WO2023055162A1 - Procédé de génération d'hydrogène de haute pureté à partir de déchets plastiques sans génération de dioxyde de carbone - Google Patents
Procédé de génération d'hydrogène de haute pureté à partir de déchets plastiques sans génération de dioxyde de carbone Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 53
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 42
- 239000001569 carbon dioxide Substances 0.000 title abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 21
- 239000013502 plastic waste Substances 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 59
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 59
- 229920003023 plastic Polymers 0.000 claims description 56
- 239000004033 plastic Substances 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 46
- 238000004519 manufacturing process Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 13
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 229910019440 Mg(OH) Inorganic materials 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 41
- 239000004926 polymethyl methacrylate Substances 0.000 description 41
- 238000002309 gasification Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 16
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000000629 steam reforming Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
Definitions
- the main source is carbon dioxide It relates to a method for producing high-purity hydrogen from waste plastic without generation.
- Waste plastic treatment methods include incineration, pyrolysis, and gasification.
- incineration generates dioxin, which is a harmful substance, and carbon dioxide, which is a cause of global warming, when burning waste plastic.
- thermal decomposition emulsification
- it is easy to recover wax, olefin-based polymers, and monomers, but it is not suitable for non-olefin-based oil.
- the disadvantage is that it is difficult to recover when untreated waste plastics are mixed. Therefore, in recent years, development of a gasification process that facilitates the treatment of mixed waste plastic and reduces the amount of air pollutants has been actively progressed.
- the steam reforming reaction generates hydrogen by reacting hydrocarbons or hydrocarbon compounds containing oxygen with steam, and feedstock is in contact with water under high temperature conditions to obtain CO, CO 2 and H 2 gases according to the following reaction formula. produces:
- the main source is carbon dioxide It is intended to provide a method for generating high-purity hydrogen from waste plastic without generation.
- One aspect of the present disclosure provides a method for generating hydrogen, which includes obtaining hydrogen by subjecting a plastic containing oxygen to a heat treatment reaction with hydroxide and water vapor, wherein the amount of CO 2 produced is about 10 mol% or less based on the total generated gas.
- the method for generating hydrogen according to the embodiments of the present invention includes hydroxide as a reactant, thereby increasing the amount and purity of hydrogen, lowering the reaction temperature to reach an appropriate hydrogen production rate, and significantly reducing the amount of carbon dioxide produced.
- carbon monoxide is formed during the reaction by heat-treating a plastic containing oxygen, and since the formed carbon monoxide forms hydrogen together with water vapor, the production amount of hydrogen is increased.
- the hydrogen generation method according to the embodiments of the present application is characterized by a low process temperature range and a high hydrogen generation rate compared to the conventional steam reforming process of plastics.
- the hydrogen production method according to the embodiments of the present application is characterized in that high purity hydrogen is produced compared to the conventional steam reforming process.
- the method for generating hydrogen according to the embodiments of the present disclosure is characterized in that carbon and oxygen contained in the reactants are captured in solid form of carbonate or bicarbonate, resulting in a remarkably low amount of carbon dioxide produced.
- the method for generating hydrogen according to embodiments of the present disclosure is characterized in that it can economically produce hydrogen because raw material procurement costs are little or extremely low by using waste plastic.
- waste plastic polyethylene terephthalate (PET) is the most used plastic in everyday life and can be procured in large quantities, and poly(methyl methacrylate) (PMMA) is used in construction and automobiles. Since it is used for purposes such as , , and electronic products, it has the advantage of high economic feasibility because it is easy to collect because the place of use is specified.
- Figure 1 in one embodiment of the present application, shows a schematic process diagram of a method for generating hydrogen.
- Figure 3 is a graph showing the hydrogen gas production rate according to the reaction temperature of the PMMA and PET gasification process through ATT (Example 1) and SG (Comparative Example 1) in one embodiment of the present application.
- Example 4 is a graph showing the carbon dioxide gas production rate according to the reaction temperature of the PMMA and PET gasification process through ATT (Example 1) and SG (Comparative Example 1) in one embodiment of the present application.
- Figure 5 shows the amount of gas generated in the PMMA and PET gasification process through ATT (Example 1) and the PP (polypropylene) and PE (polyethylene) gasification process through ATT (Comparative Example 2) in one embodiment of the present application. it's a graph
- Figure 6 is a graph showing the amount of gas generated according to the particle size of the plastic raw material.
- FIG. 7a and b are photographs of the PET raw material used in one embodiment of the present application, respectively, in the form of pellets having a diameter of 2 mm (a) and in the form of a powder having a diameter of 200 ⁇ m (b).
- Example 8 is a graph showing the amount of gas generated in an epoxy resin gasification process (Example 2) through ATT in one embodiment of the present application.
- FIG 9 is a graph showing the gas generation rate according to the reaction temperature of the epoxy resin gasification process (Example 2) through ATT in one embodiment of the present application.
- FIG 10 is a graph showing the amount of gas generated in the PET gasification process (Example 3) through ATT using Ca(OH) 2 in one embodiment of the present application.
- FIG 11 is a graph showing the gas generation rate according to the reaction temperature of the PET gasification process (Example 3) through ATT using Ca(OH) 2 in one embodiment of the present application.
- FIG. 12 is a graph showing the gas generation rate according to the reaction temperature of the PET gasification process through SG in one embodiment of the present application.
- FIG 13 a and b in one embodiment of the present application, PMMA of the PMMA gasification process through ATT (Example 4): gas production according to the NaOH mass ratio (a); And it shows the amount of gas produced (b) according to the mass ratio of PET: NaOH in the PET gasification process (Example 4) through ATT.
- 15 a to f show the gas generation rate according to the reaction temperature for each PET: NaOH mass ratio in the PET gasification process (Example 4) through ATT in one embodiment of the present application.
- step of or “step of” used throughout the present specification does not mean “step for”.
- One aspect of the present disclosure provides a method for generating hydrogen, which includes obtaining hydrogen by subjecting a plastic containing oxygen to a heat treatment reaction with hydroxide and water vapor, wherein the amount of CO 2 produced is about 10 mol% or less based on the total generated gas.
- the amount of CO 2 produced in the hydrogen generation method is about 10 mol% or less, about 9 mol% or less, about 8 mol% or less, about 7 mol% or less, about 6 mol% based on the total generated gas or less, about 5 mol% or less, about 4 mol% or less, or about 3 mol% or less.
- the hydrogen generating method comprises: (a) providing the plastic and the hydroxide to a reactor; and (b) performing heat treatment while introducing the water vapor into the reactor to obtain hydrogen and carbonate products, but may not be limited thereto. In one embodiment of the present application, (a) may further include providing water to the reactor.
- the carbonate product may be carbonate or bicarbonate.
- the carbonate product may include one or more selected from Na 2 CO 3 , K 2 CO 3 , Li 2 CO 3 , CaCO 3 , MgCO 3 and (NH 4 ) 2 CO 3 However, it may not be limited thereto.
- the plastic may include one or more selected from acrylic resin, polyethylene terephthalate (PET), and epoxy resin, but may not be limited thereto.
- the acrylic resin may include a polymer made by polymerizing one or more monomers selected from alkyl methacrylate and alkyl acrylate, but is not limited thereto may not be Specifically, the monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, and methyl methacrylate.
- the acrylic resin may be poly(methyl methacrylate) (PMMA).
- the plastic may include at least one selected from PMMA and PET.
- the hydroxide may include one or more selected from KOH, NaOH, LiOH, Ca(OH) 2 , Mg(OH) 2 and NH 4 OH, but may not be limited thereto. .
- the heat treatment reaction may be performed at about 100 ° C to about 600 ° C, but may not be limited thereto. In one embodiment of the present application, the heat treatment reaction is about 100 °C to about 600 °C, about 150 °C to about 600 °C, about 200 °C to about 600 °C, about 250 °C to about 600 °C, about 300 °C to about 600 ° C, about 100 ° C to about 550 ° C, about 150 ° C to about 550 ° C, about 200 ° C to about 550 ° C, about 250 ° C to about 550 ° C, about 300 ° C to about 550 ° C, about 100 ° C to about 500 ° C , It may be performed at about 150 ° C to about 500 ° C, about 200 ° C to about 500 ° C, about 250 ° C to about 500 ° C, or about 300 ° C to about 500 ° C, but may not be limited thereto.
- the heat treatment reaction may be performed at about 300 °C to about 500 °C.
- the temperature range of the heat treatment reaction may be a temperature range with high hydrogen generation efficiency, and the optimum temperature range may vary depending on the type of the plastic and the type of the hydroxide.
- the heat treatment reaction may be performed at atmospheric pressure, but may not be limited thereto.
- the mass ratio of the plastic and the hydroxide may be about 1: 2 to about 1: 5, but may not be limited thereto. In one embodiment of the present application, the mass ratio of the plastic to the hydroxide is about 1: 2 to about 1: 5, about 1: 3 to about 1: 5, about 1: 3.5 to about 1: 5, about 1: 2 to about 1:4.5, about 1:3 to about 1:4.5, or about 1:3.5 to about 1:4.5, but may not be limited thereto. In one embodiment of the present application, the mass ratio of the plastic and the hydroxide may be about 1:4.
- the purity of the hydrogen obtained by the hydrogen generation method may be about 70% or more. In one embodiment of the present application, the purity of the hydrogen obtained by the hydrogen generation method is about 70% or more, about 73% or more, about 75% or more, about 80% or more, about 85% or more, or about 89% or more it could be The hydrogen purity may indicate a ratio (unit: mole) of hydrogen to total products obtained by the hydrogen production method.
- the hydrogen generation amount obtained by the hydrogen generation method may be about 5 mmol or more per 1 g of plastic. In one embodiment of the present application, the amount of hydrogen produced by the hydrogen generation method is about 5 mmol or more, about 8 mmol or more, about 10 mmol or more, about 15 mmol or more, about 20 mmol or more, about 10 mmol or more per 1 g of plastic. 22 mmol or more, about 24 mmol or more, about 26 mmol or more, or about 28 mmol or more.
- the amount of carbon dioxide produced by the method for generating hydrogen may be less than about 1.2 mmol per 1 g of plastic. In one embodiment of the present application, the amount of carbon dioxide produced by the method for generating hydrogen may be less than about 1.2 mmol, less than about 1 mmol, or less than about 0.7 mmol per 1 g of plastic.
- the reaction was carried out under the same conditions as in Example 1, but without adding a base (NaOH), plastic and water were placed in a ceramic boat and steam reforming was performed. Specifically, after putting 0.05 g of plastic (PET or PMMA) and 0.15 g of water in a ceramic boat reactor, the reaction was carried out in a temperature range of 100 ° C to 600 ° C while supplying 7.59 mL of water vapor (flow rate: 23 ⁇ L / min). .
- a base NaOH
- the reaction was performed under the same reaction conditions as in Example 1, but the reaction was performed using polypropylene (PP) and polyethylene (PE) as the type of plastic. Specifically, after putting 0.05 g of plastic (PP or PE), 0.3 g of NaOH, and 0.3 g of water into a ceramic boat reactor, 4.14 mL of water vapor (flow rate: 23 ⁇ L/min) was supplied at a temperature range of 100 ° C to 600 ° C. reaction was carried out.
- PP polypropylene
- PE polyethylene
- Example 1 and Comparative Example 1 the gas produced at a reaction temperature of 100 ° C to 600 ° C was analyzed by gas chromatography to investigate the type and amount of produced gas (moles of produced gas per 1 g of plastic). (Fig. 2).
- the purity of the hydrogen gas generated from PMMA and PET was 12.79% and 10.82%, respectively, but in the case of Example 1 in which an alkali thermochemical reaction was performed by adding NaOH, the hydrogen gas generated from PMMA and PET It was confirmed that the purity of was remarkably increased to 73.49% and 94.47%, respectively.
- the amount of hydrogen produced from PMMA was 0.4327 mmol H 2 /g-PMMA in Comparative Example 1, and increased by about 65 times to 28.1 mmol H 2 /g-PMMA in Example 1.
- the amount of hydrogen produced from PET was 1.382 mmol H 2 /g-PET in Comparative Example 1, and increased about 17 times to 23.39 mmol H 2 /g-PET in Example 1. Accordingly, it was confirmed that by adding a base (NaOH) in the plastic thermal chemical reaction, the purity of hydrogen in the product gas increased, the concentration of carbon dioxide decreased, and the total amount of hydrogen produced increased.
- Example 2 Hydrogen production rate according to the reaction temperature (100 °C to 600 °C) in Example 1 and Comparative Example 1 was investigated (FIG. 3).
- Comparative Example 1 almost no hydrogen was generated in the entire temperature range (100 ° C to 600 ° C).
- PMMA showed the highest hydrogen production at 441 ° C and PET at 335 ° C
- the optimal reaction temperature range of PMMA was about 350 ° C to about 500 ° C
- the optimal reaction temperature range of PET was about 250 ° C to It was confirmed that it was about 400°C. Accordingly, it was confirmed that by adding a base (NaOH) in the plastic thermal chemical reaction, the reaction temperature, which is important for achieving a constant rate of hydrogen gas generation, can be lowered.
- NaOH base
- Example 1 and Comparative Example 2 the type and amount of generated gas (moles of generated gas per 1 g of plastic) generated at a reaction temperature of 100 ° C to 600 ° C were investigated (FIG. 5).
- PP and PE produced hydrogen of 0.857 mmol H 2 /g-PP and 0.6943 mmol H 2 /g-PE, respectively, compared to PET and PMMA of Example 1, about 20 times to About 40 times, 28.1 mmol H 2 /g-PMMA and 23.39 mmol H 2 /g-PET of hydrogen were produced.
- Example 1 the gas generation amount according to the particle size of the raw material was investigated at a reaction temperature of 100 ° C to 600 ° C (Figs. 6, 7a and 8b). Experiments were conducted under the same conditions except for the particle surface area of the raw material.
- Figure 7a is PET from Sigma Aldrich, which is a cylindrical pellet with a diameter of about 2 mm and a height of about 4 mm. It is made in powder form.
- the product gas collected in the gas bag was analyzed by gas chromatography and expressed as the number of moles of gas that can be produced per 1 g of plastic used in the experiment (raw mass).
- the PET raw material in pellet form produced only 9.381 mmol / g-PET of hydrogen, whereas the pulverized PET raw material in the form of powder less than 200 ⁇ m produced 23.39/g-PET of hydrogen. It was confirmed that the amount of hydrogen produced increased as the surface area of the reacting raw material plastic increased.
- a glass fiber reinforced epoxy substrate (MCL-E-67, manufactured by Hitachi Kasei Co., Ltd., manufactured by Hitachi Chemical Co., Ltd.), having the composition shown in Table 1 below, that is covered with copper on both sides, that is, a sample embodying waste electronic components including metal, etc., is a square with a side of 5 mm 10 g of the cut sample and 100 g of potassium carbonate were put into a 1000 cm 3 reactor and the temperature was raised while nitrogen gas was flowed at 160 cm 3 /min. Immediately after the temperature of the reactor reached approximately 100° C., steam was introduced at 1.0 g/min, and the temperature was raised to a predetermined temperature at intervals of about 20 minutes.
- MCL-E-67 manufactured by Hitachi Kasei Co., Ltd., manufactured by Hitachi Chemical Co., Ltd.
- Example 1 Comparing the production amounts of the products of Example 1 and Comparative Example 3 (reaction temperature: 675°C, amount of potassium carbonate added: 100.2 g), the hydrogen composition in the product produced from Example 1 was 73.49% (PMMA) and 94.47, respectively. % (PET), while the composition of hydrogen in the resulting product of Comparative Example 3 was found to be 6% (yield: 11.1%).
- the carbon dioxide composition is remarkably low at 3.05% (PMMA) and 2.13% (PET), whereas in Comparative Example 3, the composition of carbon dioxide is 84% (yield: 150%) was confirmed to be very high.
- the hydrogen production amount is 8.11 mmol/g, the hydrogen purity is 83.66%, and the CO 2 production amount is 0.8039 mmol/g (CO 2 production rate: 8.29%). It was confirmed, and from this, it was confirmed that hydrogen can be generated through the ATT process using Ca(OH) 2 .
- 11 shows the gas production rate according to the reaction temperature, and the highest hydrogen production amount was shown at 550 ° C, and it was confirmed that the optimal reaction temperature range was about 350 ° C to about 600 ° C. In addition, although not shown in the figure, it was confirmed that CO 2 production increased due to thermal decomposition of CaO 3- salt in a temperature range of about 600° C. or higher.
- reaction conditions were carried out in the temperature range of 100 ° C to 700 ° C (heating rate: 2 ° C / min) while supplying water vapor at a flow rate of 23 ⁇ L / min, and nitrogen as a carrier gas (flow rate: 50 mL / min) ) was used.
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Abstract
La présente demande concerne un procédé de génération d'hydrogène de haute pureté à partir de déchets plastiques sans génération de dioxyde de carbone <sb />.
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JP2001288480A (ja) * | 2000-04-03 | 2001-10-16 | Mitsubishi Materials Corp | 廃プラスチックのガス化方法及びその装置 |
JP2001322804A (ja) * | 2000-05-09 | 2001-11-20 | Mitsubishi Materials Corp | 水素ガスの製造方法及びその装置 |
JP2002179837A (ja) * | 2000-12-08 | 2002-06-26 | Toshiba Corp | 廃プラスチックの処理方法および処理装置 |
JP2011184673A (ja) * | 2010-03-10 | 2011-09-22 | Ramusa Abe:Kk | 混在廃プラスチックの熱分解方法及び混在廃プラスチックの熱分解装置 |
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JP2001288480A (ja) * | 2000-04-03 | 2001-10-16 | Mitsubishi Materials Corp | 廃プラスチックのガス化方法及びその装置 |
JP2001322804A (ja) * | 2000-05-09 | 2001-11-20 | Mitsubishi Materials Corp | 水素ガスの製造方法及びその装置 |
JP2002179837A (ja) * | 2000-12-08 | 2002-06-26 | Toshiba Corp | 廃プラスチックの処理方法および処理装置 |
JP2011184673A (ja) * | 2010-03-10 | 2011-09-22 | Ramusa Abe:Kk | 混在廃プラスチックの熱分解方法及び混在廃プラスチックの熱分解装置 |
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