Porous catalyst for producing synthesized gas and method for preparing same

Abstract

The present disclosure relates to a method for preparing a porous catalyst for the production of a pyrolytically synthesized gas, the method comprising the steps of: mixing a metal precursor including 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 the precursor gel with clay 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

Porous catalyst for synthesis gas production and method for producing the same

[0001] The present disclosure relates to a catalyst used in a process for converting a mixed gas recovered from a waste gasification process into synthesis gas. Specifically, the present disclosure provides a catalyst suitable for methane reforming and reverse Boudha reaction processes, thereby maximizing the yield of synthesis gas produced from pyrolysis gas.

[0002] The catalyst of the present disclosure can maximize the yield of synthesis gas in the gasification process of waste by providing a catalyst with low synthesis gas removal efficiency due to side reactions.

[0003] Organic waste can seriously damage the environment through decomposition and other processes during landfill disposal. Therefore, disposal must be categorized by type and processed accordingly. However, simple disposal of organic waste requires securing treatment facilities and extensive manpower, and is often more wasteful than productive. Therefore, methods and technologies for recycling organic waste are being developed. A prime example is the gasification process, which uses organic waste to produce synthesis gas, converting it into high-value-added products, and ultimately converting it into energy.

[0004] The gasification process generally refers to a series of processes that convert carbonaceous raw materials such as coal, organic waste, and biomass into synthesis gas containing hydrogen and carbon monoxide by reacting them under the supply of steam, oxygen, carbon dioxide, or a mixture thereof. Here, "synthesis gas" typically refers to a mixed gas produced by the gasification reaction and containing hydrogen and carbon monoxide, and may additionally include dry gases such as carbon dioxide and / or methane.

[0005] Gasification process technology has expanded into producing various compound feedstocks and fuels. For example, synthesis gas can be used as a feedstock for the Fischer-Tropsch synthesis reaction to produce high value-added products such as light crude oil, heavy crude oil, diesel fuel, wax, jet fuel, and lubricating oil. Furthermore, the hydrogen contained in synthesis gas, the main product of the gasification process, can be used in hydrogen power generation, ammonia production, and oil refining processes. Furthermore, it is known that methanol produced from synthesis gas can be used to produce high value-added chemicals such as acetic acid, olefins, dimethyl ether, aldehydes, fuels, and additives. However, synthesis gas produced from organic waste has a very low production yield, making it difficult to effectively produce high value-added compounds from synthesis gas.

[0006] Recently, catalytic gasification processes have been implemented to produce synthesis gas. However, the gasification process has encountered problems, such as the formation of coke, which deactivates the catalyst and causes process problems during continuous operation. Furthermore, to ensure economic viability, the relatively expensive catalyst must be recovered. However, recovering the catalyst, which is discharged in a coagulated state with coke and other aggregates, requires multiple subsequent steps (e.g., air burning), significantly reducing process efficiency.

[0007] For example, steam reforming catalysts used in conventional gasification processes rarely cause carbon deposition even under conditions of low S / C (steam / carbon ratio) when they contain noble metal-based active metal species such as Ru. However, they are easily poisoned by sulfur components contained in the raw materials, resulting in rapid deterioration of catalytic activity. Sulfur-poisoned catalysts have the disadvantage of causing carbon deposition. Furthermore, the high cost of noble metals poses a problem of reduced process economic feasibility.

[0008] Meanwhile, steam reforming is a high-temperature reaction. The high-temperature endothermic reaction that occurs during the reforming process and the process of regenerating the catalyst by removing coke generated on the catalyst surface through oxidation in the regeneration process at the rear of the reactor are repeated, which can lead to catalyst rupture. Therefore, α-alumina, which has a relatively high crush strength, is generally used as a support species. However, since α-alumina is generally sintered at high temperatures during its manufacture to increase its strength, its BET specific surface area and pore volume are extremely small. For this reason, the active metal species supported on α-alumina are easily sintered by heat exposure, resulting in deterioration of catalytic activity.

[0009] In this respect, there is a need for the development of a catalyst that is inexpensive, has excellent durability to maintain sufficient strength to avoid crushing or rupture even if coking occurs inside the catalyst, and has a high specific surface area to exhibit excellent reaction activity and reaction stability.

[0010] In addition, there is still a need for the development of a catalyst for hydrocarbon production that can efficiently convert high value-added hydrocarbons from mixed gas while improving the yield of synthesis gas obtained through gasification reaction and minimizing the generation of carbon dioxide emitted during the hydrocarbon production process.

[0011] According to one aspect of the present disclosure, a catalyst for producing pyrolysis synthesis gas having excellent catalytic activity and high durability and a method for producing the same can be provided.

[0012] According to one aspect of the present disclosure, a catalyst for producing pyrolysis synthesis gas having high reaction stability and a method for producing the same can be provided.

[0013] According to one aspect of the present disclosure, a catalyst for producing pyrolysis synthesis gas and a method for producing the same can be provided, which can further improve the production yield and carbon monoxide conversion rate of carbon monoxide using pyrolysis gas.

[0014] A method for producing a porous catalyst for producing pyrolysis synthesis gas according to the present disclosure comprises the steps of: preparing a mixed solution by mixing a metal precursor containing a group ⅧA element, a ceramic support, and a solvent; preparing a precursor gel by adding an acid to the mixed solution; preparing a mixture by mixing clay into the precursor gel; preparing a composite catalyst sol by adding an inorganic binder to the mixture; and drying and calcining the composite catalyst sol.

[0015] In one embodiment, the catalyst may be used as a steam reforming catalyst and a reverse catalytic converter process catalyst in a synthesis gas production process through hydrocarbon decomposition.

[0016] In one embodiment, the Group ⅧA element may include nickel, iron, cobalt, ruthenium, palladium, platinum, or mixtures thereof.

[0017] In one embodiment, the metal precursor may be at least one selected from hydroxides, sulfates, carbonates, nitrates, chlorides, benzoic acid, basic carbonates, formates, citric acid, diammonium sulfate, and hydrates thereof of Group ⅧA elements.

[0018] In one embodiment, the ceramic support may comprise pseudo-Boehmite.

[0019] In one embodiment, the acid may be at least one selected from organic acids including formic acid, acetic acid, propionic acid, and salicylic acid.

[0020] In one embodiment, the firing may be performed at a temperature range of 500°C to 1300°C.

[0021] The present disclosure includes a porous catalyst for producing pyrolysis synthesis gas manufactured by the above-described manufacturing method.

[0022] In one embodiment, the catalyst of the present disclosure may contain 5 to 70 wt% of a ceramic support, 0.1 to 75 wt% of a Group ⅧA element, and 0.1 to 30 wt% of clay.

[0023] In one embodiment, the catalyst may have a pore volume of 0.01 cc / g to 0.5 cc / g.

[0024] In one embodiment, the catalyst may have an average pore diameter of 300 Å or less.

[0025] In one embodiment, the Group ⅧA element may exist in the form of fine particles, and the average particle diameter of the fine particles may be from 1 nm to 20 nm.

[0026] In one embodiment, the catalyst of the present disclosure has a BET surface area of ​​10 m 2 / g to 300 m 2 It could be / g.

[0027] In one embodiment, the wear loss index of the catalyst of the present disclosure may be 15 wt% or less.

[0028] In one embodiment, the catalyst of the present disclosure may further contain 0 to 30 wt% silica.

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

[0030] In one embodiment, the catalyst of the present disclosure may be a catalyst for steam reforming and reverse Boudouard reaction for producing synthesis gas from hydrocarbons.

[0031] According to one embodiment of the present disclosure, a method for producing a porous catalyst for producing pyrolysis synthesis gas having excellent catalytic activity and high durability can be provided.

[0032] According to one embodiment of the present disclosure, a method for producing a catalyst for producing pyrolysis synthesis gas having high reaction stability can be provided by minimizing catalyst rupture due to coke formation.

[0033] According to one embodiment of the present disclosure, a catalyst for producing pyrolysis synthesis gas produced by the production method of the present disclosure can be used to produce syngas from pyrolysis gas at a high conversion rate and yield.

[0034] Figure 1 is a flowchart showing a method for manufacturing a catalyst for producing pyrolysis synthesis gas according to one embodiment.

[0035] Figure 2 is a schematic diagram showing a catalyst for producing pyrolysis synthesis gas according to one embodiment.

[0036] The present disclosure provides a detailed description of a porous catalyst for producing pyrolysis synthesis gas and a method for producing the same. The terminology used in this specification has been selected from widely used, current terms, taking into account the functions of the present disclosure. However, this may vary depending on the intentions of engineers working in the relevant fields, precedents, the emergence of new technologies, etc. Unless otherwise defined, the technical and scientific terms used may have the meaning commonly understood by those of ordinary skill in the technical field to which this invention pertains.

[0037] In this specification and the appended claims, the terms “include” or “have” mean that a feature or component described in the specification is present, and unless specifically limited, does not preclude the possibility that one or more other features or components may be added.

[0038] As used herein and in the appended claims, the singular expression "singular" includes the plural expression unless the context clearly dictates otherwise. Furthermore, the plural expression "singular" includes the singular expression unless the context clearly dictates otherwise.

[0039] In this specification and the appended claims, the terms first, second, etc. are not used in a limiting sense but are used for the purpose of distinguishing one component from another.

[0040] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specifically defined in the present specification, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0041] The term "about" or the like used in this specification and the appended claims is used to encompass the tolerance when an tolerance exists.

[0042] The term “Group VIIIA” as used in this specification and the appended claims means an element corresponding to each group in the periodic table according to the former International Union of Pure and Applied Chemistry (IUPAC).

[0043] Hereinafter, a method for manufacturing a porous catalyst for producing pyrolysis synthesis gas according to the present disclosure is described with reference to the attached drawings.

[0044] Organic waste can seriously damage the environment through decomposition and other processes during landfill disposal. Therefore, disposal must be categorized by type and processed accordingly. However, simple disposal of organic waste requires securing treatment facilities and extensive manpower, and is often more wasteful than productive. Therefore, methods and technologies for recycling organic waste are being developed. A prime example is the gasification process, which uses organic waste to produce synthesis gas, converting it into high-value-added products, and ultimately converting it into energy.

[0045] The gasification process generally refers to a series of processes that convert carbonaceous raw materials such as coal, organic waste, and biomass into synthesis gas containing hydrogen and carbon monoxide by reacting them under the supply of steam, oxygen, carbon dioxide, or a mixture thereof. Here, "synthesis gas" typically refers to a mixed gas produced by the gasification reaction and containing hydrogen and carbon monoxide, and may additionally include dry gases such as carbon dioxide and / or methane.

[0046] Gasification process technology has expanded into producing various compound feedstocks and fuels. For example, synthesis gas can be used as a feedstock for the Fischer-Tropsch synthesis reaction to produce high value-added products such as light crude oil, heavy crude oil, diesel fuel, wax, jet fuel, and lubricating oil. Furthermore, the hydrogen contained in synthesis gas, the main product of the gasification process, can be used in hydrogen power generation, ammonia production, and oil refining processes. Furthermore, it is known that methanol produced from synthesis gas can be used to produce high value-added chemicals such as acetic acid, olefins, dimethyl ether, aldehydes, fuels, and additives. However, synthesis gas produced from organic waste has a very low production yield, making it difficult to effectively produce high value-added compounds from synthesis gas.

[0047] Recently, catalytic gasification processes have been implemented to produce synthesis gas. However, the gasification process has been plagued by problems such as catalyst deactivation caused by coke formation, leading to process failures during continuous operation. Furthermore, to ensure economic viability, the relatively expensive catalyst must be recovered. However, recovering the catalyst, which is discharged in a coagulated state with coke and other contaminants, requires multiple subsequent steps (e.g., air burning), significantly reducing process efficiency.

[0048] For example, steam reforming catalysts used in conventional gasification processes are active metal species. When they contain noble metal-based active metal species such as Ru, they do not easily cause carbon precipitation even under conditions of low S / C (steam / carbon ratio). However, they are easily poisoned by sulfur components contained in the raw materials, causing the catalytic activity to deteriorate in a short period of time. Sulfur-poisoned catalysts have the defect of causing carbon precipitation. In addition, the high cost of noble metals reduces the economic feasibility of the process.

[0049] In addition, catalysts containing non-metallic active metal species, such as Ni, are relatively prone to carbon precipitation, and therefore need to be used under conditions where the steam is used in excess of the theoretical composition and the steam / carbon ratio is high. This not only complicates operation, but also increases the steam unit cost. In addition, the continuous operation conditions of the system are narrow, and an expensive control system is required to achieve this, and the entire system becomes very complex, making it uneconomical in terms of manufacturing cost and maintenance.

[0050] Meanwhile, steam reforming is a high-temperature reaction. The high-temperature endothermic reaction that occurs during the reforming process and the process of regenerating the catalyst by removing coke generated on the catalyst surface through oxidation in the regeneration process at the rear of the reactor are repeated, which can lead to catalyst rupture. Therefore, α-alumina, which has a relatively high crush strength, is generally used as a support species. However, since α-alumina is generally sintered at high temperatures during its manufacture to increase its strength, its BET specific surface area and pore volume are extremely small. For this reason, the active metal species supported on α-alumina are easily sintered by heat exposure, resulting in deterioration of catalytic activity.

[0051] Accordingly, the present applicant has invented a method for producing a porous catalyst for producing pyrolysis synthesis gas, which is economically efficient and has excellent durability to maintain sufficient strength to avoid crushing or rupture even when coking occurs inside the catalyst, and has a high specific surface area to exhibit excellent reaction activity and reaction stability.

[0052] A method for producing a porous catalyst for producing pyrolysis synthesis gas according to the present disclosure comprises the steps of: preparing a mixed solution by mixing a metal precursor containing a group ⅧA element, a ceramic support, and a solvent; preparing a precursor gel by adding an acid to the mixed solution; preparing a mixture by mixing clay into the precursor gel; preparing a composite catalyst sol by adding an inorganic binder to the mixture; and drying and calcining the composite catalyst sol.

[0053] That is, the porous catalyst for producing pyrolysis synthesis gas of the present disclosure is manufactured through a series of processes, as illustrated in FIG. 1, including mixing a metal precursor containing a Group VIIIA element and a ceramic support to prepare an aqueous mixed solution, adding an organic acid to the mixed solution to cause gelation to prepare a precursor gel, sequentially adding clay and an inorganic binder to prepare a composite catalyst sol, and drying and calcining, so that durability is improved, and even if coke is deposited inside the catalyst, cracking and rupture of the catalyst are significantly reduced, and since the Group VIIIA element, which is an active metal, is uniformly dispersed throughout the ceramic support, excellent reaction activity can be provided.

[0054] Accordingly, when a catalyst manufactured by the manufacturing method according to the present disclosure is applied to a dual circulation fluidized bed process, coking and regeneration can be repeated without the catalyst being damaged, so there is an advantage in that synthesis gas can be obtained at a high yield without catalyst deactivation even during long-term operation.

[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 through complexation between the metal precursor and the ceramic support.

[0056] In one specific example, when preparing the precursor gel, the mixed solution containing the 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 for the metal precursor and ceramic support to sufficiently complex and be converted into a gel form.

[0057] In one embodiment, the ceramic support may include aluminum, and the aluminum-containing ceramic support may include at least one selected from the group consisting of boehmite, pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum fluoride, aluminum phosphate, aluminum chloride, and aluminum sulfate. Specifically, the ceramic support including pseudo-boehmite is advantageous in that it can have strength that minimizes rupture of the catalyst due to repeated stretching and expansion of the reactor by external heating during the steam reforming reaction described below, and at the same time, has 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 a mixture thereof, and more specifically, the Group ⅧA element may include nickel, which has excellent economic efficiency and catalytic activity.

[0059] In one embodiment, the metal precursor may be at least one selected from the group comprising hydroxides, sulfates, carbonates, nitrates, chlorides, benzoic acid, basic carbonates, formates, citric acid, diammonium sulfate, and hydrates thereof of Group ⅧA elements.

[0060] As a more specific example, when the Group ⅧA element includes nickel, the metal precursor may include at least one selected from the group including nickel hydroxide, nickel sulfate, nickel carbonate, nickel nitrate, nickel chloride, nickel benzoate, basic nickel carbonate, nickel formate, nickel citrate, nickel sulfate, diammonium nickel, and hydrates thereof, but the present disclosure is not limited by the specific type of the metal precursor.

[0061] In one embodiment, the organic acid may include, but is not limited to, formic acid, acetic acid, propionic acid, salicylic acid, and the like.

[0062] In one embodiment, after the gelation is completed, clay may be mixed into the precursor gel to produce a mixture. Since the ceramic support and metal precursor are mixed in advance and gelled, and then the clay is added and mixed, the clay can be uniformly dispersed within the precursor gel without agglomeration. Accordingly, the metal precursor can be uniformly dispersed in the ceramic support of the catalyst being produced. In addition, as the specific surface area and wear resistance of the catalyst are improved, not only can long-term stability and catalyst life be improved, but also the effect of enhancing catalytic activity can be provided.

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

[0064] In one embodiment, a composite catalyst sol can be prepared by adding an inorganic binder to the mixture. The inorganic binder can increase the adhesion between the metal precursor and the ceramic support, thereby further improving the durability and wear resistance of the prepared catalyst. The inorganic binder can include, for example, non-rehydratable alumina, α-alumina, aluminum salt, silica, clay, talc, bentonite, zeolite, cordierite, titania alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconia, mullite, sepiolite, montmorillonite, hallocite, saporite, stevensite, hectorite, silica alumina, or a combination thereof.

[0065] In one embodiment, when preparing the composite catalyst sol, an additive may be added to the mixture. The additive may include, for example, one or more selected from a forming aid, a dispersant, etc. The additive may remain in the final catalyst, or may be burned away during the calcination process and not remain in the catalyst.

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

[0067] The molding auxiliary agent may include at least one selected from the group consisting of fatty acids, cellulose, polyvinyl alcohol, starch, methylcellulose, maltose, and carboxymethylcellulose, and two or more types may be used in combination as needed. However, the present disclosure is not limited to the specific type of the additive, and a person skilled in the art may appropriately select and use various additives commonly known in the art as needed.

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

[0069] The above composite catalyst sol can be dried and calcined to produce a catalyst having a size and shape that can optimize catalytic activity while oxidizing a metal precursor. Specifically, the drying can be performed by drying the composite catalyst sol using a method known in the art, but spray drying using a spray dryer facilitates solvent removal and catalyst shaping, and can shorten the time that the catalyst is exposed to heat.

[0070] In one embodiment, the calcination temperature may be 500°C to 1300°C, 500°C to 1100°C, or 500°C to 900°C. Calcining the composite catalyst sol within the above temperature range can rapidly remove the solvent contained in the mixture and oxidize the metal precursor.

[0071] In one embodiment, the dried catalyst can be selected from particles having an average particle size of 10 ㎛ to 400 ㎛, 30 ㎛ to 350 ㎛, or 50 ㎛ to 250 ㎛, thereby obtaining a catalyst having excellent specific surface area and durability.

[0072] The present disclosure includes a porous catalyst for producing pyrolysis synthesis gas prepared by the method described above. When describing the porous catalyst for producing pyrolysis synthesis gas according to the present disclosure, the metal precursor, ceramic support, clay, inorganic binder, etc. are identical or similar to those described above, and therefore the porous catalyst for producing pyrolysis synthesis gas according to the present disclosure includes all of the above-described contents.

[0073] The catalyst manufactured by the above-described method has high durability and wear resistance, and thus can maintain excellent catalytic activity without being destroyed even when the catalytic process is performed repeatedly.

[0074] In addition, since the active metal is uniformly dispersed within the ceramic support, when removing coke deposited on the catalyst surface to regenerate the catalyst during synthesis gas production described below, sintering of the active metal and deterioration of the catalyst due to the formation of hot spots can be suppressed. Accordingly, irreversible deactivation of the catalyst is minimized, the catalyst life is improved, and high reaction stability can be provided by preventing catalyst rupture.

[0075] The porous catalyst for producing pyrolysis synthesis gas according to the present disclosure contains 5 to 70 wt% of a ceramic support, 1 to 75 wt% of a group ⅧA element, and 0.1 to 30 wt% of clay, and has a pore volume of 0.01 cm 3 / g to 0.5 cm 3 / g, and the average pore diameter may be less than 300 Å.

[0076] The porous catalyst for producing pyrolysis synthesis gas having the above-described characteristics has excellent catalytic activity and specific surface area, and has improved durability so that it may not rupture even if coking occurs inside the catalyst.

[0077] In one embodiment, the Group VIIIA element is supported in the form of very fine particles inside a ceramic support, so that the area where the Group VIIIA element, which is an active metal species, comes into contact with the reactant is increased, thereby enabling excellent catalytic activity. More specifically, the average particle diameter of the Group VIIIA element particles may be 1 nm to 20 nm, 1 nm to 15 nm, or 3 nm to 12 nm. When the above range is satisfied, the Group VIIIA element can be easily supported inside the ceramic support, thereby maintaining high catalytic activity.

[0078] In one embodiment, the catalyst may contain 1 to 75 wt%, 10 to 75 wt%, or 20 to 75 wt% of a Group VIIIA element. Since the active metal is uniformly dispersed within the ceramic support, excellent catalytic activity and improved durability can be achieved even when the Group VIIIA element is contained in the above range of wt%, which is advantageous. When the Group VIIIA element is contained in a wt% less than the above range, there is a risk that the hydrocarbon conversion rate may decrease.

[0079] The porous catalyst for producing pyrolysis synthesis gas of the present disclosure can contain a high content of Group VIIIA elements, i.e., a high content of active metals. Even if coke is generated in the catalyst during the steam reforming reaction during the production of syngas, the catalyst is regenerated in the reverse Boudouard process described below, so that even if the catalyst contains a high content of Group VIIIA elements, it is not deactivated and can be used for a long period of time. Therefore, the porous catalyst for producing pyrolysis synthesis gas of the present disclosure containing a high content of Group VIIIA elements can maintain high catalytic activity for a long period of time.

[0080] In one embodiment, the porous catalyst for producing pyrolysis synthesis gas may include pseudo boehmite alumina as a ceramic support, and the content of pseudo boehmite alumina included in the porous catalyst for producing pyrolysis synthesis gas may be 5 to 70 wt%, 7 to 60 wt%, or 10 to 50 wt%. When the alumina is contained in a weight % range less than the above, the mechanical strength of the catalyst may be reduced, and when the catalyst contains alumina in a weight % exceeding the above range, there is a concern that the content of Group ⅧA elements may be reduced, thereby lowering the catalytic activity. The ceramic support has an advantage that, when producing the synthesis gas described below, when the mixed gas contains a high content of nitrogen (N) impurities, it can adsorb nitrogen components and buffer the inhibition of the catalytic activity reaction caused by the impurities.

[0081] In addition, the porous catalyst for producing pyrolysis synthesis gas may further contain silica, and the silica may be contained in an amount of 0 to 35 wt%, 0 to 30 wt%, or 1 to 25 wt%. Silica is an additive for further improving the wear resistance of the catalyst, and if the above-described wear loss index value is satisfied with only the ceramic support, the catalyst may not contain silica. If the silica is contained in an amount exceeding the above-described wt% range, the catalytic activity may be reduced.

[0082] The catalyst according to the present disclosure may contain 0.1 to 60 wt%, 1 to 50 wt%, or 10 to 30 wt% of clay. The clay may act as a binder to fix Group VIIIA elements and a ceramic support to improve catalyst strength. In one specific example, the average particle size of the clay may be 30 μm or less, 20 μm or less, or 10 μm or less, and may be, but is not limited to, 0.01 μm or more. Within the above particle size range, the clay may improve durability without inhibiting the catalytic activity of the Group VIIIA elements.

[0083] As shown in FIG. 2, the catalyst of the present disclosure has a group ⅧA active metal component, clay, and silica uniformly dispersed on a ceramic support, and is firmly fixed with a clay binder, so that it can have excellent physical properties such as mechanical strength.

[0084] In one embodiment, the porous catalyst for producing pyrolysis synthesis gas may have a wear loss index of 15 wt% or less, 10 wt% or less, or 5 wt% or less, and may be, but is not limited to, 0.5 wt% or more. The porous catalyst for producing pyrolysis synthesis gas of the present disclosure has significantly improved wear resistance, so that physical or chemical wear loss due to chemical reactions at high temperatures during steam reforming and reverse Budar reactions is significantly reduced, and thus long-term catalyst stability can be significantly improved.

[0085] The porous catalyst for producing pyrolysis synthesis gas of the present disclosure may have a pore diameter of 300 Å or less, 250 Å or less, or 200 Å or less, and may be, but is not limited to, 5 Å or more, or 10 Å or more. In addition, the pore volume of the catalyst may be 0.01 cc / g to 0.5 cc / g, 0.03 cc / g to 0.4 cc / g, or 0.05 cc / g to 0.3 cc / g, and the BET specific surface area may be 10 m 2 / g to 300 m 2 / g, 20 m 2 / g to 100 m 2 / g or 50 m 2 / g to 100 m 2 / g. When the pore volume, pore diameter, and BET specific surface area are within the above range, the active metal can be sufficiently dispersed and supported within the ceramic support, thereby improving the catalytic efficiency.

[0086] In one embodiment, the average particle size (D50) of the catalyst may be 10 μm to 500 μm, 30 μm to 300 μm, or 50 μm to 200 μm. The catalyst has excellent strength and specific surface area within the above-described range, but the present disclosure is not limited thereto.

[0087] The porous catalyst for producing pyrolysis synthesis gas according to the present disclosure may be a steam reforming catalyst and a reverse Boudouard reaction catalyst. As described below, in a process for producing synthesis gas through a gasification reaction of a mixed gas produced by heat treating organic waste, the porous catalyst promotes steam reforming and a reverse Boudouard reaction, thereby improving the production yield of synthesis gas and hydrocarbons, and enabling the stable production of synthesis gas for a long period of time with high durability.

[0088] In one example, a method for producing synthesis gas from a pyrolysis mixed gas using a porous catalyst for producing pyrolysis synthesis gas according to the present disclosure comprises the steps of: (S1) heat-treating organic waste to produce a first mixed gas; (S2) steam reforming the first mixed gas in a first fluidized bed reactor containing a catalyst to produce 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) introducing the first stream separated in step (S3) into a second fluidized bed reactor containing a catalyst and converting it into carbon monoxide through a reverse Boudouard reaction; (S5) mixing the second stream with the carbon monoxide converted in step (S4) to produce a third mixed gas; And (S6) a step of producing synthesis gas through a water gas conversion reaction from the third mixed gas; wherein steps (S2) and (S4) can be performed under a porous catalyst for producing pyrolysis synthesis gas produced by the method described above.

[0089] In one embodiment, the method for producing synthesis gas comprises steam reforming a mixed gas obtained through heat treatment of organic waste to produce a mixed reformed gas, and converting carbon dioxide contained in the mixed reformed gas into carbon monoxide through a reverse Boudouard reaction. By including the porous catalyst for producing pyrolysis synthesis gas of the present disclosure in the steam reforming process and the reverse Boudouard reaction, organic waste can be converted into synthesis gas with high efficiency, and the yield of high value-added hydrocarbons converted from the synthesis gas can be maximized.

[0090] In addition, when producing synthesis gas using the porous catalyst for producing pyrolysis synthesis gas of the present disclosure, trace amounts of metal impurities contained in the mixed gas can be adsorbed and removed, and char containing benzene, toluene, and xylene (BTX char) can be converted to coke, and the coke can be used as a carbon source for the reverse Buta reaction described below, thereby having the advantage of being able to be converted to carbon monoxide without the need to externally supply a separate carbon source such as activated carbon.

[0091] The above step (S1) is a step of generating a first mixed gas by heat-treating organic waste, in which a gasification reaction of the organic waste can occur.

[0092] In one example, in step (S1), the organic waste may be one or more selected from the group consisting of waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags. Specifically, in step (S1), one or more gasification reactions selected from the following reaction formulas 1 to 4 may be performed.

[0093] [Reaction Formula 1]

[0094] C x H y + H2O →H2+ CO (water gasification reaction)

[0095] [Reaction Formula 2]

[0096] C x H y + CO2→CO (carbon dioxide gasification reaction)

[0097] [Reaction Formula 3]

[0098] CO + 3H2→CH4+ H2O (methanation reaction)

[0099] [Reaction Formula 4]

[0100] C x H y + O2→ CO2 (oxidation reaction)

[0101] In one example, the first mixed gas may include methane, hydrogen, carbon monoxide, and carbon dioxide, and may also include various impurities such as nitrogen oxides, sulfur oxides, and hydrogen chloride.

[0102] As an example for increasing the methane content in the first mixed gas, the first mixed gas may further include one or more selected from the group consisting of landfill gas, shale gas, refinery exhaust gas, and biogas. Since the above-described landfill gas, shale gas, refinery exhaust gas, and biogas contain methane and carbon dioxide in an amount of 40% by volume or more, specifically, 50% by volume or more, since the first mixed gas further includes the above-described gases, there is an effect of further improving the production yield of synthesis gas through subsequent processes such as methane reforming reaction and reverse Budar reaction.

[0103] In one example, the C / O element ratio of the first mixed gas may be 0.01 or more, 0.05 or more, or 0.1 or more as a lower limit, and 0.9 or less, 0.8 or less, or 0.7 or less as an upper limit, and specifically 0.01 to 0.9, 0.05 to 0.8, and more specifically 0.1 to 0.7.

[0104] The method for producing hydrocarbons according to the present disclosure enables a smooth methane reforming reaction even when the first mixed gas contains a relatively high C / O element ratio within the above-described range. Specifically, since the catalyst used in the methane reforming reaction forms a cyclic process as described below, the reaction can be continuously performed regardless of catalyst deactivation due to coke that may be generated by dry reforming of methane.

[0105] In one example, the step (S1) may further include a step of purifying the first mixed gas.

[0106] The first mixed gas generated by heat treating organic waste may contain one or more impurities selected from the group consisting of tar, sulfur, nitrogen, and chlorine. Specifically, the first mixed gas may contain water-soluble impurities such as H2S, HCl, HOCl, and NH3, and insoluble impurities such as tar. These impurities contained in the first mixed gas may induce catalyst deactivation, thereby reducing the efficiency of a subsequent process. Therefore, by removing the impurities from the first mixed gas and purifying it, the efficiency of the overall process can be improved.

[0107] Step (S2) is a step of producing a second mixed gas by steam reforming methane contained in the first mixed gas in a first fluidized bed reactor. In step (S2), a reforming reaction according to the following reaction formula 5 may occur.

[0108] [Reaction Formula 5]

[0109] CH4+ H2O → CO + 3H2 (steam reforming reaction)

[0110] The reforming reaction of the above (S2) step can be carried out at a temperature of 600°C to 1400°C, 600°C to 1100°C or 600°C to 800°C and a pressure of 30 KPa to 2000 KPa, 40 KPa to 1000 KPa or 50 KPa to 500 KPa, and the ground high speed volume (GHSV) is 100 h -1 100000 h -1 , 500 h -1 10000 h -1 or 1000 to 5000 h -1 It could be.

[0111] By performing a steam reforming reaction using the porous catalyst for producing pyrolysis synthesis gas of the present disclosure, hydrocarbon reforming can be achieved at a high conversion rate even at low temperatures. Therefore, the possibility of catalyst rupture due to expansion and contraction of the reactor caused by external heating is significantly reduced, thereby significantly increasing the catalyst lifespan.

[0112] (S2) As the step is performed in a fluidized bed reactor, the catalyst used in the methane reforming reaction can be regenerated and then supplied to the subsequent reverse Buta reaction process, forming a cyclic process. As described below, since the coke accumulated in the catalyst that has undergone the steam reforming reaction serves as a carbon source for the reverse Buta reaction in the step (S4), a cyclic process of regenerating and resupplying the catalyst used in the steps (S2) and (S4) can be performed, thereby enabling a continuous reforming reaction. In addition, when methane is reformed using the steam reforming reaction, not only is the reforming reactivity improved compared to dry reforming, but there is also an effect of removing impurities such as chlorine.

[0113] (S3) Step is a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide.

[0114] In one example, the method for separating the second mixed gas into the first stream and the second stream is not limited to any known method, but the present disclosure allows separation using a carbon dioxide separation unit, and the carbon dioxide separation unit may be an Amine Scrubber. Typically, an Amine Scrubber separates components such as carbon dioxide and hydrogen sulfide from gas vapor by combining and removing carbon dioxide through an amine-based material, and can recover a gas containing hydrogen, carbon monoxide, or an inert gas. Therefore, the first mixed gas can be separated into the first stream and the second stream by using an Amine Scrubber.

[0115] As another example, the carbon dioxide separation unit may be a CCS unit (Carbon capture and storage unit). When a CCS unit is used to separate carbon dioxide, the CCS unit can adsorb and separate carbon dioxide using an adsorbent including one or more selected from calcium oxide, calcium hydroxide, dolomite, limestone, and trona, so the second mixed gas can be separated into a first stream and a second stream using the CCS unit (Carbon capture and storage unit).

[0116] The first stream may contain carbon dioxide in an amount of 40% by volume or more, 50% by volume or more, or 60% by volume or more, and in an amount of 99% by volume or less, 90% by volume or less, 80% by volume or less, or 70% by volume or less. Specifically, the first stream may contain carbon dioxide in an amount of 40% to 99% by volume, and more specifically, 50% to 80% by volume. In a carbon dioxide separation unit, when capturing carbon dioxide and separating it, in order to separate carbon dioxide with high purity, the regeneration tower where the carbon dioxide is separated from the adsorbent must be designed with a high stage, which may consume more energy. Therefore, since the first stream contains carbon dioxide in the above-described range, the carbon dioxide separation process can be performed under milder conditions.

[0117] Step (S4) is a step for converting the first stream separated in step (S3) into carbon monoxide through a reverse Buta reaction in a second fluidized bed reactor. By additionally converting the carbon dioxide contained in the first stream into carbon monoxide through the reverse Buta reaction, it is possible to prevent environmental pollution by reducing carbon dioxide emissions, while also maximizing the yield of synthesis gas. The reverse Buta reaction may involve the following reaction scheme 6.

[0118] [Reaction Formula 6]

[0119] C+CO2→ 2CO

[0120] In one example, the reverse Buta reaction catalyst of step (S4) may be the catalyst used in the steam reforming reaction of step (S2). The catalyst of the present disclosure may be used in the steam reforming reaction in step (S2), so that coke may be deposited on the catalyst. When the catalyst coked by the steam reforming reaction is introduced into the second fluidized bed reactor to perform the reverse Buta reaction, the coke acts as a carbon source, so that a synthesis gas production process can be continuously performed without a separate catalyst regeneration process.

[0121] The second synthesis gas discharged from the first fluidized bed reactor may be supplied to the second fluidized bed reactor where the reverse Buta reaction is performed by separating the catalyst by a cyclone and then supplied through a catalyst supply line. In the second fluidized bed reactor, the catalyst is regenerated by reacting with the carbon source for the reverse Buta reaction, and the regenerated catalyst may be supplied back to the first fluidized bed reactor through a recirculation line. By utilizing this catalyst circulation process, the methane reforming reaction can be performed continuously, and the process can be performed economically because there is no need to supply the carbon source required for the reverse Buta reaction from an external source.

[0122] That is, the present disclosure has the advantage of maximizing the yield of synthesis gas through methane reforming reaction and reverse Buta reaction, and also enabling continuous operation due to catalyst regeneration as the first fluidized bed reactor and the second fluidized bed reactor in which the methanation reforming reaction and reverse Buta reaction are performed form a circulation process.

[0123] In one embodiment, the reaction temperature of the step (S4) may be 600°C to 1400°C, 600°C to 1200°C, or 600°C to 1000°C, and the reaction pressure may be performed at 30 KPa to 2000 KPa, 40 KPa to 1000 KPa, or 50 KPa to 500 KPa. In addition, the step (S4) may be performed at a gaseous high speed space velocity (GHSV) of 100 h-1 100000 h -1 , 500 h -1 10000 h -1 or 1000 h -1 5000 h -1 Under these conditions, the raw material gas and steam containing the above-described mixed gas can be brought into contact with a porous catalyst for decomposing hydrocarbons according to the present disclosure. Long-term operation is possible under the above-described temperature, pressure, and space velocity conditions, and the catalytic activity can also be increased.

[0124] Step (S5) is a step of generating a third mixed gas by mixing the second stream separated from the carbon dioxide separation unit and the carbon monoxide converted by the reverse Budda reaction in step (S4). The third mixed gas may include hydrogen and carbon monoxide.

[0125] Step (S6) is a process for generating synthesis gas by controlling the ratio of carbon monoxide and hydrogen in the third mixed gas through a water-gas shift reaction. The third mixed gas can be converted through the water-gas shift reaction to satisfy an appropriate hydrogen:carbon monoxide ratio for the subsequent catalytic reaction process. The water-gas shift reaction may involve the following chemical formula 7.

[0126] [Chemical Formula 7]

[0127] CO + H2O → H2 + CO2

[0128] 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 a temperature of 100°C to 400°C, specifically 100°C to 300°C, and a pressure of 20 bar to 80 bar, specifically 25 bar to 70 bar.

[0129] The synthesis gas produced by the above-described water-gas shift reaction may have a hydrogen:carbon monoxide ratio of 1.5 to 3:1, specifically 1.9 to 2.1:1. As the hydrogen:carbon monoxide ratio in the synthesis gas satisfies the above-described range, the subsequent catalytic reaction process can be performed smoothly.

[0130] In one embodiment, after step (S6), the method may further include a step (S7) of generating hydrocarbons from the synthesis gas through a catalytic reaction. Step (S7) is a step of converting the synthesis gas generated in step (S6) into a hydrocarbon fraction, which may be converted into an appropriate hydrocarbon fraction through a catalytic reaction. The catalytic reaction is not limited to any reaction capable of converting the synthesis gas into a hydrocarbon fraction, but may specifically be a Fischer-Tropsch reaction.

[0131] In one example, when the catalytic reaction of step (S7) is a Fischer-Tropsch reaction, a reaction involving the following chemical formula 8 can be performed using the synthesis gas produced in step (S6) as a raw material.

[0132] [Chemical Formula 8]

[0133] nCO + 2nH2→C n H 2n + nH2O

[0134] The above Fischer-Tropsch reaction can be carried out under a catalyst containing cobalt, nickel or iron, and can include alumina, silica, titania, etc. as a support, and can include a noble metal such as Pt, Ru, Re, etc. as a cocatalyst.

[0135] Additionally, the Fischer-Tropsch reaction can be carried out at a temperature of 100°C to 500°C or 200°C to 350°C, and a pressure of 10 atm to 50 atm or 10 atm to 30 atm, but the present disclosure is not limited thereto.

[0136] Hereinafter, embodiments of the present disclosure will be further described with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the examples are possible within the scope and technical idea of ​​the present invention, and it is natural that such changes and modifications fall within the scope of the appended claims.

[0137] (Manufacturing Example 1) Manufacturing of Ni / MgO / Al2O3 catalyst

[0138] Based on 100 parts by weight of water, 10 parts by weight of pseudo-boehmite alumina and 95 parts by weight of nickel nitrate hexahydrate were mixed to prepare a mixed solution. 1 part by weight of formic acid was added while stirring the mixed solution, and the mixture was reacted for 3 hours to gelate, thereby 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, and the resulting solid mixture was mixed with the precursor gel. 10 parts by weight of colloidal silica (Ludox AS40, Aldrich) was added, and 5 parts by weight of water was further added and stirred vigorously to prepare a composite catalyst sol. The composite catalyst sol was spray-dried and sieved to recover catalyst particles having a particle size of 50 to 250 μm. The recovered catalyst was dried in an oven at 120°C and calcined at 550°C for 3 hours to produce a catalyst.

[0139] The characteristics of the catalyst manufactured by the method of Manufacturing Example 1 were analyzed. The wear index was measured using an wear resistance measuring device (3-hole attrition tester) according to the standard according to ASTM D 5757-95. The nickel content in the catalyst was calculated through XRF (X-Ray Flourescence Spectrometry) analysis, and the XRF analysis was measured using an ARL QUANT'X from Thermo. The BET surface area, total pore volume, and pore size were measured using a Tristar 3000 instrument from Micromeritics by a nitrogen physical adsorption-desorption method.

[0140] The catalyst of Manufacturing Example 1 was confirmed to have excellent wear resistance with a wear index of 3.5 wt%. In addition, the BET surface area of ​​the catalyst was 79 m 2 / g, the total pore volume was 0.2 cc / g, and the average pore diameter was 34 Å. The average particle size was 131 ㎛, the average particle diameter (D50) was 126 ㎛, and fine particles of 50 ㎛ or less were present at 4 wt%. The XRF analysis results confirmed that the content of Ni in the catalyst was 30.1 wt%.

[0141] (Example 1)

[0142] After 1000 g of urban solid waste was fed into a pyrolysis reactor, steam was introduced and heat-treated under conditions of 1200°C and 250 kPa under alumina beads to recover the first mixed gas.

[0143] The temperature of the first mixed gas was lowered, and impurities such as Cl, S, and N contained in the mixed gas were removed through a scrubber, and the purified first mixed gas was recovered.

[0144] The first mixed gas from which the above impurities were removed was supplied to a first fluidized bed reactor containing the catalyst manufactured in Manufacturing Example 1 at a space velocity of 2 L / g-cat / h, and steam was simultaneously supplied to manufacture a second mixed gas through steam reforming at 750°C.

[0145] The second mixed gas was introduced into the Amine Scrubber, and the carbon dioxide in the second mixed gas was captured in the Amine Scrubber, and the second mixed gas from which the carbon dioxide was separated was separated into a second stream. Specifically, the second mixed gas was introduced into the first Amine Scrubber, and CO2 was captured in an aqueous solution (Amine Solution) containing monoethanolamine (MEA) at 50°C, and the uncaptured gas was recovered as the second stream. The Amine Solution of the first Amine Scrubber, which includes CO2, was introduced into the second Amine Scrubber, and was separated into the Amine Solution and CO2 at 100°C, and the CO2 was recovered as the first stream.

[0146] The recovered first stream was fed into the second fluidized bed reactor and converted into carbon monoxide through a reverse Buta reaction. The reverse Buta reaction was performed in the second fluidized bed reactor filled with the catalyst of Preparation Example 1 used in the steam reforming reaction, and was performed by supplying the first stream at a space velocity of 2 L / g-cat / h. At this time, the catalyst inactivated by coke deposition due to the steam reforming reaction was introduced as a carbon source, and the catalyst activated by removing the coke was reintroduced into the first fluidized bed reactor.

[0147] The carbon monoxide converted from the first stream and the second stream were introduced into a gas mixing unit and mixed at 200°C to produce a third mixed gas. The third mixed gas was introduced into a synthesis gas production unit and, through a water gas shift reaction, produced a synthesis gas having a molar ratio of H2:CO of 1:2.

[0148] Synthesis gas was supplied to a hydrocarbon conversion unit, and the injection rate was set so that the volume ratio of carbon monoxide: hydrogen: argon was 63.2:31.3:5.5 at a space velocity of 5000 L / kg-cat / h under a Co / ZnO (Cobalt Zinc oxide) catalyst, and the Fischer-Tropsch reaction was performed at a reaction temperature of 300°C and 10 bar for 60 hours to recover hydrocarbon fraction.

[0149] As a result, the yield of synthesis gas was 48%, and the yield of hydrocarbon oil using the synthesis gas was 87%.

[0150] In addition, it was found that the catalyst activity was excellent as the yield change rate was maintained within 5% without any decrease in the activity of the catalyst when operated continuously 10 times using the method of Example 1.

[0151] (Example 2)

[0152] The same procedure as Example 1 was followed, except that landfill gas was mixed into the first mixed gas.

[0153] As a result, the yield of synthesis gas was 48%, and the yield of hydrocarbon fraction using the synthesis gas was 86%. Furthermore, the yield after 10 consecutive reactions was maintained within 5%, indicating that the catalyst has excellent stability.

[0154] (Comparative Example 1)

[0155] The same procedure as Example 1 was followed, except that the catalyst of Manufacturing Example 1 was not used in the steam reforming process and the reverse nitride reaction process, and a Ni / Al2O3 catalyst containing 30 wt% of Ni on an alumina bead was used.

[0156] As a result, the yield of synthesis gas was the same at 48%, and the yield of hydrocarbon fraction using the synthesis gas was also similar at 84% until the first three recyclings, but there was a problem with catalyst wear from the first operation, so the catalyst loss rate occurred at about 15% for each operation. In particular, there was a problem that the catalyst activity continuously decreased as the nickel, which is an active metal, was quickly lost on the catalyst surface as the process progressed.

[0157] When the third run was completed, the catalytic activity was reduced by approximately 20%, showing significantly lower durability and long-term stability compared to the porous catalyst for pyrolysis synthesis gas production of the present disclosure. After the reaction was completed, when the catalyst properties were checked, agglomeration between catalysts was observed in many cases, resulting in multiple catalyst particles clumped together. This indicates that sintering between nickel particles was induced by hot spots generated during the catalytic reaction, resulting in the catalyst particles existing in an agglomerated form.

[0158] Through the above examples and comparative examples, when the catalyst manufactured by the method of Manufacturing Example 1 was adopted in steam reforming and reverse Buddha reaction, the yield of hydrocarbons was measured to be 86% or more without a decrease in catalytic activity due to loss of catalyst and active metal even after repeated operation more than 10 times, confirming that stable process operation for a long period of time with high efficiency is possible. Therefore, it was found that the porous catalyst for producing pyrolysis synthesis gas of the present disclosure can achieve very excellent synthesis gas conversion rate and hydrocarbon production efficiency. In addition, it was found that the catalytic activity was maintained even when continuously reacted compared to conventional catalysts, showing very excellent durability.

[0159] The above description is merely an example of applying the principles of the present disclosure, and other configurations may be included without departing from the scope of the present invention.

Claims

1. A step of preparing a mixed solution by mixing a metal precursor containing a group ⅧA element, a ceramic support, and a solvent; A step of preparing a precursor gel by adding acid to the above mixed solution; A step of preparing a mixture by mixing clay into the above precursor gel; A step of preparing a composite catalyst sol by adding an inorganic binder to the above mixture; and A method for producing a porous catalyst for producing pyrolysis synthesis gas, comprising the steps of drying and calcining the above composite catalyst sol.

2. In paragraph 1, A method for producing a porous catalyst for producing pyrolysis synthesis gas, wherein the catalyst is used as a steam reforming catalyst and a reverse catalytic process catalyst in a synthesis gas production process through hydrocarbon decomposition.

3. In paragraph 1, A method for producing a porous catalyst for producing pyrolysis synthesis gas, wherein the above Group ⅧA element is a metal including nickel, iron, cobalt, ruthenium, palladium, platinum or a mixture thereof.

4. In paragraph 1, A method for producing a porous catalyst for producing a pyrolysis synthesis gas, wherein the metal precursor is at least one selected from the group comprising a hydroxide, a sulfate, a carbonate, a nitrate, a chloride, benzoic acid, a basic carbonic acid, formic acid, citric acid, diammonium sulfate or a hydrate thereof of a Group ⅧA element.

5. In paragraph 1, The above ceramic support is a method for producing a porous catalyst for producing pyrolysis synthesis gas including pseudo-Boehmite.

6. In paragraph 1, A method for producing a porous catalyst for producing pyrolysis synthesis gas, wherein the acid is at least one selected from organic acids including formic acid, acetic acid, propionic acid, and salicylic acid.

7. In paragraph 1, A method for producing a porous catalyst for producing pyrolysis synthesis gas, wherein the above-mentioned calcination is performed at a temperature range of 500°C to 1300°C.

8. A porous catalyst for producing pyrolysis synthesis gas, manufactured by a method according to any one of claims 1 to 7.

9. In paragraph 8, The catalyst is a porous catalyst for producing pyrolysis synthesis gas, containing 5 to 70 wt% of a ceramic support, 0.1 to 75 wt% of a group ⅧA element, and 0.1 to 30 wt% of clay.

10. In paragraph 8, A porous catalyst for producing pyrolysis synthesis gas, wherein the pore volume of the catalyst is 0.01 cc / g to 0.5 cc / g.

11. In paragraph 8, A porous catalyst for producing pyrolysis synthesis gas, wherein the average pore diameter of the catalyst is 300 Å or less.

12. In paragraph 9, A porous catalyst for producing pyrolysis synthesis gas, wherein the above group ⅧA element exists in the form of fine particles, and the average particle diameter of the fine particles is 1 to 20 nm.

13. In paragraph 8, The BET surface area of ​​the above catalyst is 10 m 2 / g to 300 m 2 / g, porous catalyst for producing pyrolysis synthesis gas.

14. In paragraph 8, A porous catalyst for producing pyrolysis synthesis gas, wherein the wear loss index of the catalyst is 15 wt% or less.

15. In paragraph 8, A porous catalyst for producing pyrolysis synthesis gas, wherein the catalyst further contains 0 to 30 wt% of silica.

16. In paragraph 8, A porous catalyst for producing thermal decomposition synthesis gas, wherein the average particle size (D50) of the catalyst is 10 to 500 μm.

17. In paragraph 8, The above catalyst is a porous catalyst for producing pyrolysis synthesis gas, which is a catalyst for steam reforming reaction and reverse Boudouard reaction for producing synthesis gas from hydrocarbons.

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