Method for manufacturing hydrocarbon composite reforming catalyst and hydrocarbon composite reforming catalyst manufactured thereby

Abstract

The present invention relates to a method for manufacturing a hydrocarbon composite reforming catalyst and a hydrocarbon composite reforming catalyst manufactured thereby. In one specific embodiment, the method for manufacturing a hydrocarbon composite reforming catalyst comprises: a support containing magnesium aluminate (MgAl2O4); and an active metal and an enhancer dispersed in the support, wherein the active metal includes nickel (Ni) and cobalt (Co), and the enhancer includes yttrium (Y).

Description

Method for manufacturing a hydrocarbon composite reforming catalyst and a hydrocarbon composite reforming catalyst manufactured thereby

[0001] The present invention relates to a method for manufacturing a hydrocarbon composite reforming catalyst and a hydrocarbon composite reforming catalyst manufactured thereby.

[0002]

[0003] Reforming reactions for producing synthesis gas from hydrocarbons (such as methane) can be classified according to the reforming material as follows: (1) steam reforming of methane (SRM), (2) partial oxidation of methane (POM), (3) carbon dioxide reforming of methane (CDR), and (4) combined steam and CO2 reforming with methane (CSCR).

[0004] (1) Steam Reforming Reaction (SRM): CH4 + H2O → 3H2 + CO

[0005] (2) Partial Oxidation Reaction (POM): CH4 + 0.5O2 → 2H2 + CO

[0006] (3) Carbon Dioxide Reforming Reaction (CDR): CH4 + CO2 → 2H2 + 2CO

[0007] (4) Steam and Carbon Dioxide Combined Reforming Reaction (CSCR): 3CH4 + 2H2O + CO2 → 8H2 + 4CO.

[0008] Due to the differences in the reforming materials used in the above reforming reactions, the molar ratio of hydrogen to carbon monoxide in the synthesis gas produced from each reaction varies. Therefore, the reforming material can be appropriately selected according to the optimal ratio required in subsequent processes where the synthesis gas produced from each reforming reaction is applied. In other words, in this technical field, each reforming reaction is recognized as a distinct reaction system, and research is being conducted to develop optimal catalysts suitable for each reforming system.

[0009] Currently, various methods for producing synthesis gas capable of controlling the H2 / CO molar ratio by performing the reforming reaction of methane, represented by natural gas, are being studied. Among these, interest is growing in the combined reforming reaction using steam and carbon dioxide, because it has the advantage of being able to utilize carbon dioxide, the main culprit of global warming, as a reactant, and the advantage of being able to produce synthesis gas (H2 / CO = 1.8~2.2 molar ratio) suitable for Fischer-Tropsch synthesis.

[0010] In the complex reforming reaction of methane, catalysts such as precious metal series (Ru, Rh, Pd, Pt), pyrochloro oxides, perovskite oxides, and nickel and cobalt series are widely used. Although precious metal catalysts are advantageous because they have high activity and can reduce carbon deposition, they are difficult to use commercially due to their high cost. Therefore, these disadvantages are sometimes compensated for by supporting various metals on catalyst supports such as alumina, silica, and zeolite (Patent Documents 1 and 2).

[0011] However, catalysts containing various precious metals and nickel or cobalt had the problem of being difficult to use for a long time under high temperature conditions due to carbon deposition caused by the carbon monoxide disequilibrium reaction (Boudouard reaction) or the methane decomposition reaction (CH4→ 2H2+ C).

[0012] [Prior Art Literature]

[0013] (Patent Document 1) Republic of Korea Published Patent Application No. 10-2015-0129566

[0014] (Patent Document 2) Republic of Korea Registered Patent Publication No. 10-1432621

[0015]

[0016] One objective of the present invention is to provide a hydrocarbon composite reforming catalyst that exhibits excellent catalytic activity during the hydrocarbon composite reforming reaction, resulting in excellent hydrocarbon conversion rates and carbon monoxide conversion rates, and excellent resistance to carbon deposition.

[0017] Another objective of the present invention is to provide a hydrocarbon composite reforming catalyst that exhibits excellent catalytic activity and stability even during long-term operation.

[0018] Another objective of the present invention is to provide a hydrocarbon composite reforming catalyst with excellent eco-friendliness, economic efficiency, and productivity.

[0019] Another objective of the present invention is to provide a hydrocarbon composite reforming catalyst having excellent durability and excellent bonding strength and dispersibility between its constituent components.

[0020] Another objective of the present invention is to provide a hydrocarbon composite reforming catalyst capable of easily controlling the H2 / CO ratio of the synthesis gas during a hydrocarbon composite reforming reaction.

[0021] Another objective of the present invention is to provide a method for manufacturing the hydrocarbon composite reforming catalyst.

[0022] Another objective of the present invention is to provide a method for producing synthesis gas using the hydrocarbon composite reforming catalyst.

[0023]

[0024] One aspect of the present invention relates to a hydrocarbon composite reforming catalyst. In one embodiment, the hydrocarbon composite reforming catalyst comprises a support comprising magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, wherein the active metal comprises nickel (Ni) and cobalt (Co), and the promoter comprises yttrium (Y).

[0025] In one embodiment, the hydrocarbon composite reforming catalyst may comprise 60 to 90 weight% of a support, 2 to 30 weight% of an active metal, and 3 to 25 weight% of a promoter.

[0026] In one embodiment, the active metal may contain nickel and cobalt in a weight ratio of 1:2 to 1:10.

[0027] In one embodiment, the nickel and cobalt may have a crystal diameter of 1 to 50 nm.

[0028] In one embodiment, the hydrocarbon composite reforming catalyst may contain the active metal and the promoter in a weight ratio of 1:0.3 to 1:3.

[0029] Another aspect of the present invention relates to a method for manufacturing the hydrocarbon composite reforming catalyst. In one embodiment, the method for manufacturing the hydrocarbon composite reforming catalyst comprises the steps of: preparing a first mixture by adding a co-precipitating agent to a magnesium (Mg) precursor and an aluminum (Al) precursor; aging the first mixture to form a co-precipitate; calcining the co-precipitate to produce an intermediate; impregnating the intermediate with an active metal precursor and an enhancer precursor to produce a second mixture; and calcining the second mixture to produce a calcined product; wherein the active metal precursor comprises nickel (Ni) and cobalt (Co), and the enhancer precursor comprises yttrium (Y).

[0030] In one embodiment, the co-precipitating agent comprises one or more of sodium hydroxide and ammonia, and the first mixture may have a pH of 10 or higher.

[0031] In one embodiment, the above-mentioned co-precipitate may be prepared by including the step of raising the temperature of the first mixture to 40 to 90°C and aging it for 10 hours or more.

[0032] In one embodiment, prior to the step of calcining the co-precipitate, the step of drying the co-precipitate at 70 to 150°C may be further included.

[0033] In one embodiment, prior to the step of calcining the second mixture, the method may further include the step of drying the second mixture at 70 to 150°C.

[0034] In one embodiment, the above-mentioned co-precipitate and the second mixture may each be calcined at 500 to 1100°C.

[0035] In one embodiment, the calcined product comprises a support comprising magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, wherein the active metal comprises nickel (Ni) and cobalt (Co), and the promoter may comprise yttrium (Y).

[0036] In one embodiment, the sintered product may comprise 60 to 90 weight% of a support, 2 to 30 weight% of an active metal, and 3 to 25 weight% of a promoter.

[0037] In one embodiment, the active metal may contain nickel and cobalt in a weight ratio of 1:2 to 1:10.

[0038] In one embodiment, the calcined product may contain the active metal and the promoter in a weight ratio of 1:0.3 to 1:3.

[0039] Another aspect of the present invention relates to a method for producing synthesis gas using the hydrocarbon composite reforming catalyst. In one embodiment, the method for producing synthesis gas comprises the step of producing synthesis gas containing hydrogen (H2) and carbon monoxide (CO) by carrying out a composite reforming reaction of hydrocarbons in the presence of the hydrocarbon composite reforming catalyst.

[0040] In one embodiment, before carrying out the complex reforming reaction of the hydrocarbon, the method may further include the step of reducing the hydrocarbon complex reforming catalyst in a hydrogen (H2) containing gas atmosphere.

[0041] In one embodiment, the hydrocarbon composite reforming reaction may be carried out at a reaction temperature of 600 to 1000°C and a pressure range of 1 to 10 bar.

[0042] In one embodiment, the hydrocarbon complex reforming reaction can be carried out while maintaining methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.1 to 10:0.1 to 5:0.1 to 5.

[0043]

[0044] The hydrocarbon composite reforming catalyst of the present invention exhibits excellent catalytic activity during the hydrocarbon composite reforming reaction, resulting in excellent hydrocarbon conversion rates and carbon monoxide conversion rates; excellent resistance to carbon deposition occurring during the hydrocarbon composite reforming reaction; excellent catalytic activity and stability even during long-term operation; excellent eco-friendliness, economic efficiency, and productivity; excellent durability; excellent bonding strength and dispersibility between constituent components; and the ability to easily control the H2 / CO ratio of the synthesis gas during the hydrocarbon composite reforming reaction.

[0045] Furthermore, the present invention includes an appropriate amount of yttrium as a promoter in a spinel-structured catalyst carrier supported with nickel and cobalt as active metals, thereby suppressing carbon deposition occurring during the steam-carbon dioxide combined reforming reaction of methane and enabling the catalytic activity to be maintained stably for a long time. At the same time, by using nickel and cobalt, which are cheaper than precious metals, as the main components of the catalytic activity, it has a very useful effect in terms of economy.

[0046]

[0047] Figure 1 shows the XRD graph of Example 1.

[0048] Figure 2 shows the XRD graphs of Example 1 and Comparative Example 1.

[0049] Figure 3 is a graph of the TGA measurement results of the composite reforming catalyst after the hydrocarbon composite reforming reaction of Example 3 and Comparative Examples 1 to 4.

[0050] Figure 4(a) shows the carbon dioxide conversion rate with respect to reaction time during the hydrocarbon complex reforming reaction of Examples 1 to 3, and Figure 4(b) is a graph showing the methane conversion rate with respect to reaction time during the hydrocarbon complex reforming reaction of Examples 1 to 3.

[0051] Figure 5 is a graph of the TGA measurement results of the composite reforming catalyst after the hydrocarbon composite reforming reaction of Examples 1 to 3.

[0052]

[0053] In describing the present invention, if it is determined that a detailed description of related known technologies or configurations could unnecessarily obscure the essence of the invention, such detailed description will be omitted.

[0054] Furthermore, the terms described below are defined in consideration of their functions in the present invention; since these may vary depending on the intentions or practices of the user or operator, their definitions should be based on the content throughout this specification describing the present invention.

[0055]

[0056] Hydrocarbon composite reforming catalyst

[0057] One aspect of the present invention relates to a hydrocarbon composite reforming catalyst (or catalyst). In one embodiment, the hydrocarbon composite reforming catalyst comprises a support comprising magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, wherein the active metal comprises nickel (Ni) and cobalt (Co), and the promoter comprises yttrium (Y).

[0058] Meanwhile, coke (or carbon) generated in hydrocarbon complex reforming reactions causes problems such as reducing catalyst activity, damaging the catalyst, and increasing differential pressure within the reactor; therefore, suppressing coke formation in hydrocarbon complex reforming catalysts is very important.

[0059] In this invention, by including yttrium (Y) as a promoter in an optimal ratio on a spinel-structured catalyst support loaded with nickel (Ni) and cobalt (Co) as catalytic active components, coke formation (carbon deposition) occurring during the steam-carbon dioxide combined reforming reaction of hydrocarbons (methane) is suppressed, thereby enabling the catalytic activity to be maintained stably for a long time. At the same time, by using nickel, cobalt, and yttrium, which are cheaper than precious metals, as the main components of the catalytic activity, it has a very useful effect in terms of economics.

[0060] In the present invention, the support comprises a spinel-structured magnesium aluminate (MgAl2O4). The magnesium aluminate is a material characterized by high basicity, strong chemical resistance, high mechanical strength, and a high specific surface area, and has the advantages of high thermal stability and increasing the dispersion of metal when used as a catalyst support. There are various methods for manufacturing magnesium aluminate, the most common of which are the sol-gel process and the solid-state reaction method. The sol-gel process has the advantage of enabling synthesis at low temperatures and obtaining products with uniform particle size and high purity, whereas the solid-state reaction method is a simpler and more economical method, but has the disadvantage that it is difficult to control particle size and shape.

[0061] In one embodiment, the support may be included in an amount of 60 to 90 weight percent based on the total weight of the hydrocarbon composite reforming catalyst. When included in this range, the resistance to coke deposition during the hydrocarbon composite reforming reaction is excellent, so the catalyst activity and carbon dioxide conversion rate are excellent, and the durability of the catalyst may be excellent. For example, the support may be included in an amount of 65 to 90 weight percent, 65 to 85 weight percent, or 67 to 82 weight percent.

[0062] In one embodiment, the active metal is supported within the support and includes nickel (Ni) and cobalt (Co).

[0063] In one embodiment, the active metal may be included in an amount of 2 to 30 weight% based on the total weight of the hydrocarbon composite reforming catalyst. When included within this range, the dispersibility and bonding strength within the support are excellent, the catalytic activity is excellent, and the resistance to coke formation is excellent. For example, the active metal may be included in an amount of 4 to 27 weight%, 6 to 25 weight%, 6 to 22 weight%, 6 to 20 weight%, or 9 to 18 weight%. For example, the active metal may be included in an amount of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 weight% based on the total weight of the hydrocarbon composite reforming catalyst.

[0064] The nickel (Ni) can serve to enhance resistance to coke formation through strong interaction with the support. In one embodiment, the nickel may be included in an amount of 1 to 15 weight% relative to the total weight of the hydrocarbon composite reforming catalyst. When included within this range, excellent dispersibility and bonding strength within the support, excellent catalytic activity, and excellent resistance to coke formation may be achieved. For example, the nickel may be included in an amount of 3 to 15 weight%, 5 to 15 weight%, 5 to 12 weight%, or 8 to 12 weight%. For example, the nickel may be included in an amount of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 weight% relative to the total weight of the hydrocarbon composite reforming catalyst.

[0065] The above cobalt (Co) has high catalytic activity for the decomposition of carbon-carbon (CC) bonds at low temperatures and possesses excellent oxidizing ability.

[0066] In one embodiment, the cobalt may be included in an amount of 1 to 15 weight% based on the total weight of the hydrocarbon composite reforming catalyst. When included within this range, the dispersibility and bonding strength within the support are excellent, the catalytic activity is excellent, and the resistance to coke formation is excellent. For example, the cobalt may be included in an amount of 1 to 12 weight%, 1 to 10 weight%, 1 to 8 weight%, or 1 to 6 weight%. For example, the cobalt may be included in an amount of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 weight% based on the total weight of the hydrocarbon composite reforming catalyst.

[0067] In one sphere, the nickel and cobalt may be in the form of a nickel-cobalt bimetallic compound. When the nickel and cobalt are included in the form of a bimetallic compound, the loading capacity and reduction properties of the nickel and cobalt within the support can be improved.

[0068] In one embodiment, the nickel and cobalt may have a crystal diameter of 1 to 50 nm. Under these conditions, the loading capacity and reduction properties of nickel and cobalt within the support can be improved. For example, the nickel and cobalt may have a crystal diameter of 1 to 40 nm, 1 to 20 nm, 5 to 15 nm, or 7 to 9 nm.

[0069] In one embodiment, the active metal may contain nickel and cobalt in a weight ratio of 1:2 to 1:10. When included within this weight ratio range, the formation of a nickel-cobalt bimetallic compound is facilitated, the increase in the proportion of a single metal is suppressed, and the loading capacity and reduction characteristics of nickel and cobalt within the support can be improved. For example, the active metal may contain nickel and cobalt in a weight ratio of 1:2 to 1:8, 1:2 to 1:7, 1:2 to 1:5, or 1:2 to 1:4.

[0070] The above-mentioned promoter includes yttrium (Y). Yttrium (Y), used as a promoter, prevents the oxidation of the nickel and cobalt and serves to inhibit sintering.

[0071] In one embodiment, the promoter may be included in an amount of 3 to 25 weight% based on the total weight of the hydrocarbon composite reforming catalyst. Including it within this range prevents a decrease in the activity of the composite reforming catalyst due to coke deposition without impairing the dispersibility of the active metal. For example, the promoter may be included in an amount of 5 to 20 weight%, 8 to 20 weight%, or 10 to 20 weight%. For example, the promoter may be included in an amount of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 weight% based on the total weight of the hydrocarbon composite reforming catalyst.

[0072] In one embodiment, the hydrocarbon composite reforming catalyst may contain the active metal and the promoter in a weight ratio of 1:0.3 to 1:3. When included within this weight ratio range, the dispersibility and bonding strength of the active metal and the promoter within the support are excellent, the catalytic activity is excellent, and the resistance to coke deposition is excellent. For example, the hydrocarbon composite reforming catalyst may contain the active metal and the promoter in a weight ratio of 1:0.3 to 1:2 or 1:0.3 to 1:1.8.

[0073] In one embodiment, the support may have an average pore size of 10 to 50 nm. The size may be the maximum length or diameter of the pores. Under these conditions, the resistance to high-temperature coke deposition is excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support may have an average pore size of 10 to 35 nm.

[0074] In one embodiment, the support has a specific surface area (BET) of 90 m² 2 It may be greater than / g. Under the above conditions, high-temperature coke deposition resistance is excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support has a specific surface area (BET) of 90 to 150 m² 2 / g can be.

[0075] In one embodiment, the support has a total pore volume of 0.40 cm³ 3 It may be greater than / g. Under the above conditions, durability and resistance to high-temperature coke deposition are excellent, composite reforming catalyst activity is excellent, and the thermal stability of the reforming catalyst may be excellent. For example, the above composite reforming catalyst has a pore volume of 0.40~0.70 cm³ 3 / g or 0.46~0.65cm 3 It can be / g.

[0076] In one embodiment, the hydrocarbon composite reforming catalyst may have effective peaks in the regions where the diffraction angle (2θ) values ​​in the X-ray diffraction (XRD) spectrum are 18–22˚, 30–34˚, 35–38˚, 42–48˚, 58–62˚, 58–66˚, 74–76˚, and 77–79˚, respectively. Under these conditions, the catalyst activity is excellent, resulting in excellent hydrocarbon conversion rates and carbon monoxide conversion rates, and excellent resistance to carbon deposition occurring during the hydrocarbon composite reforming reaction. For example, the above hydrocarbon composite reforming catalyst may have effective peaks in regions where the diffraction angle (2θ) value is 18–22˚, 30–34˚, 35–38˚, 42–48˚, 58–62˚, 58–66˚, 74–76˚, and 77–79˚ in an X-ray diffraction (XRD) spectrum using CuKα rays of 1.54–2.0 Å.

[0077]

[0078] The catalyst for the combined reforming reaction of methane according to the present invention has high resistance to carbon (coke) deposition, so it can be usefully used to produce synthesis gas composed of hydrogen and carbon monoxide from methane by the combined reforming of steam and carbon dioxide.

[0079] The method for manufacturing the catalyst carrier according to the present invention may include a co-precipitation method, a precipitation method, a sol-gel method, a melting method, or an impregnation method, but is not limited thereto. In terms of ease of forming a spinel structure, the co-precipitation method may be used. Furthermore, the method of supporting the catalyst active component containing a promoter on the catalyst carrier is not particularly limited and any method generally used in this field may be applied without limitation. However, in terms of reproducibility and economic feasibility, the incipient wetness impregnation method may be applied.

[0080] In one embodiment, the method for manufacturing a catalyst according to the present invention is described as follows based on the co-precipitation method and the initial wet impregnation method.

[0081]

[0082] Method for manufacturing a hydrocarbon composite reforming catalyst

[0083] Another aspect of the present invention relates to a method for manufacturing the hydrocarbon composite reforming catalyst. In one embodiment, the method for manufacturing the hydrocarbon composite reforming catalyst comprises: (S10) a step of manufacturing a first mixture; (S20) a step of forming a co-precipitate; (S30) a step of manufacturing an intermediate; (S40) a step of manufacturing a second mixture; and (S50) a step of manufacturing a calcined product.

[0084] More specifically, the method for manufacturing the hydrocarbon composite reforming catalyst comprises: (S10) a step of preparing a first mixture by adding a co-precipitating agent to a magnesium (Mg) precursor and an aluminum (Al) precursor; (S20) a step of aging the first mixture to form a co-precipitate; (S30) a step of preparing an intermediate by calcining the co-precipitate; (S40) a step of preparing a second mixture by impregnating the intermediate with an active metal precursor and an promoter precursor; and (S50) a step of preparing a calcined product by calcining the second mixture.

[0085] Hereinafter, the method for manufacturing the above-mentioned hydrocarbon composite reforming catalyst will be explained in detail step by step.

[0086]

[0087] (S10) First mixture preparation step

[0088] The above step is to prepare a first mixture by adding a co-precipitating agent to a magnesium (Mg) precursor and an aluminum (Al) precursor.

[0089] The magnesium precursor and aluminum precursor may be used without limitation as long as they are compounds containing magnesium (Mg) and aluminum (Al), respectively. For example, they may include one or more of salt compounds and complexes containing magnesium and aluminum, respectively. For example, the magnesium precursor and aluminum precursor may each include one or more of nitrates, acetate salts, and halide salts of magnesium and aluminum, respectively.

[0090] The first mixture may further include a solvent. For example, to ensure a uniform mixture of the magnesium precursor and the aluminum precursor, the mixture may be mixed in a state where it is dissolved or dispersed in a solvent. Any solvent capable of dissolving or dispersing the magnesium precursor and the aluminum precursor may be used without limitation. Examples include water, such as distilled water or purified water; alcohols, such as methanol, ethanol, or isopropanol; toluene; glycol; and dimethylformamide. Preferably, it may be water. The content of the solvent is not particularly limited as long as it is sufficient to dissolve both the magnesium precursor and the aluminum precursor.

[0091] The above-mentioned co-precipitating agent is included to adjust the pH of the first mixture to uniformly precipitate the salt-form precursors of the first mixture, thereby forming a support. In one embodiment, the co-precipitating agent may include one or more of sodium hydroxide and ammonia. For example, the co-precipitating agent may be in the form of a basic solution. For example, the co-precipitating agent may include one or more of a sodium hydroxide solution and an aqueous ammonia solution.

[0092] In one embodiment, the first mixture may have a pH of 10 or higher. Under these conditions, the magnesium precursor and aluminum precursor in the form of salt are uniformly precipitated, allowing the support to be easily prepared.

[0093] For example, the first mixture above can be adjusted to a pH of 10 or higher by adding a co-precipitating agent to the magnesium (Mg) precursor and aluminum (Al) precursor.

[0094]

[0095] (S20) Co-precipitation formation step

[0096] The above step is to age the first mixture to form a co-precipitate.

[0097] In one embodiment, the co-precipitate may be prepared by including the step of raising the temperature of the first mixture to 40 to 90°C and aging it for at least 10 hours. Under these conditions, the reaction of the first mixture proceeds sufficiently, so that the active metal and the promoter can be easily dispersed and supported while having excellent durability of the support. For example, the co-precipitate may be prepared by raising the temperature of the first mixture to 40 to 70°C and aging it for 10 to 30 hours or 15 to 25 hours.

[0098] In one embodiment, prior to the step of calcining the co-precipitate, the method may further include a step of drying the co-precipitate at 70 to 150°C. Under the drying conditions, the solvent evaporates smoothly into the pores of the support, the drying time is shortened, cracking of the support is prevented, and aggregation of magnesium and aluminum can be prevented.

[0099] For example, the above-mentioned co-precipitate can be dried at 70 to 150°C for 8 hours or more. Under these conditions, magnesium and aluminum aggregation can be prevented while preventing damage to the support. For example, the drying can be performed for 8 to 20 hours. The drying can be carried out using conventional methods such as hot air or an oven.

[0100]

[0101] (S30) Intermediate manufacturing step

[0102] The above step is a step of preparing an intermediate by calcining the above co-precipitate.

[0103] In one embodiment, the above co-precipitate can be sintered at 500 to 1100°C. When sintered under the above temperature conditions, a support having nano-sized crystals with a high surface area and spinel structure is formed, and high dispersion loading of an active metal can be facilitated.

[0104] In one embodiment, the above-mentioned co-precipitate may be calcined at 500 to 1100°C in an oxidizing atmosphere. The above-mentioned oxidizing atmosphere may include oxygen and air, etc. Additionally, the calcination may vary depending on conditions such as the calcination temperature, size and amount of the co-precipitate, but may be carried out for, for example, 1 to 24 hours.

[0105]

[0106] (S40) Second mixture preparation step

[0107] The above step is to prepare a second mixture by impregnating the intermediate with an active metal precursor and an enhancer precursor.

[0108] In one embodiment, the active metal precursor comprises nickel (Ni) and cobalt (Co), and the promoter precursor comprises yttrium (Y).

[0109] For example, the active metal precursor may include a nickel precursor and a cobalt precursor, and the promoter precursor may include an yttrium precursor.

[0110] In one embodiment, the nickel precursor, cobalt precursor, and yttrium precursor may be used without limitation as long as they are compounds containing nickel (Ni), cobalt (Co), or yttrium (Y), respectively. For example, they may include salt compounds or complexes containing nickel, cobalt, or yttrium. More specifically, the nickel precursor, cobalt precursor, and yttrium precursor may each include one or more of nitrates, acetate salts, and halide salts of nickel, cobalt, and yttrium.

[0111] In one embodiment, the second mixture may further include a solvent. For example, the nickel precursor, cobalt precursor, and yttrium precursor may be mixed in a state where they are dissolved or dispersed in a solvent for uniform mixing. Any solvent capable of dissolving or dispersing the nickel precursor, cobalt precursor, and yttrium precursor may be used without limitation. Examples include water, such as distilled water or purified water; alcohols such as methanol, ethanol, or isopropanol; toluene; glycol; and dimethylformamide. Preferably, it may be water. The content of the solvent is not particularly limited as long as it is sufficient to dissolve all of the nickel precursor, cobalt precursor, and yttrium precursor.

[0112] At this time, when preparing the second mixture, the order of loading the nickel precursor, cobalt precursor, and yttrium precursor onto the intermediate is not particularly limited. For example, the second mixture can be prepared by injecting them in sequence or by injecting them simultaneously for impregnation. As an example, they can be injected in sequence, one of the nickel, cobalt, and yttrium precursors can be injected first and then the remaining precursor can be injected simultaneously, two of the precursors can be injected simultaneously and then the remaining precursor can be injected, or all three precursors can be injected simultaneously for impregnation.

[0113] In one embodiment, prior to the step of calcining the second mixture, the method may further include a step of drying the second mixture at 70 to 150°C. Under the drying conditions, drying is easily performed and the drying time is shortened, and while preventing aggregation of the active metal and the promoter component, damage such as cracks on the surface of the catalyst can be prevented.

[0114] For example, the second mixture can be dried at 70 to 150°C for at least 8 hours. Under these conditions, aggregation of the active metal and promoter components can be prevented while preventing damage to the support. For example, the drying can be performed for 8 to 20 hours. The drying can be carried out using conventional methods such as hot air or an oven.

[0115]

[0116] (S50) Calcined product manufacturing step

[0117] The above step is a step of producing a sintered product by sintering the above second mixture.

[0118] In one embodiment, the second mixture may be calcined at 500 to 1100°C. When calcined under these conditions, the phenomenon of reduced active sites due to sintering of the catalytic active metal is prevented, and damage such as the occurrence of catalyst cracks is prevented, while a calcined product (catalyst) with a structure in which an active component and a promoter are dispersed and supported on a spinel-structured support is easily formed, and excellent resistance to coke deposition and excellent catalytic activity during hydrocarbon composite modification can be achieved.

[0119] In one embodiment, the second mixture may be calcined at 500 to 1100°C in an oxidizing atmosphere containing one or more of oxygen and air. Under these conditions, a calcined product (catalyst) can be easily formed while preventing damage such as the occurrence of catalyst cracks.

[0120] In one embodiment, the calcination time of the second mixture may vary depending on conditions such as the calcination temperature, the size and content of the components of the second mixture, but may be carried out for, for example, 1 to 24 hours.

[0121] In one embodiment, the second mixture can be heated gradually at a heating rate of 10°C / min or less to reach the sintering temperature. Under these conditions, rapid evaporation and oxidation of the solvent component of the second mixture can be prevented, thereby preventing the occurrence of cracks and voids in the sintered product (catalyst) and preventing a decrease in mechanical strength.

[0122] In one embodiment, the calcined product comprises a support comprising magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, wherein the active metal comprises nickel (Ni) and cobalt (Co), and the promoter may comprise yttrium (Y).

[0123] The above support, active metal, and promoter may be the same as the constituent components of the aforementioned composite reforming catalyst.

[0124] In one embodiment, the sintered product may comprise 60 to 90 weight% of a support, 2 to 30 weight% of an active metal, and 3 to 25 weight% of a promoter.

[0125] In one embodiment, the nickel and cobalt may have a crystal diameter of 1 to 50 nm. Under these conditions, the loading capacity and reduction properties of nickel and cobalt within the support can be improved. For example, the nickel and cobalt may have a crystal diameter of 1 to 40 nm, 1 to 20 nm, 5 to 15 nm, or 7 to 9 nm.

[0126] In one embodiment, the active metal may contain nickel and cobalt in a weight ratio of 1:2 to 1:10. When included within this weight ratio range, the formation of a nickel-cobalt bimetallic compound is facilitated, the increase in the proportion of a single metal is suppressed, and the loading capacity and reduction characteristics of nickel and cobalt within the support can be improved. For example, the active metal may contain nickel and cobalt in a weight ratio of 1:2 to 1:8, 1:2 to 1:6, 1:2 to 1:5, or 1:2 to 1:4.

[0127] In one embodiment, the hydrocarbon composite reforming catalyst may contain the active metal and the promoter in a weight ratio of 1:0.3 to 1:3. When included within this weight ratio range, the dispersibility and bonding strength of the active metal and the promoter within the support are excellent, the catalytic activity is excellent, and the resistance to coke deposition is excellent. For example, the hydrocarbon composite reforming catalyst may contain the active metal and the promoter in a weight ratio of 1:0.3 to 1:2 or 1:0.3 to 1:1.8.

[0128] In one embodiment, the support may have an average pore size of 10 to 50 nm. The size may be the maximum length or diameter of the pores. Under these conditions, the resistance to high-temperature coke deposition is excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support may have an average pore size of 10 to 35 nm.

[0129] In one embodiment, the support has a specific surface area (BET) of 90 m² 2 It may be greater than / g. Under the above conditions, high-temperature coke deposition resistance is excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support has a specific surface area (BET) of 90 to 150 m² 2 / g can be.

[0130] In one embodiment, the support has a total pore volume of 0.40 cm³ 3 It may be greater than / g. Under the above conditions, durability and resistance to high-temperature coke deposition are excellent, composite reforming catalyst activity is excellent, and the thermal stability of the reforming catalyst may be excellent. For example, the above composite reforming catalyst has a pore volume of 0.40~0.70 cm³ 3 / g or 0.46~0.65cm 3 It can be / g.

[0131]

[0132] Method for producing synthesis gas using a hydrocarbon composite reforming catalyst

[0133] Another aspect of the present invention relates to a method for producing synthesis gas using the hydrocarbon composite reforming catalyst. In one embodiment, the method for producing synthesis gas comprises the step of producing synthesis gas containing hydrogen (H2) and carbon monoxide (CO) by carrying out a composite reforming reaction of hydrocarbons in the presence of the hydrocarbon composite reforming catalyst.

[0134] The above hydrocarbon composite reforming catalyst may be the same as that described above.

[0135] In one embodiment, the complex reforming reaction of hydrocarbons (methane) during the production of the synthesis gas may proceed according to the following reaction scheme 1:

[0136] [Reaction Equation 1]

[0137] 3CH4 + 2H2O + CO2 → 8H2 + 4CO

[0138] As shown in Reaction Scheme 1 above, the synthesis gas production method may use methane, water vapor, and carbon dioxide as reactants. In one embodiment, the synthesis gas may have a molar ratio of water vapor to methane (water vapor / methane) of 0.5 to 1. Additionally, the synthesis gas may have a molar ratio of carbon dioxide to methane (carbon dioxide / methane) of 0.5 to 1. When performing a complex reforming reaction within the above molar ratios, the molar ratio of hydrogen (H2) to carbon monoxide (CO) in the synthesis gas product may be controlled to 1 / 25 to 2.5 / 1.

[0139] In one embodiment, before carrying out the complex reforming reaction of the hydrocarbon, the method may further include a step of reducing the hydrocarbon complex reforming catalyst in a hydrogen (H2) containing gas atmosphere. When the reduction treatment is performed under these conditions, the oxide of the catalyst-active metal is reduced, so that the catalytic activity during the hydrocarbon complex reforming reaction may be excellent. For example, the reduction may be carried out at 600 to 1000°C.

[0140] In one embodiment, the hydrocarbon composite reforming reaction may be carried out at a reaction temperature of 600 to 1000°C and a pressure range of 1 to 10 bar.

[0141] Under the above reaction temperature conditions, the hydrocarbon conversion rate is thermodynamically excellent, resulting in an excellent synthesis gas yield, and the efficiency of the composite reforming reaction is excellent while preventing catalyst sintering, which can lead to excellent economic feasibility. For example, the above reaction temperature may be 700 to 900°C.

[0142] When the reaction is performed under the above pressure conditions, the thermodynamic hydrocarbon conversion rate is excellent, resulting in an excellent synthesis gas yield and preventing carbon deposition. For example, the above reaction can be carried out at 1 to 5 bar.

[0143] The above hydrocarbon composite reforming process can be carried out by injecting a reaction gas composition (or reactant) comprising methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2).

[0144] In one embodiment, the hydrocarbon complex reforming reaction can be carried out while maintaining the reaction gas composition of methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.1 to 10:0.1 to 5:0.1 to 5. Under these conditions, the production yield of the product per unit catalyst is excellent, heat transfer within the reactor is easy, and the hydrocarbon conversion rate is excellent, allowing for easy achievement of the product yield. For example, the complex reforming reaction can be carried out while maintaining the molar ratio of methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.8 to 1.5:0.3 to 0.8:0.1 to 0.5.

[0145] In one sphere, the above hydrocarbon complex reforming reaction can be carried out by injecting the gas composition at a space velocity (GHSV) of 10,000 to 100,000 / h. Under these conditions, the production yield of the product per unit catalyst is excellent, heat transfer within the reactor is easy, and the hydrocarbon conversion rate is excellent, so the yield of the product can be easily achieved.

[0146]

[0147] Hereinafter, the structure and operation of the present invention will be explained in more detail through preferred embodiments. However, these are presented as preferred examples of the present invention and should not be interpreted in any way as limiting the present invention. Details not described herein can be sufficiently technically inferred by those skilled in the art, so such descriptions will be omitted.

[0148]

[0149] Hereinafter, the structure and operation of the present invention will be explained in more detail through preferred embodiments of the present invention. However, the following embodiments are intended to aid in understanding the present invention, and the scope of the present invention is not limited to the following embodiments.

[0150]

[0151] Examples and Comparative Examples

[0152] Example 1

[0153] (1) Preparation of the first mixture: 12.82 g of magnesium (Mg) precursor (Mg(NO3)2·6H2O) and 37.51 g of aluminum (Al) precursor (Al(NO3)3·9H2O) were dissolved in 150 mL of distilled water, and then a co-precipitating agent (30% (w / v) aqueous ammonia solution) was added while stirring until the pH became 10 or higher to prepare the first mixture (pH 10 or higher).

[0154] (2) Formation of co-precipitate: The first mixture was heated to 50°C and aged for 20 hours to form a co-precipitate. The co-precipitate was repeatedly filtered and washed with distilled water and dried in a drying oven at 120°C for 12 hours.

[0155] (3) Preparation of intermediate: The dried co-precipitate was placed in a kiln and calcined in air at 800°C for 6 hours to prepare an intermediate (spinel-structured MgAl2O4 support).

[0156] (4) Preparation of the second mixture: 5.67 g of nickel precursor (Ni(NO3)2·6H2O) and 1.71 g of cobalt precursor (Co(NO3)2·6H2O) as active metal precursors, and 4.41 g of promoter precursor (yttrium precursor (Y(NO3)3·6H2O)) were dissolved in 12 g of distilled water, and then impregnated into 10 g of the intermediate to prepare the second mixture, and then the second mixture was dried in a drying oven at 110°C for 12 hours.

[0157] (5) Preparation of calcined product: The dried second mixture was placed in a kiln and calcined in air at 800°C for 6 hours to prepare a calcined product (composite reforming catalyst).

[0158] The above calcined product [Ni(10)Co(3)Y(10)] comprises a support including magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, wherein the calcined product comprises 77% by weight of the support based on the total weight, 10% by weight of nickel (Ni) and 3% by weight of cobalt (Co) as the active metal precursor, and 10% by weight of yttrium (Y) as the promoter precursor.

[0159]

[0160] Example 2

[0161] A calcined product (composite reforming catalyst) was prepared in the same manner as in Example 1, except that 2.01 g of a promoter precursor (yttrium precursor (Y(NO3)3·6H2O)) was impregnated into an intermediate to prepare a second mixture.

[0162] The above calcined product [Ni(10)Co(3)Y(5)] comprises a support containing magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, wherein the calcined product comprises 82% by weight of the support based on the total weight, 10% by weight of nickel (Ni) and 3% by weight of cobalt (Co) as the active metal precursor, and 5% by weight of yttrium (Y) as the promoter precursor.

[0163]

[0164] Example 3

[0165] A calcined product (composite reforming catalyst) was prepared in the same manner as in Example 1, except that 10.13 g of a promoter precursor (yttrium precursor (Y(NO3)3·6H2O)) was impregnated into an intermediate to prepare a second mixture.

[0166] The above calcined product [Ni(10)Co(3)Y(20)] comprises a support including magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, wherein the calcined product comprises 67% by weight of the support based on the total weight, 10% by weight of nickel (Ni) and 3% by weight of cobalt (Co) as the active metal precursor, and 20% by weight of yttrium (Y) as the promoter precursor.

[0167]

[0168] Comparative Example 1

[0169] A calcined product (composite reforming catalyst) was prepared in the same manner as in Example 1, except that the promoter precursor (yttrium precursor (Y(NO3)3·6H2O)) was not added.

[0170] The above calcined product [Ni(10)Co(3)] comprises a support including magnesium aluminate (MgAl2O4) and an active metal dispersed in the support, wherein the calcined product comprises 87% by weight of the support based on the total weight and comprises 10% by weight of nickel (Ni) and 3% by weight of cobalt (Co) as the active metal precursor.

[0171]

[0172] Comparative Example 2

[0173] A calcined product (composite reforming catalyst) was prepared in the same manner as in Example 1, except that 5.50 g of a zirconium precursor (Zr(NO3)2·xH2O) was impregnated into an intermediate to prepare a second mixture instead of the above-mentioned promoter precursor (yttrium precursor).

[0174] The above calcined product [Ni(10)Co(3)Zr(20)] comprises a support including magnesium aluminate (MgAl2O4), an active metal dispersed in the support, and zirconium (Zr). The calcined product comprises 67% by weight of the support based on the total weight, and the active metal precursor comprises 10% by weight of nickel (Ni) and 3% by weight of cobalt (Co), and 20% by weight of zirconium (Zr).

[0175]

[0176] Comparative Example 3

[0177] A calcined product (composite reforming catalyst) was prepared in the same manner as in Example 1, except that a second mixture was prepared by impregnating an intermediate with 6.03 g of a cerium precursor (Ce(NO3)3·6H2O) and 1.59 g of a lanthanum precursor (La(NO3)3·6H2O) instead of the above-mentioned promoter precursor (yttrium precursor).

[0178] The above calcined product [Ni(10)Co(3)CeLa(20)] comprises a support containing magnesium aluminate (MgAl2O4), an active metal dispersed in the support, and zirconium (Zr). The calcined product comprises 67% by weight of the support based on the total weight, and the active metal precursor comprises 10% by weight of nickel (Ni) and 3% by weight of cobalt (Co), 4% by weight of lanthanum (La), and 16% by weight of cerium (Ce).

[0179]

[0180] Comparative Example 4

[0181] A calcined product (composite reforming catalyst) was prepared in the same manner as in Example 1, except that a second mixture was prepared by impregnating an intermediate with 6.03 g of a cerium precursor (Ce(NO3)3·6H2O) and 1.12 g of a zirconium precursor (Zr(NO3)2·xH2O) instead of the above-mentioned promoter precursor (yttrium precursor).

[0182] The above calcined product [Ni(10)Co(3)CeZr(20)] comprises a support including magnesium aluminate (MgAl2O4), an active metal dispersed in the support, and zirconium (Zr). The calcined product comprises 67% by weight of the support based on the total weight, and the active metal precursor comprises 10% by weight of nickel (Ni) and 3% by weight of cobalt (Co), 4% by weight of zirconium (La), and 16% by weight of cerium (Ce).

[0183]

[0184] Experimental Example

[0185] (1) X-ray diffraction analysis of hydrocarbon composite reforming catalysts: For the hydrocarbon composite reforming catalysts of Example 1 and Comparative Example 1, the crystal structure was analyzed through X-ray diffraction (XRD) spectra using CuKα rays of 1.54 to 2.0 Å.

[0186] Figure 1 below shows the XRD analysis graph of the hydrocarbon composite reforming catalyst of Example 1, and Figure 2 shows the XRD analysis graph of the hydrocarbon composite reforming catalysts of Example 1 and Comparative Example 1.

[0187] Referring to the results of FIGS. 1 and FIGS. 2 above, it was found that Example 1 had effective peaks in regions where the diffraction angle (2θ) values ​​were 18~22˚, 30~34˚, 35~38˚, 42~48˚, 58~62˚, 58~66˚, 74~76˚, and 77~79˚, and that peaks corresponding to nickel oxide (NiO), magnesium aluminate (MgAl2O4) support, nickel (Ni) (111), and yttrium oxide (Y2O3) were detected.

[0188]

[0189] (2) Evaluation of H2 and CO2 conversion rates and carbon deposition amount during hydrocarbon composite reforming reaction: For the composite reforming catalysts prepared in Example 3 and Comparative Examples 1 to 4 among the above examples and comparative examples, a composite reforming reaction of hydrocarbon (methane) with water vapor and carbon dioxide was performed to measure the catalytic activity. The catalytic activity of the catalyst for the composite reforming reaction was measured by the following method, and the results are shown in FIG. 3.

[0190] For the measurement of catalytic activity during the above combined reforming reaction, the catalysts of the above examples and comparative examples were each loaded into a typical 1 / 2-inch quartz reactor prepared in the laboratory. In addition, prior to performing the combined reforming reaction, the catalysts were reduced at 800°C for 1 hour in a mixed gas atmosphere of N2 and 10 volume% H2.

[0191] Methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) were injected into the reactor as reactants in a molar ratio of 1:1:0.5:0.33. The reactor temperature was 750°C for 8 hours followed by 700°C for 7 hours, the reaction pressure was set to atmospheric pressure (1 atm), and the space velocity (GHSV) was adjusted to 40,800 / h.

[0192] The composition of the gas before and after the combined reforming reaction was measured using a micro gas chromatograph (iGC7200A) directly connected to the reactor to measure the conversion rates of carbon dioxide and methane. As a result, it was found that Example 3 had higher conversion rates of carbon dioxide (CO2) and methane (CH4) compared to Comparative Examples 1 to 4 at all reaction temperature conditions (700°C and 750°C) during the hydrocarbon combined reforming reaction, and that the catalytic activity did not decrease even during the long-term hydrocarbon combined reforming reaction.

[0193] In addition, carbon deposition of the composite reforming catalysts of the examples and comparative examples was measured through thermogravimetric analysis (TGA, Mettler Toledo-TGA / DSC1 Star System), and the weight loss of the samples according to temperature was measured, and the results are shown in Figure 3 below.

[0194] Figure 3 below is a graph of the TGA measurement results of the composite reforming catalysts after the hydrocarbon composite reforming reaction of Example 3 and Comparative Examples 1 to 4. Referring to Figure 3, it was confirmed that Example 3 had superior resistance to coke deposition compared to Comparative Examples 1 to 4, and thus the amount of coke generated during the hydrocarbon composite reforming reaction was the smallest.

[0195]

[0196] (3) Evaluation of activity of composite reforming catalyst: To measure the catalytic activity according to the promoter content of the composite reforming catalysts of Examples 1 to 3 above, a composite reforming reaction of methane with water vapor and carbon dioxide was performed. The catalytic activity of the catalyst for the composite reforming reaction was measured by the following method, and the results are shown in FIGS. 4 and FIGS. 5.

[0197] For the measurement of catalytic activity during the above combined reforming reaction, the catalysts of Examples 1 to 3 were each loaded into a typical 1 / 2-inch quartz reactor prepared in the laboratory. Additionally, prior to performing the combined reforming reaction, the catalysts were reduced at 800°C for 1 hour in a mixed gas atmosphere of N2 and 10 volume% H2.

[0198] Methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) were injected into the reactor as reactants in a molar ratio of 1:1:0.5:0.33. The reactor temperature was 800°C for 8 hours followed by 750°C for 7 hours, the reaction pressure was set to atmospheric pressure (1 atm), and the space velocity (GHSV) was adjusted to 81,600 / h.

[0199] The composition of the gas before and after the combined reforming reaction was measured using a micro gas chromatograph (iGC7200A) directly connected to the reactor to measure the conversion rates of carbon dioxide and methane, and the results are shown in Figure 4 below. In addition, carbon deposition of the combined reforming catalysts of the examples and comparative examples was measured through thermogravimetric analysis (TGA, Mettler Toledo-TGA / DSC1 Star System), and the weight loss of the samples according to temperature was measured, and the results are shown in Figure 5 below.

[0200] Figure 4(a) below shows the carbon dioxide conversion rate with respect to reaction time during the hydrocarbon composite reforming reaction of Examples 1 to 3, Figure 4(b) is a graph showing the methane conversion rate with respect to reaction time during the hydrocarbon composite reforming reaction of Examples 1 to 3, and Figure 5 is a graph of the TGA measurement results of the composite reforming catalyst after the hydrocarbon composite reforming reaction of Examples 1 to 3.

[0201] Referring to Figures 4 and 5 above, although the change in catalyst performance and coke production amount according to yttrium content was not significant, it was confirmed that the amount of coke was smallest in the catalyst prepared in Example 1.

[0202]

[0203] The present invention has been described above with reference to embodiments. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the invention.

Claims

1. A support comprising magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, and The above active metal comprises nickel (Ni) and cobalt (Co), and the above promoter comprises yttrium (Y), forming a hydrocarbon composite reforming catalyst.

2. In claim 1, the hydrocarbon composite reforming catalyst comprises 60 to 90 weight% of a support, 2 to 30 weight% of an active metal, and 3 to 25 weight% of a promoter.

3. The hydrocarbon composite reforming catalyst according to claim 1, wherein the active metal comprises nickel and cobalt in a weight ratio of 1:2 to 1:

10.

4. In claim 1, the above nickel and cobalt are hydrocarbon composite reforming catalysts having a crystal diameter of 1 to 50 nm.

5. In paragraph 1, the hydrocarbon composite reforming catalyst is, A hydrocarbon composite reforming catalyst comprising the above active metal and promoter in a weight ratio of 1:0.3 to 1:

3.

6. A step of preparing a first mixture by adding a co-precipitating agent to a magnesium (Mg) precursor and an aluminum (Al) precursor; A step of aging the above first mixture to form a co-precipitate; A step of preparing an intermediate by calcining the above-mentioned co-precipitate; A step of preparing a second mixture by impregnating the above intermediate with an active metal precursor and an enhancer precursor; and The method includes the step of producing a sintered product by calcining the second mixture; A method for preparing a hydrocarbon composite reforming catalyst, wherein the active metal precursor comprises nickel (Ni) and cobalt (Co), and the promoter precursor comprises yttrium (Y).

7. In paragraph 6, the above-mentioned co-precipitating agent comprises one or more of sodium hydroxide and ammonia, and A method for manufacturing a hydrocarbon composite reforming catalyst, wherein the first mixture above has a pH of 10 or higher.

8. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 6, comprising the step of raising the temperature of the first mixture to 40 to 90°C and aging it for 10 hours or more.

9. In paragraph 6, prior to the step of calcining the above-mentioned co-precipitate, A method for manufacturing a hydrocarbon composite reforming catalyst, further comprising the step of drying the above-mentioned co-precipitate at 70 to 150°C.

10. In claim 6, prior to the step of calcining the second mixture, A method for manufacturing a hydrocarbon composite reforming catalyst, further comprising the step of drying the second mixture at 70 to 150°C.

11. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 6, wherein the above-mentioned co-precipitate and the second mixture are each calcined at 500 to 1100°C.

12. In claim 6, the calcined product comprises a support comprising magnesium aluminate (MgAl2O4) and an active metal and a promoter dispersed in the support, and A method for preparing a hydrocarbon composite reforming catalyst in which the active metal comprises nickel (Ni) and cobalt (Co), and the promoter comprises yttrium (Y).

13. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 12, wherein the calcined product comprises 60-90% by weight of a support, 2-30% by weight of an active metal, and 3-25% by weight of a promoter.

14. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 12, wherein the active metal comprises nickel and cobalt in a weight ratio of 1:2 to 1:

10.

15. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 12, wherein the calcined product comprises the active metal and the promoter in a weight ratio of 1:0.3 to 1:

3.

16. A step of producing a synthesis gas containing hydrogen (H2) and carbon monoxide (CO) by carrying out a hydrocarbon composite reforming reaction in the presence of a hydrocarbon composite reforming catalyst according to any one of claims 1 to 5; comprising a method for producing synthesis gas using a hydrocarbon composite reforming catalyst.

17. In paragraph 16, before carrying out the complex reforming reaction of the above hydrocarbon, A method for producing synthesis gas using a hydrocarbon composite reforming catalyst, further comprising the step of reducing the above hydrocarbon composite reforming catalyst in a hydrogen (H2) containing gas atmosphere.

18. A method for producing synthesis gas using a hydrocarbon composite reforming catalyst, wherein, in claim 16, the hydrocarbon composite reforming reaction is carried out at a reaction temperature of 600 to 1000°C and a pressure range of 1 to 10 bar.

19. A method for producing synthesis gas using a hydrocarbon composite reforming catalyst, wherein the hydrocarbon composite reforming reaction according to claim 16 is carried out while maintaining methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.1 to 10:0.1 to 5:0.1 to 5.

Images