A porous structure catalyst for hydrocarbon pre-reforming reaction and manufacturing method thereof

Abstract

One embodiment of the present invention provides a catalyst for a hydrocarbon pre-reforming reaction comprising: a porous structure; and precious metal particles dispersed on the surface, inside, or in the pores of the porous structure, wherein the porous structure is in the form of a monolith or a foam (cube foam).

Description

Technology Field

[0001] The present invention relates to a porous structural catalyst for hydrocarbon pre-reforming reactions in the form of a porous foam, in which a small amount of highly dispersed Ru precious metal with excellent low-temperature activity is supported, and a method for manufacturing the same. Background Technology

[0003] Currently, the global population is increasing due to industrialization and technological prosperity, thereby creating a corresponding need for greater energy consumption. Consequently, global warming is accelerating, causing severe climate change and casting uncertainty over the sustainability of humanity. To address these issues, the world is striving to shift away from a fossil fuel-based society toward renewable energy, spearheaded by sustainable development and carbon neutrality. Consequently, research and development in technologies such as nuclear power, nuclear fusion, and hydrogen are continuously gaining interest. Fuel cells are emerging as a power generation tool for sustainable development by converting chemical energy into electrical energy through the electrochemical reaction of fuel.

[0004] Fuel cells are classified into alkaline fuel cells (AFC), phosphoric acid fuel cells (PAFC), polymer electrolyte fuel cells (PEMFC), molten carbonate fuel cells (MCFC), and solid oxide fuel cells (SOFC) depending on the electrolyte material used. Polymer electrolyte fuel cells (PEMFC) require the most demanding fuel processing, whereas it is known that solid oxide fuel cells (SOFC) can achieve sufficient fuel processing through internal reforming within the stack alone.

[0005] Solid oxide fuel cells (SOFCs), referred to as third-generation fuel cells, operate at high temperatures of 600 to 1000°C, making them the most efficient among existing fuel cells in terms of power conversion. Therefore, if SOFCs are commercialized, CO2 emissions during the process of converting fossil fuels into electrical energy can be drastically reduced compared to conventional power generation methods.

[0006] Unlike phosphoric acid fuel cells or polymer electrolyte fuel cells that operate at temperatures below 200°C, SOCFs can accelerate reactions without using expensive platinum catalysts due to their high-temperature operation. Furthermore, because internal reactions at the anode side are possible at high temperatures, they offer the advantage of utilizing various fuels other than hydrogen, such as natural gas and coal gas. Additionally, the ability to recover high-quality waste heat and enable combined cycle power generation can improve the efficiency of the entire power generation system. In particular, unlike molten carbonate fuel cells, solid oxide fuel cells do not use liquid electrolytes, which eliminates issues related to material corrosion and electrolyte loss replenishment.

[0007] The principle of a general solid oxide fuel cell is that when air and fuel are supplied to each electrode of a unit cell consisting of an oxygen ion-conducting electrolyte and an air electrode (cathode) and a fuel electrode (anode) located on either side of it, a reduction reaction of oxygen occurs at the air electrode to generate oxygen ions. The oxygen ions that move through the electrolyte to the fuel electrode then react with hydrogen supplied to the fuel electrode to produce water. At this time, electrons are generated at the fuel electrode and consumed at the air electrode, so electricity flows when the two electrodes are connected to each other.

[0008] Fuel reforming in a fuel cell refers to converting the fuel provided as a feedstock into the fuel required by the fuel cell stack.

[0009] Depending on the method of supplying hydrogen, which is the reaction feedstock for SOFC (Solid Oxide Fuel Cell) systems, there are internal reforming methods, which produce hydrogen directly by performing methane reforming inside the fuel cell, and external reforming methods, which supply hydrogen after partial external reforming.

[0010] When steam reforming of natural gas occurs at high temperatures exceeding 600 degrees, coking can occur, potentially deactivating the catalyst. To prevent this, some C2 or higher hydrocarbon compounds contained in the natural gas are pre-reformed. Generally, this pre-reformation process converts higher hydrocarbons into hydrogen and C1 compounds (CO, CO2, CH4). Its purpose is to resolve the issue of carbon deposition caused by the thermal decomposition of higher hydrocarbons and to extend catalyst life by removing residual sulfur components from the reaction gas after the desulfurization process. Such adiabatic pre-reformation is widely applied in chemical process industries, such as purification processes, hydrogen production processes for methanol and ammonia synthesis, and CO / H2 mixed gas production processes for the synthesis of various compounds.

[0011] The application of such a pre-reforming reactor not only reduces fuel consumption for heat supply to the furnace by recovering heat from the flue gas to preheat the reaction gas, but also enables operation at a low S / C ratio, thereby reducing steam usage and resulting in significant energy savings. In the case of SOFC systems, utilizing the heat generated from the catalytic combustor can be expected to increase system efficiency.

[0012] The steam reforming reaction of higher hydrocarbons (n>1) is an irreversible reaction in which all are converted into CO and H2 without the formation of intermediate products. The generated CO and H2 are converted into CH4 and CO2 through the exothermic water-gas shift reaction and methanation reaction, and the gas composition after the pre-reforming reaction is determined by the degree of reaction equilibrium between the two equations. Since the pre-reforming reaction is an endothermic reaction that mainly occurs at low temperatures below 600°C, the development of catalysts with excellent low-temperature activity is required. The problem to be solved

[0014] The present invention aims to solve the problems of carbon deposition and sulfur poisoning, the use of an excessive amount of metal precursors, and the use of an excessive amount of catalyst in existing Ni-supported pellet catalysts for the pre-reforming reaction of hydrocarbon compounds, which are used to prevent coking that occurs when the steam reforming reaction of natural gas at a high temperature of 600 degrees or higher, which is one of the reactions supplying hydrogen as a reaction raw material for a solid oxide fuel cell (SOFC) system, takes place.

[0015] The present invention has been devised to solve the aforementioned problems, and one embodiment of the present invention provides a catalyst for a hydrocarbon pre-reforming reaction in the form of a porous foam supported with Ru.

[0016] In addition, another embodiment of the present invention provides a method for manufacturing the catalyst for the hydrocarbon pre-reforming reaction.

[0017] The technical problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned technical problems will be clearly understood by those skilled in the art to which the present invention belongs from the description below. means of solving the problem

[0019] As a technical means for achieving the aforementioned technical problem, one aspect of the present invention is,

[0020] A catalyst for a hydrocarbon pre-reforming reaction is provided, comprising: a porous structure; and precious metal particles dispersed on the surface, inside, or in the pores of the porous structure; wherein the porous structure is in the form of a monolith or a foam (cube foam).

[0021] The porous structure may be characterized by being made of at least two types of metal materials and having a monolith or foam form in which a metal oxide is coated on the surface of the metal material.

[0022] The above metal oxide may be characterized as being at least one metal oxide selected from the group consisting of aluminum (Al), magnesium (Mg) and silicon (Si).

[0023] The above porous structure may be a metal material such as ferrochrome (FeCr) alloy, nickel-chromium (NiCr) alloy, aluminum (Al), or stainless steel (SUS), or silicon carbide (SiC).

[0024] The above precious metal particles may be characterized as being ruthenium (Ru) particles.

[0025] Total unit volume of the above-mentioned hydrocarbon pre-reforming catalyst: 7.67 x 10⁻⁶ -3 With respect to L, the dispersion weight of the precious metal particles may be characterized as being 0.005g to 0.05g.

[0026] The BET surface area of ​​the above porous structure is 15 to 60 m² 2 It may be characterized by being / g.

[0027] The degree of dispersion of precious metal particles in the above porous structure may be characterized as being 0.02% to 4.0%.

[0028] In paragraph 1,

[0029] The total surface area of ​​the precious metal particles of the above porous structure is 0.1 to 13 m² 2 It may be characterized by being / g.

[0031] Another aspect of the present invention is,

[0032] A hydrocarbon pre-reforming reaction apparatus comprising a catalyst for a hydrocarbon pre-reforming reaction according to claim 1 is provided.

[0033] The above hydrocarbon pre-reforming reactor is a tubular, plate, or shell-tube type heat-exchanger reactor, with S / C = 1.0 to 3.0 and GHSV = 2,000 to 10,000 h -1 It may be characterized by operating under operating conditions of T≤ 600℃.

[0035] Another aspect of the present invention is,

[0036] A method for manufacturing a catalyst for a hydrocarbon pre-reforming reaction is provided, characterized by comprising: a step of manufacturing a composite by impregnating a metal oxide carrier into a porous structure in the form of a monolith or foam (S1); a step of immersing the composite in a precious metal precursor (S2); and a step of aging the composite immersed in the precious metal precursor by adding a basic precipitating agent (S3).

[0037] In the above S2 step, the metal precursor may be characterized as being Ru-nitrosylnitrate.

[0038] In the above S3 step, the basic precipitating agent may be characterized as being at least one selected from the group consisting of urea, sodium hydroxide (NaOH), potassium hydroxide (KOH), and water ammonia (NH3).

[0039] In the above S3 step, the aging step may be characterized by being performed for 6 to 60 hours at a temperature of 80 to 110℃. Effects of the invention

[0041] According to an embodiment of the present invention,

[0042] The above catalyst for hydrocarbon pre-reforming reaction can improve low-temperature activity by supporting a small amount of Ru precious metal, which has excellent low-temperature activity, in a highly dispersed manner, thereby avoiding the difficulty of supporting an excess amount of Ni catalyst in a highly dispersed and uniform manner.

[0043] According to one embodiment of the present invention,

[0044] The above-mentioned catalyst for hydrocarbon pre-reforming reaction can be made easy to load into and recover from a reactor, similar to conventional pellet catalysts, by applying a cube-shaped foam having a porous structure with well-developed internal pores.

[0045] According to one embodiment of the present invention,

[0046] The above-mentioned catalyst for hydrocarbon pre-reforming reaction can provide a complex geometric structure in the form of a porous foam, which not only facilitates mixing between reactants but also allows for easy heat absorption and release into and out of the reactor due to its sponge-like structure, thereby enabling excellent response characteristics.

[0047] According to one embodiment of the present invention,

[0048] The above-mentioned catalyst for hydrocarbon pre-reforming reactions can maintain excellent performance even at high space velocities where a large amount of reactants must be processed, thereby enabling the design of a compact reactor.

[0049] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the composition of the invention described in the description or claims of the present invention. Brief explanation of the drawing

[0051] Figure 1 is a simplified flowchart of a method for manufacturing a catalyst for a hydrocarbon pre-reforming reaction. Figure 2 is a photographic image of a monolith and a foam used as structures in Examples 1 and 2. Figure 3 shows scanning electron microscope (SEM) image data of the example, comparative example, and pellet catalyst. Figure 4 is the result data of Experimental Example 1. Figure 5 is the result data of Experimental Example 2. Specific details for implementing the invention

[0052] The present invention will be described in more detail below. However, the present invention may be implemented in various different forms and is not limited by the embodiments described herein, and is defined only by the claims set forth below.

[0053] Additionally, the terms used in this invention are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. Throughout the specification of this invention, the term 'comprising' any component means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0055] The first aspect of the present invention is,

[0056] A catalyst for a hydrocarbon pre-reforming reaction is provided, comprising: a porous structure; and precious metal particles dispersed on the surface, inside, or in the pores of the porous structure; wherein the porous structure is in the form of a monolith or a foam (cube foam).

[0058] Hereinafter, a catalyst for a hydrocarbon pre-reforming reaction according to the first aspect of the present invention will be described in detail.

[0060] In one embodiment of the present invention, the porous structure may be characterized as being made of at least two types of metal materials and having a monolith or foam form in which a metal oxide is coated on the surface of the metal material.

[0061] In one embodiment of the present invention, the catalyst is classified according to its shape into pellets, tablets, rings, balls, lumps, monoliths, and extrusions. The monolith catalyst used in the present invention has a clearly superior pressure loss ratio to geometric surface area, and compared to other catalyst structures such as pellets, the pressure loss per presented geometric surface area is significantly lower, making it efficient and economical for handling large volumetric flow rates.

[0062] In one embodiment of the present invention, since the pre-reforming reaction is an endothermic reaction that mainly occurs at low temperatures of 600°C or lower, the development of a catalyst with excellent low-temperature activity is required. Conventional pre-reforming catalysts mainly use pellet catalysts supported with an excess amount of Ni catalyst (Ni > 30 wt%). However, Ni catalysts are susceptible to carbon deposition and sulfur poisoning, which causes the catalyst to become easily deactivated. In addition, an excess amount of Ni active metal is required due to low reaction activity.

[0063] In one embodiment of the present invention, according to the prior art, pellet catalysts have low catalyst utilization efficiency due to their low heat and mass transfer characteristics, so an excess amount of pellet catalyst is used, resulting in an excessive reactor volume, which leads to difficulties in designing a compact reactor, slow response characteristics, pressure loss, and channeling. In addition, pellet catalysts have low catalyst utilization efficiency due to their low heat and mass transfer characteristics, so an excess amount of pellet catalyst is used, which leads to an excessive reactor volume, which leads to difficulties in designing a compact reactor, slow response characteristics, pressure loss, and channeling.

[0064] In one embodiment of the present invention, a multi-channel monolithic structure catalyst is applied to overcome the problems of the pellet catalyst described above, and in particular, metal monolithic catalysts with excellent heat transfer characteristics have been mainly applied. However, due to the unidirectional long channel characteristics of monolithic catalysts, heat and mass transfer limitation may occur at the boundary layer along the channel walls.

[0065] In one embodiment of the present invention, a foam-type catalyst having a porous structure with developed internal pores may be applied to overcome the limitations of the monolith catalyst. The porous foam structure can provide a complex geometric structure, which facilitates mixing of reactants; furthermore, due to its sponge-like structure, it facilitates heat absorption and release into and out of the reactor and exhibits excellent response characteristics. In addition, it can maintain excellent performance even at high space velocities where a large amount of reactants must be processed, enabling the design of a compact reactor.

[0066] In one embodiment of the present invention, the metal oxide may be characterized as being at least one metal oxide selected from the group consisting of aluminum (Al), magnesium (Mg) and silicon (Si), more specifically, a metal nitrate (Mg-nitrate, Al-nitrate, Si-nitrate).

[0067] In one embodiment of the present invention, the porous structure may be a metal material such as ferrochrome (FeCr) alloy, nickel-chromium (NiCr) alloy, aluminum (Al), or stainless steel (SUS), or silicon carbide (SiC) material.

[0068] In one embodiment of the present invention, a ferrochrome (FeCr) alloy is a type of iron alloy and is an alloy of iron and chromium. The raw materials for the alloy are chromite FeCr2O4 and coke as a reducing agent, and quicklime or fluorite may also be added. Ferrochrome is classified into high-carbon, low-carbon, and ultra-low-carbon types depending on the carbon content.

[0069] In one embodiment of the present invention, the nickel-chromium (NiCr, Nichrome) alloy is a non-magnetic alloy containing nickel and chromium. Commonly supplied alloys typically contain 80% nickel and 20% chromium, but many variations of the basic composition are possible depending on various applications. Alloys containing 16–17% or more chromium and 7–8% or more nickel are known as stainless steel (SUS, Steel Use Stainless) or heat-resistant alloys; stainless steel containing 18% chromium and 8% nickel, and heat-resistant alloys containing 25% chromium and 20% nickel are mainly used. Due to their relatively high electrical resistance and oxidation resistance at high temperatures, they are widely used as heating elements in electric ovens, toasters, and hair dryers.

[0070] In one embodiment of the present invention, silicon carbide (SiC) is a material with high moisture resistance among fine ceramics that withstands high temperatures of 1400°C or higher, is resistant to thermal shock, and has excellent chemical stability. It is used in parts requiring high density due to its high thermal conductivity and low coefficient of thermal expansion. In addition, it has high strength and stiffness in high-temperature atmospheres, high wettability, and oxidation resistance, and is used in composite materials with metals, plastics, and ceramics.

[0071] In one embodiment of the present invention, the precious metal particles may be characterized as being ruthenium (Ru) particles. Ruthenium does not react with most chemical substances, unlike other platinum group elements. Ruthenium is mostly used as a thick-film resistor and a corrosion-resistant electrical contact, and ruthenium has excellent catalytic activity at low temperatures.

[0072] In one embodiment of the present invention, the total unit volume of the catalyst for the hydrocarbon pre-reforming reaction is 7.67 x 10⁻⁶ -3With respect to L, the dispersion weight of the precious metal particles may be characterized as being 0.005g to 0.05g. If the dispersion weight is less than the above-described range, the catalyst coating may not be properly formed, which may lower the catalyst activity; if it exceeds the above-described range, it may be inefficient and economically undesirable due to the use of more metal precursors than necessary.

[0073] In one embodiment of the present invention, the BET surface area of ​​the porous structure is 15 m² 2 / g or more, 20 m 2 / g or more, 25 m 2 / g or more, 30 m 2 / g or more, 35 m 2 / g or more, 40 m 2 / g or more, 45 m 2 / g or more, 50 m 2 It may be / g or more, and 80 m 2 / g or less, 75 m 2 / g or less, 70 m 2 / g or less, 65 m 2 / g or less, 60 m 2 / g or less, 55 m 2 It may be / g or less, most preferably 15 to 60 m 2 It may be characterized by being / g. If the above-described range is exceeded, the volume of the porous structure catalyst may unnecessarily increase or the required level of strength may not be secured, and if it is below the above-described range, a decrease in hydrocarbon pre-reforming efficiency may occur.

[0074] In one embodiment of the present invention, the dispersion of precious metal particles in the porous structure may be 0.01% or more, 0.02% or more, 0.05% or more, 0.07% or more, 1.0% or more, 1.5% or more, 2.0% or more, 2.5% or more, 3.0% or more, 5.0% or less, 4.5% or less, 4.0% or less, 3.5% or less, 3.0% or less, most preferably 0.03% or less, or 1.0 to 4.0%. If the range is less than the above-described range, the precious metal may not be uniformly supported, resulting in low catalytic activity; if the range is exceeded, an unnecessarily large amount of metal precursor may be required, which may not be economically desirable.

[0075] In one embodiment of the present invention, the total surface area of ​​the precious metal particles of the porous structure is 0.08 m² 2 / g or more, 0.1 m 2 / g or more, 0.12 m 2 / g or more, 0.14 m 2 / g or more, 0.16 m 2 / g or more, 0.18 m 2 / g or more, 0.2 m 2 / g or more, 4 m 2 / g or more, 5 m 2 / g or more, 6 m 2 / g or more, 7 m 2 / g or more, 8 m 2 / g or more than 9 m 2 It may be / g or more, and 15 m 2 / g or less, 14 m 2 / g or less, 13 m 2 / g or less, 12 m 2It is characterized by being / g or less, most preferably 0.1 to 0.220 m 2 / g or 5 to 13 m 2 It may be / g. If it is below the aforementioned range, uniform dispersion is difficult and metal activity is not sufficiently achieved, making it difficult to produce a catalyst within a controllable range, which may make process manufacturing difficult.

[0077] A second aspect of the present invention provides a hydrocarbon pre-reforming reaction apparatus comprising a catalyst for a hydrocarbon pre-reforming reaction according to claim 1.

[0079] Detailed explanations have been omitted for parts that overlap with the first aspect of the present invention; however, the content explained regarding the first aspect of the present invention may be applied equally to the second aspect even if such explanations are omitted.

[0081] Hereinafter, a hydrocarbon pre-reforming reaction apparatus comprising a catalyst for a hydrocarbon pre-reforming reaction according to the second aspect of the present invention will be described.

[0082] In one embodiment of the present invention, the hydrocarbon pre-reforming reactor is a tubular, plate-type, or shell-tube type heat-exchanger reactor, with S / C = 1.0 to 3.0 and GHSV = 2,000 to 10,000 h -1 It may be characterized by operating under operating conditions of T≤ 600℃.

[0083] In one embodiment of the present invention, the tubular device is structured such that heat transfer tubes are inserted concentrically into an outer shell, and fluid is flowed through the inside of the heat transfer tubes and the annular portion of the outer shell to exchange heat. The structure is relatively simple and inexpensive, and units of the same size can be easily connected in series or parallel to increase the heat transfer area. However, as the heat transfer area increases, the required volume per heat transfer area becomes larger and the price becomes higher compared to a multi-tube type, so it is often used for heat transfer areas of 20 or less.

[0084] In one embodiment of the present invention, the plate-type device is a heat exchanger having a structure in which heat transfer plates, press-formed into an uneven shape considering flow paths and strength, are stacked so that fluids flow alternately through each. Since the heat transfer plates can be disassembled, cleaning is completely performed and maintenance inspection is easy, and the capacity can be adjusted by adding or removing the number of heat transfer plates. Types in which the heat transfer surface can be opened use rubber or synthetic resin gaskets, so they are not suitable for high temperature or high pressure applications. They are widely used for heat exchange between liquids.

[0085] In one embodiment of the present invention, the shell-tube type device is the most widely used heat exchanger and can achieve a wide range of heat transfer amounts, thus having a very wide range of applications and high reliability and efficiency.

[0086] In one embodiment of the present invention, S / C (Steam / carbon-ratio) represents the supply ratio of natural gas and steam, and GHSV represents the space velocity.

[0088] The third aspect of the present invention provides a method for manufacturing a catalyst for a hydrocarbon pre-reforming reaction according to claim 1.

[0090] Detailed explanations have been omitted for parts that overlap with the first and second aspects of this invention; however, the contents explained for the first and second aspects of this invention may be applied in the same way even if such explanations are omitted in the third aspect.

[0092] One aspect of the present invention is,

[0093] A method for manufacturing a catalyst for a hydrocarbon pre-reforming reaction is provided, characterized by comprising: a step of manufacturing a composite by impregnating a metal oxide carrier into a porous structure in the form of a monolith or foam (S1); a step of immersing the composite in a precious metal precursor (S2); and a step of aging the composite immersed in the precious metal precursor by adding a basic precipitating agent (S3).

[0095] In one embodiment of the present invention, the metal precursor may be characterized as being Ru-nitrosylnitrate. Ru-nitrosylnitrate is widely used as a precursor for manufacturing Ru-based catalysts. A ruthenium(III) nitrate solution may be used as a precursor for synthesizing the following, and may also be used as an activated carbon-supported Ru catalyst for the hydrothermal decomposition of alkali lignin, or as a submicrometer crystalline metal ruthenate powder by spray pyrolysis.

[0096] In one embodiment of the present invention, the basic precipitating agent may be characterized as being at least one selected from the group consisting of urea, sodium hydroxide (NaOH), potassium hydroxide (KOH), and water ammonia (NH3).

[0097] In one embodiment of the present invention, the aging step may be characterized by being performed for 6 to 60 hours at a temperature of 80 to 110°C.

[0099] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0101] Example 1: Preparation of Ru-coated monolith catalyst

[0102] To coat a magnesium aluminate carrier layer on a monolith made of FeCr alloy, it is immersed in a metal nitrate (Mg-nitrate, Al-nitrate) solution. Afterward, it is immersed in a Ru-nitrosylnitrate precursor solution and undergoes an aging process by adding a basic precipitating agent to allow Ru particles to form on the surface of the monolith.

[0104] Example 2: Preparation of Ru-coated cubeform catalyst

[0105] To coat a magnesium aluminate carrier layer on a foam made of NiCrAl alloy, it is immersed in a metal nitrate (Mg-nitrate, Al-nitrate) solution. Afterward, it is immersed in a Ru-nitrosylnitrate precursor solution and undergoes an aging process by adding a basic precipitating agent to allow Ru particles to form on the surface of the monolith.

[0107] Comparative Example 1: Preparation of Ni-coated monolith catalyst

[0108] To coat a magnesium aluminate carrier layer on a monolith made of FeCr alloy, it is immersed in a metal nitrate (Mg-nitrate, Al-nitrate) solution. Afterward, it is immersed in a nickel nitrate precursor solution and a precipitating agent is added to undergo an aging process so that Ni particles can be formed on the surface of the monolith.

[0110] Comparative Example 2: Preparation of Ni-coated cubeform catalyst

[0111] To coat a magnesium aluminate carrier layer on a foam made of NiCrAl alloy, it is immersed in a metal nitrate (Mg-nitrate, Al-nitrate) solution. Afterwards, it is immersed in a nickel nitrate precursor solution and undergoes an aging process by adding a basic precipitating agent so that Ni particles can be formed on the surface of the monolith.

[0113] Experimental Example 1: Catalytic Properties

[0114] Figure 2 shows the monolith and foam catalyst used in Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention.

[0115] The catalyst coating amount, BET surface area, metal dispersion, and metal surface area of ​​Examples 1 and 2 and Comparative Examples 1 and 2 were measured and shown in Table 1.

[0117] Comparative Example 1 (Ni monolith catalyst) Comparative Example 2 (Ni-form catalyst) Example 1 (Ru monolith catalyst) Example 2 (Ruform catalyst) Ni pellet catalyst Catalyst coating amount_active metal (g) 0.4001 0.4891 0.0093 0.0338 3.8919 Catalyst coating amount (g) 0.412 0.503 0.040 0.048 - BET surface area (m2 / g) 19.5 19.1 54.8 19.7 103 Metal dispersion (%) 0.05 0.06 3.10 0.02 50.0 Metal surface area (m² / g) 0.01 0.41 11.33 0.16 3.84

[0118] Referring to Table 1 above, it can be seen that the catalyst coating amount and the active metal catalyst coating amount of Examples 1 and 2, which are supported with Ru metal, are significantly lower compared to Comparative Examples 1 and 2, which are supported with Ni metal. Through this, it can be seen that if Ru is used, a catalyst with high activity can be prepared with a small amount of metal support.

[0119] Figure 3 shows scanning electron microscope (SEM) image data of Examples 1 and 2, Comparative Examples 1 and 2, and pellet catalysts. It can be seen that the shape in the scanning electron microscope image differs depending on the type of metal.

[0121] Experimental Example 2: Catalyst Performance Evaluation

[0122] Hydrocarbon preliminary reforming reaction experiments were conducted to evaluate the performance of the catalysts prepared as described in the examples and comparative examples.

[0123] The hydrocarbon pre-reforming reaction experiment had a space velocity (GHSV) of 8,000 h -1 The reaction was carried out at a temperature of 350-600 ℃. Prior to the reaction experiment, catalytic reduction was performed at 600 ℃ for 1 hour under a 20% H2 / N2 atmosphere, and natural gas and steam were used as reaction gases, with a supply ratio of Steam / carbon-ratio (S / C) = 3.0.

[0124] Looking at the data shown in Fig. 4, it can be seen that a monolith catalyst (Example 1) with a highly dispersed and uniformly supported Ru active metal, with about 1 / 390th of Ru supported, exhibits equivalent reaction activity to a pellet catalyst supported with a high content of Ni.

[0125] Table 2 shows the results of evaluating the preliminary reforming reaction activity of pellet catalysts and monolith catalysts (Example 1, Comparative Example 2).

[0126] Under reaction conditions, the space velocity (GHSV) is 8,000 h -1The reaction temperature is 500℃ and the S / C ratio is 3.0, which is the same as the above conditions, and the content of active metal packed in the same reaction volume is pellet catalyst (Ni=3.89g), Comparative Example 1 (Ni monolith catalyst=0.40g), and Example 1 (Ru monolith catalyst=0.01g), respectively. It can be seen that the monolith catalyst coated with Ru catalyst showed equivalent reaction activity even when using only about 1 / 390 of the pellet catalyst.

[0128] catalyst Pellet catalyst Example 1 Comparative Example 1 Amount of active metal (g) 3.89 0.01 0.40 Carbon Conversion (%) 43.1 43.0 38.3

[0130] Experimental Example 3: Catalyst Performance Evaluation

[0131] Figure 5 shows the results of evaluating the preliminary reforming reaction activity of the Ru monolith catalyst (Example 1) and the Ru foam catalyst (Example 2).

[0132] Under reaction conditions, the space velocity (GHSV) is 8,000 h -1 The reaction temperature is 350-600℃, and the S / C ratio is 3.0. The content of the active metal packed in the same reaction volume is Example 1 (Ru monolith catalyst = 0.01g), Example 2 (Ru foam catalyst = 0.03g), and Comparative Example 2 (Ni foam catalyst = 0.49g), respectively.

[0133] It can be seen that while both the Ru catalyst-coated monolith catalyst and the foam catalyst showed equivalent reaction activity, the Ni foam catalyst, which had 16 to 49 times more active metal supported in the same reaction volume, showed the lowest reaction activity.

[0135] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form.

[0136] The scope of the present invention is defined by the claims set forth below, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

Claims

Claim 1 A catalyst for a hydrocarbon pre-reforming reaction comprising: a porous structure; and precious metal particles dispersed on the surface, inside, or in the pores of the porous structure; wherein the porous structure is in the form of a monolith or foam (cube foam) with magnesium aluminate, which is a metal oxide, coated on its surface, and the precious metal particles are ruthenium (Ru) particles. Claim 2 ◈Claim 2 was abandoned upon payment of the registration fee.◈ A catalyst for a hydrocarbon pre-reforming reaction, wherein, in Claim 1, the porous structure is made of at least two types of metal materials. Claim 3 delete Claim 4 In claim 1, the porous structure is a catalyst for a hydrocarbon pre-reforming reaction, made of a metal material such as ferrochrome (FeCr) alloy, nickel-chromium (NiCr) alloy, aluminum (Al), or stainless steel (SUS), or silicon carbide (SiC). Claim 5 delete Claim 6 In claim 1, the total unit volume of the catalyst for the hydrocarbon pre-reforming reaction is 7.67 x 10⁻⁶ -3 A catalyst for a hydrocarbon pre-reforming reaction, characterized in that, with respect to L, the dispersion weight of the precious metal particles is 0.005g to 0.05g. Claim 7 In claim 1, the BET surface area of ​​the porous structure is 15 to 60 m² 2 Catalyst for hydrocarbon pre-reforming reaction characterized by having / g Claim 8 A catalyst for a hydrocarbon pre-reforming reaction according to claim 1, characterized in that the dispersion degree of precious metal particles in the porous structure is 0.02% to 4.0%. Claim 9 ◈Claim 9 was abandoned upon payment of the registration fee.◈ In Claim 1, the total surface area of ​​the precious metal particles of the porous structure is 0.1 to 13 m² 2 A catalyst for a hydrocarbon pre-reforming reaction characterized by having / g Claim 10 A hydrocarbon pre-reforming reaction apparatus comprising a catalyst for a hydrocarbon pre-reforming reaction according to claim 1. Claim 11 In paragraph 10, the hydrocarbon pre-reforming reactor is a tubular, plate, or shell-tube type heat-exchanger reactor, with a Steam / carbon ratio (S / C) of 1.0 to 3.0 and a space velocity (GHSV) of 2,000 to 10,000 h -1 A hydrocarbon pre-reforming reaction device characterized by operating under operating conditions of T≤ 600℃. Claim 12 A method for manufacturing a catalyst for a hydrocarbon pre-reforming reaction, comprising: a step (S1) of preparing a composite by impregnating a porous structure in the form of a monolith or foam with a metal nitrate solution containing magnesium nitrate (Mg-nitrate) and aluminum nitrate (Al-nitrate); a step (S2) of immersing the composite in a precious metal precursor; and a step (S3) of adding a basic precipitating agent to the composite immersed in the precious metal precursor and aging it, wherein the precious metal precursor is Ru-nitrosylnitrate. Claim 13 delete Claim 14 A method for preparing a catalyst for a hydrocarbon pre-reforming reaction, characterized in that, in step S3 above, the basic precipitating agent is at least one selected from the group consisting of urea, sodium hydroxide (NaOH), potassium hydroxide (KOH), and water ammonia (NH3). Claim 15 A method for manufacturing a catalyst for a hydrocarbon pre-reforming reaction, wherein, in the above S3 step, the aging step is performed for 6 to 60 hours at a temperature condition of 80 to 110 ℃.

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