Porous catalyst for synthesis gas preparation and preparation method thereof

Abstract

The invention relates to a preparation method of a porous catalyst for preparing pyrolysis synthesis gas. The preparation method comprises the following steps: mixing a metal precursor containing VIII A group elements, a ceramic carrier and a solvent to prepare a mixed solution; adding an acid to the mixed solution to prepare a precursor gel; mixing clay into the precursor gel to prepare a mixture; adding an inorganic binder to the mixture to prepare a composite catalyst sol; and drying and calcining the composite catalyst sol.

Description

Technical Field

[0001] This invention relates to a catalyst used in a process for converting a mixed gas recovered during the gasification of waste into syngas. Specifically, it provides a catalyst suitable for methane reforming and reverse Boudouar reaction processes, said catalyst maximizing the yield of syngas produced from pyrolysis gases.

[0002] The catalyst of this invention can maximize the yield of syngas during the gasification of waste by providing a catalyst that reduces the efficiency of syngas removal due to side reactions. Background Technology

[0003] Organic waste can severely damage the environment during landfilling due to decomposition, requiring collection based on its specific characteristics and proper disposal through prescribed processes. However, simple disposal of organic waste necessitates the establishment of treatment facilities and consumes significant manpower, resulting in greater waste compared to production processes. Therefore, methods and technologies for recycling organic waste have been developed in recent years. A representative technology is the gasification process, which utilizes organic waste to produce syngas and convert it into high-value-added products for energy conversion.

[0004] Gasification typically refers to a series of processes that convert carbonaceous feedstocks such as coal, organic waste, and biomass into syngas containing hydrogen and carbon monoxide by reacting them with a supply of steam, oxygen, carbon dioxide, or a mixture thereof. In this context, "syngas" usually refers to a mixed gas produced through the gasification reaction that contains hydrogen and carbon monoxide, and may further contain dry gas such as carbon dioxide and / or methane.

[0005] Gasification technology has expanded to produce feedstocks and fuels for various compounds. For example, syngas can be used as a feedstock for the Fischer-Tropsch synthesis reaction to produce high-value-added products such as light oils, heavy oils, diesel fuel, waxes, aviation fuels, and lubricating oil bases. Furthermore, hydrogen from syngas, a major byproduct of gasification, can be used in hydrogen power generation, ammonia production, and oil refining processes. Additionally, it is known that methanol produced from syngas can be used to obtain high-value-added chemical substances such as acetic acid, olefins, dimethyl ether, aldehydes, fuels, and additives. However, the yield of syngas produced from organic waste is extremely low, making it difficult to efficiently produce high-value-added compounds from syngas.

[0006] In recent years, catalyst-based gasification processes have been used to produce syngas. However, the generation of coke during gasification leads to catalyst deactivation, causing process failures during continuous operation. Furthermore, to ensure economic efficiency, the relatively expensive catalyst needs to be recovered. However, recovering the catalyst, which is discharged in the form of coke and other aggregates, requires multiple subsequent processes (such as air burning), resulting in a significant reduction in process efficiency.

[0007] As an example, when the steam reforming catalyst used in existing gasification processes contains noble metal-based active metal components such as Ru, carbon precipitation is minimal even under low S / C (steam / carbon ratio) conditions. However, a drawback is that sulfur poisoning can easily occur due to the sulfur content in the feedstock, leading to a rapid deterioration of catalytic activity, and the sulfur-poisoned catalyst becomes the cause of carbon precipitation. Furthermore, the high price of noble metals reduces the economic viability of the process.

[0008] Furthermore, steam reforming is a high-temperature reaction. The high-temperature endothermic reaction during reforming and the regeneration process at the reactor end, which involves oxidizing and removing coke from the catalyst surface to regenerate the catalyst, are repeated, leading to catalyst breakage. Therefore, α-alumina, with its relatively high crushing strength, is often used as the support component. However, to improve the strength of α-alumina, it is typically calcined at high temperatures during preparation, resulting in a very small BET specific surface area or pore size. Consequently, the active metal component supported on α-alumina is prone to sintering upon heating, leading to a deterioration in catalytic activity.

[0009] In this regard, there is a need to develop a catalyst that is inexpensive, has excellent durability, maintains sufficient strength to prevent breakage and cracking even when carbon buildup occurs inside the catalyst, and has a high specific surface area, thereby exhibiting excellent reactivity and reaction stability.

[0010] Furthermore, there is still a need to develop a catalyst for hydrocarbon production that can improve the yield of syngas obtained through gasification reactions, thereby efficiently converting the mixed gas into high-value-added hydrocarbons while minimizing the generation of carbon dioxide in the hydrocarbon production process. Summary of the Invention

[0011] (a) Technical problems to be solved According to one aspect of the present invention, a catalyst for the preparation of pyrolysis syngas with excellent catalytic activity and high durability, and a method thereof, can be provided.

[0012] According to one aspect of the present invention, a catalyst for the preparation of pyrolysis syngas with high reaction stability and a method thereof can be provided.

[0013] According to one aspect of the present invention, a catalyst for the preparation of pyrolysis syngas and a method thereof can be provided, wherein the catalyst can further improve the yield and conversion rate of carbon monoxide prepared from pyrolysis gas.

[0014] (II) Technical Solution The method for preparing a porous catalyst for pyrolysis syngas production according to the present invention includes the following steps: mixing a metal precursor containing a Group VIIIA element, a ceramic support, and a solvent to prepare a mixed solution; adding an acid to the mixed solution to prepare a precursor gel; mixing clay into the precursor gel to prepare a mixture; adding an inorganic binder to the mixture to prepare a composite catalyst sol; and drying and calcining the composite catalyst sol.

[0015] In one specific embodiment, the catalyst can be used as a steam reforming catalyst and a catalyst for the reverse Boudouar process in a process for producing syngas via hydrocarbon cracking.

[0016] In one specific implementation, the Group VIIIA elements may include nickel, iron, cobalt, ruthenium, palladium, platinum, or mixtures thereof.

[0017] In one specific embodiment, the metal precursor may be any one or more selected from group VIIIA elements, including hydroxides, sulfates, carbonates, nitrates, chlorides, benzoates, basic carbonates, formates, citrates, diammonium sulfates, and their hydrates.

[0018] In one specific embodiment, the ceramic carrier may include pseudo-boehmite.

[0019] In one specific embodiment, the acid may be one or more organic acids selected from formic acid, acetic acid, propionic acid, and salicylic acid.

[0020] In one specific implementation, the calcination can be carried out in a temperature range of 500°C to 1300°C.

[0021] The present invention includes a porous catalyst for the preparation of pyrolysis syngas obtained by the above preparation method.

[0022] In one specific embodiment, the catalyst of the present invention may contain 5% to 70% by weight of a ceramic support, 0.1% to 75% by weight of a Group VIIIA element, and 0.1% to 30% by weight of clay.

[0023] In one specific embodiment, the pore volume of the catalyst can be from 0.01 cubic centimeters (cc) / g to 0.5 cubic centimeters / g.

[0024] In one specific embodiment, the average pore diameter of the catalyst may be less than 300 Å.

[0025] In one specific implementation, the Group VIIIA element may exist in the form of microparticles, with an average particle size of 1 nm to 20 nm.

[0026] In one specific embodiment, the BET specific surface area of ​​the catalyst of the present invention can be 10 m². 2 / g to 300m 2 / g.

[0027] In one specific embodiment, the wear index of the catalyst of the present invention can be less than 15% by weight.

[0028] In one specific embodiment, the catalyst of the present invention may further contain 0% to 30% by weight of silicon dioxide.

[0029] In one specific embodiment, the average particle size (D50) of the catalyst of the present invention can be from 10 μm to 500 μm.

[0030] In one specific embodiment, the catalyst of the present invention can be a catalyst for steam reforming reactions for producing syngas from hydrocarbons and a catalyst for the reverse boudouard reaction.

[0031] (III) Beneficial Effects According to one embodiment of the present invention, a method for preparing a porous catalyst for pyrolysis syngas production that simultaneously possesses excellent catalytic activity and high durability can be provided.

[0032] According to one embodiment of the present invention, a method for preparing a catalyst for pyrolysis syngas production can be provided, wherein the catalyst minimizes catalyst breakage due to coke generation and thus has high reaction stability.

[0033] According to one embodiment of the present invention, syngas can be prepared from pyrolysis gas with high conversion and high yield by using a catalyst for pyrolysis syngas preparation prepared by the preparation method according to the present invention. Attached Figure Description

[0034] Figure 1 A flowchart illustrating a method for preparing a catalyst for pyrolysis syngas production according to one embodiment is provided.

[0035] Figure 2This is a schematic diagram illustrating a catalyst for the preparation of pyrolysis syngas according to one embodiment. Detailed Implementation

[0036] This invention provides a detailed description of the porous catalyst for pyrolysis syngas production and its preparation method. The terminology used in this specification has been chosen to reflect the functionality of the invention, using conventionally widely used terms whenever possible. However, these terms may differ depending on the intent or practice of those skilled in the art, the emergence of new technologies, etc. Unless otherwise defined, the technical and scientific terms used may have the meanings commonly understood by those skilled in the art to which this invention pertains.

[0037] In this specification and claims, terms such as “comprising,” “including,” or “having” refer to the presence of a feature or constituent element described in the specification, and unless otherwise specifically defined, the possibility of adding more than one other feature or constituent element is not excluded in advance.

[0038] In this specification and claims, unless expressly stated otherwise, singular expressions include plural expressions. Furthermore, unless expressly stated otherwise, plural expressions include singular expressions.

[0039] In this specification and claims, the terms "first" and "second" are not intended to be limiting, but rather to distinguish one constituent element from other constituent elements.

[0040] Furthermore, the numerical ranges used in this specification include lower and upper limits, all values ​​within that range, increments logically derived from the form and width of the defined range, all values ​​defined therein, and all possible combinations of upper and lower limits of numerical ranges defined in different forms from each other. In this specification, unless otherwise specifically defined, values ​​outside the defined numerical range that may arise due to experimental errors or rounding are also included within the defined numerical ranges.

[0041] The degree terms such as “about” used in this specification and claims are intended to indicate that allowable error is included when error is permissible.

[0042] As used in this specification and claims, the term "Group VIIIA" refers to the elements corresponding to each group in the periodic table of the former International Union of Pure and Applied Chemistry (IUPAC).

[0043] Hereinafter, with reference to the accompanying drawings, the preparation method of the porous catalyst for pyrolysis syngas preparation according to the present invention will be described.

[0044] Organic waste can severely damage the environment during landfilling due to decomposition, requiring collection based on its specific characteristics and proper disposal through prescribed processes. However, simple disposal of organic waste necessitates the establishment of treatment facilities and consumes significant manpower, resulting in greater waste compared to production processes. Therefore, methods and technologies for recycling organic waste have been developed in recent years. A representative technology is the gasification process, which utilizes organic waste to produce syngas and convert it into high-value-added products for energy conversion.

[0045] Gasification processes generally refer to a series of processes that convert carbonaceous feedstocks such as coal, organic waste, and biomass into syngas containing hydrogen and carbon monoxide by reacting them with a supply of steam, oxygen, carbon dioxide, or a mixture thereof. Here, "syngas" typically refers to a mixed gas produced through a gasification reaction that contains hydrogen and carbon monoxide, and may further contain dry gases such as carbon dioxide and / or methane.

[0046] Gasification technology has expanded to produce feedstocks and fuels for various compounds. For example, syngas can be used as a feedstock for Fischer-Tropsch synthesis to produce high-value-added products such as light oils, heavy oils, diesel fuel, waxes, aviation fuels, and lubricating oil bases. Furthermore, hydrogen from syngas, a major byproduct of gasification, can be used in hydrogen power generation, ammonia production, and oil refining processes. Additionally, it is known that methanol produced from syngas can be used to obtain high-value-added chemical substances such as acetic acid, olefins, dimethyl ethers, aldehydes, fuels, and additives. However, the yield of syngas produced from organic waste is extremely low, making it difficult to efficiently produce high-value-added compounds from syngas.

[0047] In recent years, catalyst-based gasification processes have been developed for the production of syngas. However, catalyst deactivation occurs during gasification due to the generation of coke and other contaminants, leading to process failures during continuous operation. Furthermore, to ensure economic efficiency, the relatively expensive catalyst needs to be recovered. However, recovering the catalyst discharged in the form of coke and other aggregates requires multiple subsequent processes (such as air combustion), resulting in a significant reduction in process efficiency.

[0048] As an example, when the steam reforming catalyst used in existing gasification processes contains precious metal-based active metal components such as Ru, carbon precipitation is minimal even under low S / C (steam / carbon ratio) conditions. However, a drawback is that sulfur poisoning easily occurs due to the sulfur content in the feedstock, leading to a rapid deterioration of catalytic activity, and the sulfur-poisoned catalyst becomes the cause of carbon precipitation. Furthermore, the high price of precious metals reduces the economic viability of the process.

[0049] Furthermore, catalysts containing non-metallic active metal components such as Ni are relatively prone to carbon precipitation, thus requiring operation under conditions of high steam / carbon ratios (using excess steam compared to the theoretical composition). This not only complicates operation but also increases steam consumption per unit volume. In addition, the system has limited continuous operation capabilities; achieving continuous operation requires an expensive control system, making the entire system highly complex and uneconomical in terms of both preparation cost and maintenance.

[0050] Furthermore, steam reforming is a high-temperature reaction. The high-temperature endothermic reaction during reforming and the regeneration process at the reactor end, which involves oxidizing and removing coke from the catalyst surface to regenerate the catalyst, are repeated, leading to catalyst breakage. Therefore, α-alumina, with its relatively high crushing strength, is often used as the support component. However, to improve the strength of α-alumina, it is typically calcined at high temperatures during preparation, resulting in a very small BET specific surface area or pore size. Consequently, the active metal component supported on α-alumina is prone to sintering upon heating, leading to a deterioration in catalytic activity.

[0051] Therefore, the applicant has invented a method for preparing a porous catalyst for pyrolysis syngas production. The catalyst has excellent economic efficiency and excellent durability. Even if carbon deposits occur inside the catalyst, it can maintain sufficient strength without breaking or cracking. At the same time, it has a high specific surface area, thus exhibiting excellent reactivity and reaction stability.

[0052] The method for preparing a porous catalyst for pyrolysis syngas production according to the present invention includes the following steps: mixing a metal precursor containing a Group VIIIA element, a ceramic support, and a solvent to prepare a mixed solution; adding an acid to the mixed solution to prepare a precursor gel; mixing clay into the precursor gel to prepare a mixture; adding an inorganic binder to the mixture to prepare a composite catalyst sol; and drying and calcining the composite catalyst sol.

[0053] That is, such as Figure 1 As shown, the porous catalyst for pyrolysis syngas production of the present invention is prepared through the following series of processes: a metal precursor containing a Group VIIIA element and a ceramic support are mixed to prepare an aqueous mixed solution; an organic acid is added to the mixed solution to perform gelation to prepare a precursor gel; then clay and an inorganic binder are added sequentially to prepare a composite catalyst sol; and the catalyst is dried and calcined. Therefore, the catalyst can have improved durability, and even if coke is deposited inside the catalyst, the occurrence of catalyst cracking and breakage can be significantly reduced. Furthermore, the Group VIIIA element, as an active metal, is uniformly dispersed throughout the ceramic support, thus providing excellent reactivity.

[0054] Therefore, when the catalyst prepared according to the method of the present invention is applied to a dual-circulation fluidized bed process, the catalyst can be repeatedly coked and regenerated without damage, thus having the advantage of obtaining syngas in high yield even during long-term operation without catalyst deactivation.

[0055] When an organic acid is added to a mixed solution containing the metal precursor, ceramic support, and solvent, a precursor gel can be formed by the composite formation between the metal precursor and the ceramic support.

[0056] In one specific embodiment, when preparing the precursor gel, the mixed solution of the added organic acid is stirred for 1 to 10 hours, 1 to 8 hours, or 2 to 5 hours to induce gelation, thereby providing a reaction time in which the metal precursor and the ceramic support can be fully composited and transformed into a gel form.

[0057] In one embodiment, the ceramic support may comprise aluminum, and the aluminum-containing ceramic support may comprise one or more selected from boehmite, boehmite, aluminum alkoxide, aluminum nitrate, aluminum fluoride, aluminum phosphate, aluminum chloride, and aluminum sulfate. Specifically, when the ceramic support comprises boehmite, it has the following advantages: the catalyst can achieve sufficient strength, thereby minimizing catalyst breakage caused by repeated expansion and contraction of the reactor due to external heating in the steam reforming reaction described below, while the catalyst can have an excellent specific surface area.

[0058] In one embodiment, the Group VIIIA element may be a metal including nickel, iron, cobalt, ruthenium, palladium, platinum, or mixtures thereof, and more specifically, the Group VIIIA element may include nickel, which has excellent economy and catalytic activity.

[0059] In one specific embodiment, the metal precursor may be any one or more selected from group VIIIA elements, including hydroxides, sulfates, carbonates, nitrates, chlorides, benzoates, basic carbonates, formates, citrates, diammonium sulfates, and their hydrates.

[0060] As a more specific example, when Group VIIIA elements include nickel, the metal precursor may include one or more selected from nickel hydroxide, nickel sulfate, nickel carbonate, nickel nitrate, nickel chloride, nickel benzoate, basic nickel carbonate, nickel formate, nickel citrate, nickel ammonium sulfate and their hydrates, but the present invention is not limited to the specific types of metal precursors.

[0061] In one specific implementation, the organic acid may include formic acid, acetic acid, propionic acid, salicylic acid, etc., but is not limited to these.

[0062] In one embodiment, after gelation, clay can be mixed into the precursor gel to prepare a mixture. Because the ceramic support and metal precursor are pre-mixed and gelled before the clay is added and mixed, the clay can be uniformly dispersed in the precursor gel without aggregation. Therefore, the metal precursor can be uniformly dispersed in the ceramic support of the prepared catalyst. Furthermore, since the specific surface area and wear resistance of the catalyst are improved, it can provide the effects of improved long-term stability and catalyst lifetime, and enhanced catalytic activity.

[0063] In one specific embodiment, the clay may include kaolin, montmorillonite, bentonite, smectite, illite, vermiculite, or combinations thereof, but the invention is not limited thereto.

[0064] In one embodiment, an inorganic binder may be added to the mixture to prepare a composite catalyst sol. The inorganic binder can improve the adhesion between the metal precursor and the ceramic support, thereby further improving the durability and abrasion resistance of the resulting catalyst. The inorganic binder may include, for example, non-rehydratable alumina, α-alumina, aluminum salts, silica, clay, talc, bentonite, zeolite, cordierite, titanium dioxide, alkali metal salts, alkaline earth metal salts, rare earth metal salts, zirconium oxide, mullite, sepiolite, montmorillonite, halloysite, soapstone, stevensite, lithium soapstone, aluminosilicates, or combinations thereof.

[0065] In one specific embodiment, additives may be further added to the mixture during the preparation of the composite catalyst sol. Exemplarily, the additives may include one or more selected from molding aids, dispersants, etc. The additives may remain in the final catalyst, or they may be removed by combustion through calcination, thus leaving no residue in the catalyst.

[0066] A dispersant may be added to improve the dispersibility of the particles contained in the composite catalyst sol and to promote the reaction. More specifically, the dispersant may include one or more selected from polycarboxylic acid ammonium salt, ammonium citrate, trisodium citrate, citric acid, ammonia, acetic acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0067] Molding aids may include one or more selected from fatty acids, cellulose, polyvinyl alcohol, starch, methylcellulose, maltose and carboxymethylcellulose, and two or more may be used in combination as needed. However, the present invention is not limited to the specific types of additives. Those skilled in the art may appropriately select and use various additives known in the art as needed.

[0068] As a non-limiting example, additional solvents may be added as needed during the preparation of the composite catalyst sol to promote the dispersion of the inorganic binder and clay.

[0069] The composite catalyst sol can be dried and calcined to oxidize the metal precursor, thereby preparing a catalyst with an optimized size and shape for catalytic activity. Specifically, regarding the drying, the composite catalyst sol can be dried using methods known in the art; however, when using a spray dryer, the solvent can be easily removed and the catalyst can be shaped, and the time the catalyst is exposed to heat can be shortened.

[0070] In one specific embodiment, the calcination temperature can be 500°C to 1300°C, 500°C to 1100°C, or 500°C to 900°C. Calcination of the composite catalyst sol within these temperature ranges can rapidly remove the solvent contained in the mixture and oxidize the metal precursor.

[0071] In one specific embodiment, particles with an average particle size of 10 μm to 400 μm, 30 μm to 350 μm, or 50 μm to 250 μm are screened from the dry catalyst to obtain a catalyst with excellent specific surface area and durability.

[0072] This invention includes a porous catalyst for pyrolysis syngas preparation prepared by the above method. In describing the porous catalyst for pyrolysis syngas preparation according to the present invention, the metal precursor, ceramic support, clay, inorganic binder, etc., are the same as or similar to those described above; therefore, the porous catalyst for pyrolysis syngas preparation according to the present invention includes all of the above-described contents.

[0073] The catalyst prepared by the above method has high durability and high wear resistance, so it can maintain excellent catalytic activity without being destroyed even if the catalytic process is repeated.

[0074] Furthermore, since the active metal is uniformly dispersed within the ceramic support, during the synthesis gas preparation process described below, when regenerating the catalyst by removing the coke deposited on the catalyst surface, sintering of the active metal and catalyst degradation caused by hot spots can be suppressed. Therefore, irreversible catalyst deactivation can be minimized, thereby extending catalyst lifetime and preventing catalyst breakage, thus providing high reaction stability.

[0075] The porous catalyst for pyrolysis syngas preparation according to the present invention may contain 5% to 70% by weight of a ceramic support, 1% to 75% by weight of a Group VIIIA element, and 0.1% to 30% by weight of clay, and the pore volume may be 0.01 cm³. 3 / g to 0.5cm 3 / g, with an average pore diameter of less than 300 Å.

[0076] The porous catalyst for pyrolysis syngas preparation with the above characteristics has excellent catalytic activity and specific surface area, and improved durability, so that it can remain intact even if carbon deposits occur inside the catalyst.

[0077] In one embodiment, the Group VIIIA element is loaded into a ceramic support in the form of very fine particles. This increases the contact area between the Group VIIIA element (as the active metal component) and the reactants, thereby resulting in excellent catalytic activity. More specifically, the average particle size of the Group VIIIA element can be 1 nm to 20 nm, 1 nm to 15 nm, or 3 nm to 12 nm. When these ranges are met, the Group VIIIA element can be easily loaded into the ceramic support, thus maintaining high catalytic activity.

[0078] In one specific embodiment, the catalyst may contain 1% to 75% by weight, 10% to 75% by weight, or 20% to 75% by weight of Group VIIIA elements. Because the active metal is uniformly dispersed within the ceramic support, the catalyst exhibits excellent catalytic activity and improved durability even when the content of Group VIIIA elements is within the aforementioned weight range, thus offering an advantage. When the content of Group VIIIA elements is below the aforementioned weight range, there is a risk of reduced hydrocarbon conversion.

[0079] The porous catalyst for pyrolysis syngas production of the present invention can contain a high content of Group VIIIA elements, i.e., a high content of active metals. Even if coke is produced in the catalyst during the steam reforming reaction during syngas production, the catalyst can be regenerated in the reverse Boudouar process described below. Therefore, even with a high content of Group VIIIA elements, the catalyst can be used for a long time without catalyst deactivation. Thus, the porous catalyst for pyrolysis syngas production of the present invention, containing a high content of Group VIIIA elements, can maintain high catalytic activity for a long period.

[0080] In one specific embodiment, the porous catalyst for pyrolysis syngas preparation may comprise pseudoboehmite alumina as a ceramic support, wherein the content of pseudoboehmite alumina in the porous catalyst may be 5% to 70% by weight, 7% to 60% by weight, or 10% to 50% by weight. When the alumina content in the catalyst is less than the above-mentioned weight range, the mechanical strength of the catalyst may decrease; when the alumina content in the catalyst exceeds the above-mentioned weight range, the catalytic activity may decrease due to the reduced content of Group VIIIA elements. The advantage of the ceramic support is that, in the preparation of syngas described below, when the mixed gas contains a high content of nitrogen (N) impurities, the ceramic support can adsorb the nitrogen components, thereby mitigating the inhibitory effect of impurities on the catalytic reaction activity.

[0081] Furthermore, the porous catalyst for pyrolysis syngas production may further contain silica, wherein the silica content can be from 0 wt% to 35 wt%, 0 wt% to 30 wt%, or 1 wt% to 25 wt%. Silica is an additive used to further improve the catalyst's wear resistance; when the aforementioned wear index value can be met using only a ceramic support, the catalyst may not contain silica. When the silica content exceeds the aforementioned wt% range, the catalytic activity may decrease.

[0082] The catalyst according to the invention may contain 0.1% to 60% by weight, 1% to 50% by weight, or 10% to 30% by weight of clay. The clay can act as a binder to improve the strength of the catalyst by immobilizing the Group VIIIA element and the ceramic support. As a specific embodiment, the average particle size of the clay may be less than 30 μm, less than 20 μm, or less than 10 μm, and non-limitingly, may be greater than 0.01 μm. Within the above particle size range, the clay can improve durability without impairing the catalytic activity of the Group VIIIA element.

[0083] In the catalyst of the present invention, such as Figure 2 As shown, the Group VIIIA active metal components, clay, and silica are uniformly dispersed in a ceramic carrier and firmly fixed by a clay binder, thus exhibiting excellent physical properties, such as mechanical strength.

[0084] In one embodiment, the wear index of the porous catalyst for pyrolysis syngas preparation can be less than 15% by weight, less than 10% by weight, or less than 5% by weight, and non-limitingly, can be more than 0.5% by weight. The porous catalyst for pyrolysis syngas preparation of the present invention has significantly improved wear resistance, and therefore can significantly reduce physical or chemical wear losses caused by chemical reactions at high temperatures during steam reforming and reverse Boudouar reactions, thereby significantly improving the long-term stability of the catalyst.

[0085] The porous catalyst for pyrolysis syngas preparation of the present invention has a pore diameter of 300 Å or less, 250 Å or less, or 200 Å or less, and non-limitingly, can be 5 Å or more or 10 Å or more. Furthermore, the pore volume of the catalyst can be from 0.01 cubic centimeters / g to 0.5 cubic centimeters / g, 0.03 cubic centimeters / g to 0.4 cubic centimeters / g, or 0.05 cubic centimeters / g to 0.3 cubic centimeters / g, and the BET specific surface area can be 10 m². 2 / g to 300m 2 / g、20m 2 / g to 100m 2 / g or 50m 2 / g to 100m 2 / g. When the pore volume, pore diameter, and BET specific surface area are within the above range, the active metal can be fully dispersed and loaded in the ceramic support, thereby improving the catalytic efficiency.

[0086] In one specific embodiment, the average particle size (D50) of the catalyst can be from 10 μm to 500 μm, 30 μm to 300 μm, or 50 μm to 200 μm. Within the above ranges, the catalyst exhibits excellent strength and specific surface area, but the invention is not limited thereto.

[0087] The porous catalyst for pyrolysis syngas production according to the present invention can be a steam reforming catalyst and a reverse Boudouar reaction catalyst. As described below, in a process for producing syngas through the gasification reaction of a mixed gas (generated by thermal treatment of organic waste), the catalyst can promote the steam reforming reaction and the reverse Boudouar reaction, thereby increasing the yield of syngas and hydrocarbons and enabling the long-term stable production of syngas with high durability.

[0088] In one example, a method for preparing syngas from a pyrolysis mixed gas using the porous catalyst for pyrolysis syngas preparation of the present invention may include the following steps: (S1) thermally treating organic waste to generate a first mixed gas; (S2) steam reforming the first mixed gas in a first fluidized bed reactor containing the catalyst to generate a second mixed gas; (S3) separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) flowing the first stream separated in step (S3) into a second fluidized bed reactor containing the catalyst and converting it into carbon monoxide via a reverse Boudouar reaction; (S5) mixing the second stream and the carbon monoxide converted in step (S4) to prepare a third mixed gas; and (S6) generating syngas from the third mixed gas via a water-gas shift reaction, wherein steps (S2) and (S4) can be performed using the porous catalyst for pyrolysis syngas preparation prepared by the above method.

[0089] In one specific embodiment, in the method for preparing syngas, a mixed gas obtained through the thermal treatment of organic waste can be steam reformed to prepare a mixed reformed gas, and the carbon dioxide contained in the mixed reformed gas can be converted into carbon monoxide via a reverse Boudouar reaction. By incorporating the porous catalyst for pyrolysis syngas preparation of the present invention into the steam reforming process and the reverse Boudouar reaction, organic waste can be efficiently converted into syngas, and the yield of high-value-added hydrocarbons converted from the syngas can be maximized.

[0090] Furthermore, when using the porous catalyst for pyrolysis syngas preparation of the present invention to prepare syngas, it has the advantage that trace amounts of metallic impurities contained in the mixed gas can be adsorbed and removed, and that carbon containing benzene, toluene and xylene (BTX char) can be converted into coke. Moreover, the coke can be used as a carbon source for the reverse Boudouar reaction described below, so that it can be converted into carbon monoxide without the need to supply a separate carbon source such as activated carbon from the outside.

[0091] The step (S1) is to heat-treat the organic waste to generate a first mixed gas, in which the gasification reaction of the organic waste can occur.

[0092] In one example, the organic waste in step (S1) can be one or more selected from waste plastics, solid waste, biomass, waste oil, waste tires, and metered garbage bags. Specifically, step (S1) may be accompanied by one or more gasification reactions selected from the following reaction formulas 1 to 4.

[0093] [Reaction Formula 1] C x H y +H2O H2 + CO (water-coal gasification reaction) [Reaction 2] C x H y +CO2 CO (carbon dioxide vaporization reaction) [Reaction 3] CO + 3H2 CH4 + H2O (Methanation reaction) [Reaction 4] C x H y +O2 CO2 (oxidation reaction) In one example, the first mixed gas may contain methane, hydrogen, carbon monoxide and carbon dioxide, and may also contain various impurities such as nitrogen oxides, sulfur oxides, and hydrogen chloride.

[0094] As an example of increasing the methane content in the first mixed gas, the first mixed gas may further contain one or more selected from landfill gas, shale gas, refinery waste gas, and biogas. The methane and carbon dioxide content in the aforementioned landfill gas, shale gas, refinery waste gas, and biogas is 40% by volume or more, specifically 50% by volume or more. Therefore, since the first mixed gas further contains the aforementioned gases, it has the effect of further improving the syngas production yield through methane reforming and reverse Boudouar reaction as subsequent processes.

[0095] In one example, the lower limit of the C / O element ratio of the first mixed gas can be above 0.01, above 0.05, or above 0.1, and the upper limit can be below 0.9, below 0.8, or below 0.7. Specifically, the C / O element ratio of the first mixed gas can be from 0.01 to 0.9 or from 0.05 to 0.8, and more specifically, it can be from 0.1 to 0.7.

[0096] In the method for preparing hydrocarbons according to the present invention, the methane reforming reaction can proceed smoothly even if the first mixed gas has a relatively high C / O elemental ratio within the aforementioned range. Specifically, since the catalyst used in the methane reforming reaction can form a cyclic process as described below, it has the effect of sustaining the reaction, regardless of catalyst deactivation caused by coke that may be produced during the dry reforming of methane.

[0097] In one example, after step (S1), a further step of purifying the first mixed gas may be included.

[0098] The first mixed gas (generated by thermal treatment of organic waste) may contain one or more impurities selected from tar, sulfur, nitrogen, and chlorine. Specifically, the first mixed gas may contain water-soluble impurities such as H2S, HCl, HOCl, and NH3, as well as non-water-soluble impurities such as tar. These impurities contained in the first mixed gas can cause catalyst deactivation, which may reduce the efficiency of subsequent processes. Therefore, purification by removing impurities from the first mixed gas can improve the efficiency of the entire process.

[0099] Step (S2) is a step of steam reforming the methane contained in the first mixed gas in the first fluidized bed reactor to prepare the second mixed gas. Step (S2) may be accompanied by the reforming reaction shown in the following reaction formula 5.

[0100] [Reaction 5] CH4+H2O CO + 3H₂ (steam reforming reaction) The reforming reaction in step (S2) can be carried out at temperatures of 600°C to 1400°C, 600°C to 1100°C, or 600°C to 800°C and pressures of 30 kPa to 2000 kPa, 40 kPa to 1000 kPa, or 50 kPa to 500 kPa, with a space velocity (GHSV) of 100 h⁻¹. -1 Up to 100,000h -1 500h -1 Up to 10000h -1 or 1000h -1 Up to 5000h -1 .

[0101] By using the porous catalyst for pyrolysis syngas preparation of the present invention for steam reforming reactions, hydrocarbons can be reformed at high conversion rates even at low temperatures. Therefore, the possibility of catalyst breakage due to reactor expansion and contraction caused by external heating can be significantly reduced, thereby significantly extending catalyst lifetime.

[0102] Since step (S2) is carried out in a fluidized bed reactor, a cyclic process can be formed whereby the catalyst used in the methane reforming reaction is added to the reverse Boudouar reaction process as a subsequent process, regenerated, and then resupplyed. As described below, since the coke accumulated in the catalyst after steam reforming acts as a carbon source for the reverse Boudouar reaction in step (S4), a cyclic process can be performed to regenerate and resupply the catalyst used in steps (S2) and (S4), thereby achieving a continuous reforming reaction. Furthermore, when methane is reformed using steam reforming, the reforming reactivity is improved compared to dry reforming, and it also has the effect of removing impurities such as chlorine.

[0103] Step (S3) is the step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide.

[0104] In one example, the method for separating the second mixed gas into a first stream and a second stream is not limited, as long as it is a known method. However, in this invention, a carbon dioxide separation unit can be used for separation, which can be an amine scrubber. Typically, amine scrubbers use amine substances to bind and remove carbon dioxide, separating components such as carbon dioxide and hydrogen sulfide from gas vapors, and recovering gases containing hydrogen, carbon monoxide, or inert gases. Therefore, an amine scrubber can be used to separate the second mixed gas into a first stream and a second stream.

[0105] As another example, the carbon dioxide separation unit can be a carbon capture and storage unit (CCS unit). When using a CCS unit to separate carbon dioxide, the CCS unit can adsorb and separate carbon dioxide by using one or more adsorbents selected from calcium oxide, calcium hydroxide, dolomite, limestone or natural alkali. Therefore, the CCS unit can be used to separate a second mixed gas into a first stream and a second stream.

[0106] In the first feed stream, the lower limit of the carbon dioxide content can be 40% by volume or more, 50% by volume or more, or 60% by volume or more, and the upper limit can be 99% by volume or less, 90% by volume or less, 80% by volume or less, or 70% by volume or less. Specifically, the carbon dioxide content in the first feed stream can be from 40% by volume to 99% by volume, and more specifically, from 50% by volume to 80% by volume. In the carbon dioxide separation unit, during the separation after carbon dioxide capture, in order to separate carbon dioxide with high purity, the regeneration tower that separates carbon dioxide from the adsorbent needs to be designed with a high number of trays, which may consume more energy. Therefore, since the carbon dioxide content in the first feed stream is within the above range, the carbon dioxide separation process can be carried out under milder conditions.

[0107] Step (S4) is a step in which the first feed stream separated in step (S3) is converted into carbon monoxide via a reverse Boudouar reaction in the second fluidized bed reactor. Further conversion of carbon dioxide contained in the first feed stream into carbon monoxide via the reverse Boudouar reaction has the following effects: it can reduce carbon dioxide emissions, thereby preventing environmental pollution, while maximizing the yield of syngas. The reverse Boudouar reaction can be represented by the following reaction formula 6.

[0108] [Reaction Formula 6] C + CO2 2CO In one example, the reverse Boudouar reaction catalyst in step (S4) can be the catalyst used in the steam reforming reaction of step (S2). The catalyst of the present invention can be used in the steam reforming reaction of step (S2), allowing coke to be deposited in the catalyst. When the catalyst coked by the steam reforming reaction is introduced into the second fluidized bed reactor for the reverse Boudouar reaction, the coke acts as a carbon source, thus enabling continuous syngas production without a separate catalyst regeneration process.

[0109] The second mixed gas discharged from the first fluidized bed reactor can be separated from the catalyst by a cyclone separator and supplied to the second fluidized bed reactor for the reverse Boudouar reaction via a catalyst supply line. In the second fluidized bed reactor, the catalyst can react and be regenerated as a carbon supply source for the reverse Boudouar reaction. The regenerated catalyst can be resupplyed to the first fluidized bed reactor via a recirculation line. When using this catalyst recycling process, methane reforming can be carried out continuously without the need for an external carbon supply source for the reverse Boudouar reaction, thus enabling an economical process.

[0110] That is, the advantage of the present invention is that the yield of syngas can be maximized through methane reforming and reverse Boudouar reaction. At the same time, the first fluidized bed reactor and the second fluidized bed reactor that carry out methane reforming and reverse Boudouar reaction form a circulating process, so continuous operation can be achieved through catalyst regeneration.

[0111] In one specific embodiment, in step (S4), the reaction temperature can be 600°C to 1400°C, 600°C to 1200°C, or 600°C to 1000°C, and the reaction pressure can be 30 kPa to 2000 kPa, 40 kPa to 1000 kPa, or 50 kPa to 500 kPa. Furthermore, in step (S4), the space velocity (GHSV) is 100 h⁻¹. -1 Up to 100,000h -1 500h -1 Up to 10000h -1 or 1000h -1 Up to 5000h -1 Under the specified conditions, the feed gas containing the mixed gas and water vapor can be contacted with the porous catalyst for hydrocarbon cracking according to the present invention. Long-term operation can be achieved under the above-described temperature, pressure, and space velocity conditions, and catalytic activity can also be improved.

[0112] Step (S5) involves mixing the second stream separated from the carbon dioxide separation unit with the carbon monoxide converted in step (S4) via the reverse Boudouar reaction to generate a third mixed gas. The third mixed gas may contain hydrogen and carbon monoxide.

[0113] Step (S6) is a process of adjusting the ratio of carbon monoxide to hydrogen in the third gas mixture to generate syngas via a water-gas shift reaction. The third gas mixture can be converted via a water-gas shift reaction to achieve a suitable hydrogen:carbon monoxide ratio for the catalytic reaction in subsequent processes. The water-gas shift reaction can be represented by the following reaction formula 7.

[0114] [Reaction Formula 7] CO + H₂O H2+CO2 The water-gas shift reaction can be carried out in the presence of a catalyst containing Fe and Cr. The water-gas shift reaction can be carried out at temperatures ranging from 100°C to 400°C (specifically from 100°C to 300°C) and pressures ranging from 20 bar to 80 bar (specifically from 25 bar to 70 bar).

[0115] The hydrogen to carbon monoxide ratio in the syngas generated by the water-gas shift reaction can be from 1.5 to 3:1, specifically from 1.9 to 2.1:1. Since the hydrogen to carbon monoxide ratio in the syngas meets the above range, the subsequent catalytic reaction process can proceed smoothly.

[0116] In one specific embodiment, following step (S6), a further step (S7) may be included: generating hydrocarbons from the syngas via a catalytic reaction. Step (S7) is the step of converting the syngas generated in step (S6) into a hydrocarbon fraction, which can be achieved through a catalytic reaction. The catalytic reaction is not limited, as long as it can convert the syngas into a hydrocarbon fraction, but specifically it can be a Fischer-Tropsch synthesis reaction.

[0117] In one instance, when the catalytic reaction in step (S7) is a Fischer-Tropsch synthesis reaction, the syngas generated in step (S6) can be used as a feedstock for a reaction accompanied by the following reaction formula 8.

[0118] [Reaction Equation 8] nCO + 2nH2 C n H 2n +nH2O The Fischer-Tropsch synthesis reaction can be carried out in the presence of a catalyst containing cobalt, nickel or iron, the support can contain alumina, silicon dioxide, titanium dioxide, etc., and the co-catalyst can contain noble metals such as Pt, Ru, Re.

[0119] Furthermore, the Fischer-Tropsch synthesis reaction can be carried out at temperatures of 100°C to 500°C or 200°C to 350°C and pressures of 10 to 50 atm or 10 to 30 atm, but the present invention is not limited thereto.

[0120] The embodiments of the present invention will be further described below with reference to specific experimental examples. The embodiments and comparative examples included in the experimental examples are only for illustrating the present invention and do not limit the scope of the claims. Various changes and modifications can be made to the embodiments within the scope of the present invention and the technical concept, which will be obvious to those skilled in the art, and these variations and modifications also fall within the scope of the claims.

[0121] (Preparation Example 1) Preparation of Ni / MgO / Al2O3 catalyst A mixed solution was prepared by mixing 10 parts by weight of boehmite-type alumina and 95 parts by weight of nickel nitrate hexahydrate, using 100 parts by weight of water as a base. While stirring the mixed solution, 1 part by weight of formic acid was added, and the mixture was reacted for 3 hours to gel, thus preparing a precursor gel. 30 parts by weight of clay and 1.5 parts by weight of MgO oxide were added and mixed using a homogenizer to prepare a solid mixture. This solid mixture was mixed with the precursor gel, and then 10 parts by weight of colloidal silica (Ludox AS40, Aldrich) was added, followed by 5 parts by weight of water. The mixture was stirred vigorously to prepare a composite catalyst sol. The composite catalyst sol was spray-dried and separated using a sieve to recover catalyst particles with a particle size of 50 μm to 250 μm. The recovered catalyst was dried in an oven at 120 °C and calcined at 550 °C for 3 hours to prepare the catalyst.

[0122] The properties of the catalyst prepared by the method of Preparation Example 1 were analyzed. The wear index was measured using a 3-hole attrition tester according to ASTM D 5757-95. The nickel content in the catalyst was calculated by X-ray fluorescence spectrometry (XRF) analysis using a Thermo Fisher Scientific ARL QUANT'X. The BET specific surface area, total pore volume, and pore diameter were measured using a nitrogen physical adsorption-desorption method and a Micromeritics Tristar 3000 instrument.

[0123] The catalyst of Preparation Example 1 was confirmed to have an attrition index of 3.5% by weight, exhibiting excellent attrition resistance. Furthermore, the catalyst's BET specific surface area was confirmed to be 79 m². 2 The total pore volume was 0.2 cm³ / g, and the average pore size was 34 Å. The catalyst had an average particle size of 131 μm, an average particle size (D50) of 126 μm, and contained 4% by weight of microparticles smaller than 50 μm. XRF analysis confirmed that the Ni content in the catalyst was 30.1% by weight.

[0124] (Example 1) 1000g of municipal solid waste is added to a pyrolysis reactor, and then water vapor is introduced and heat-treated under alumina beads at a temperature of 1200℃ and 250kPa to recover the first mixed gas.

[0125] The temperature of the first mixed gas is reduced, and impurities such as Cl, S, and N contained in the mixed gas are removed by a scrubber, thereby recovering the purified first mixed gas.

[0126] The first mixed gas, after removing impurities, is supplied at a space velocity of 2 L / g-catalyst (cat) / h to a first fluidized bed reactor containing the catalyst prepared in Preparation Example 1, while water vapor is supplied simultaneously, and a second mixed gas is prepared by steam reforming at 750°C.

[0127] The second mixed gas flows into the amine scrubber, where carbon dioxide is captured. The second mixed gas, having separated from carbon dioxide, is then separated into a second feed stream. Specifically, the second mixed gas flows into the first amine scrubber, where CO2 is captured at 50°C by an aqueous solution containing monoethanolamine (MEA) (amine solution). The uncaptured gas is recovered as the second feed stream. The amine solution containing CO2 from the first amine scrubber flows into the second amine scrubber, where it is separated into amine solution and CO2 at 100°C. The CO2 is recovered as the first feed stream.

[0128] The recovered first feed stream flows into the second fluidized bed reactor, where it is converted into carbon monoxide via a reverse Boudouar reaction. This reverse Boudouar reaction is carried out in the second fluidized bed reactor filled with the catalyst from Preparation Example 1 used in the steam reforming reaction, and the first feed stream is supplied at a space velocity of 2 L / g-catalyst / h. At this time, the catalyst, deactivated by coke deposition during the steam reforming reaction, is added as a carbon source, and the catalyst, activated by removing the coke, is reintroduced into the first fluidized bed reactor.

[0129] The carbon monoxide converted from the first feed stream flows into the gas mixing unit and mixes with the second feed stream at 200°C to generate a third mixed gas. The third mixed gas flows into the syngas generation unit, where it is used to produce syngas with a molar ratio of H2:CO of 1:2 via a water-gas shift reaction.

[0130] Syngas is supplied to the hydrocarbon conversion unit, and the injection rate is set such that, under the Co / ZnO (Cobalt / Zinc oxide) catalyst, the space velocity is 5000 L / kg-catalyst / h, the volume ratio of carbon monoxide:hydrogen:argon is 63.2:31.3:5.5, and the Fischer-Tropsch synthesis reaction is carried out for 60 hours at a reaction temperature of 300°C and a pressure of 10 bar, thereby recovering the hydrocarbon fraction.

[0131] As a result, the syngas yield was 48%, and the hydrocarbon fraction using the syngas yielded 87%.

[0132] Furthermore, when the method of Example 1 was run 10 times consecutively, the activity of the catalyst did not decrease, and the change rate of the above-mentioned yield remained within 5%, thus indicating that the catalytic activity was excellent.

[0133] (Example 2) The process is carried out using the same method as in Example 1, except that landfill gas is mixed in the first mixed gas.

[0134] As a result, the syngas yield was 48%, and the hydrocarbon fraction using the syngas yielded 86%. Furthermore, the yield remained below 5% after 10 consecutive reactions, indicating that the catalyst possesses excellent stability.

[0135] (Comparative Example 1) The process was carried out using the same method as in Example 1, except that the catalyst of Preparation Example 1 was not used in the steam reforming process and the reverse Boudouar reaction process; instead, a Ni / Al2O3 catalyst with 30% by weight of Ni supported on alumina beads was used.

[0136] As a result, the syngas yield was also 48%, and the hydrocarbon fraction yield using the syngas was 84% ​​in the first three recycling cycles, which was at a similar level. However, catalyst wear was present from the first run, resulting in a catalyst loss rate of approximately 15% per run. In particular, since nickel, as the active metal, is only loaded on the catalyst surface, it is rapidly lost from the catalyst surface as the process progresses, leading to a continuous decrease in catalytic activity.

[0137] The catalytic activity decreased by approximately 20% after three runs, thus exhibiting significantly reduced durability and long-term stability compared to the porous catalyst for pyrolysis syngas production of this invention. Upon completion of the reaction, the catalyst's morphology was examined, revealing a large number of agglomerated catalyst particles due to aggregation. This indicates that hot spots generated during the catalytic reaction induced sintering between nickel particles, ultimately leading to the aggregated state of the catalyst particles.

[0138] The above examples and comparative examples confirm that when the catalyst prepared by the method of Preparation Example 1 is used in steam reforming and reverse Boudouar reactions, even after more than 10 repeated runs, the catalytic activity does not decrease due to the loss of catalyst and active metal, and the measured hydrocarbon yield is over 86%, achieving efficient and long-term stable process operation. Therefore, it is evident that the porous catalyst for pyrolysis syngas production of the present invention can achieve excellent syngas conversion rate and hydrocarbon generation efficiency. Furthermore, compared with existing catalysts, the porous catalyst for pyrolysis syngas production of the present invention maintains catalytic activity even during continuous reactions, thus exhibiting excellent durability.

[0139] The above description is merely an example of applying the principles of the present invention, and other configurations may be included without departing from the scope of the present invention.

Claims

1. A method for preparing a porous catalyst for pyrolysis syngas production, wherein, The preparation method includes the following steps: A mixed solution is prepared by mixing a metal precursor containing a Group VIIIA element, a ceramic support, and a solvent. An acid is added to the mixed solution to prepare a precursor gel; Clay was mixed into the precursor gel to prepare a mixture; An inorganic binder is added to the mixture to prepare a composite catalyst sol; and The composite catalyst sol was dried and calcined.

2. The method for preparing a porous catalyst for pyrolysis syngas production according to claim 1, wherein, The catalyst is used as a steam reforming catalyst and a catalyst for the reverse Boudouar process in the process of producing syngas by hydrocarbon cracking.

3. The method for preparing a porous catalyst for pyrolysis syngas production according to claim 1, wherein, The Group VIIIA elements are metals including nickel, iron, cobalt, ruthenium, palladium, platinum, or mixtures thereof.

4. The method for preparing a porous catalyst for pyrolysis syngas production according to claim 1, wherein, The metal precursor is any one or more selected from the group VIIIA elements, including hydroxides, sulfates, carbonates, nitrates, chlorides, benzoates, basic carbonates, formates, citrates, diammonium sulfates, or their hydrates.

5. The method for preparing a porous catalyst for pyrolysis syngas production according to claim 1, wherein, The ceramic carrier includes pseudoboehmite.

6. The method for preparing a porous catalyst for pyrolysis syngas production according to claim 1, wherein, The acid is selected from one or more organic acids, including formic acid, acetic acid, propionic acid, and salicylic acid.

7. The method for preparing a porous catalyst for pyrolysis syngas production according to claim 1, wherein, The calcination is carried out in a temperature range of 500°C to 1300°C.

8. A porous catalyst for the preparation of pyrolysis syngas, wherein, The catalyst is prepared by the method according to any one of claims 1 to 7.

9. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The catalyst contains 5% to 70% by weight of a ceramic support, 0.1% to 75% by weight of a Group VIIIA element, and 0.1% to 30% by weight of clay.

10. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The catalyst has a pore volume of 0.01 cubic centimeters / g to 0.5 cubic centimeters / g.

11. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The catalyst has an average pore diameter of less than 300 Å.

12. The porous catalyst for pyrolysis syngas preparation according to claim 9, wherein, The Group VIIIA elements exist in the form of microparticles, the average particle size of which is 1 nm to 20 nm.

13. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The catalyst has a BET specific surface area of ​​10 m². 2 / g to 300m 2 / g.

14. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The wear index of the catalyst is less than 15% by weight.

15. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The catalyst further contains 0% to 30% by weight of silicon dioxide.

16. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The average particle size D50 of the catalyst is from 10 μm to 500 μm.

17. The porous catalyst for pyrolysis syngas preparation according to claim 8, wherein, The catalyst is a catalyst used in steam reforming reactions to produce syngas from hydrocarbons and a catalyst used in the reverse Boudouar reaction.

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