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

Abstract

The present invention relates to a method for manufacturing a hydrocarbon composite reforming catalyst and a hydrocarbon composite reforming catalyst manufactured thereby. In one embodiment, the method for manufacturing a hydrocarbon composite reforming catalyst comprises the steps of: preparing a mixture through solvent-deficient precipitation (SDP) of an aluminum precursor, an active metal precursor, a magnesium precursor, and a basic precipitant; and calcining the mixture.

Description

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

[0001] The present invention relates to a method for manufacturing a hydrocarbon composite reforming catalyst and a hydrocarbon composite reforming catalyst manufactured thereby. More specifically, the present invention relates to a method for manufacturing a catalyst for the steam / CO2 composite reforming of hydrocarbons and a catalyst for the steam / CO2 composite reforming of hydrocarbons manufactured according to this method.

[0002]

[0003] Since hydrogen emits only pure water when burned, the demand for it is rapidly increasing as an eco-friendly future energy source. Accordingly, various methods for producing hydrogen are being developed, among which is the method of producing hydrogen through methane reforming.

[0004] Syngas production by methane reforming is a widely used method, accounting for nearly half of the world's total hydrogen production, and is primarily carried out through a steam reforming process in which methane and steam are reacted over a high-temperature catalyst. However, the steam reforming of methane proceeds as a highly endothermic reaction, and the development of improved catalysts is required to enhance the methane conversion rate and suppress oxidation reactions, which are by-products. Accordingly, the production of syngas by dry methane reforming is currently being studied, taking into account greenhouse gas reduction and energy efficiency.

[0005] Methane dry reforming is a method of producing synthesis gas by reacting methane and carbon dioxide over a catalyst, offering advantages such as greenhouse gas reduction and process simplification. However, the commercialization of methane dry reforming has been difficult due to catalyst deactivation caused by severe carbon deposition (coking) occurring on the catalyst surface.

[0006] These wet and dry methane reforming reactions each have issues that need improvement and use H2O and CO2, respectively, as reformers; therefore, a combined reforming reaction that reforms methane by mixing wet and dry reformers is considered a highly effective technology. However, to expand the application of combined reforming technology, it is essential to improve the performance and durability of the catalysts used.

[0007] Meanwhile, precious metal, non-precious metal, and metal oxide catalysts are generally being developed for methane reforming reactions. On the other hand, nickel (Ni) catalysts are applicable to industrial fields due to their low cost and the possibility of large-scale production.

[0008] However, nickel catalysts face difficulties in commercialization due to deactivation and sintering issues resulting in activity loss caused by sintering, coke formation, and deposition; therefore, selecting an appropriate support capable of effectively dispersing the nickel catalyst is crucial.

[0009] Supports used in the preparation of nickel catalysts include ZrO2, CeO2, TiO2, Ta2O5, Nb2O5, GdO2, La2O3, MgO, Al2O3, and MgAl2O4. Meanwhile, when a support is applied to ensure the uniform dispersion of the active metal, the support can significantly affect the performance of the catalyst, and the support can improve the stability of the catalyst by interacting with the active metal.

[0010] Among the supports, magnesium aluminate (MgAl2O4) is a material with high chemical stability, mechanical strength, and thermal shock resistance. In particular, due to its high melting point, it is difficult to sinter, so it is expected that problems caused by sintering can be solved when applied to a dry methane catalyst.

[0011] Non-patent document 1 (Meso-porous Ni / Mg / Al catalysts for methane reforming with CO2) discloses Ni / MgxAlyOz as a catalyst for dry methane reforming reactions. It discloses that the catalyst improves the dispersion of Ni through strong interactions between Ni and Al-Mg, delays the sintering of Ni during the reforming process, and that the highly dispersed Ni promotes increased CO2 adsorption and CH4 decomposition, resulting in lower coke formation and higher catalytic reaction stability. However, the above-mentioned non-patent document 1 was manufactured by a co-precipitation method, which has a somewhat complex manufacturing process and had limitations in that it was applicable only to dry methane reforming reactions using carbon dioxide.

[0012] Meanwhile, catalysts for methane reforming reactions can be prepared by various methods such as co-precipitation, sol-gel processes, and molten salt synthesis methods, and the ratio of each component of the catalyst may differ, and there may be significant differences in catalytic activity depending on these differences.

[0013] Patent Document 1 (Korean Registered Patent Publication No. 10-1594901) relates to a catalyst for methane composite reforming using steam and carbon dioxide, comprising a carrier having a spinel structure of MgAl2O4-NiAl2O4, a nickel catalyst supported on said carrier, and cerium oxide (CeO2). x It is disclosed that the catalyst comprises a co-catalyst (where x is a rational number from 15 to 2), and the carrier is a mixture of MgAl2O4 nanoparticles and NiAl2O4 nanoparticles or a solid solution containing MgAl2O4 and NiAl2O4, thereby supporting nickel in a highly dispersed manner while solving the coking problem caused by the growth of nickel metal, thereby improving catalytic activity and long-term stability, and simplifying the process by manufacturing the catalyst without using water.

[0014] However, in the case of the above catalyst, the problem of nickel high dispersion and coking is solved only by the spinel structure of MgAl2O4-NiAl2O4, so there is a limitation that the effect of Patent Document 1 cannot be achieved with only the MgAl2O4 support.

[0015] Accordingly, the present invention provides a method for manufacturing a catalyst for methane composite reforming with a novel composition that improves hydrogen yield by effectively converting methane by preventing carbon deposition and sintering of the catalyst, as well as reforming methane with a composite component of steam and carbon dioxide by preparing Ni / MgAl2O4 using a solvent deficient precipitation (SDP) method containing nickel (Ni) and magnesium aluminate (MgAl2O4).

[0016] [Prior Art Literature]

[0017] (Patent Document 1) Republic of Korea Registered Patent Publication No. 10-1594901

[0018] (Non-patent Document 1) The evaluation of autothermal methane reforming for hydrogen production over Ni / CeO-2 catalysts (International Journal of Hydrogen Energy, Volume 43, Issue 49, 6 December 2018, Pages 22340-22346)

[0019]

[0020] One objective of the present invention is to provide a method for manufacturing a hydrocarbon composite reforming catalyst that exhibits excellent catalytic activity during the hydrocarbon composite reforming reaction, resulting in excellent hydrocarbon conversion rates and carbon monoxide conversion rates, and excellent resistance to carbon deposition.

[0021] Another objective of the present invention is to provide a method for manufacturing a hydrocarbon composite reforming catalyst having excellent catalytic activity and stability even during long-term operation.

[0022] Another objective of the present invention is to provide a method for manufacturing a hydrocarbon composite reforming catalyst with excellent eco-friendliness, economic efficiency, and productivity.

[0023] Another objective of the present invention is to provide a method for manufacturing a hydrocarbon composite reforming catalyst that has excellent durability and excellent bonding strength and dispersibility between its constituent components.

[0024] Another objective of the present invention is to provide a method for manufacturing a hydrocarbon composite reforming catalyst capable of controlling H2 / CO in synthesis gas during a hydrocarbon composite reforming reaction.

[0025] Another objective of the present invention is to provide a hydrocarbon composite reforming catalyst produced by the above-described method for producing a hydrocarbon composite reforming catalyst.

[0026] Another objective of the present invention is to provide a method for complex hydrocarbon reforming using the above-described hydrocarbon complex reforming catalyst.

[0027]

[0028] One aspect of the present invention relates to a method for manufacturing a hydrocarbon composite reforming catalyst. In one embodiment, the method for manufacturing the hydrocarbon composite reforming catalyst comprises the steps of: preparing a mixture by solvent-deficient precipitation (SDP) of an aluminum precursor, an active metal precursor, a magnesium precursor, and a basic precipitating agent; and calcining the mixture.

[0029] In one embodiment, the basic precipitating agent may include one or more of ammonium carbonate, ammonium bicarbonate, alkylammonium carbonate, alkylammonium bicarbonate, ammonium hydroxide, sodium bicarbonate, and sodium carbonate.

[0030] In one embodiment, the mixture may be in the form of a gel or dough.

[0031] In one embodiment, the mixture may comprise 100 parts by weight of the aluminum precursor, 1 to 60 parts by weight of the active metal precursor, 5 to 150 parts by weight of the magnesium precursor, and 30 to 160 parts by weight of the basic precipitating agent.

[0032] In one embodiment, the mixture may contain the magnesium precursor, the basic precipitating agent, and the aluminum precursor in a weight ratio of 1:0.5 to 4:1 to 4.

[0033] In one embodiment, the above firing can be carried out at 300 to 1000°C.

[0034] The above active metal precursor may include one or more metal precursors selected from nickel (Ni), vanadium (V), chromium (Cr), cobalt (Co), platinum (Pt), palladium (Pd), copper (Cu), molybdenum (Mo), gold (Au), silver (Ag), zinc (Zn), rhodium (Rh), and ruthenium (Ru).

[0035] In one embodiment, the calcined product may comprise a porous support comprising magnesium aluminate (MgAl2O4) and an active metal dispersed in the support.

[0036] In one embodiment, the sintered product may comprise 70 to 99 weight percent of a support and 1 to 30 weight percent of an active metal.

[0037] In one embodiment, prior to the step of calcining the mixture, the step of drying the mixture at 50 to 150°C may be further included.

[0038] Another aspect of the present invention relates to a hydrocarbon composite reforming catalyst produced by the above-described method for producing a hydrocarbon composite reforming catalyst.

[0039] In one embodiment, the hydrocarbon composite reforming catalyst comprises a porous support comprising magnesium aluminate (MgAl2O4); and an active metal dispersed in the support.

[0040] In one embodiment, the hydrocarbon composite reforming catalyst may comprise 70 to 99 weight% of a support and 1 to 30 weight% of an active metal.

[0041] In one embodiment, the active metal may include one or more of nickel (Ni), vanadium (V), chromium (Cr), cobalt (Co), platinum (Pt), palladium (Pd), copper (Cu), molybdenum (Mo), gold (Au), silver (Ag), zinc (Zn), rhodium (Rh), and ruthenium (Ru).

[0042] In one embodiment, the hydrocarbon composite reforming catalyst may have a methane (CH4) conversion rate of 63% or more and a carbon dioxide (CO2) conversion rate of 70% or more at a reaction temperature of 800°C during the hydrocarbon composite reforming reaction.

[0043] Another aspect of the present invention relates to a method for complex hydrocarbon reforming using the hydrocarbon complex reforming catalyst. In one embodiment, the method for complex hydrocarbon reforming comprises: a step of reducing the hydrocarbon complex reforming catalyst in a hydrogen (H2) gas atmosphere; and a step of carrying out a complex reforming reaction of a hydrocarbon in the presence of the reduced hydrocarbon complex reforming catalyst to produce a synthesis gas containing hydrogen (H2) and carbon monoxide (CO).

[0044] In one embodiment, the hydrocarbon complex reforming reaction can be carried out at a reaction temperature of 750 to 900°C while maintaining methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.1 to 10:0.1 to 5:0.1 to 10.

[0045] In one embodiment, the hydrocarbon composite reforming reaction may have a methane (CH4) conversion rate of 63% or more and a carbon dioxide (CO2) conversion rate of 70% or more at a reaction temperature of 800°C.

[0046]

[0047] When the method for manufacturing a hydrocarbon composite reforming catalyst according to the present invention and the composite reforming catalyst manufactured thereby are applied, the catalyst activity during the hydrocarbon composite reforming reaction is excellent, resulting in excellent hydrocarbon conversion rate and carbon monoxide conversion rate; the catalyst activity and stability are excellent even during long-term operation; the catalyst exhibits excellent eco-friendliness, economic efficiency, and productivity; the catalyst exhibits excellent durability; the bonding strength and dispersibility between constituent components are excellent; and the H2 / CO ratio in the synthesis gas during the hydrocarbon composite reforming reaction can be controlled.

[0048] In particular, by preparing the catalyst using the SDP method, the present invention can not only improve process efficiency but also enable mass production, increase the dispersion of the active metal, and strengthen the interaction between the active metal and the support. Accordingly, the durability of the catalyst and the methane complex reforming reaction can be enhanced through the defect structure present on the catalyst surface.

[0049] In addition, the catalyst prepared according to the present invention has the advantage of reducing greenhouse gas emissions compared to conventional wet reforming reactions using only steam, compared to hydrocarbon reforming reactions using only steam or carbon dioxide as a reformer, and can mitigate carbon deposition occurring in dry reforming by adding steam, and can control the H2 / CO ratio in the synthesis gas.

[0050] Therefore, when using the catalyst of the present invention, the methane conversion rate is high and long-term operation is possible.

[0051]

[0052] Figure 1 is a graph showing the hydrogen and carbon monoxide conversion rates and the hydrogen / carbon monoxide ratio during a hydrocarbon composite reforming reaction using examples and comparative examples.

[0053]

[0054] In describing the present invention, if it is determined that a detailed description of related known technologies or configurations could unnecessarily obscure the essence of the invention, such detailed description will be omitted.

[0055] Furthermore, the terms described below are defined in consideration of their functions in the present invention; since these may vary depending on the intentions or practices of the user or operator, their definitions should be based on the content throughout this specification describing the present invention.

[0056]

[0057] Method for manufacturing a hydrocarbon composite reforming catalyst

[0058] One aspect of the present invention relates to a method for manufacturing a hydrocarbon composite reforming catalyst (or a method for manufacturing a composite reforming catalyst). In one embodiment, the method for manufacturing a hydrocarbon composite reforming catalyst comprises (S10) a step of preparing a mixture; and (S20) a step of calcination.

[0059] More specifically, the method for manufacturing the hydrocarbon composite reforming catalyst comprises: (S10) a step of preparing a mixture by solvent-deficient precipitation (SDP) of an aluminum precursor, an active metal precursor, a magnesium precursor, and a basic precipitating agent; and (S20) a step of calcining the mixture.

[0060] Hereinafter, the method for manufacturing the above-mentioned hydrocarbon composite reforming catalyst will be explained in detail step by step.

[0061]

[0062] (S10) Mixture preparation step

[0063] The above step is to prepare a mixture by solvent-deficient precipitation (SDP) of an aluminum precursor, an active metal precursor, a magnesium precursor, and a basic precipitating agent.

[0064] In one embodiment, the mixture may not contain a solvent. Solvent Deficient Precipitation (SDP) is a method of preparing a mixture without adding a solvent, which allows for the preparation of a catalyst in a shorter time compared to other synthesis methods, enables mass production, increases the dispersion of the active metal on the support, and strengthens the interaction between the active metal and the support. Accordingly, the prepared composite reforming catalyst exhibits excellent durability, and the methane composite reforming reaction can be enhanced by the defect structure present on the surface of the composite reforming catalyst.

[0065] In one embodiment, the aluminum precursor may include one or more of aluminum nitrate nonahydrate (Al(NO3)3·9H2O), aluminum chloride (AlCl3), aluminum chloride hexahydrate (AlCl3·6H2O), aluminum hydroxide hydrate (Al(OH)3·xH2O), aluminum sulfate hydrate (Al2(SO4)3·xH2O), and aluminum ammonium sulfate dodecabahydrate (AlNH4(SO4)2·12H2O). When the aluminum precursor is included, the miscibility and dispersibility are excellent, and the mixture can be prepared without the use of a solvent, so a porous support containing magnesium aluminate can be easily formed through a solvent-deficient precipitation method.

[0066] In one embodiment, the active metal precursor may include a precursor of one or more metals selected from nickel (Ni), vanadium (V), chromium (Cr), cobalt (Co), platinum (Pt), palladium (Pd), copper (Cu), molybdenum (Mo), gold (Au), silver (Ag), zinc (Zn), rhodium (Rh), and ruthenium (Ru).

[0067] The active metal precursor may include one or more of active metal nitrate hydrate, active metal sulfate hydrate, and active metal chloride hydrate. When the active metal precursor is included, the miscibility and dispersibility are excellent, and the mixture can be prepared without the use of a solvent, so a composite reforming catalyst can be easily formed through a solvent-deficient precipitation method. For example, the active metal precursor may include a metal nitrate. For example, the metal (active metal) may include nickel (Ni). The nickel precursor may include one or more of nickel nitrate hexahydrate (Ni(NO3)2·6H2O), nickel nitrate tetrahydrate (Ni(NO3)2·4H2O), nickel sulfate heptahydrate (NiSO4·7H2O), nickel sulfate hexahydrate (NiSO4·6H2O), and nickel chloride hexahydrate (NiCl2·6H2O).

[0068] In one embodiment, the active metal precursor may be included in an amount of 1 to 60 parts by weight per 100 parts by weight of the aluminum precursor. When included under the above content conditions, sufficient activity can be exhibited during the complex reforming reaction of hydrocarbons while preventing aggregation of the active metal, and when preparing a mixture through the solvent deficiency precipitation (SDP) process, the active metal particles are fined and the degree of dispersion is improved, thereby further enhancing catalytic activity. For example, the active metal precursor may be included in an amount of 1 to 50 parts by weight, 1 to 40 parts by weight, 3 to 30 parts by weight, 3 to 20 parts by weight, or 3 to 15 parts by weight.

[0069] For example, the active metal precursor comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 56, 57, 58, with respect to 100 parts by weight of the aluminum precursor. It may contain 59 or 60 parts by weight.

[0070] In one embodiment, the magnesium (Mg) precursor may include one or more of magnesium acetate tetrahydrate (Mg(CH3COO)2·4H2O), magnesium chloride tetrahydrate (MgCl2·4H2O), magnesium nitrate hexahydrate (Mg(NO3)2·6H2O), magnesium carbonate hydrate (MgCO3·xH2O), magnesium hydroxide (Mg(OH)2), magnesium sulfate heptahydrate (MgSO4·7H2O), magnesium sulfate hydrate (MgSO4·H2O), magnesium sulfate (MgSO4), magnesium bromide (MgBr2), and magnesium iodide (MgI2). When the magnesium precursor is included, the miscibility and dispersibility are excellent, and the mixture can be prepared without the use of a solvent, so a porous support containing magnesium aluminate can be easily formed through a solvent-deficient precipitation method.

[0071] In one embodiment, the magnesium precursor may be included in an amount of 5 to 150 parts by weight per 100 parts by weight of the aluminum precursor. When included under the above content conditions, the mixability and dispersibility are excellent, and carbon deposition and sintering phenomena of the manufactured composite reforming catalyst are prevented, thereby enabling high catalytic activity for a long time and improving the hydrocarbon conversion rate. For example, the magnesium precursor may be included in an amount of 10 to 130 parts by weight, 20 to 110 parts by weight, 20 to 90 parts by weight, 20 to 80 parts by weight, 25 to 70 parts by weight, 30 to 60 parts by weight, 30 to 50 parts by weight, or 30 to 45 parts by weight.

[0072] For example, the magnesium precursor comprises 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 56, 57, 58, 59, 60, 61, with respect to 100 parts by weight of the aluminum precursor. 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, It may include 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, or 150 parts by weight.

[0073] In one embodiment, the basic precipitating agent may include one or more of ammonium carbonate, ammonium bicarbonate, alkylammonium carbonate, alkylammonium bicarbonate, ammonium hydroxide, sodium bicarbonate, and sodium carbonate. When the basic precipitating agent is included, the miscibility and dispersibility are excellent, and the mixture can be prepared without the use of a solvent. Therefore, the precursors can be precipitated in a solvent-free state due to the basic precipitating agent, and a composite modified catalyst can be easily formed through a solvent-deficient precipitation method.

[0074] In one embodiment, the basic precipitating agent may be included in an amount of 30 to 160 parts by weight per 100 parts by weight of the aluminum precursor. When included under the above content conditions, the miscibility and dispersibility are excellent, and the precursors may precipitate in the absence of a solvent due to the basic precipitating agent. Furthermore, the composite reforming catalyst can be easily prepared through the solvent-deficient precipitation method, and the durability and catalytic activity of the composite reforming catalyst may be excellent. For example, the basic precipitating agent may be included in an amount of 40 to 140 parts by weight, 40 to 120 parts by weight, 60 to 100 parts by weight, 70 to 100 parts by weight, or 80 to 95 parts by weight.

[0075] In one embodiment, the basic precipitating agent comprises 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, with respect to 100 parts by weight of the aluminum precursor. 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, It may include 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, or 160 parts by weight.

[0076] In one embodiment, the mixture may contain the magnesium precursor, the basic precipitating agent, and the aluminum precursor in a weight ratio of 1:0.5 to 4:1 to 4. When included under the above weight ratio conditions, the miscibility and dispersibility are excellent, and the mixture can be prepared without the use of a solvent, allowing the composite reforming catalyst to be easily prepared through a solvent-deficient precipitation method, and the durability and catalytic activity of the composite reforming catalyst may be excellent. For example, the mixture may contain the magnesium precursor, the basic precipitating agent, and the aluminum precursor in a weight ratio of 1:1 to 3:1 to 4, a weight ratio of 1:2 to 3:1 to 3, or a weight ratio of 1:2 to 3:2.5 to 3.5.

[0077] In one embodiment, the mixture may be prepared by grinding and uniformly mixing an aluminum precursor, an active metal precursor, a magnesium precursor, and a basic precipitating agent. The mixture may be prepared by mixing the aforementioned components until they become a gel or paste, and by dry grinding and mixing using a ball mill and a mortar and pestle to finely refine the particles and increase the degree of dispersion.

[0078] The above aluminum precursor, active metal precursor, magnesium precursor, and basic precipitant may change from a solid to a liquid state during the grinding and mixing, and then undergo a phase change back to a solid state to produce a mixture. For example, the mixture may be in the form of a gel or dough.

[0079] In one embodiment, the mixing may be carried out at 10 to 50°C. Under these conditions, the mixability and dispersibility are excellent, so a mixture in the form of a gel or dough can be easily formed.

[0080] In one embodiment, prior to the step of calcining the mixture, the step of drying the mixture at 50 to 150°C may be further included. During the drying, the crystal water contained in the precursor component can be easily removed to enable the formation of intermediate nanoparticles. The drying can be performed by conventional methods and is not limited to the following, but as examples, room temperature, oven, and hot air drying may be used.

[0081]

[0082] (S20) Sintering stage

[0083] The above step is a step of preparing a sintered product by calcining the above mixture. In one embodiment, the calcination may be carried out at 300 to 1000°C. Under these conditions, a sintered product in which an active metal is dispersed and supported on a magnesium aluminate support can be easily prepared. For example, the calcination may be carried out at 750 to 900°C for 1 to 8 hours.

[0084] In one embodiment, the calcined product may comprise a porous support comprising magnesium aluminate (MgAl2O4) and an active metal dispersed in the support.

[0085] In one embodiment, the active metal may include one or more of nickel (Ni), vanadium (V), chromium (Cr), cobalt (Co), platinum (Pt), palladium (Pd), copper (Cu), molybdenum (Mo), gold (Au), silver (Ag), zinc (Zn), rhodium (Rh), and ruthenium (Ru).

[0086] In one embodiment, the calcined product may comprise 70 to 99 weight percent of a support and 1 to 30 weight percent of an active metal. Under these conditions, the interaction between the support and the active metal is enhanced, which prevents carbon deposition during the composite reforming reaction and improves the durability of the composite reforming catalyst of the present invention, and allows for high activity in methane composite reforming by steam and carbon dioxide reformers due to the defect structure present on the catalyst surface.

[0087] For example, the above-mentioned sintered product may contain 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 weight percent of the support based on the total weight.

[0088] For example, the above-mentioned calcined product may contain 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 weight percent of the active metal based on the total weight.

[0089] In one embodiment, the support may have an average pore size of 20 to 70 nm. The size may be the maximum length or diameter of the pores. Under these conditions, the high-temperature coke deposition resistance may be excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support may have an average pore size of 35 to 60 nm.

[0090] In one embodiment, the support has a specific surface area (BET) of 70 m² 2 It may be greater than / g. Under the above conditions, high-temperature coke deposition resistance is excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support has a specific surface area (BET) of 70 to 150 m² 2 / g or 75~95m 2 / g can be.

[0091] In one embodiment, the support has a total pore volume of 0.20 cm³ 3 It may be greater than / g. Under the above conditions, durability and resistance to high-temperature coke deposition are excellent, the modification catalyst activity is excellent, and the thermal stability of the modification catalyst may be excellent. For example, the support has a pore volume of 0.20 to 0.50 cm³ 3 / g or 0.30~0.45cm 3 It can be / g.

[0092]

[0093] Hydrocarbon composite reforming catalyst produced by the method for producing a hydrocarbon composite reforming catalyst

[0094] Another aspect of the present invention relates to a hydrocarbon composite reforming catalyst produced by the above-described method for producing a hydrocarbon composite reforming catalyst.

[0095] In one embodiment, the hydrocarbon composite reforming catalyst comprises a porous support comprising magnesium aluminate (MgAl2O4); and an active metal dispersed in the support.

[0096] In one embodiment, the hydrocarbon composite reforming catalyst may comprise 70 to 99 weight% of a support and 1 to 30 weight% of an active metal.

[0097] In one embodiment, the hydrocarbon composite reforming catalyst may contain 70 to 99 weight percent of the support based on the total weight. When included within this content range, the resistance to coke deposition is excellent, resulting in excellent catalyst activity and hydrocarbon and carbon dioxide conversion rates, as well as excellent durability. For example, the support may be included in an amount of 75 to 99 weight percent, 80 to 99 weight percent, 85 to 99 weight percent, 90 to 99 weight percent, or 92 to 99 weight percent. For example, the hydrocarbon composite reforming catalyst may contain 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 weight percent of the support based on the total weight.

[0098] In one embodiment, the active metal may include one or more of nickel (Ni), vanadium (V), chromium (Cr), cobalt (Co), platinum (Pt), palladium (Pd), copper (Cu), molybdenum (Mo), gold (Au), silver (Ag), zinc (Zn), rhodium (Rh), and ruthenium (Ru). When the active metal is included, reactivity and high-temperature thermal stability are excellent, and the durability of the catalyst may be excellent. For example, the active metal may include nickel.

[0099] In one embodiment, the hydrocarbon composite reforming catalyst may contain 1 to 30 weight percent of the active metal based on the total weight of the hydrocarbon composite reforming catalyst. When included within this content range, reactivity and high-temperature thermal stability are excellent, and the durability of the catalyst may be excellent. For example, the active metal may be included in 1 to 25 weight percent, 1 to 20 weight percent, 1 to 15 weight percent, 1 to 10 weight percent, or 1 to 8 weight percent. For example, the hydrocarbon composite reforming catalyst may contain 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 weight percent of the active metal based on the total weight.

[0100] In one embodiment, the support may have an average pore size of 20 to 70 nm. The size may be the maximum length or diameter of the pores. Under these conditions, the high-temperature coke deposition resistance may be excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support may have an average pore size of 35 to 60 nm.

[0101] In one embodiment, the support has a specific surface area (BET) of 70 m² 2 It may be greater than / g. Under the above conditions, high-temperature coke deposition resistance is excellent, and the composite reforming catalyst activity and durability may be excellent. For example, the support has a specific surface area (BET) of 70 to 150 m² 2 / g or 75~95m2 / g can be.

[0102] In one embodiment, the support has a total pore volume of 0.20 cm³ 3 It may be greater than / g. Under the above conditions, durability and resistance to high-temperature coke deposition are excellent, the modification catalyst activity is excellent, and the thermal stability of the modification catalyst may be excellent. For example, the support has a pore volume of 0.20 to 0.50 cm³ 3 / g or 0.30~0.45cm 3 It can be / g.

[0103] In one embodiment, the hydrocarbon composite reforming catalyst has a total pore volume of 0.01 to 0.10 cm³ 3 It may be / g. Under the above conditions, durability and resistance to high-temperature coke deposition are excellent, reforming catalyst activity is excellent, and the thermal stability of the reforming catalyst may be excellent. For example, the hydrocarbon composite reforming catalyst has a total pore volume of 0.01 to 0.06 cm³ 3 / g can be.

[0104] In one embodiment, the hydrocarbon composite reforming catalyst has a specific surface area (BET) of 1 m² 2 It may be greater than / g. Under the above conditions, high-temperature coke deposition resistance is excellent, and the activity and durability of the composite reforming catalyst may be excellent. For example, the hydrocarbon composite reforming catalyst has a specific surface area (BET) of 1 to 10 m² 2 / g or 2~8m 2 / g can be.

[0105] In one embodiment, the hydrocarbon composite reforming catalyst may have a methane (CH4) conversion rate of 63% or more and a carbon dioxide (CO2) conversion rate of 70% or more at a reaction temperature of 800°C during a hydrocarbon composite reforming reaction. Under the above conditions, the methane and carbon dioxide conversion rates of the composite reforming catalyst may be excellent. For example, the carbon dioxide composite reforming catalyst may have a methane (CH4) conversion rate of 63-70%, 63-68%, or 65-68% and a carbon dioxide (CO2) conversion rate of 70-80%, 70-78%, or 70-75% at a reaction temperature of 800°C during a hydrocarbon composite reforming reaction using carbon dioxide and water vapor (H2O).

[0106] In one embodiment, the hydrocarbon composite reforming reaction using the hydrocarbon composite reforming catalyst may have a hydrogen / carbon monoxide (H2 / CO) molar ratio of 1.5 to 3.5 at a reaction temperature of 800°C. Under these conditions, the catalytic activity and the conversion rate of hydrocarbons and carbon dioxide may be excellent. For example, it may be 1.8 to 2.5.

[0107] When the method for manufacturing a hydrocarbon composite reforming catalyst according to the present invention and the composite reforming catalyst manufactured thereby are applied, the catalyst activity during the hydrocarbon composite reforming reaction is excellent, resulting in excellent hydrocarbon conversion rate and carbon monoxide conversion rate; the catalyst activity and stability are excellent even during long-term operation; the catalyst exhibits excellent eco-friendliness, economic efficiency, and productivity; the catalyst exhibits excellent durability; the bonding strength and dispersibility between constituent components are excellent; and the H2 / CO ratio in the synthesis gas during the hydrocarbon composite reforming reaction can be controlled.

[0108] In particular, by preparing the catalyst using the SDP method, the present invention can not only improve process efficiency but also enable mass production, increase the dispersion of the active metal, and strengthen the interaction between the active metal and the support. Accordingly, the durability of the catalyst and the methane complex reforming reaction can be enhanced through the defect structure present on the catalyst surface.

[0109] In addition, the catalyst prepared according to the present invention has the advantage of reducing greenhouse gas emissions compared to conventional wet reforming reactions using only steam, compared to hydrocarbon reforming reactions using only steam or carbon dioxide as a reformer, and can mitigate carbon deposition occurring in dry reforming by adding steam, and can control the H2 / CO ratio in the synthesis gas.

[0110] Therefore, when using the catalyst of the present invention, the methane conversion rate is high and long-term operation is possible.

[0111]

[0112] Hydrocarbon composite reforming method using a hydrocarbon composite reforming catalyst

[0113] Another aspect of the present invention relates to a method for complex hydrocarbon reforming using the hydrocarbon complex reforming catalyst. In one embodiment, the method for complex hydrocarbon reforming comprises: a step of reducing the hydrocarbon complex reforming catalyst in a hydrogen (H2) gas atmosphere; and a step of carrying out a complex reforming reaction of a hydrocarbon in the presence of the reduced hydrocarbon complex reforming catalyst to produce a synthesis gas containing hydrogen (H2) and carbon monoxide (CO).

[0114] The above hydrocarbon composite reforming method can produce high-value gases, such as hydrogen and carbon monoxide, through a thermocatalytic reaction with methane and steam using carbon dioxide and steam (H2O) as reformers, by utilizing the above composite reforming catalyst.

[0115] In one embodiment, the reduction can be carried out at 700 to 900°C in the mixed gas atmosphere. Under these conditions, catalytic activity may be excellent.

[0116] The above synthesis gas may include methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2).

[0117] In one embodiment, the hydrocarbon complex reforming reaction can be carried out at a reaction temperature of 750 to 900°C while maintaining methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.1 to 10:0.1 to 5:0.1 to 10. Under these conditions, the catalytic activity is excellent, resulting in an excellent carbon dioxide conversion rate and excellent resistance to carbon deposition on the catalyst. For example, the hydrocarbon complex reforming reaction can be carried out while maintaining methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.2 to 1 to 0.5 to 2:0.1 to 1.

[0118] In one embodiment, the hydrocarbon complex reforming reaction may supply synthesis gas containing methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) while maintaining a space velocity (GHSV) of 20,000 to 80,000 / h. Under these conditions, the catalyst and reaction performance are excellent, so the conversion rate of carbon dioxide and hydrocarbons may be excellent.

[0119] In one embodiment, the hydrocarbon composite reforming reaction using the hydrocarbon composite reforming catalyst may have a methane (CH4) conversion rate of 63% or more and a carbon dioxide (CO2) conversion rate of 70% or more at a reaction temperature of 800°C. Under the above conditions, the methane and carbon dioxide conversion rates of the composite reforming catalyst may be excellent. For example, the carbon dioxide composite reforming catalyst may have a methane (CH4) conversion rate of 63-70%, 63-68%, or 65-68% and a carbon dioxide (CO2) conversion rate of 70-80%, 70-78%, or 70-75% at a reaction temperature of 800°C during a hydrocarbon composite reforming reaction using carbon dioxide and water vapor (H2O).

[0120] In one embodiment, the hydrocarbon composite reforming reaction using the hydrocarbon composite reforming catalyst may have a hydrogen / carbon monoxide (H2 / CO) molar ratio of 1.5 to 3.5 at a reaction temperature of 800°C. Under these conditions, the catalytic activity and the conversion rate of hydrocarbons and carbon dioxide may be excellent. For example, it may be 1.8 to 2.3.

[0121]

[0122] Hereinafter, the structure and operation of the present invention will be explained in more detail through preferred embodiments of the present invention. However, the following embodiments are intended to aid in understanding the present invention, and the scope of the present invention is not limited to the following embodiments.

[0123]

[0124] Examples and Comparative Examples

[0125] Examples

[0126] (1) Preparation of mixture: 27.00 g of aluminum precursor (Al(NO3)3·9H2O), 1.338 g of active metal precursor (Ni(NO3)2·6H2O), and 9.231 g of magnesium precursor (Mg(NO3)2·6H2O) were mixed with 23.50 g of basic precipitating agent (ammonium bicarbonate, NH4HCO3) without solvent and prepared by solvent-deficient precipitation (SDP). Specifically, the above precursor components were ground and mixed in a mortar at room temperature for 30 minutes to prepare a gel-type (wet gel) mixture.

[0127] (2) Calcination of mixture: The mixture was transferred to a crucible and calcined at 800°C for 6 hours under static air conditions to produce a calcined product. The calcined product (composite reforming catalyst) contained 95-99 wt% of a porous support containing magnesium aluminate (MgAl2O4) and 1-5 wt% of an active metal (nickel) dispersed in the support.

[0128]

[0129] Comparative Example 1

[0130] Catalyst preparation by co-precipitation: To prepare a catalyst by co-precipitation, 27.00 g of aluminum precursor (Al(NO3)3·9H2O), 1.338 g of active metal precursor (Ni(NO3)2·6H2O), and 9.231 g of magnesium precursor (Mg(NO3)2·6H2O) were added to 200 cc of distilled water and stirred at room temperature to produce a mixed solution. Subsequently, a 28% aqueous ammonia solution was added to the mixed solution, the pH was adjusted to 10, and the temperature of the mixed solution was raised to 50°C and aged for 20 hours. The sample collected after aging was filtered and washed with distilled water, and then dried at 100°C for about 12 hours. Afterward, the dried sample was transferred to a crucible and calcined in air at 800°C for 6 hours to produce a calcined product (composite reforming catalyst).

[0131]

[0132] Comparative Example 2

[0133] Catalyst preparation by sol-gel method: To prepare a catalyst by the sol-gel method, 27.00 g of aluminum precursor (Al(NO3)3·9H2O), 1.338 g of active metal precursor (Ni(NO3)2·6H2O), 9.231 g of magnesium precursor (Mg(NO3)2·6H2O), and 23.80 g of citric acid were added to 200 cc of distilled water and stirred at room temperature for 1 hour to prepare a mixed composition. Then, the mixed composition was evaporated and dried at 80°C until it became a gel type, and then the dried material was transferred to an oven and further dried at 110°C for about 12 hours. The additionally dried material was transferred to a crucible and pre-calcined in air at 270°C, and then the temperature was raised to 800°C and calcined for 6 hours to prepare a calcined product (composite reforming catalyst).

[0134]

[0135] Experimental Example

[0136] Evaluation of H2 and CO2 conversion rates during hydrocarbon complex reforming reaction: For the above examples and comparative examples, the H2 and CO2 conversion rates were evaluated using the following complex reforming reaction system (catalyst performance evaluation device).

[0137] Specifically, Examples 1 and 4 and Comparative Examples 1 and 2 were loaded into a quartz tube to a height of 1.7 cm in a reactor of a combined reforming reaction system (a fixed-bed reactor equipped with a 1 / 4-inch quartz tube). Then, the loaded catalysts of the Examples and Comparative Examples were reduced for 1 hour under a hydrogen atmosphere (100% H2) at 800°C, and then a methane / carbon dioxide combined reforming reaction was performed.

[0138] In addition, the gas mixture for the above-mentioned complex reforming reaction consisted of methane (CH4), carbon dioxide (CO2), steam (moisture) (H2O), and nitrogen (N2) supplied in a molar ratio of 1:0.33:0.67:0.22 using a mass flow control (MFC) and a syringe pump, and the reaction was carried out by homogeneously mixing in a mixing chamber. The complex reforming reaction was conducted for 15 hours under conditions of a reaction temperature of 800°C and a space velocity (GHSV) of 50,000 / h. The reaction gas, unreacted gas, and steam generated after passing through the reactor loaded with the catalyst were used for steam condensation through a trap set to -5°C, and the gas after the reaction was measured using a gas chromatography (GC) system (YL6500) equipped with a thermal conductivity detector (TCD). Excluding the initial reaction destabilization time, the average results of the hydrogen and carbon monoxide conversion rates during the complex reforming reaction time are shown in Figure 1 below.

[0139] Figure 1 is a graph showing the hydrogen and carbon monoxide conversion rates and the hydrogen / carbon monoxide ratio during a hydrocarbon composite reforming reaction using the example and comparative example. Referring to the results in Figure 1, it was confirmed that the example showed superior conversion rates of methane and carbon dioxide at the methane composite reforming reaction temperature (800°C) compared to Comparative Example 1, which was prepared using the co-precipitation method, and Comparative Example 2, which was prepared using the sol-gel method.

[0140]

[0141] The present invention has been described above with reference to embodiments. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the invention.

Claims

1. A step of preparing a mixture by solvent deficiency precipitation (SDP) of an aluminum precursor, an active metal precursor, a magnesium precursor, and a basic precipitating agent; and A method for manufacturing a hydrocarbon composite reforming catalyst comprising the step of calcining the above mixture.

2. A method for preparing a hydrocarbon composite reforming catalyst according to claim 1, wherein the basic precipitating agent comprises one or more of ammonium carbonate, ammonium bicarbonate, alkylammonium carbonate, alkylammonium bicarbonate, ammonium hydroxide, sodium bicarbonate, and sodium carbonate.

3. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 1, wherein the mixture is in the form of a gel or dough.

4. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 1, wherein the mixture comprises 100 parts by weight of the aluminum precursor, 1 to 60 parts by weight of the active metal precursor, 5 to 150 parts by weight of the magnesium precursor, and 30 to 160 parts by weight of the basic precipitating agent.

5. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 4, wherein the mixture comprises the magnesium precursor, the basic precipitating agent, and the aluminum precursor in a weight ratio of 1:0.5 to 4:1 to 4.

6. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 1, wherein the calcination is carried out at 300 to 1000°C.

7. A method for preparing a hydrocarbon composite reforming catalyst according to claim 1, wherein the active metal precursor comprises one or more metal precursors selected from nickel (Ni), vanadium (V), chromium (Cr), cobalt (Co), platinum (Pt), palladium (Pd), copper (Cu), molybdenum (Mo), gold (Au), silver (Ag), zinc (Zn), rhodium (Rh), and ruthenium (Ru).

8. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 1, wherein the calcined product comprises a porous support comprising magnesium aluminate (MgAl2O4) and an active metal dispersed in the support.

9. A method for manufacturing a hydrocarbon composite reforming catalyst according to claim 8, wherein the calcined product comprises 70 to 99 weight% of a support and 1 to 30 weight% of an active metal.

10. In claim 1, prior to the step of calcining the mixture, A method for manufacturing a hydrocarbon composite reforming catalyst, further comprising the step of drying the above mixture at 50 to 150°C.

11. A hydrocarbon composite reforming catalyst produced by a method for producing a hydrocarbon composite reforming catalyst according to any one of claims 1 to 10.

12. A porous support comprising magnesium aluminate (MgAl2O4); and A hydrocarbon composite reforming catalyst comprising an active metal dispersed in the above support.

13. In claim 12, the hydrocarbon composite reforming catalyst comprises 70 to 99 weight% of a support and 1 to 30 weight% of an active metal.

14. A hydrocarbon composite reforming catalyst according to claim 13, wherein the active metal comprises one or more of nickel (Ni), vanadium (V), chromium (Cr), cobalt (Co), platinum (Pt), palladium (Pd), copper (Cu), molybdenum (Mo), gold (Au), silver (Ag), zinc (Zn), rhodium (Rh), and ruthenium (Ru).

15. In paragraph 12, the hydrocarbon composite reforming catalyst is a hydrocarbon composite reforming catalyst having a methane (CH4) conversion rate of 63% or more and a carbon dioxide (CO2) conversion rate of 70% or more at a reaction temperature of 800℃ during a hydrocarbon composite reforming reaction.

16. A step of reducing the hydrocarbon composite reforming catalyst according to any one of claims 12 to 15 in a hydrogen (H2) gas atmosphere; and A hydrocarbon composite reforming method comprising the step of producing a synthesis gas containing hydrogen (H2) and carbon monoxide (CO) by carrying out a hydrocarbon composite reforming reaction in the presence of the above-mentioned reduced hydrocarbon composite reforming catalyst.

17. A hydrocarbon complex reforming method according to claim 16, wherein the hydrocarbon complex reforming reaction is carried out at a reaction temperature of 750 to 900°C while maintaining methane (CH4), carbon dioxide (CO2), steam (H2O), and nitrogen (N2) in a molar ratio of 1:0.1 to 10:0.1 to 5:0.1 to 10.

18. In paragraph 16, the hydrocarbon complex reforming reaction is a hydrocarbon complex reforming method having a methane (CH4) conversion rate of 63% or more and a carbon dioxide (CO2) conversion rate of 70% or more at a reaction temperature of 800℃.

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