WO2023158147A1 - Catalyseur à base de transporteur d'hydrogène organique liquide pour une réaction de déshydrogénation et son procédé de préparation - Google Patents

Catalyseur à base de transporteur d'hydrogène organique liquide pour une réaction de déshydrogénation et son procédé de préparation Download PDF

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WO2023158147A1
WO2023158147A1 PCT/KR2023/001834 KR2023001834W WO2023158147A1 WO 2023158147 A1 WO2023158147 A1 WO 2023158147A1 KR 2023001834 W KR2023001834 W KR 2023001834W WO 2023158147 A1 WO2023158147 A1 WO 2023158147A1
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catalyst
liquid organic
organic hydrogen
hydrogen carrier
dehydrogenation
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Korean (ko)
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박지훈
김상준
권순일
김수민
정관용
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한국화학연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes

Definitions

  • the present invention relates to a liquid organic hydrogen carrier-based dehydrogenation reaction catalyst and a method for preparing the same, and more particularly, to a liquid organic hydrogen carrier capable of efficiently dehydrogenating hydrogen from a liquid organic hydrogen carrier by introducing a Joule heating method. It relates to a catalyst for hydrogen carrier-based dehydrogenation reaction and a method for preparing the same.
  • renewable energy such as wind power, tidal power, geothermal energy, hydrogen energy, solar energy, etc. is in the limelight, and each energy source has advantages and disadvantages.
  • Renewable energy is difficult to supply and demand smoothly due to the instability of energy sources over time and the natural environment. Therefore, in order to effectively replace conventional fossil fuels, technology for storing and supplying surplus energy to stably supply energy is required. development is needed for
  • hydrogen energy is (i) the most energy efficient per unit mass, (ii) combustion produces only water and no other harmful by-products, and (iii) water, the main source of hydrogen, is abundant in nature and used. Since it is converted to water after use, it is advantageous in terms of reuse, and (iv) it is attracting attention because it is suitable for securing competitiveness in the precision and IT industries as a distributed power source that uses hydrogen as a fuel.
  • hydrogen can be produced using other renewable energies such as solar energy and wind power, and can be widely applied not only to various energy sources but also to other industrial fields (eg, various petrochemical fields) at home and abroad. It is emerging as a key energy source in the future.
  • Hydrogen has an excellent energy storage capacity per mass, but a low energy storage capacity per volume, so hydrogen can be used efficiently.
  • Storage technology is the biggest obstacle to the practical use of hydrogen energy. Therefore, research into a technology for storing as much hydrogen as possible in a storage medium that is as light and as small as possible and releasing it efficiently has been actively conducted.
  • Patent Documents 0001 and 0002 As an alternative to this, as a material having hydrogen storage capacity, research on various inorganic materials, inorganic-organic composites, etc. is in progress, but recently, reversible catalytic hydrogenation using organic materials, specifically liquid organic hydrogen carriers (LOHCs) / Hydrogen storage technology by dehydrogenation reaction has been developed (Patent Documents 0001 and 0002).
  • LOHCs liquid organic hydrogen carriers
  • LOHC technology has advantages such as being able to operate in a low pressure range and easily regenerating stored materials, and also, due to the handling and high energy density, which are advantages of liquid fossil fuels, it can replace the existing liquid fuel transportation and storage infrastructure. It is possible to provide a practical hydrogen storage system capable of efficient transportation and storage.
  • a dehydrogenation reaction is performed using a catalyst synthesized by impregnating a noble metal catalyst into a support such as alumina or carbon.
  • the catalyst prepared in this way is physically desorbed due to the low dispersion of the metal catalyst in the process of applying the metal on the surface of the support, the reduction in the specific surface area of the catalyst due to the aggregation of the metal catalyst during the reaction, and the low bonding between the metal catalyst and the support. etc., and because of this, the catalyst prepared by the impregnation method has low activity and physical durability.
  • Patent Document 0003 A system for effectively supplying thermal energy required for the LOHC dehydrogenation reaction by heating to activate the catalyst inside the LOHC to desorb hydrogen has not yet been disclosed.
  • the liquid organic hydrogen carriers used in the LOHC technology have a large specific heat
  • the entire liquid organic hydrogen carrier must be heated.
  • the boiling point of is similar, there is a problem in that the reaction efficiency is reduced because the liquid organic hydrogen carrier is vaporized.
  • the dehydrogenation reaction of desorbing hydrogen from the liquid organic hydrogen carrier in which hydrogen is stored is an endothermic reaction, even if sufficient heat energy required for the LOHC dehydrogenation reaction is supplied from the outside, the endothermic reaction causes the temperature to drop on the surface and inside the catalyst. , there was an issue of supplying more external heat than necessary or reducing the efficiency of the catalyst.
  • Patent Document 1 US Patent Registration No. 7901491 (published date: 2009.10.01)
  • Patent Document 2 Korean Patent Registration No. 2338162 (Announcement date: 2021.12.10)
  • Patent Document 3 Korean Patent Registration No. 2332811 (Public Date: 2021.10.07)
  • the main object of the present invention is to solve the above-mentioned problems, and in a liquid organic hydrogen carrier-based dehydrogenation reaction, only the catalyst is Joule-heated selectively to save energy and at the same time to give the catalyst activity with high response even during the endothermic reaction. It is to provide a liquid organic hydrogen carrier-based catalyst for dehydrogenation reaction capable of carrying out dehydrogenation reaction at a fast reaction rate.
  • Another object of the present invention is to provide a method for preparing a liquid organic hydrogen carrier-based dehydrogenation catalyst that can be simply prepared at a low cost compared to conventional dehydrogenation catalysts while maintaining and improving catalytic activity.
  • one embodiment of the present invention is a liquid organic hydrogen carrier-based dehydrogenation catalyst for dehydrogenation in a liquid organic hydrogen carrier using Joule heating, in which heat can be generated by Joule heating.
  • a support made of a material with; and a catalytically active metal supported on the support.
  • the catalytically active metal may be characterized in that it is alloyed and supported on the catalyst support by thermal shock.
  • the catalytically active metal is platinum (Pt), iridium (Ir), osmium (Os), rhodium (Rh), ruthenium (Ru), palladium (Pd), gold (Au), silver (Ag), Cobalt (Co), Iron (Fe), Nickel (Ni), Manganese (Mn), Copper (Cu), Scandium (Sc), Titanium (Ti), Vanadium (V), Chromium (Cr), Zirconium (Zr), yttrium (Y), niobium (Nb), molybdenum (Mo), cadmium (Cd), iridium (Ir), tin (Sn), 2 species selected from the group consisting of yttrium (Y) and tungsten (W) More than that can be characterized.
  • the catalytically active metal may be characterized in that it comprises 0.1% by weight to 50% by weight based on the total weight of the catalyst.
  • the catalyst support may be characterized in that at least one selected from the group consisting of activated carbon, carbon fiber, carbon tube, fullerene, carbon black and carbide.
  • the catalyst support is composed of corrugate, plate, monolith, foam, fiber, granule and mesh. It may be characterized in that it is a shape selected from the group.
  • Another embodiment of the present invention is a method for preparing a catalyst for dehydrogenation of a liquid organic hydrogen carrier, wherein the catalyst for dehydrogenation of a liquid organic hydrogen carrier is dehydrogenated by Joule heating.
  • a method for preparing a catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier comprising the step of supporting a catalytically active metal on a support of a material generating heat.
  • the supporting of the catalytically active metal comprises the steps of (a) coating the catalytically active metal on a carbon-containing catalyst support; and (b) applying thermal shock to the catalyst support coated with the catalytically active metal.
  • the heat shock in step (b) may be characterized by heating at a temperature of 500 ° C to 2,500 ° C by applying a current of 0.1 A to 30 A.
  • the thermal shock of step (b) may be performed 1 to 30 times.
  • Another embodiment of the present invention is a method for producing hydrogen by dehydrogenation of a liquid organic hydrogen carrier, wherein a current is applied to the catalyst to perform a dehydrogenation reaction.
  • a method for producing hydrogen is provided.
  • the temperature of the surface of the catalyst support by applying the current may be 500 ° C to 2,500 ° C.
  • the liquid organic hydrogen carrier-based catalyst for dehydrogenation reaction according to the present invention is prepared by alloying a previously used single-component precious metal-based catalyst with a relatively easy and inexpensive metal and thermal shock to prepare a catalyst, A catalyst with excellent durability can be easily prepared at low cost without desorption, and the particle structure of the catalytically active metal can be formed and controlled so that the specific surface area of the catalyst is not reduced, thereby improving catalytic activity.
  • the catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier according to the present invention is selectively and uniformly heated through Joule heating in a liquid organic hydrogen carrier having a high specific heat, it is very advantageous for energy saving and miniaturization of the system, and thus various hydrogen emission systems.
  • FIG. 1 is a schematic diagram of an alloy catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of a method for preparing a catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier according to an embodiment of the present invention.
  • Figure 3 is a graph of the results of measuring the dehydrogenation reaction of the liquid organic hydrogen carrier-based dehydrogenation catalyst according to Example 1 and Comparative Example 1 of the present invention.
  • Figure 4 is a graph of the results of measuring the dehydrogenation reaction of the liquid organic hydrogen carrier-based dehydrogenation catalyst according to Examples 2 to 4 and Comparative Example 2 of the present invention.
  • a description of a positional relationship for example, when the positional relationship of two parts is described with ' ⁇ on', ' ⁇ on top', ' ⁇ below', 'next to', etc., 'right away' Unless ' or 'directly' is used, one or more other parts may be placed between the two parts.
  • a description of a temporal relationship for example, when a temporal precedence relationship is described as 'after', 'continue to', 'after ⁇ ', 'before', etc., 'immediately' or 'directly' As long as ' is not used, non-continuous cases may also be included.
  • liquid organic hydrogen carrier-based dehydrogenation reactions proceed in unsaturated hydrocarbon compounds with large specific heats such as benzene, toluene, naphthalene, and biphenyl compounds, so heat transfer in liquid organic hydrogen carrier-based dehydrogenation reactions and mass transfer are very important.
  • unsaturated hydrocarbon compound exists in a liquid state during the dehydrogenation reaction, heat transfer and mass transfer are more important than gaseous reactions, so it is very important to develop a catalyst that facilitates heat transfer and mass transfer. .
  • the present invention provides a catalyst capable of Joule heating, which can perform dehydrogenation by selectively heating only the catalyst in the liquid organic hydrogen carrier-based dehydrogenation reaction, compared to conventional platinum-based catalysts, which are relatively easy to obtain and inexpensive, and metal and thermal shock.
  • a catalyst with excellent physical durability can be easily manufactured at low cost, and the particle structure of the catalytically active metal can be formed and controlled so that the specific surface area of the catalyst is not reduced.
  • a catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier capable of significantly improving catalytic activity can be provided.
  • FIG. 1 is a schematic diagram of a catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier according to an embodiment of the present invention
  • FIG. 2 is a method for preparing a catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier according to an embodiment of the present invention. It is a schematic diagram for
  • the liquid organic hydrogen carrier-based dehydrogenation catalyst 100 is a liquid organic hydrogen carrier-based dehydrogenation catalyst for dehydrogenation in a liquid organic hydrogen carrier using Joule heating, a carbon-containing catalyst support (110); and a catalytically active metal 120 bound to the catalyst support.
  • the catalyst support 110 is a carbon-containing compound capable of Joule heating and can be applied without limitation.
  • the catalyst support is supported on the outer circumferential surface or/and the inner circumferential surface in a state in which the catalytically active metal 120 is alloyed.
  • the catalytically active metal includes a bimetallic alloy metal or multi-component high-entropy alloys, for example platinum (Pt), iridium (Ir), osmium (Os), Rhodium (Rh), Ruthenium (Ru), Palladium (Pd), Gold (Au), Silver (Ag), Cobalt (Co), Iron (Fe), Nickel (Ni), Manganese (Mn), Copper (Cu), Scandium (Sc), Titanium (Ti), Vanadium (V), Chromium (Cr), Zirconium (Zr), Yttrium (Y), Niobium (Nb), Molybdenum (Mo), Cadmium (Cd), Iridium (Ir), It may be two or more selected from the group consisting of tin (Sn), yttrium (Y), and tungsten (W).
  • Pt platinum
  • Ir iridium
  • Rhodium Rh
  • Ruthenium Ru
  • the catalytically active metal may be supported on the catalyst support in an amount of 0.1% to 50% by weight based on the total weight of the catalyst.
  • liquid organic hydrogen carrier-based dehydrogenation catalyst according to the present invention may contain other metals as catalytically active metals in addition to the metals described above, and may be binary or ternary as well as various multi-component metal catalysts.
  • the catalytically active metal is alloyed by thermal shock, and in this process, metal elements are melted and strongly bound and supported on the catalyst support to which the heat source has been supplied. Due to this, even during the dehydrogenation reaction by Joule heating, problems such as physical separation of the catalytically active metal do not occur, so that the catalyst does not significantly decrease in activity even when used for a long time, and can be stable.
  • catalytically active metals can be grown by adjusting the applied current value, preferably 0.1 A to 30 A. A current corresponding to can be applied.
  • the time for applying the electric power is preferably adjusted within the range of 0.001 sec to 10 sec according to the target degree of dispersion and the size of the catalytically active metal particles, but may be further progressed if necessary.
  • the size of the catalytically active metal particles can be controlled by repeatedly performing thermal shock at specific time intervals ranging from 0.001 sec to 10 sec.
  • the catalytically active metal supported on the catalyst support may have an average particle size of 0.1 nm to 50 nm, preferably 1 nm to 3 nm. If the average particle size of the catalytically active metal is less than 0.1 nm, it is difficult to expect an effective dehydrogenation reaction because the amount of the catalytic alloy element supported is significantly smaller than that of the catalyst support. Since it is bonded to the support in the form of a single element separated by atom catalyst), reactivity with organics for LOHC having a relatively high molecular weight may be reduced. On the other hand, when the average particle size of the catalytically active metal exceeds 50 nm, the active surface of the catalyst becomes smaller compared to the amount of supported catalyst, and thus the catalytic efficiency may decrease. problems may arise.
  • the liquid organic hydrogen carrier-based catalyst for dehydrogenation reaction prepares a catalyst by applying a thermal shock through Joule heating to a catalyst support carrying a catalytically active metal, so that it can be prepared in a short time compared to conventional catalyst preparation methods.
  • a uniform nanoparticle size and degree of dispersion of the catalytically active metal can be provided by a simple method, and the catalyst particle structure can be formed and controlled by controlling the current and time of Joule heating.
  • alloys, intermetallic alloys, and amorphous alloys advantageous to the dehydrogenation reaction are prepared by applying thermal shock through Joule heating to the catalyst support on which the catalytically active metal is supported.
  • a novel catalyst in the form of (metallic glass) can be obtained.
  • the catalytically active metal 120 may be coated on the carbon-containing catalyst support 110 first.
  • the catalytically active metal may be coated on the catalyst support using a metal precursor 121 such as a salt or complex of the catalytically active metal.
  • a metal precursor 121 such as a salt or complex of the catalytically active metal.
  • water-soluble salts specifically acetates, nitrates, sulfates, carbonates, hydroxides, halides, and hydrates thereof may be exemplified, and as complexes, acetylacetonate complexes, phosphine complexes, etc. can be exemplified.
  • nitrate or a hydrate thereof may be used.
  • the metal precursors of the catalytically active metal may be brought into contact with the catalyst support in the form of a solution in water or a solvent.
  • the catalyst support is brought into contact with the metal precursor solution for a predetermined period of time, and the supporting temperature is maintained at room temperature.
  • a usual follow-up procedure for example, filtration and drying steps to remove moisture or solvent may be performed.
  • the drying temperature may be adjusted at 50 °C to 120 °C. Such drying is to be understood as illustrative.
  • the metal precursors may be mixed and brought into contact with the catalyst support, and one metal precursor among the catalytically active metals may be brought into contact with the catalyst support first, and then the metal precursors of the remaining metals may be mixed or brought into contact sequentially.
  • the catalyst support 110 coated with the catalytically active metal 120 is subjected to thermal shock through Joule heating to prepare a catalyst for a dehydrogenation reaction.
  • the step of applying a thermal shock through Joule heating to the catalyst support supported with the catalytically active metal is applying a thermal shock by applying a current of 0.1 A to 30 A in a vacuum condition or a reducing atmosphere in which an inert gas is injected.
  • a thermal shock by applying a current of 0.1 A to 30 A in a vacuum condition or a reducing atmosphere in which an inert gas is injected.
  • the intensity of the thermal shock showed a characteristic proportional to the amount of power applied to the catalyst support per unit area, and it is preferable to apply appropriate voltage and current values according to the resistance of the catalyst support. Alloying of the catalytically active metal may be induced by controlling the amount of current and voltage applied.
  • the time for applying power is preferably adjusted within the range of 0.001 seconds to 10 seconds according to the target dispersion and particle size, but may include more progress if necessary.
  • alloying or particle size can be controlled by repeatedly performing thermal shock at specific time intervals ranging from 0.001 second to 10 seconds.
  • the number of times of application of the thermal shock may be repeated 1 to 30 times in consideration of crystallinity and catalytic activity of the catalytically active metal and process efficiency, but is not limited thereto.
  • the catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier according to the present invention prepared as described above is prepared by alloying a conventionally used platinum-based catalyst with a relatively easy and inexpensive metal and thermal shock to prepare a catalyst, Catalysts with excellent durability without desorption of active metals can be simply prepared at low cost, and catalyst activity can be improved by forming and controlling the particle structure of the catalysts so that the catalyst activity and specific surface area per mass of catalyst metal are not reduced. there is.
  • the catalyst for dehydrogenation reaction based on a liquid organic hydrogen carrier according to the present invention is applied to a hydrogen emission system that generates and emits hydrogen for application to fuel cells and hydrogen combustion devices such as automobiles and various electronic products to generate hot air or electric heaters.
  • a hydrogen emission system that generates and emits hydrogen for application to fuel cells and hydrogen combustion devices such as automobiles and various electronic products to generate hot air or electric heaters.
  • the catalyst be selectively heated through heating through joule heating, but also the heating intensity of the catalyst can be easily controlled by adjusting the voltage and current applied to the catalyst.
  • the present invention is a method for producing hydrogen by dehydrogenation of a liquid organic hydrogen carrier, wherein a current is applied to the catalyst according to the present invention to perform a dehydrogenation reaction in the liquid organic hydrogen carrier.
  • a method for producing hydrogen by dehydrogenation is provided.
  • the temperature of the surface of the catalyst support by applying the current may be characterized in that it is 500 ° C to 2,500 ° C. If the temperature is less than 500 ° C, ligands in the catalytically active metal precursor may not be completely removed or may not be melted and synthesized, so dehydrogenation may be incomplete. If the temperature exceeds 2,500 ° C, sintering of the catalytically active metal element ) effect, the particle size may become relatively large or the catalyst support may be damaged, which may cause deterioration of catalyst activity.
  • metal precursor hexachloroplatinic acid H 2 PtCl 6 ⁇ xH 2 O
  • calcination was performed at 350 ° C. for 1 hour in an argon (Ar) atmosphere, and then reduced at 450 ° C. for 1 hour in a hydrogen atmosphere, so that the catalytically active metal (Pt) was supported at 3 wt% based on the total weight of platinum carbon.
  • a monolith Pt carbon monolith
  • PtCu alloy catalyst particles of 1:1 Pt and Cu 0.0102 g of Pt precursor [tetramine platinum nitrate (H 12 N 6 O 6 Pt)] and 0.0033 g of Cu precursor [copper acetate (CuCO 2 CH 3 )] g was mixed with 0.3 g of DI water to obtain a precursor solution, and 0.3 g of the aqueous solution in which the obtained precursor was dissolved was applied to a 1 cm ⁇ 4.8 cm activated carbon fiber (ACF) sheet catalyst support with a micropipette. It was applied evenly over the entire area.
  • ACF activated carbon fiber
  • the activated carbon fiber support coated with the mixture After drying the activated carbon fiber support coated with the mixture for 1 hour in an oven at 110 ° C., it was placed in a thermal shock chamber capable of applying voltage to both ends, and then Ar was flowed to maintain a reducing atmosphere. Thereafter, thermal shock was performed at 160 V and 12 A for 0.5 seconds to prepare a dehydrogenation catalyst (PtCu/ACF) containing 13.5 wt% of the catalytically active metal PtCu mixture based on the total weight of the catalyst.
  • PtCu/ACF dehydrogenation catalyst
  • Pt precursor [tetramine platinum nitrate (H 12 N 6 O 6 Pt)] and Pd precursor [palladium nitrate hydrate (N 2 O 6 Pd)] )] 0.0155 g was mixed with 0.3 g of DI water to obtain a precursor solution, and 0.3 g of an aqueous solution in which the obtained precursor was dissolved was added to an activated carbon fiber (ACF) sheet catalyst support having a size of 1 cm ⁇ 4.8 cm. It was evenly applied over the entire area using a micropipette.
  • ACF activated carbon fiber
  • the activated carbon fiber support coated with the mixture After drying the activated carbon fiber support coated with the mixture for 1 hour in an oven at 110 ° C., it was placed in a thermal shock chamber capable of applying voltage to both ends, and then Ar was flowed to maintain a reducing atmosphere. Thereafter, thermal shock was performed at 160 V and 12 A for 0.5 seconds to prepare a dehydrogenation catalyst (PtCu/ACF) containing 25.8% by weight of the catalytically active metal PtPd mixture based on the total weight of the catalyst.
  • PtCu/ACF dehydrogenation catalyst
  • Pt precursor [tetramine platinum nitrate (H 12 N 6 O 6 Pt)], Pd precursor [ Palladium nitrate hydrate (N 2 O 6 Pd)] 0.0062 g, Cu precursor [copper acetate (CuCO 2 CH 3 )] 0.0013 g, Ni precursor [nickel nitrate hexahydrate (Ni(NO 3 ) 2 6H 2 O) ] 0.0032 g and Co precursor [cobalt nitrate hexahydrate (Co(NO 3 ) 2 6H 2 O)] were mixed with 0.3 g of DI water to obtain a precursor solution, and 0.3 g of an aqueous solution in which the obtained precursor was dissolved was uniformly applied to the entire area using a micropipette on an activated carbon fiber (ACF) sheet catalyst support having a size of 1 cm ⁇ 4.8 cm.
  • ACF activated carbon fiber
  • the activated carbon fiber catalyst support coated with the mixture After drying the activated carbon fiber catalyst support coated with the mixture for 1 hour in an oven at 110 ° C., it was placed in a thermal shock chamber capable of applying voltage to both ends, and then Ar was flowed to maintain a reducing atmosphere. . Thereafter, thermal shock was performed at 160 V and 12 A for 0.5 seconds to prepare a dehydrogenation catalyst (PtPdCuNiCo/ACF) containing 18% by weight of the catalytically active metal PtPdCuNiCo mixture based on the total weight of the catalyst.
  • a dehydrogenation catalyst PtPdCuNiCo/ACF
  • Pt precursor tetramine platinum nitrate (H 12 N 6 O 6 Pt)
  • DI water DI water
  • 0.3 g of the aqueous solution in which the obtained precursor was dissolved was mixed with 1 cm ⁇ 4.8 cm. It was uniformly applied to the entire area using a micropipette on an activated carbon fiber (ACF) sheet catalyst support of the same size. After drying the activated carbon fiber catalyst support coated with the mixture for 1 hour in an oven at 110 ° C., it was placed in a thermal shock chamber capable of applying voltage to both ends, and then Ar was flowed to maintain a reducing atmosphere. . Then, the reaction was performed under conditions of 160 V and 12 A for 0.5 seconds to prepare a catalyst for dehydrogenation (Pt/ACF) containing 10.2% by weight of the catalytically active metal Pt mixture based on the total weight of the catalyst.
  • Pt/ACF catalyst for dehydrogenation
  • Comparative Example 1 is a general dehydrogenation catalyst type.
  • the system (Example 1) for selectively heating and activating the catalyst by Joule heating inside the liquid organic hydrogen carrier is more effective than the case where heat is supplied from the outside in the endothermic reaction (Comparative Example 1) in the dehydrogenation reaction.
  • the catalyst groups in Examples 2 to 4 in which Pt is alloyed with more than one type show a higher dehydrogenation reaction under the same reaction conditions than Pt / ACF composed of only a single Pt element, which is Comparative Example 2. It was confirmed that it was effective in releasing hydrogen.
  • the amount of Pt used in the preparation in Examples 2 to 4 was the same as the amount of Pt used in the preparation in Comparative Example 2, but it was found that the dehydrogenation reaction was improved when Pt was alloyed with two or more types of elements. It was confirmed that there is a technological inventive step that can reduce the amount of expensive precious metal catalysts and increase the dehydrogenation activity.

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Abstract

La présente invention concerne un catalyseur à base de transporteur d'hydrogène organique liquide pour une réaction de déshydrogénation et son procédé de préparation et, plus particulièrement, un catalyseur à base de transporteur d'hydrogène organique liquide pour une réaction de déshydrogénation et son procédé de préparation, le catalyseur pouvant déshydrogéner efficacement de l'hydrogène d'un transporteur d'hydrogène organique liquide par adoption d'un procédé de chauffage par effet Joule.
PCT/KR2023/001834 2022-02-17 2023-02-08 Catalyseur à base de transporteur d'hydrogène organique liquide pour une réaction de déshydrogénation et son procédé de préparation WO2023158147A1 (fr)

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