 and the silicon raw material 202 for hydrogen gas production are mixed to obtain a mixed solution 208.
  • the silicon raw material 202 for producing hydrogen gas is sludge (mud)
  • the temperature of the mixed liquid 208 in the reaction tank 201 is raised by the heater 207 before the silicon raw material 202 for producing hydrogen gas is charged.
  • the heater 207 is controlled while measuring the temperature of the mixed liquid 208 with a thermometer 209.
  • the temperature of the mixed liquid 208 is controlled by the heater 207 so as to be 50 ° C. to 90 ° C. (preferably 60 ° C. to 80 ° C.).
  • the reaction rate becomes slow (hydrogen gas generation is reduced).
  • the temperature of the mixed liquid 208 is suitably 50 ° C. to 90 ° C.
  • the heating of the heater 207 is weakened or stopped. If the generation of reaction heat further increases and the temperature of the mixed solution 208 becomes higher than the upper limit even when the heater 207 is turned off, the mixed solution 208 is cooled by the cooler 210. At the same time, the injection of the silicon raw material 202 for producing hydrogen gas is reduced or stopped.
  • the concentration of the aqueous NaOH solution is preferably 1 mol / L to 8 mol / L, and more preferably 3 mol / L to 4 mol / L.
  • the concentration of the NaOH aqueous solution exceeds 8 mol / L, the viscosity of the NaOH aqueous solution becomes too high and it becomes difficult to uniformly mix with the silicon raw material 202 for producing hydrogen gas.
  • the silicon raw material 202 for producing hydrogen gas is injected, sodium metasilicate is formed, so that the viscosity of the mixed solution 208 is further increased and uniform mixing is difficult.
  • the reaction may be non-uniform.
  • the concentration of the NaOH aqueous solution is preferably 1 mol / L to 8 mol / L.
  • the silicon raw material A for hydrogen gas production or hydrogen gas produced according to the flowchart of FIG. A silicon raw material B for production is used. Since the silicon raw material A for hydrogen gas production or the silicon raw material B for hydrogen gas production used in the present invention contains a certain amount of oil or a reaction suppressing substance, the silicon particles and the aqueous alkali solution are suppressed from reacting rapidly. However, since the oil or reaction inhibitor is not so much as to inhibit the reaction, it generates a theoretical amount of hydrogen gas.
  • the silicon particles and the aqueous alkaline solution 204 react slowly, the silicon particles and the aqueous alkaline solution 204 can continue to react for a long time, and hydrogen gas can be generated constantly.
  • the alkaline aqueous solution 204 and the silicon raw material 202 for producing hydrogen gas are injected continuously in principle.
  • the silicon raw material 202 for producing hydrogen gas used in the hydrogen gas producing apparatus 200 of the present invention does not react rapidly, the alkaline aqueous solution 204 and the silicon raw material 202 for producing hydrogen gas can be injected continuously.
  • Alkali By continuously injecting the aqueous solution 204 and the silicon raw material 202 for producing hydrogen gas, the hydrogen gas can be obtained stably and continuously.
  • the injection rates of the alkaline aqueous solution 204 and the silicon raw material 202 for producing hydrogen gas are not always constant. This is because even if the alkaline aqueous solution 204 and the silicon raw material 202 for producing hydrogen gas are injected at a constant rate, the hydrogen gas generation rate may not be constant.
  • the injection rate of the alkaline aqueous solution 204 is such that the alkali concentration of the mixed solution 208 in the reaction vessel 201 is a predetermined value (1 mol / L to 8 mol / L when using an aqueous NaOH solution, preferably 3 mol / L to 4 mol / L).
  • the alkali concentration is measured and the change rate (time differentiation) of the alkali concentration is calculated, and the injection rate of the alkaline aqueous solution 204 is feedback-controlled.
  • the alkali concentration of the mixed liquid 208 is measured by titrating the liquid sampled from the neutralization titration sampling terminal 211 with a neutralization titration apparatus (not shown). Depending on the control result, the injection of the alkaline aqueous solution 204 may be interrupted.
  • SiO 2 (OH) 2 2 ⁇ of the reaction formula (4) is accumulated in the reaction tank 201.
  • This hydrate (SiO 2 (OH) 2 2 ⁇ ) is so-called water glass and has a pH buffering action. Therefore, even if the pH of the mixed solution 208 is measured, the alkali concentration cannot be accurately known. Therefore, instead of the pH of the liquid mixture 208, the sample of the liquid mixture 208 is titrated to measure the alkali concentration.
  • the injection rate of the silicon raw material 202 for producing hydrogen gas is controlled so that the temperature of the mixed solution 208 in the reaction vessel 201 becomes a predetermined value (50 ° C. to 90 ° C., preferably 60 ° C. to 80 ° C.). .
  • the temperature is measured with a thermometer 209 and the rate of change (time differentiation) of the temperature is calculated to determine the injection rate of the silicon raw material 202 for producing hydrogen gas.
  • Feedback control Depending on the control result, the injection of the alkaline aqueous solution 204 and the silicon raw material 202 for producing hydrogen gas may be interrupted. Furthermore, the liquid mixture 208 may be cooled by the cooler 210.
  • the temperature of the mixed liquid 208 rises due to reaction heat.
  • the temperature of the mixed solution 208 is lowered by the injection of the alkaline aqueous solution 204 and the injection of the silicon raw material 202 for producing hydrogen gas (because the temperature of the alkaline aqueous solution 204 and the silicon raw material 202 for producing hydrogen gas is lower than the mixed solution 208. Is).
  • the alkaline aqueous solution 204 and the silicon raw material 202 for hydrogen gas production before the injection are kept at about 20 ° C. It is desirable to keep it in
  • the hydrogen gas generation rate can be made constant.
  • the injection of the silicon raw material 202 for producing hydrogen gas may be interrupted.
  • the hydrogen gas generated in the reaction tank was led to a condenser.
  • a scrubber 214 is provided between the reaction vessel 201 and the condenser 213 in order to solve the fourth problem (clogging with alkaline aqueous solution mist and silicon particles). Hydrogen gas generated in the reaction vessel 201 is guided to the scrubber 214.
  • the scrubber 214 can remove the alkaline aqueous solution mist, metasilicate hydrate, and silicon particles scattered from the reaction vessel 201 before entering the condenser 213.
  • a chemical-resistant (for example, vinyl chloride) processing container is filled with a large number of chemical-resistant fillers (for example, small baskets made of polyethylene) with a high gap ratio.
  • a treatment liquid in the case of the present invention, water or an acid aqueous solution, preferably dilute sulfuric acid
  • the gas to be treated includes hydrogen gas, water vapor, alkaline aqueous solution mist, metasilicate hydrate mist, and silicon particles.
  • the gas P reacts with the processing liquid while passing through the gaps in the packing.
  • the alkaline aqueous solution mist is neutralized or dissolved by the treatment liquid.
  • the metasilicate hydrate mist and silicon particles are washed away by the treatment liquid.
  • the gas Q that has passed through the scrubber 214 contains hydrogen gas and water vapor, but does not contain alkaline aqueous solution mist, metasilicate hydrate mist, or silicon particles. Thereby, since the gas Q (hydrogen gas and water vapor) is obtained, the clogging of the condenser 213 can be eliminated.
  • the gas Q that has passed through the scrubber 214 is a mixture of hydrogen gas and water vapor
  • the water Q is removed through the condenser 213.
  • the gas Q is cooled by, for example, cooling water, and water vapor is condensed to remove moisture.
  • the hydrogen gas processed by the condenser 213 contains almost no moisture.
  • the dew point temperature of the condenser 213 is determined according to the specifications of the hydrogen gas supply destination.
  • a back pressure regulator 215 is installed on the outlet side of the condenser to regulate the pressure from the reaction tank 201 to the condenser 213.
  • the pressure in the reaction vessel 201 is measured with a pressure gauge 212.
  • This regulation pressure is preferably 0.05 MPa to 0.5 MPa, more preferably 0.05 MPa to 0.15 MPa.
  • hydrogen gas is generated above the regulation pressure, the hydrogen gas is sent to the compressor 216, compressed and pressurized, and stored in the cylinder 217.
  • the pressurization by the compressor 216 depends on the standard of the cylinder 217, but is 35 MPa or 70 MPa in the case of a hydrogen station of a fuel cell vehicle (FCV).
  • the purity of the hydrogen gas processed by the condenser 213 is high (for example, 99.9%), it can be used as it is depending on the application.
  • the hydrogen gas processed in the condenser 213 is packed in the cylinder 217 through the compressor 216, and becomes hydrogen gas as a product.
  • the hydrogen gas is passed through a hydrogen gas purifier 218 for processing.
  • the hydrogen gas purification device 218 is, for example, a palladium alloy film. Since the palladium alloy film does not pass a gas other than hydrogen gas (for example, nitrogen gas, oxygen gas, or rare gas), the hydrogen gas that has passed through the palladium alloy film becomes a high-purity hydrogen gas.
  • the high-purity hydrogen gas is converted into high-pressure high-purity hydrogen gas by the compressor 216 and packed in the cylinder 217, and becomes high-purity hydrogen gas as a product.
  • SiO 2 (OH) 2 2 ⁇ of the reaction formula (4) is accumulated. When H 2 O is subtracted from this, it becomes SiO 3 2 ⁇ , which is a metasilicate ion.
  • This hydrate (SiO 2 (OH) 2 2 ⁇ ) is so-called water glass. Water glass exhibits strong alkalinity by hydrolysis and has a pH buffering action. If hydrate (SiO 2 (OH) 2 2 ⁇ ) accumulates to some extent in the reaction vessel 201, it is necessary to remove the hydrate (SiO 2 (OH) 2 2 ⁇ ).
  • the concentration of hydrate (SiO 2 (OH) 2 2 ⁇ ) can be measured simultaneously with the neutralization titration described above. To what extent the concentration of hydrate (SiO 2 (OH) 2 2 ⁇ ) should be continued is determined by comprehensively considering the cost of hydrogen gas production and the like.
  • the silicon waste was centrifuged with a centrifugal separator B (3000 rpm) to obtain a solid A, and further the solid A was dried in a drying furnace at 105 ° C. to obtain a solid B.
  • the composition of the solid B was 97% by weight of silicon particles and 3% by weight of propylene glycol.
  • the amount of oil contained in the solid B is set to a desired value (0.1% by weight of silicon particles). Any value in the range of up to 10% by weight).
  • Fig. 3 shows the effect of oil or reaction inhibitors in hydrogen gas production experiments.
  • the horizontal axis represents time, and the vertical axis represents hydrogen gas generation amount (cumulative).
  • the horizontal axis represents time, and the vertical axis represents the temperature of the mixture of silicon particles and an aqueous alkali solution.
  • the curve A shows sludge obtained by mixing pure (not containing oil or reaction inhibitor) silicon particles (1.2 g) and 17 g of pure water with a 3.4 mol / L NaOH aqueous solution (1 .2 liters) is a graph in the case of injecting into a reaction tank (2 liters) containing 5 liters with a syringe for 5 seconds.
  • a solid C120 aggregate of silicon particles from which oil has been removed through a high-temperature furnace 118 shown in the flowchart of FIG.
  • curve B shows a silicon raw material for producing hydrogen gas containing 3% by weight of oil and silicon particles (1.2 g) and 17 g of pure water mixed with a 3.4 mol / L NaOH aqueous solution ( It is a graph at the time of inject
  • the silicon raw material for producing hydrogen gas containing 3% by weight of oil corresponds to sludge A117 in the flowchart of FIG.
  • the oil is propylene glycol.
  • reaction time of pure silicon particles and water sludge is about 30 seconds
  • reaction time of silicon raw material for hydrogen gas production (curve B) containing 3% by weight of oil is about 800 seconds. It is. Therefore, by including 3% by weight of oil, the reaction rate becomes about 1/27. Such a mild reaction can be controlled.
  • the temperature change of the mixed solution of silicon particles and alkaline aqueous solution shows that in the case of pure silicon particles (curve A), the temperature of the mixed solution decreases by 0.7 ° C. immediately after silicon particle injection. However, it rose 2.7 ° C immediately. The reason why the temperature decreased by 0.7 ° C first is that the sludge was at room temperature. The reason why the temperature rose by 2.7 ° C. is that the mixed solution was heated by the reaction heat. In the case of silicon particles mixed with 3% by weight of oil (curve B), the temperature change of the mixed solution is within 1 ° C. throughout the reaction. This is because the reaction is slow and the amount of heat of reaction generated per hour is small.
  • FIG. 4 shows a silicon raw material A for hydrogen gas production in which silicon particles, 3% by weight of oil (propylene glycol) of silicon particles, and pure water having a weight three times that of silicon particles are mixed. It is a graph which shows the amount of hydrogen gas generation
  • the horizontal axis of the graph is time, the left vertical axis is hydrogen gas amount (cumulative), and the right vertical axis is temperature.
  • the injection amount of silicon particles is 4.8 g / min.
  • the cumulative hydrogen gas amount increased in proportion to the time, and the maximum hydrogen gas generation rate was 3 liters / minute.
  • the injection of the silicon raw material A for producing hydrogen gas was stopped in 221 seconds, but the hydrogen gas continued to be generated after that, and the generation has not been completed even after 1500 seconds.
  • the amount of hydrogen gas generated after the injection of the silicon raw material A for producing hydrogen gas was more than three times the amount of hydrogen gas generated during the injection of the silicon raw material A for producing hydrogen gas.
  • the temperature of the mixed solution also rose in proportion to the time.
  • the injection of the silicon raw material A for producing hydrogen gas was stopped in 221 seconds, but after that, the temperature rose with the same slope, rose 8.6 ° C., and then slowly dropped. However, the temperature has not yet returned to the pre-reaction temperature in 1500 seconds.
  • FIG. 5 shows a silicon raw material A for hydrogen gas production in which silicon particles, 3% by weight of oil (propylene glycol) of silicon particles, and pure water 3 times the weight of silicon particles are mixed.
  • a graph showing the amount of hydrogen gas generated and the temperature change of the mixture when continuously injected into a reaction tank (2 liters) containing a 4 mol / L NaOH aqueous solution (1.2 liters) with a Mono pump for 857 seconds. is there.
  • the horizontal axis of the graph is time, the left vertical axis is hydrogen gas amount (cumulative), and the right vertical axis is temperature.
  • the injection amount of silicon particles is 1.3 g / min.
  • the amount of hydrogen gas generated increases in proportion to the time during the injection of the silicon raw material A for hydrogen gas production, and the generation rate (gradient of the graph) after the injection of the silicon raw material A for hydrogen gas production is stopped. Be gentle.
  • the maximum hydrogen gas generation rate during the injection of the silicon raw material A for hydrogen gas production was 1.2 liters / minute.
  • the amount of hydrogen gas generated after the injection of the silicon raw material A for producing hydrogen gas was about 1 ⁇ 2 of the amount of hydrogen gas generated during the injection of sludge.
  • the temperature of the mixed liquid rises almost in proportion to time, and when the injection of the silicon raw material A for hydrogen gas production is stopped, the temperature of the mixed liquid gradually decreases, The temperature returned to the pre-reaction temperature around 1400 seconds.
  • the maximum temperature increase was only 2.2 ° C.
  • the cause of the temperature rise of the liquid mixture was reaction heat, not heating by a heater. From the graph of temperature change, it is estimated that the injection amount of the silicon raw material A for producing hydrogen gas is almost matched to the capacity of the reaction vessel. Thus, if the injection amount of the silicon raw material A for hydrogen gas production is appropriate for the capacity of the reaction vessel, the hydrogen gas can be produced continuously and stably.
  • the above description relates to a silicon raw material for producing hydrogen gas produced from silicon scrap generated by a multi-wire saw.
  • silicon scrap generated by dicer cutting, lapping, etc. can be used as a silicon raw material for hydrogen gas production by appropriately changing the flowchart of FIG.
  • Dicer cutting does not contain oil because pure water is used instead of coolant. Therefore, silicon scrap generated by dicer cutting can be centrifuged and dried, and then mixed with an appropriate reaction-suppressing substance to obtain a silicon raw material for producing hydrogen gas.
  • coolant including oil
  • abrasive grains are mixed with silicon scraps. After removing the abrasive grains, silicon raw materials for hydrogen gas production are processed in the same way as silicon scraps generated by a multi-wire saw. Can do.
  • silicon waste is generated during the manufacturing process of the silicon wafer.
  • silicon scrap has been discarded, but the cost burden and environmental burden due to disposal cannot be ignored.
  • hydrogen gas can be obtained constantly from silicon waste, and silicon waste that has been discarded can be used.

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PCT/JP2014/074516 2013-11-12 2014-09-17 水素ガス製造用シリコン原料ａ、水素ガス製造用シリコン原料ｂ、水素ガス製造用シリコン原料ａの製造方法、水素ガス製造用シリコン原料ｂの製造方法、水素ガス製造方法および水素ガス製造装置 WO2015072224A1 (ja)

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MYPI2016000885A MY176196A (en) 2013-11-12 2014-09-17 Silicon material a for hydrogen gas production, silicon material b for hydrogen gas production, method for producing silicon material a for hydrogen gas production, method for producing silicon material b for hydrogen gas production, method for producing hydrogen gas, and device for producing hydrogen gas

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