Acetylene, method for producing acetylene, and acetylene derivatives

Abstract

To provide acetylene utilizable as a raw material for various bioplastics while reducing loads on the environment, to provide a method for producing the acetylene, and to provide an acetylene derivative.SOLUTION: According to an aspect of the present invention, there is provided acetylene, wherein the acetylene contains carbon atoms derived from biomass.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to acetylene, a method for producing acetylene, and an acetylene derivative. [Background Art]

[0002] In recent years, demand for bioplastics has been increasing from the perspective of reducing environmental load. As bioplastics, bio-polyethylene has been marketed and is expected to contribute to the reduction of carbon dioxide emissions (see Patent Document 1). At present, the types of bioplastics that can be produced are limited, and there is a demand for the development of compounds that can be used as raw materials for more types of bioplastics. [Prior Art Literature] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Laid-open No. 2010-511634 [Summary of Invention] [Problem to be Solved by the Invention]

[0004] In view of the above circumstances, the present invention aims to provide acetylene that can be used as a raw material for various bioplastics, a method for producing acetylene, and an acetylene derivative while reducing environmental load. [Means for Solving the Problem]

[0005] According to one aspect of the present invention, there is provided acetylene containing carbon atoms derived from biomass.

[0006] According to this aspect, acetylene that can be used as a raw material for various bioplastics can be supplied while reducing environmental load. [Mode for Carrying Out the Invention]

[0007] The following describes embodiments of acetylene, a method for producing acetylene, and acetylene derivatives. The various features shown in the embodiments below can be combined with each other.

[0008] <Acetylene and acetylene derivatives> The acetylene in this embodiment contains carbon atoms derived from biomass. Using such acetylene makes it possible to manufacture various types of bioplastics while reducing the environmental burden. Therefore, it can contribute to the realization of a carbon-recycling society. Furthermore, the acetylene derivative of this embodiment is a modified version of the above-mentioned acetylene. Here, modification refers to changing a part of the molecule of a compound through a chemical reaction, or combining multiple molecules of a compound (for example, dimerization). Even when using such an acetylene derivative, it is possible to manufacture various types of bioplastics while reducing the burden on the environment.

[0009] Specifically, acetylene can be used to produce ethylene by hydrogenation, acrylonitrile by reacting it with hydrogen cyanide, vinyl chloride by reacting it with hydrogen chloride, acrylic acid by reacting it with carbon monoxide and water, monovinylacetylene by dimerization, chloroprene monomer (2-chloro-1,3-butadiene) by reacting it with hydrogen chloride after dimerization, vinyl acetate by reacting it with acetic acid, polyacetylene by polymerization, and acetaldehyde by reacting it with water. Acrylic acid can also be used to produce acrylic acid esters by reacting it with alcohol. In particular, it is preferable that the acetylene derivative is at least one selected from the group consisting of ethylene, acrylonitrile, vinyl chloride, acrylic acid, acrylic acid esters, and monovinylacetylene. Furthermore, acetylene black can also be produced by the thermal decomposition of acetylene.

[0010] Ethylene is used, for example, as a raw material for polyethylene, ethylene vinyl acetate copolymer (EVA), and ethylene propylene rubber (EPR). Acrylonitrile is used, for example, as a raw material for polyacrylonitrile, ABS resin, AS resin, acrylamide, and nitrile rubber. Vinyl chloride is used, for example, as a raw material for polyvinyl chloride. Acrylic acid is used, for example, as a raw material for polyacrylic acid (PAA) and polyacrylamide. Acrylic acid esters are used, for example, as raw materials for polymethyl acrylate (PMA), polyethyl acrylate (PEA), polybutyl acrylate (PBA), and polyethylhexyl acrylate (PEHA). Monovinyl acetylene is used, for example, as a raw material for polyvinyl acetylene. Chloroprene monomer is used, for example, as a raw material for polychloroprene.

[0011] Such acetylene is as defined in ASTM D6866. 14 The biomass content measured by the 1C isotope assay method is preferably between 0.01% and 100%, preferably between 0.1% and 80%, and more preferably between 1% and 60%. If the biomass content is below the above upper limit, acetylene, which is a raw material for bioplastics, can be supplied at a lower cost. On the other hand, if the biomass content is above the above lower limit, it is easier to contribute to the realization of a carbon-recycling society.

[0012] Here, biomass content refers to the proportion of biomass-derived carbon atoms contained in acetylene. This biomass content refers to the radioactive carbon contained only in biomass-derived materials. 14 This can be determined by measuring the amount of C) contained in acetylene. The same applies to metal carbides. In this specification, biomass is defined in ASTM D6866. 14Accelerator Mass Spectrometry (AMS), a type of 14C isotope analysis method, is used to determine the total carbon atoms contained in acetylene. 14 It can be determined by measuring the percentage of C (percent Modern Carbon: pMC) and calculating the proportion (content) of carbon atoms derived from biomass. Furthermore, the biomass-derived carbon atoms are preferably derived from at least one of the following: charcoal, pulp char, lignin char, coconut shell char, bagasse char, and sorghum char. It is more preferable that charcoal and / or pulp char is included, and even more preferable that charcoal is included. The advantages of using charcoal as biomass will be described in detail later.

[0013] <Method for producing acetylene> The acetylene described above can be produced, for example, by the following acetylene production method. The method for producing acetylene according to this embodiment comprises the steps of: preparing a carbon source containing biomass and a metal source; heating the carbon source and metal source in an electric furnace to obtain metal carbide; and reacting the metal carbide with water to obtain acetylene. Here, metal carbide is a compound represented by the chemical formula: MC or MC2 (where M is a metal atom). Each step will be described below.

[0014] <<Preparation process>> First, prepare a carbon source containing biomass and a metal source. Examples of biomass include plant-derived biomass and animal-derived biomass. These waste materials may be used individually or in combination of two or more types. Examples of plant-derived biomass include: logging timber; wood products such as wood chips, chips and branches produced from sawmills; agricultural crops such as corn, sugarcane, wheat, rice, soybeans, rapeseed and sorghum; agricultural crop residues such as rice straw, wheat straw, corn stalks and leaves, coconut shells, and bagasse (the residue after squeezing sugarcane); grasses (herbaceous plants) such as switchgrass and miscanthus; algae such as seaweed and microalgae; lignocelluloses such as pulp and lignin; and pericarp, seeds, vegetable oil, etc. Examples of animal-derived biomass include: manure of livestock (cattle, pigs, chickens, etc.); livestock by-products such as livestock bones or internal organs; and animal oil, etc.

[0015] Furthermore, biomass may use components after separation by a specific method. For example, a lignocellulosic biomass may be prepared as the biomass, and an insoluble fraction containing lignin (lignin-containing component) may be separated and recovered from the lignocellulosic biomass by a dilute sulfuric acid method or a concentrated sulfuric acid method for use. In addition, biomass may be directly used as a carbon source, or a carbide obtained after carbonization may be used as the carbon source. The fixed carbon content in the carbon source can be adjusted, for example, by controlling the temperature during carbonization of biomass (carbonization temperature). Specifically, the content of fixed carbon (carbon atoms) in the carbon source is preferably about 85% by mass or more, more preferably about 90% by mass or more, still more preferably about 95% by mass or more, and may be 100% by mass. In this case, metal carbides with reduced impurity content and acetylene can be obtained in high yield. The fixed carbon content in the carbon source can be measured in accordance with JIS M 8812:2006.

[0016] Among those described above, non-edible biomass, particularly a carbide of non-edible biomass, is preferred as the biomass. This is because when non-edible biomass is used, there is no need to consider competition with food. In particular, the biomass preferably contains at least one selected from the group consisting of charcoal, pulp carbide, lignin carbide (lignin-containing component carbide), coconut shell carbide, bagasse carbide and sorghum carbide, more preferably contains charcoal and / or pulp carbide, and still more preferably contains charcoal. Charcoal is readily available and excellent in handleability, so when used in combination with coke, it has the advantage of being easily mixed uniformly. In addition, charcoal and pulp carbide contain no phosphorus compound, or only contain an extremely small amount even if they do contain phosphorus compound, so the content of impurities such as calcium phosphide (metal phosphide) contained in the obtained metal carbide can be sufficiently reduced. Therefore, when acetylene is produced using such metal carbide, the generation of toxic substances such as phosphine derived from the above impurities can be suitably prevented, resulting in high safety.

[0017] In addition, among charcoals, it is preferable to use hard charcoal. When hard charcoal is used, it is less likely to be crushed during mixing with coke or in the subsequent heating step, making it easier to produce metal carbide more stably. Specific examples of charcoal include white charcoal, black charcoal, sawdust charcoal, industrial charcoal, and the like. These charcoals may be used alone as one type, or two or more types may be used in combination. Specifically, a sample obtained by cutting a carbon source into a size of 35 mm × 35 mm × 10 mm preferably has a crushing strength measured in accordance with JIS Z 8841:1993 of about 30 kgf or more.

[0018] In addition, briquettes and molded coal produced by calcining briquettes can also be suitably used as the carbon source. Such briquettes can be obtained by pulverizing and sizing biomass with a pulverizer to obtain pulverized biomass, mixing the obtained pulverized biomass with a binder with a mixer, and then molding the mixture with a molding machine. The crushing strength of these carbon sources is preferably around 30 kgf or more, more preferably around 35 kgf or more, and even more preferably around 40 kgf or more. The upper limit of the crushing strength of the carbon source is not particularly limited, but is approximately 60 kgf. The crushing strength of the carbon source can be, for example, between 30 kgf and 60 kgf. This effectively prevents the carbon source from collapsing during charging or inside the electric furnace.

[0019] Such a carbon source preferably has a volatile content of about 5% by mass or less, more preferably about 4% by mass or less, and even more preferably about 3% by mass or less, as measured according to JIS M 8812:2006. The lower limit of the volatile content of the carbon source is not particularly limited, but is about 0.01% by mass. The volatile content of the carbon source can be, for example, between 0.01% by mass and 5% by mass. This effectively prevents the carbon source from burning during storage, etc. Furthermore, the phosphorus atom content in the carbon source is preferably about 200 ppm or less, more preferably about 150 ppm or less, 100 ppm or less, 60 ppm or less, 50 ppm or less, and even more preferably about 40 ppm or less. In this case, even when acetylene is produced using the resulting metal carbide, the generation of toxic substances such as phosphine can be sufficiently prevented, thereby further enhancing safety.

[0020] However, if the carbon source contains a small amount of phosphorus atoms, the leakage of highly flammable acetylene can be detected by detecting the odor of phosphorus compounds derived from calcium phosphide (metal phosphide). From this perspective as well, safety can be improved. Specifically, the phosphorus atom content in the carbon source is preferably about 0.1 ppm or more, preferably about 0.5 ppm or more, about 1 ppm or more, about 5 ppm or more, about 10 ppm or more, about 15 ppm or more, about 20 ppm or more, more preferably about 25 ppm or more, and even more preferably about 30 ppm or more. The phosphorus atom content in the carbon source can be, for example, about 0.1 ppm to 200 ppm.

[0021] The sulfur atom content in the carbon source is preferably 0.1% by mass (1000 ppm) or less, more preferably around 800 ppm or less, even more preferably around 600 ppm or less, particularly preferably around 400 ppm or less, and most preferably around 200 ppm or less. In this case, the generation of hydrogen sulfide can be suppressed, thereby increasing safety. Furthermore, the generation of sulfur oxides can also be suppressed, reducing corrosion and other damage to manufacturing equipment for metal carbides and bioplastics. The lower limit of the sulfur atom content in the carbon source is not particularly limited, but is approximately 50 ppm. The sulfur atom content in the carbon source can be, for example, between 50 ppm and 1000 ppm. The phosphorus and sulfur atom content in the carbon source can be measured in accordance with JIS M 8813:2004.

[0022] The ash content in the carbon source is preferably about 13% by mass or less, more preferably about 10% by mass or less, even more preferably about 5% by mass or less, and particularly preferably about 3% by mass or less. In this case, even if the ash is a compound that is reduced in the electric furnace, the amount is small, so it is possible to effectively prevent or suppress the wasteful consumption of the carbon source and electricity. It is also possible to reduce the number of times that the work of periodically removing the reduced ash products accumulated at the bottom of the electric furnace (cleaning) is performed. Furthermore, it is possible to improve the purity of the metal hydroxide produced as a by-product when acetylene is generated by reacting metal carbide with water. The lower limit of the ash content in the carbon source is not particularly limited and may be 0% by mass. The ash content in the carbon source can be, for example, 0% by mass or more and 13% by mass or less. Here, ash refers to the residue of inorganic components that remains after a carbon source is completely combusted in air (usually between 550°C and 800°C). The ash content in the carbon source can be measured in accordance with JIS M 8812:2006.

[0023] On the other hand, examples of metal sources include alkaline earth metal oxides, alkaline earth metal carbonates, alkaline earth metal hydroxides, alkaline earth metal sulfates, and alkaline earth metal chlorides. These metal sources may be used individually or in combination of two or more. The metal source preferably contains an oxide of an alkaline earth metal, and more preferably contains calcium oxide. Calcium oxide (CaO) is an unstable substance obtained, for example, by thermal decomposition of calcium carbonate (CaCO3) at about 900°C. For this reason, calcium oxide is suitable as a metal source due to its high reactivity. Calcium carbide, barium carbide, and magnesium carbide are preferred as metal carbides.

[0024] <<Heating process>> Next, the mixture of the carbon source and the metal source is placed in an electric furnace (carbide electric furnace) and heated. This causes the carbon source and the metal source to react, yielding metal carbide. The heating temperature is not particularly limited, but is preferably between 1700°C and 2200°C, and more preferably between 1900°C and 2100°C. The heating time is also not particularly limited, but when the above heating temperatures are used, it is preferably between 2 minutes and 3 hours, and more preferably between 30 minutes and 1.5 hours. By heating under these conditions, the reaction between the carbon source and the metal source can be sufficiently advanced.

[0025] The heating atmosphere is preferably an argon atmosphere. This prevents the unwanted combustion of carbon monoxide and hydrogen generated during the reaction between the carbon source and the metal source. The amount of carbon source is preferably 30 to 400 parts by mass, more preferably 50 to 300 parts by mass, and even more preferably 70 to 200 parts by mass, per 100 parts by mass of metal source. By reacting in such a ratio, the yield of metal carbide can be sufficiently increased. The carbon source and metal source are preferably in particulate form. This increases the contact area between the carbon source and the metal source, thereby improving their reaction efficiency.

[0026] The average particle size of the carbon source is not particularly limited, but is preferably between 8 mm and 50 mm, more preferably between 8 mm and 30 mm, and even more preferably between 8 mm and 10 mm. Furthermore, while the average particle size of the metal source is not particularly limited, it is preferably between 8 mm and 50 mm, more preferably between 8 mm and 30 mm, and even more preferably between 8 mm and 10 mm. In this specification, the average particle size refers to the particle size (D50) at which the cumulative value in the volume-based cumulative particle size distribution obtained by laser diffraction scattering reaches 50%. The laser diffraction scattering method is measured in accordance with the method described in JIS Z 8825:2013 "Particle size analysis - Laser diffraction and scattering method".

[0027] By using biomass as a carbon source, when combined with coke, the combustion of the biomass, which has a lower ignition temperature than coke, is expected to begin first, and the heat generated by this combustion is expected to accelerate the combustion of the coke. As a result, the reaction between the carbon source and the metal source can be smoothly guided into the aforementioned heating temperature range where the reaction proceeds smoothly. This effect is particularly pronounced when using charcoal among biomass sources. Charcoal is suitable for use in combination with coke because of its high carbon atom-to-hydrogen atom ratio. Furthermore, charcoal is preferable because its lower electrical conductivity compared to coke makes it less likely to cause electrical short circuits in the electric furnace. Furthermore, using charcoal has the advantage of preventing a significant increase in the cost of manufacturing metal carbide, as it eliminates the need to drastically alter the configuration of the electric furnace or add new manufacturing equipment.

[0028] Prior to the above heating (main heating), preheating may be performed by heating the mixture at a lower heating temperature than the above heating temperature. By performing such preheating, the amount of carbon source consumed during the main heating can be reduced, and the yield of metal carbide can be further increased. Suitable fuels for preheating include charcoal, which has a low ignition temperature among the carbon sources, and electric furnace gas (a mixture of carbon monoxide and hydrogen) emitted during main heating. Using charcoal as preheating fuel allows for a smooth transition from preheating to main heating. On the other hand, using electric furnace gas as preheating fuel allows for efficient energy utilization while effectively preventing air pollution. Furthermore, in this heating process, the biomass content of the resulting metal carbide can be adjusted within the above range by changing the mixing ratio of biomass (charcoal) and coke. Therefore, in the mass balance method, the mixing ratio of biomass and coke can be changed according to the demand for biomass, thus allowing for appropriate responses to fluctuations in demand.

[0029] Furthermore, the heating process may include recovering the gas produced in the electric furnace, which contains at least carbon monoxide and hydrogen. That is, the method for producing acetylene may further include a step of recovering the gas produced in the electric furnace, which contains at least carbon monoxide and hydrogen. The recovered carbon monoxide and hydrogen may be used, for example, as an energy source when converting calcium carbonate to calcium oxide, or when converting metal carbide to acetylene, and may also be used to convert carbon compounds. In the latter case, the method for producing acetylene may further include a step of reacting at least carbon monoxide with hydrogen to obtain a carbon compound. This allows for the effective utilization of gases generated in the metal carbide production process. Examples of these carbon compounds include acrylic acid, olefins (jet fuel), and acetylene black.

[0030] <<Acetylene Production Process>> Next, the metal carbide is reacted with water to produce acetylene. The amount of water added is preferably between 2 moles and 10 moles per mole of metal carbide, and more preferably between 2.5 moles and 5 moles. This allows the reaction between metal carbide and water to proceed sufficiently. The holding temperature in the reaction between metal carbide and water is preferably between 80°C and 200°C, and more preferably between 100°C and 180°C. By maintaining the reaction temperature within this range, the vaporization of water can be effectively prevented, allowing the reaction with metal carbide to proceed sufficiently.

[0031] The metal carbide may be in block form, but it is preferable that it be in particulate form. By using particulate metal carbide, the contact area with water can be increased. As a result, the reaction between the metal carbide and water can proceed without excess or deficiency. In this case, the average particle size of the metal carbide is not particularly limited, but is preferably between 1 mm and 150 mm, and more preferably between 5 mm and 120 mm. In this case, the above effects can be further improved.

[0032] Furthermore, various types of water can be used, such as tap water, distilled water, deionized water, pure water, ultrapure water, and RO (reverse osmosis). Since the reaction between metal carbide and water described above is an exothermic reaction, the heat generated may be recovered and used in the reaction between the carbon source and the metal source as described above. Furthermore, the slaked lime (calcium hydroxide) produced at this time can be suitably used, for example, as a cement admixture.

[0033] The metal carbide reacts with pure water to generate acetylene, and the sulfur atom content in the metal carbide is preferably about 100 ppm or less, more preferably about 90 ppm or less, even more preferably about 80 ppm or less, particularly preferably about 50 ppm or less, and may even be 0 ppm. The metal carbide reacts with pure water to generate acetylene, and the phosphorus atom content in the metal carbide is preferably 1 ppm to 320 ppm, more preferably 5 ppm to 250 ppm, even more preferably 10 ppm to 200 ppm, and particularly preferably 20 ppm to 180 ppm. The metal carbide reacts with pure water to generate acetylene, and the ash content in the metal carbide is preferably about 10% by mass or less, more preferably about 8% by mass or less, even more preferably about 5% by mass or less, particularly preferably about 3% by mass or less, and may even be 0% by mass. Furthermore, they may be provided in the following embodiments.

[0034] (1) Acetylene, which contains carbon atoms derived from biomass.

[0035] (2) The acetylene described in (1) above, as specified in ASTM D6866 14 Acetylene with a biomass content of 0.01% to 100% as measured by the 1C isotope assay method.

[0036] (3) Acetylene according to (1) or (2) above, wherein the biomass-derived carbon atoms are carbon atoms derived from at least one of charcoal, pulp char, lignin char, coconut shell char, bagasse char, and sorghum char.

[0037] (4) A method for producing acetylene, comprising the steps of: preparing a carbon source containing biomass and a metal source; heating the carbon source and the metal source in an electric furnace to obtain a metal carbide; and reacting the metal carbide with water to obtain the acetylene described in any one of (1) to (3) above.

[0038] (5) A method for producing acetylene as described in (4) above, wherein the content of phosphorus atoms in the carbon source is 200 ppm or less.

[0039] (6) A method for producing acetylene as described in (5) above, wherein the content of phosphorus atoms is 0.1 ppm or more.

[0040] (7) A method for producing acetylene according to any one of (4) to (6) above, wherein the ash content in the carbon source is 13% by mass or less.

[0041] (8) A method for producing acetylene according to any one of (4) to (7) above, wherein the content of sulfur atoms in the carbon source is 0.1% by mass or less.

[0042] (9) A method for producing acetylene according to any one of (4) to (8) above, wherein the carbon source has a volatile content of 5% by mass or less as measured in accordance with JIS M 8812:2006.

[0043] (10) A method for producing acetylene according to any one of (4) to (9) above, wherein the content of fixed carbon in the carbon source is 85% by mass or more.

[0044] (11) A method for producing acetylene according to any one of (4) to (10) above, wherein the biomass includes at least one of charcoal, pulp char, lignin char, coconut shell char, bagasse char, and sorghum char.

[0045] (12) A method for producing acetylene according to any one of (4) to (11) above, wherein a sample of the carbon source cut to a size of 35 mm × 35 mm × 10 mm has a crushing strength of 30 kgf or more as measured in accordance with JIS Z 8841:1993.

[0046] (13) A method for producing acetylene according to any one of (4) to (12) above, wherein the metal source includes an oxide of an alkaline earth metal.

[0047] (14) A method for producing acetylene according to any one of (4) to (13) above, further comprising the step of recovering a gas produced in the electric furnace and containing at least carbon monoxide and hydrogen.

[0048] (15) A method for producing acetylene as described in (14) above, further comprising the step of reacting at least the carbon monoxide with the hydrogen to obtain a carbon compound.

[0049] (16) A method for producing acetylene according to any one of (4) to (15) above, wherein the biomass is crushed and granulated with a crusher to obtain crushed biomass, the crushed biomass and a binder are mixed with a mixer, and then molded with a molding machine to obtain a briquette, and the briquette is used as the carbon source.

[0050] (17) A method for producing acetylene according to any one of (4) to (15) above, wherein lignocellulosic biomass is prepared as the biomass, lignin-containing components are separated and recovered from the lignocellulosic biomass, the lignin-containing components are carbonized to obtain lignin-containing component carbon, and the lignin-containing component carbon is used as the carbon source.

[0051] (18) An acetylene derivative which is a modified acetylene according to any one of (1) to (3) above.

[0052] (19) The acetylene derivative described in (18) above, wherein the acetylene derivative is at least one selected from the group consisting of ethylene, acrylonitrile, vinyl chloride, acrylic acid, acrylate ester, and monovinylacetylene. Of course, this is not always the case.

[0053] Finally, while various embodiments relating to this disclosure have been described, these are presented as examples only and are not intended to limit the scope of the invention. These novel embodiments can be implemented in a variety of other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims and their equivalents. [Examples]

[0054] The following describes acetylene and methods for producing acetylene in more detail using the following examples and comparative examples, but these are not limited to the following examples.

[0055] 1. Preparation of raw materials <Carbon source> • White charcoal: Made by South Sky Co., Ltd., "Kishu Binchotan" • Nara Black Charcoal: Manufactured by Yachi Forestry Co., Ltd., "Black Charcoal" • Oga charcoal: Manufactured by Pearl Metal Co., Ltd., "Oga Binchotan" • Coconut shell: Manufactured by Enerab Japan, "PKS (Palm Kernel Shell)" • Bagasse: Made by Bagasse Garden Co., Ltd., "dried bagasse" • Anthracite: Hong Gai charcoal from Vietnam • Wood chips: Komeri Co., Ltd. "Natural Season Blend Smoking Chips Value Pack" The above-mentioned white charcoal, oak black charcoal, sawdust charcoal, and anthracite were each crushed and separated using a sieve so that the average particle size was approximately 10 mm. <Calcium source (metal source)> • Calcium oxide: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., calcium oxide, 99.9% <Barium source (metal source)> Barium carbonate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 99.9%

[0056] 2. Production of metal carbides and acetylene (Example 1) First, a mixture was obtained by mixing 111 parts by mass of white charcoal as a carbon source and 155 parts by mass of calcium oxide as a calcium source, so that the amount of fixed carbon to be charged was 100 parts by mass. Next, this mixture was placed in a multi-purpose high-temperature furnace (Fuji Denpa Kogyo Co., Ltd., "High Multi Series") and heated at 2000°C for 1 hour while flowing argon at a rate of 7 L / hr. This yielded calcium carbide. The average particle size of the obtained calcium carbide was 10 mm. Subsequently, 2.5 moles of distilled water were added to 1 mole of calcium carbide to produce acetylene. The reaction temperature was maintained at 120°C during this time.

[0057] (Example 2) Calcium carbide and acetylene were obtained in the same manner as in Example 1, except that 133 parts by mass of charcoal were used as the carbon source. (Example 3) Calcium carbide and acetylene were obtained in the same manner as in Example 1, except that 111 parts by mass of sawdust charcoal were used as the carbon source.

[0058] (Example 4) Calcium carbide and acetylene were obtained in the same manner as in Example 1, except that 56 parts by mass of white charcoal and 59 parts by mass of anthracite were used as the carbon source. (Example 5) Calcium carbide and acetylene were obtained in the same manner as in Example 1, except that 11 parts by mass of white charcoal and 106 parts by mass of anthracite were used as carbon sources.

[0059] (Example 6) Calcium carbide and acetylene were obtained in the same manner as in Example 1, except that 1 part by mass of white charcoal and 116 parts by mass of coke were used as the carbon source.

[0060] (Example 7) Coconut shells were placed in a multi-purpose high-temperature furnace (Fuji Denpa Kogyo Co., Ltd., "High Multi Series") and heated at 800°C while flowing argon at a rate of 7 L / hr until the fixed carbon content reached 90% by mass, thereby obtaining coconut shell carbide. Next, 111 parts by mass of the coconut shell carbide and 195 parts by mass of calcium oxide as a calcium source were mixed to obtain a mixture. This mixture was then placed in the multi-purpose high-temperature furnace and heated at 2000°C for 1 hour while flowing argon at a rate of 7 L / hr, thereby obtaining calcium carbide. Subsequently, acetylene was obtained using the obtained calcium carbide in the same manner as in Example 1.

[0061] (Example 8) Bagasse was placed in a multi-purpose high-temperature furnace (Fuji Radio Industries Co., Ltd., "High Multi Series") and heated at 800°C while flowing argon at a rate of 7 L / hr until the fixed carbon content reached 90% by mass, thereby obtaining bagasse carbide. Next, 111 parts by mass of the bagasse carbide and 195 parts by mass of calcium oxide as a calcium source were mixed to obtain a mixture. This mixture was then placed in the multi-purpose high-temperature furnace and heated at 2000°C for 1 hour while flowing argon at a rate of 7 L / hr, thereby obtaining calcium carbide. Subsequently, acetylene was obtained using the obtained calcium carbide in the same manner as in Example 1.

[0062] (Example 9) The bagasse carbide obtained in Example 8 was crushed in a disc mill to obtain bagasse carbide powder (crushed bagasse carbide) with an average particle size of 350 μm. Next, 100 parts by mass of bagasse carbide powder and 8 parts by mass of asphalt binder were mixed in a batch-type mixer until the moisture content reached 7% by mass. Then, the mixture was molded at a linear pressure of 10 kN / cm using a double-roll molding machine with a recess of 34.8 mm × 30 mm × 9.4 mm to obtain bagasse carbide briquettes. After measuring the crushing strength, 111 parts by mass of the bagasse carbide briquettes were mixed with 195 parts by mass of calcium oxide as a calcium source to obtain a mixture. Next, this mixture was placed in a multi-purpose high-temperature furnace and heated at 2000°C for 1 hour while flowing argon at a rate of 7 L / hr. This yielded calcium carbide. Then, acetylene was obtained using the obtained calcium carbide in the same manner as in Example 1.

[0063] (Example 10) Wood chips were hydrolyzed using the concentrated sulfuric acid method, and the residue was obtained by filtration. The obtained residue was washed with hot water at 80°C, and then sequentially washed with acetone, ethyl acetate, and toluene to obtain wood chip-derived lignin. The obtained wood chip-derived lignin was then placed in a multi-purpose high-temperature furnace (Fuji Denpa Kogyo Co., Ltd., "High Multi Series") and heated at 800°C while flowing argon at a rate of 7 L / hr until the fixed carbon content reached 90% by mass, thereby obtaining wood chip-derived lignin carbide. Next, 111 parts by mass of the wood chip-derived lignin carbide and 195 parts by mass of calcium oxide as a calcium source were mixed to obtain a mixture. Next, this mixture was placed in a multi-purpose high-temperature furnace and heated at 2000°C for 1 hour while flowing argon at a rate of 7 L / hr. This yielded calcium carbide. Then, acetylene was obtained using the obtained calcium carbide in the same manner as in Example 1.

[0064] (Example 11) The lignin derived from wood chips obtained in Example 10 was heated at 300°C to obtain wood chip-derived lignin semi-carbide. 100 parts by mass of the wood chip-derived lignin semi-carbide and 8 parts by mass of asphalt binder were mixed in a batch-type mixer to obtain wood chip-derived lignin semi-carbide pellets. The wood chip-derived lignin semi-carbide pellets were then placed in a multi-purpose high-temperature furnace (Fuji Denpa Kogyo Co., Ltd., "High Multi Series"), and a pressure of 20 MPa was applied using a press. Under a reduced pressure atmosphere of 10 Pa, the mixture was heated at 800°C until the fixed carbon content reached 90% by mass to obtain wood chip-derived lignin molded charcoal. Next, 111 parts by mass of the wood chip-derived lignin molded charcoal and 195 parts by mass of calcium oxide as a calcium source were mixed to obtain a mixture. This mixture was then placed in a multi-purpose high-temperature furnace and heated at 2000°C for 1 hour while argon was flowed at a rate of 7 L / hr. This yielded calcium carbide. Subsequently, acetylene was obtained using the obtained calcium carbide in the same manner as in Example 1.

[0065] (Example 12) A mixture was obtained by mixing 111 parts by mass of lignin carbide derived from wood chips, obtained in Example 10, with 411 parts by mass of barium carbonate as a barium source. Next, this mixture was placed in a multipurpose high-temperature furnace and heated at 1550°C for 1 hour while flowing argon at a rate of 7 L / hr. This yielded barium carbide. Subsequently, acetylene was obtained using the obtained calcium carbide in the same manner as in Example 1.

[0066] (Comparative example) Calcium carbide and acetylene were obtained in the same manner as in Example 1, except that 118 parts by mass of anthracite were used as the carbon source.

[0067] 3. Measurement 3-1. Measurement of Biomass Content The biomass carbon sources used in each example and comparative example, and the metal carbides and acetylene obtained in each example and comparative example, were measured by accelerator mass spectrometry (AMS) in accordance with ASTM D6866, and the biomass content was calculated according to the following formula. Biomass percentage (%) = Biomass carbon source, metal carbide, or acetylene 14 Mass of C / Total mass of carbon atoms in biomass carbon source, calcium carbide, or acetylene × 100

[0068] 3-2. Measurement of phosphorus and sulfur atom content in biomass carbon sources and anthracite. The phosphorus and sulfur content (phosphorus content and sulfur content) in biomass carbon sources and anthracite was measured in accordance with JIS M 8813:2004. 3-3. Measurement of carbon atom (fixed carbon) content in biomass carbon sources and anthracite. The carbon content (fixed carbon content) in biomass carbon sources and anthracite was measured in accordance with JIS M 8812:2006.

[0069] 3-4. Measurement of ash content in biomass carbon sources The ash content in the biomass carbon source was measured in accordance with JIS M 8812:2006. 3-5. Measurement of the crushing strength of biomass carbon sources A biomass carbon source was molded into a 35mm x 35mm x 10mm sample. The crush strength of this sample was measured according to JIS Z 8841:1993.

[0070] 3-6. Measurement of phosphorus atom content in metal carbide Acetylene gas was generated from metal carbide in accordance with JIS K 1901:2003. The phosphine content in the acetylene gas was measured in accordance with JIS K 1901:2003. From the phosphine content in the acetylene, the phosphorus content in the metal carbide was calculated as follows.

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[0071] 3-7. Measurement of sulfur atom content in metal carbides Acetylene gas was generated from metal carbide in accordance with JIS K 1901:2003. The hydrogen sulfide content in the acetylene gas was measured in accordance with JIS K 1901:2003. From the hydrogen sulfide content in the acetylene, the sulfur atom content in the metal carbide was calculated as follows.

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[0072] 3-8. Measurement of ash content in metal carbide Calcium hydroxide was obtained by reacting 100 parts by mass of calcium carbide from Examples 1-11 and Comparative Examples with 58 parts by mass of pure water. The obtained calcium hydroxide was dried at 150°C until the moisture content was 0.1% by mass or less. The purity of the calcium hydroxide was measured according to JIS K 8575:2025. Barium hydroxide was obtained by reacting 100 parts by mass of barium carbide from Example 12 with 30 parts by mass of pure water. The obtained barium hydroxide was dried at 150°C until the moisture content was 0.1% by mass or less. The purity of the barium hydroxide was measured according to JIS K 1417-1992. The ash content in the metal carbide was calculated as follows from the purity of calcium hydroxide or barium hydroxide measured as described above.

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[0073] These results are shown in Tables 1 and 2 below. [Table 1]

[0074] [Table 2]

[0075] As shown in Tables 1 and 2, it was confirmed that acetylene reflecting the biomass content of metal carbide can be produced. Furthermore, it was confirmed that acetylene with a biomass content corresponding to the mass balance can be produced.

Claims

1. A method for producing acetylene, A process for preparing a carbon source containing biomass and a metal source, A step of heating the carbon source and the metal source in an electric furnace to obtain metal carbide, The process includes reacting the aforementioned metal carbide with water to obtain acetylene containing carbon atoms derived from biomass, A method for producing acetylene, wherein the phosphorus atom content in the carbon source is 0.1 ppm or more and 200 ppm or less.

2. In the method for producing acetylene according to claim 1, A method for producing acetylene, wherein the ash content in the carbon source is 13% by mass or less.

3. In the method for producing acetylene according to claim 1, A method for producing acetylene, wherein the sulfur atom content in the carbon source is 0.1% by mass or less.

4. In the method for producing acetylene according to claim 1, The carbon source is a method for producing acetylene, wherein the volatile content measured according to JIS M 8812:2006 is 5% by mass or less.

5. In the method for producing acetylene according to claim 1, A method for producing acetylene, wherein the content of fixed carbon in the carbon source is 85% by mass or more.

6. In the method for producing acetylene according to claim 1, A method for producing acetylene, wherein the biomass includes at least one of charcoal, pulp char, lignin char, coconut shell char, bagasse char, and sorghum char.

7. In the method for producing acetylene according to claim 1, A sample of the carbon source cut to a size of 35 mm x 35 mm x 10 mm has a crushing strength of 30 kgf or more, as measured according to JIS Z 8841:1993, in the method for producing acetylene.

8. In the method for producing acetylene according to claim 1, The aforementioned metal source is an oxide of an alkaline earth metal, and the method is a method for producing acetylene.

9. In the method for producing acetylene according to claim 1, A method for producing acetylene, further comprising the step of recovering a gas produced in the electric furnace and containing at least carbon monoxide and hydrogen.

10. In the method for producing acetylene according to claim 9, A method for producing acetylene, further comprising the step of reacting at least the carbon monoxide with the hydrogen to obtain a carbon compound.

11. In the method for producing acetylene according to claim 1, A method for producing acetylene, comprising crushing and sizing the biomass using a crusher to obtain crushed biomass, mixing the crushed biomass and a binder using a mixer, then molding the mixture using a molding machine to obtain a briquette, and using the briquette as the carbon source.

12. In the method for producing acetylene according to claim 1, A method for producing acetylene, comprising: preparing lignocellulosic biomass as the biomass; separating and recovering lignin-containing components from the lignocellulosic biomass; carbonizing the lignin-containing components to obtain lignin-containing component carbonized material; and using the lignin-containing component carbonized material as the carbon source.

13. A method for producing acetylene derivatives, Acetylene is obtained by the method for producing acetylene according to any one of claims 1 to 12. A method for producing an acetylene derivative, comprising modifying the aforementioned acetylene to obtain an acetylene derivative, which is a modified form of acetylene.

14. In the method for producing an acetylene derivative according to claim 13, A method for producing an acetylene derivative, wherein the acetylene derivative is at least one selected from the group consisting of ethylene, acrylonitrile, vinyl chloride, acrylic acid, acrylic acid ester, and monovinylacetylene.

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