Catalyst

Abstract

Disclosed herein is a catalyst. Disclosed herein is a catalyst capable of effectively producing useful components, for example, useful components (branched olefins and / or isoparaffins, etc.) that can be applied as a fuel, from a raw material containing CO and / or CO 2 or a raw material containing a hydrocarbon compound. Disclosed herein is a catalyst that suppresses the production of unnecessary components (for example, short-chain hydrocarbons or aromatic compounds) and the generation of coke and the like during the production process of the useful components. Disclosed herein is a catalyst that exhibits a high conversion rate and selectivity and is not deactivated during a reaction process.

Description

catalyst

[0001] This application claims the benefit of priority to Republic of Korea Patent Application No. 10-2024-0083431, filed June 26, 2024, the entire contents of which are incorporated herein by reference.

[0002] The present specification discloses a catalyst.

[0003] CO2 emitted during fossil fuel-based energy production is a major contributor to climate change, including global warming. Therefore, various attempts exist to capture and utilize this CO2, with catalytic CO2 hydrogenation being one such approach (Non-patent Document 1). This reaction utilizes methods such as Fischer-Tropsch Synthesis (FTS) and Methanol-to-Olefin (MTO). Methods reported to date can be broadly categorized into two types.

[0004] The first type is a method of producing hydrocarbons such as liquid fuels, olefins, and aromatic compounds through Fischer-Tropsch Synthesis (FTS) followed by the Reverse Water-Gas Shift (RWGS) reaction that converts CO2 to CO using an Fe catalyst (Non-patent Document 2).

[0005] The second type is a method of converting CO2 into methanol using a catalyst (In2O3 or Cu / ZnO / Al2O3 series) and producing high value-added products (e.g. gasoline, etc.) through additional reactions (Non-patent Document 3).

[0006] E-Fuel (Electricity-based fuel) is a liquid hydrocarbon fuel synthesized from captured CO2 and hydrogen electrolyzed from water, representing a future transportation fuel that achieves carbon neutrality. E-fuels contain diverse components, including linear alkanes, branched alkanes, cyclic alkanes, and aromatic compounds. Isoparaffins, in particular, are considered essential components of sustainable E-fuels due to their high stability, low freezing point, and cleaner combustion properties compared to aromatic compounds.

[0007] The FTS pathway exhibits high CO2 conversion and produces long-chain hydrocarbons, but zeolites induce cracking, resulting in the production of short-chain hydrocarbons and aromatic compounds with carbon numbers lower than C12. The methanol-based route effectively produces isoparaffins, but oligomerization is inhibited, carbon chain growth is restricted by zeolites, and the conversion rate is low. The oxygenate-based route has a very low conversion rate.

[0008] Therefore, there is a need to develop a new catalyst capable of producing isoparaffins from CO2.

[0009] <Prior Art Literature>

[0010] <Non-patent literature>

[0011] (비특허문헌 1) Ra, E. C.; Kim, K. Y.; Kim, E. H.; Lee, H.; An, K.; Lee, J. S. Recycling Carbon Dioxide through Catalytic Hydrogenation: Recent Key Developments and Perspectives. ACS Catal. 2020, 10 (19), 11318-11345. DOI: 10.1021 / acscatal.0c02930

[0012] (비특허문헌 2) Choi, Y. H.; Jang, Y. J.; Park, H.; Kim, W. Y.; Lee, Y. H.; Choi, S. H.; Lee, J. S. Carbon Dioxide Fischer-Tropsch Synthesis: A New Path to Carbon-Neutral Fuels. Appl. Catal., B 2017, 202, 605-610, DOI: 10.1016 / j.apcatb.2016.09.072

[0013] (비특허문헌 3) Sharma, P.; Sebastian, J.; Ghosh, S.; Creaser, D.; Olsson, L. Recent Advances in Hydrogenation of CO2 into Hydrocarbons via Methanol Intermediate over Heterogeneous Catalysts. Catal. Sci. Technol. 2021, 11 (5), 1665-1697, DOI: 10.1039 / D0CY01913E

[0014] The present specification discloses a catalyst. The purpose of the present specification is to disclose a catalyst that can effectively produce a useful component, for example, a useful component (such as isoparaffin) that can be used as a fuel, from a raw material containing CO and / or CO2 or a raw material containing a hydrocarbon compound. The purpose of the present specification is to provide a catalyst that suppresses the production of unnecessary components (such as short-chain hydrocarbons or aromatic compounds) and suppresses the generation of coke and the like during the production process of the useful component. The purpose of the present specification is to disclose a catalyst that exhibits high conversion and selectivity and is not deactivated during the reaction process.

[0015] The term room temperature means the natural temperature that is not heated or cooled, and for example, the room temperature referred to herein may be any temperature within the range of about 10°C to 30°C, or a temperature of about 23°C, about 25°C, or about 27°C.

[0016] Among the properties mentioned in this specification, properties that are affected by the measurement temperature are properties measured at room temperature, unless otherwise specified.

[0017] The unit of temperature referred to in this specification is Celsius (℃), unless otherwise specified.

[0018] The term atmospheric pressure refers to the natural pressure that is neither pressurized nor depressurized, and typically atmospheric pressure can mean a pressure of about 730 mmHg to 790 mmHg.

[0019] Among the properties mentioned in this specification, properties that are affected by the measurement pressure are properties measured at atmospheric pressure, unless otherwise specified.

[0020] Among the properties mentioned in this specification, properties affected by measurement humidity are properties measured at standard humidity, unless otherwise specified.

[0021] Standard humidity means a relative humidity within the range of 40% to 60% relative humidity, for example, a relative humidity of about 55% or about 60%.

[0022] As used herein, the term Cn hydrocarbon (where n is any number) means a hydrocarbon compound having n carbon atoms or a mixture of hydrocarbon compounds having n carbon atoms.

[0023] In this specification, the term Cn+ hydrocarbon (n is any number) means a hydrocarbon compound having n or more carbon atoms or a mixture of hydrocarbon compounds having n or more carbon atoms.

[0024] In this specification, the term Cn-m hydrocarbon (n and m are arbitrary numbers, n < m) means a hydrocarbon compound having n to m carbon atoms or a mixture of hydrocarbon compounds having n to m carbon atoms.

[0025] The present specification discloses a catalyst.

[0026] The catalyst may be an isomerization catalyst. For example, the catalyst may be a catalyst capable of promoting the production of branched hydrocarbons (e.g., branched olefins and / or isoparaffins).

[0027] For example, the catalyst can be used to increase the fraction of branched hydrocarbons in hydrocarbons produced using CO2 and / or CO as raw materials. Examples of reactions that produce hydrocarbons using CO2 and / or CO as raw materials include CO2 or CO hydrogenation reactions such as RWGS (Reverse Water-Gas Shift) and / or FTS (Fischer-Tropsch Synthesis) reactions. For example, the catalyst can be involved in a reaction that increases the fraction of branched hydrocarbons in hydrocarbons produced by the hydrogenation reaction. The branched hydrocarbons formed in the above-described reaction may be, for example, branched olefins and / or branched paraffins. Hydrocarbons containing such branched hydrocarbons can be usefully used, for example, as so-called E-fuels.

[0028] The catalyst may include a first metal and a second metal. The first and / or second metal may be included in the catalyst in the form of an oxide. For example, the catalyst may include an oxide of the first metal and an oxide of the second metal.

[0029] The oxide of the first metal may be a support that supports the second metal and / or the oxide of the second metal. The oxide of the second metal may be present in the catalyst together with the oxide of the first metal, which is the support, and may be supported on the support, for example.

[0030] The first metal or the oxide of the first metal above may include a monoclinic phase or a tetragonal phase crystal, and the second metal or the oxide of the second metal may include an amorphous phase or a monoclinic phase crystal.

[0031] In a suitable example, when the first metal or the oxide of the first metal in the catalyst comprises a monoclinic phase crystal, the second metal or the oxide of the second metal may be an amorphous phase.

[0032] In another suitable example, when the first metal or the oxide of the first metal in the catalyst comprises a tetragonal phase crystal, the second metal or the oxide of the second metal may comprise a monoclinic phase crystal.

[0033] The crystal structure of the above catalyst can be evaluated in the manner described in “1. Catalyst Analysis Method,” “Analysis Example 1. Analysis of Catalyst,” and “Analysis Example 2. Analysis of Catalyst” of the present specification.

[0034] The above combination means that the distribution of the components exhibiting catalytic activity within the catalyst is adjusted to suit the desired catalytic action, based on the amount of the components. A catalyst comprising a crystal structure of this combination and / or being amorphous can be obtained through the catalyst preparation method disclosed herein.

[0035] The first metal in the above may be at least one selected from the group consisting of zirconium, aluminum, titanium, and silicon. Accordingly, the oxide of the first metal may be at least one selected from the group consisting of zirconia, alumina, titania, and silica. In a suitable example, the first metal may be zirconium, and thus the oxide of the first metal may be zirconia.

[0036] The second metal in the above may be tungsten, and therefore, the oxide of the second metal may be tungsten oxide.

[0037] A catalyst in which the above-described second metal and / or its oxide is supported on the above-described first metal and / or its oxide can effectively exhibit the catalytic action intended in the present specification.

[0038] In the above catalyst, the second metal or the oxide of the second metal may exhibit an appropriate surface density. The lower limit of the surface density may be about 1, 3, 5, or 7, and the upper limit may be about 30, 25, 20, 15, 10, or 8. The surface density may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. This range of surface density may mean that a component exhibiting catalytic activity is distributed in an appropriate ratio and crystal form within the catalyst. The above surface density can be evaluated in the manner described in “1. Catalyst Analysis Method,” “Analysis Example 1. Analysis of Catalyst,” and “Analysis Example 2. Analysis of Catalyst” of this specification, and its unit is W / m 2 am.

[0039] The catalyst may exhibit an appropriate specific surface area. The lower limit of the specific surface area may be about 1, 5, 10, 15, or 20, and the upper limit may be about 50, 45, 40, 35, 30, or 25. The specific surface area may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. A catalyst having such a specific surface area may appropriately exhibit the intended catalytic activity. The specific surface area may be evaluated in the manner described in "1. Catalyst Analysis Method," "Analytical Example 1. Analysis of Catalyst," and "Analytical Example 2. Analysis of Catalyst" of the present specification, and the unit thereof is m 2 / g is.

[0040] The catalyst may exhibit an appropriate level of pore volume. The lower limit of the pore volume may be about 0.001, 0.005, 0.01, 0.03, or 0.05, and the upper limit may be about 0.5, 0.1, 0.09, 0.08, or 0.075. The pore volume may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. A catalyst having such a pore volume may appropriately exhibit the intended catalytic activity. The above specific surface area can be evaluated in the manner described in “1. Catalyst Analysis Method,” “Analysis Example 1. Analysis of Catalyst,” and “Analysis Example 2. Analysis of Catalyst” of this specification, and its unit is cm 3 / g is.

[0041] The above catalyst may exhibit an appropriate level of mean pore diameter. The lower limit of the mean pore diameter may be about 1, 3, 5, 7, 9, 11, or 13, and the upper limit may be about 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15. The average pore diameter may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. A catalyst having such an average pore diameter may appropriately exhibit the intended catalytic activity. The average pore diameter may be within a range that is equal to or greater than any one of the lower limits described above, or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above, as described in "1. Method for analyzing catalyst," "Analyzing example 1. Analysis of catalyst," and "Analyzing example 2. It can be evaluated in the manner described in “Analysis of the catalyst”, and the unit is nm.

[0042] The catalyst may have one or more acid sites selected from the group consisting of so-called BrØnsted acid sites and Lewis acid sites, and may suitably include at least BrØnsted acid sites. The presence or absence of the acid sites can be confirmed by the method described in “1. Method for analyzing catalyst,” “Analytical Example 1. Analysis of catalyst,” and “Analytical Example 2. Analysis of catalyst” of the present specification.

[0043] In addition, the catalyst can be confirmed to desorb NH3 at a temperature within the range of 50°C to 210°C in NH3-TPD analysis. The analysis can be performed and confirmed in the manner described in “1. Method for analyzing catalyst,” “Analytical example 1. Analysis of catalyst,” and “Analytical example 2. Analysis of catalyst” of the present specification.

[0044] The characteristics of the above catalyst mean that the acid sites that affect the hydrogenation of CO2 and / or CO exist in an appropriate form and at an appropriate concentration and strength, and therefore, a catalyst that satisfies the above characteristics can exhibit the appropriate catalytic activity intended in the present specification.

[0045] The weight ratio of the first metal to the second metal on the surface of the catalyst, particularly, can be controlled. For example, the lower limit of the weight ratio (M2 / M1) of the second metal (M2) to the first metal (M1) on the surface of the catalyst can be about 3, 5, 7, 9, 11, or 12, and the upper limit can be about 50, 45, 40, 35, 30, 25, 20, 18, 16, 14, or 13. The weight ratio M2 / M1 can be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. This weight ratio can be obtained by XPS analysis, and the method for obtaining it is described in “1. Catalyst Analysis Method,” “Analysis Example 1. Analysis of Catalyst,” and “Analysis Example 2. Analysis of Catalyst” of this specification.

[0046] The content of the second metal in the catalyst can be controlled to an appropriate level. The lower limit of the content of the second metal can be about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5, and the upper limit can be about 20, 15, 10, 8, or 6. The content can be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The desired crystal form and / or catalytic activity can be secured within this content range. The content of the second metal can be confirmed by ICP-OES analysis, and the unit is weight%. Specifically, it can be evaluated in the manner described in “1. Catalyst Analysis Method,” “Analysis Example 1. Analysis of Catalyst,” and “Analysis Example 2. Analysis of Catalyst” of this specification.

[0047] The catalyst may further comprise, in addition to the first and second metals, a third metal different from the first and second metals or an oxide of the third metal. The third metal may be a metal different from the first and second metals and having catalytic activity. Examples of such metals include, but are not limited to, platinum.

[0048] The third metal, for example, platinum, may be present in the catalyst in an amount that is not detected in XPS and / or XRD analysis of the catalyst, but may be detected in EDS mapping analysis. The XPS analysis, XRD analysis, and EDS mapping analysis may be evaluated in the manner described in “1. Method for Catalyst Analysis,” “Analytical Example 1. Analysis of Catalyst,” and “Analytical Example 2. Analysis of Catalyst” of the present specification.

[0049] The fact that the third metal is not detected in the XPS and / or XRD analysis as described above, but is detected in the EDS mapping analysis, means that the third metal is uniformly distributed within the catalyst without agglomeration, etc., and in this state, the catalytic effect of the third metal can be maximized.

[0050] The content of the third metal in the catalyst can be controlled to an appropriate level. The lower limit of the content of the third metal may be about 0.001, 0.003, 0.005, 0.007, 0.009, or 0.01, and may be about 2, 1.5, 1, 0.5, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.015. The content may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The desired catalytic activity can be secured within this content range. The content of the second metal can be confirmed by ICP-OES analysis, and the unit is weight percent. Specifically, it can be evaluated in the manner described in "1. Catalyst Analysis Method," "Analysis Example 1. Analysis of Catalyst," and "Analysis Example 2. Analysis of Catalyst" of this specification.

[0051] One exemplary catalyst may be a catalyst wherein the second metal comprises at least tungsten and the third metal comprises at least platinum.

[0052] One exemplary catalyst may be a catalyst wherein the first metal comprises at least zirconium, the second metal comprises at least tungsten, and the third metal comprises at least platinum.

[0053] To produce a catalyst having the characteristics described above, the manufacturing method of the catalyst can be controlled. For example, the catalyst can be manufactured using a method similar to the so-called incipient wetness impregnation method.

[0054] For example, a catalyst comprising the first and second metals can be prepared in the following manner.

[0055] For example, the method for producing the catalyst may include a first step of mixing a solution containing a second metal or a precursor of the second metal with a first metal or a precursor of the first metal; and a second step of calcining the mixture of the first step.

[0056] The method for manufacturing the above catalyst includes, in the first step, a step of mixing a solution containing a second metal (or a precursor of the second metal) corresponding to an active metal and a first metal (or a precursor of the first metal) as a carrier.

[0057] Precursors of the first or second metal may include, for example, a salt or acid containing the metal, or a hydrate of the salt or acid. In the field of synthesizing catalysts containing metals, various suitable precursors are known according to the desired metal, and such precursors can be used.

[0058] Examples of solvents applicable for the preparation of a solution containing the second metal (or a precursor of the second metal) include aqueous solvents such as water, organic solvents, or mixed solvents of two or more selected from aqueous and / or organic solvents. Examples of applicable organic solvents include, but are not limited to, alcohols having 1 to 20 carbon atoms, such as ethanol, or hydrocarbon solvents having 1 to 20 carbon atoms, such as hexane.

[0059] When preparing the above solution, the concentration of the second metal in the second metal precursor present in the solution can be adjusted. For example, the lower limit of the concentration can be about 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or 65 wt%, and the upper limit can be about 85 wt%, 80 wt%, 75 wt%, or 70 wt%. The concentration can be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0060] When preparing the solution, the concentration of the second metal present in the solution can be adjusted. For example, the lower limit of the concentration may be about 0.1 wt%, 0.5 wt%, 1.0 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, or 3.5 wt%, and the upper limit may be about 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%, 8 wt%, 6 wt%, or 4 wt%. The concentration may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0061] In the first step, the weight ratio of the solution containing the second metal or the precursor of the second metal to the weight of the first metal or the precursor of the first metal can be adjusted. For example, in the mixing in the first step, the lower limit of the weight ratio of the solution containing the second metal or the precursor of the second metal to 100 parts by weight of the first metal or the precursor of the first metal may be about 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, or 4.5 parts by weight, and the upper limit may be about 30 parts by weight, 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, or 5 parts by weight. The weight ratio may be within a range that is greater than or equal to any one of the lower limits described above; or within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0062] The mixing in the first step, in one example, may be performed by grinding or pulverizing the mixture while mixing the weight of the solution containing the second metal or the precursor of the second metal with the first metal or the precursor of the first metal. For example, the mixing may be performed while grinding the mixture in a container such as a mortar. This can increase the impregnation or support efficiency of the second metal into the carrier, and more effectively produce a catalyst exhibiting the desired crystal form, etc.

[0063] In the second stage, the mixture of the first stage can be calcined to obtain a catalyst.

[0064] The above firing can be performed at an appropriate temperature for an appropriate time.

[0065] For example, the lower limit of the firing temperature may be about 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C or 800°C, and the upper limit may be about 2,000°C, 1,500°C, 1,000°C, 950°C, 900°C, 850°C, 800°C, 750°C, 700°C, 650°C, 600°C, 550°C or 500°C. The firing temperature is within a range that is equal to or greater than any one of the lower limits described above; Or within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0066] For example, the lower limit of the time for performing the firing may be about 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours, and the upper limit may be about 20 hours, 15 hours, 10 hours, 8 hours, 6 hours, 4 hours, or 3.5 hours. The time for performing the firing may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0067] Between the first and second steps, a step of drying the mixture of the first step may be performed as an additional process. At this time, the drying temperature may be adjusted in consideration of the boiling point of the solvent applied for preparing the solution of the first step, etc.

[0068] For example, the lower limit of the drying temperature may be about 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, or 110°C, and the upper limit may be about 200°C, 180°C, 160°C, 140°C, or 120°C. The drying temperature may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0069] For example, the lower limit of the difference (Td-Tb) between the drying temperature (Td) in the drying process and the boiling point (Tb) of the solvent applied for preparing the solution in the first step may be about 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C or 10°C, and the upper limit may be about 30°C, 25°C, 20°C, 15°C, 14°C, 13°C, 12°C, 11°C or 10°C. The difference (Td-Tb) may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0070] There is no special limitation on the drying time, and it can be adjusted within a range where appropriate removal of the applied solvent is possible.

[0071] In the case where the drying process is performed between the first and second steps, the firing process can be performed sequentially after the drying process by raising the temperature to the firing temperature at a constant heating rate.

[0072] At this time, the lower limit of the heating rate may be approximately 0.5°C / min, 1°C / min, 1.5°C / min, or 2°C / min, and the upper limit may be approximately 10°C / min, 9°C / min, 8°C / min, 7°C / min, 6°C / min, 5°C / min, 4°C / min, 3°C / min, or 2.5°C / min. The heating rate may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0073] Meanwhile, for example, a catalyst including all of the first to third metals can be manufactured by an impregnation method.

[0074] For example, the manufacturing method may include a first step of mixing a third metal or a precursor of the third metal with a support; and a second step of calcining the mixture of the first step.

[0075] Precursors of the third metal may include, for example, a salt or acid containing the metal, or a hydrate of the salt or acid. In the field of synthesizing catalysts containing metals, various suitable precursors are known depending on the desired metal, and such precursors can be used.

[0076] Additionally, the carrier may be a second metal or a precursor of the second metal as described above. In another example, the carrier may be a catalyst comprising the first and second metals as described above.

[0077] In the first step, the weight ratio of the third metal or the precursor of the third metal and the carrier can be adjusted. For example, in the mixing in the first step, the lower limit of the weight ratio of the third metal or the precursor of the third metal to 100 parts by weight of the carrier may be about 0.0001 parts by weight, 0.0005 parts by weight, 0.001 parts by weight, 0.003 parts by weight, 0.005 parts by weight, 0.007 parts by weight, 0.009 parts by weight, or 0.01 parts by weight, and the upper limit may be about 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, 0.5 parts by weight, 0.1 parts by weight, 0.08 parts by weight, 0.06 parts by weight, 0.04 parts by weight, 0.02 parts by weight, or 0.015 parts by weight. The weight ratio may be within a range that is greater than or equal to any one of the lower limits described above; or within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0078] In the second stage, the mixture of the first stage can be calcined to obtain a catalyst.

[0079] The above firing can be performed at an appropriate temperature for an appropriate time.

[0080] For example, the lower limit of the firing temperature may be about 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, or 500°C, and the upper limit may be about 2,000°C, 1,500°C, 1,000°C, 950°C, 900°C, 850°C, 800°C, 750°C, 700°C, 650°C, 600°C, 550°C, or 500°C. The firing temperature may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0081] For example, the lower limit of the time for performing the firing may be about 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours, and the upper limit may be about 20 hours, 15 hours, 10 hours, 8 hours, 6 hours, 4 hours, or 3.5 hours. The time for performing the firing may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0082] Between the first and second steps, a step of drying the mixture of the first step may be performed as an additional process. At this time, the drying temperature may be adjusted taking into account the boiling point of the applied solvent, etc.

[0083] For example, the lower limit of the drying temperature may be about 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, or 110°C, and the upper limit may be about 200°C, 180°C, 160°C, 140°C, or 120°C. The drying temperature may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0084] There is no special limitation on the drying time, and it can be adjusted within a range where appropriate removal of the applied solvent is possible.

[0085] In the case where the drying process is performed between the first and second steps, the firing process can be performed sequentially after the drying process by raising the temperature to the firing temperature at a constant heating rate.

[0086] At this time, the lower limit of the heating rate may be approximately 0.5°C / min, 1°C / min, 1.5°C / min, or 2°C / min, and the upper limit may be approximately 10°C / min, 9°C / min, 8°C / min, 7°C / min, 6°C / min, 5°C / min, 4°C / min, 3°C / min, or 2.5°C / min. The heating rate may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0087] By applying the above method and adjusting the content of each component in the process, the desired catalyst can be obtained.

[0088] The present specification also discloses a method comprising the step of applying the catalyst to obtain a product.

[0089] For example, the method may include a step of reacting a raw material in the presence of the catalyst described above to obtain a product.

[0090] At this time, the raw material and the product may each be a hydrocarbon compound, or at least include the hydrocarbon compound. In this process, the catalyst may function to promote an isomerization reaction within the raw material. At this time, the isomerization reaction may be a reaction in which the fraction of a specific isomer in the distribution of hydrocarbon compounds within the product increases. Therefore, through the reaction, the proportion of isomers of a specific hydrocarbon compound contained in the raw material may increase in the product. At this time, the specific isomer may be, for example, one or more selected from the group consisting of branched olefins and isoparaffins. Therefore, through the reaction, the fraction of isomers of one or more hydrocarbon compounds selected from the group consisting of branched olefins and isoparaffins within the product may increase compared to the fraction of isomers of the corresponding hydrocarbon compound contained in the raw material.

[0091] In another example, the catalyst may be involved in the so-called CO hydrogenation and / or CO2 hydrogenation, or in a reaction subsequent to the hydrogenation reaction.

[0092] For example, the raw material including the hydrocarbon compound in the above-mentioned reaction may be a result of the CO hydrogenation reaction and / or the CO2 hydrogenation reaction.

[0093] Thus, for example, the method may include a first step of reacting a raw material including at least one selected from the group consisting of CO and CO2 in the presence of an Fe-based catalyst to obtain a first product; and a second step of reacting the first product in the presence of the above-described catalyst to obtain a second product.

[0094] The reaction of the first step may be a known CO hydrogenation reaction and / or CO2 hydrogenation reaction, and may be, for example, one or more reactions selected from the group consisting of a RWGS (Reverse water-gas shift) reaction and a FTS (Fischer-Tropsch Synthesis) reaction.

[0095] The type of Fe-based catalyst used in the reaction of the first step is not particularly limited, and any catalyst known to be applicable to CO hydrogenation and / or CO2 hydrogenation, for example, the RWGS (Reverse water-gas shift) reaction and / or FTS (Fischer-Tropsch Synthesis) reaction, may be appropriately selected and used.

[0096] The product of the reaction of the first step and the product of the reaction of the second step may each be a hydrocarbon compound, or may at least include the hydrocarbon compound. In this process, the catalyst may function to promote an isomerization reaction in the raw material (the product of the reaction of the first step) in the second step. At this time, the isomerization reaction may be a reaction in which the fraction of a specific isomer in the distribution of hydrocarbon compounds in the product increases. Therefore, through the reaction, the proportion of isomers of a specific hydrocarbon compound contained in the raw material may increase in the product. At this time, the specific isomer may be, for example, one or more selected from the group consisting of branched olefins and isoparaffins. Therefore, through the reaction, the fraction of isomers of one or more hydrocarbon compounds selected from the group consisting of branched olefins and isoparaffins in the product may increase compared to the fraction of isomers of the corresponding hydrocarbon compound contained in the raw material.

[0097] The process conditions for carrying out the above reaction are not particularly limited, and known appropriate conditions may be applied.

[0098] The present specification discloses a catalyst. The present specification discloses a catalyst capable of effectively producing a useful component, for example, a useful component applicable as a fuel (branched olefins and / or isoparaffins, etc.), from a raw material containing CO and / or CO2 or a raw material containing a hydrocarbon compound. The present specification discloses a catalyst that suppresses the production of unnecessary components (for example, short-chain hydrocarbons or aromatic compounds) and suppresses the generation of coke, etc. during the production of the useful component. The present specification discloses a catalyst that exhibits high conversion and selectivity and is not deactivated during the reaction process.

[0099] Figure 1 shows N2 adsorption-desorption isotherms confirmed for the catalyst of the example.

[0100] Figure 2 shows N2 adsorption-desorption isotherms confirmed for the catalyst of the example.

[0101] Figure 3 shows N2 adsorption-desorption isotherms confirmed for the catalyst of the example.

[0102] Figure 4 shows N2 adsorption-desorption isotherms confirmed for the catalyst of the example.

[0103] Figure 5 is an N2 adsorption-desorption isotherm confirmed for the catalyst of the example.

[0104] Figure 6 shows the results of analyzing the tungsten surface density of the catalysts of Examples 1 to 5.

[0105] Figure 7 is an XRD pattern of the catalysts of Examples 1 to 5.

[0106] Figure 8 is a Raman spectrum of the catalysts of Examples 1 to 5.

[0107] Figure 9 shows UV-vis spectra and corresponding Kubelka-Munk function spectra of the catalysts of Examples 1 to 5.

[0108] Figure 10 is a HAADF-STEM image of the catalysts of Examples 1 to 5.

[0109] Figure 11 shows the results of EDS mapping analysis for the catalysts of Examples 1 to 5.

[0110] Figure 12 shows the Py-DRIFT analysis results for the catalysts of Examples 1 to 5.

[0111] Figure 13 shows the NH3-TPD analysis results for the catalysts of Examples 1 to 5.

[0112] Figure 14 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0113] Figure 15 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0114] Figure 16 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0115] Figure 17 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0116] Figure 18 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0117] Figure 19 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0118] Figure 20 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0119] Figure 21 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0120] Figure 22 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0121] Figure 23 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0122] Figure 24 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0123] Figure 25 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0124] Figure 26 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0125] Figure 27 is a drawing showing the analysis results for the product obtained in Test Example 1.

[0126] Figure 28 shows the results of EDS mapping analysis for the catalysts of Examples 6 to 9.

[0127] Figure 29 is an XRD pattern of the catalysts of Examples 6 to 9.

[0128] Figure 30 shows the NH3-TPD analysis results for the catalysts of Examples 6 to 9.

[0129] Figure 31 shows the Py-DRIFT analysis results for the catalysts of Examples 6 to 9.

[0130] Figure 32 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0131] Figure 33 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0132] Figure 34 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0133] Figure 35 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0134] Figure 36 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0135] Figure 37 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0136] Figure 38 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0137] Figure 39 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0138] Figure 40 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0139] Figure 41 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0140] Figure 42 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0141] Figure 43 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0142] Figure 44 is a drawing showing the analysis results for the product obtained in Test Example 2.

[0143] Figure 45 is a drawing showing the results of a stability test for the catalyst of the example.

[0144] Figure 46 is a drawing showing the results of a stability test for the catalyst of the example.

[0145] Figure 47 is a diagram schematically showing the operation of the catalyst disclosed in this specification.

[0146] Hereinafter, the catalyst disclosed in this specification is described through examples and the like, but the scope of the catalyst is not limited by the contents presented below.

[0147]

[0148] 1. Catalyst analysis method

[0149] The content of metals (such as Pt and W) in each catalyst was confirmed using ICP-OES (Inductively coupled plasma optical emission spectroscopy) on a Varian 700-ES instrument.

[0150] The surface area, pore size and pore volume of the catalyst were measured by checking the amount of N2 adsorption / desorption at -196°C (77K) using a BELCAT-max instrument (Bel Co.), and calculated according to the BET (Brunauer-Emmett-Teller) method.

[0151] XRD (X-Ray diffraction) analysis was performed on a D / MAX2500V instrument (Rigaku) ​​using Cu-Kα radiation (λ = 0.154178 nm, 40 kV, and 200 mA), through which the crystal structure was determined.

[0152] High-resolution transmission electron microscopy (HR-TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and energy-dispersive X-ray spectroscopy (EDS) were performed using a JEM-2100F (JEOL) instrument operating at 200 kV, and the distribution of Pt and W in the catalyst was investigated.

[0153] XPS (X-ray photoelectron spectroscopy) analysis was performed using a K-alpha (ThermoFischer) system with a monochromatic Al Kα X-ray source (8.339 Å). All spectra were calibrated against the C 1s spectrum (284.8 eV).

[0154] The surface density of tungsten (W) etc. was determined by Raman spectroscopy using an Alpha 300R instrument (WITec) with 532 nm laser excitation, which provides information on the crystalline phases of WOx and ZrO2 in the catalyst.

[0155] UV-Vis spectroscopy was performed using the diffuse reflectance technique on a Cary 5000 spectrophotometer (Agilent Technologies). To characterize the surface acidity based on the surface density of tungsten (W), NH3-TPD (Temperature-programmed desorption of NH3) analysis was performed using a BELCAT II system (Bel Co.). 200 mg of the catalyst was pre-reduced at 400°C for 1 h under a H2 flow of 30 sccm, and NH3 adsorption was performed at 50°C for 1 h using 10% NH3 / He. Subsequently, the catalyst was purged with pure He to remove physically adsorbed NH3. Desorption was performed by ramping the temperature from 50°C to 600°C at a rate of 10°C / min.

[0156] Diffuse reflectance infrared Fourier transform spectroscopy adsorbed by pyridine (Py-DRIFT) was performed using a Thermo Fisher Scientific Nicolet 6700 spectrometer to identify acid sites. For Py-DRIFT analysis, the catalyst was purged with He gas at 200°C, and pyridine was injected into the cell at 50°C. Py-DRIFT spectra were collected during pyridine treatment under He for 20 minutes.

[0157] Thermogravimetric analysis (TGA) was performed using a TGA 5500 instrument (TA instrument), which confirmed the amount of coke deposited on the catalyst used. After the CO2 hydrogenation reaction, the catalyst was heated from 50 to 900°C at a rate of 10°C / min under an air flow of 40 mL / min.

[0158]

[0159] 2. Product analysis method

[0160] Gas products generated from the reactor were fed to an online GC (Agilent Technologies 7820A) and analyzed for N2, CO, and CO2 using a Thermal Conductivity Detector (Carboxen 1000 column).

[0161] C1 to C6 hydrocarbons were analyzed using the same GC system equipped with a Flame Ionization Detector (FID, HP Plot Q column). Liquid hydrocarbon products collected in the cold trap (0°C) were analyzed using GC-mass spectrometry (Agilent Technologies 7890 B) and offline GC (Agilent Technologies 6890A) equipped with a Flame Ionization Detector (HP Plot Q column) and an HP-5 column.

[0162] CO2 conversion rate (X) during the reaction process CO2 )(%) was calculated using the following formula A.

[0163] [Formula A]

[0164]

[0165] Selectivity for methane (CH4) was calculated using equation B below.

[0166] [Formula B]

[0167]

[0168] Selectivity for C2 to C4 hydrocarbons was calculated using Equation C below.

[0169] [Formula C]

[0170]

[0171] The selectivity for C5+ hydrocarbons was calculated using Equation D below.

[0172] [Formula D]

[0173]

[0174] The selectivity for CO was calculated using the following equation E.

[0175] [Formula E]

[0176]

[0177] The selectivity for Ci hydrocarbons was calculated using the following equation F.

[0178] [Formula F]

[0179]

[0180] To further analyze the liquid products of the CO2 hydrogenation reaction, an Avance NEO 600 (Bruker) instrument operating at 600 MHz was used. 1 H- and 13 C-NMR (Nuclear Magnetic Resonance) analysis was performed.

[0181]

[0182] Manufacturing Example 1. Synthesis of NaFe catalyst

[0183] The Fe catalyst (Na-promoted Fe3O4 catalyst) was synthesized by the co-precipitation method reported in the literature (NATURE COMMUNICATIONS, 2017, 8(1), 15174, DOI: 10.1038 / ncomms15174). 42.03 g of FeCl3·6H2O (97%, Thermo Fisher Scientific Chemicals) and 16.75 g of FeCl2·4H2O (98%, Alfa-Aesar) were added with stirring to deionized water containing 6.9 mL of HCl (35.0–37.0%, Samchun) to prepare an Fe precursor solution. NaOH solution (1.5 mol / L) was prepared by dissolving NaOH (98%, Samchun) in deionized water. While stirring at 60°C, the NaOH solution was added dropwise to the Fe precursor solution until the pH reached 10, thereby forming a precipitate in the Fe precursor solution. The formed precipitate was filtered, washed, and dried at 80°C for 5 to 6 hours to prepare a catalyst.

[0184]

[0185] Example 1.

[0186] The catalyst was prepared in the following manner: Ammonium metatungstate hydrate ((NH4)6H2W 12 O 40 ·xH2O)(99.99%, Sigma-Aldrich) was dissolved in 10 mL of deionized water to prepare an aqueous solution. The concentration of tungsten (W) in the ammonium metatungstate hydrate was approximately 66.5 wt%, and the concentration of tungsten (W) in the aqueous solution was approximately 0.8 wt%. The aqueous solution was ground in a mortar and mixed with zirconia (IV) hydroxide (Zr (OH) 4 )(97%, Sigma-Aldrich) to obtain a powder. The obtained powder was dried at 110°C and then calcined for 3 hours at a ramping rate of 2°C / min to 800°C in an air-exposed ambient atmosphere to produce a catalyst (catalyst including tungsten (W) impregnated in zirconia (support)) (1WZ). The mixing was performed such that the weight ratio (A:Z) of ammonium metatungstate hydrate (A) and zirconia (IV) hydroxide (Z) was approximately 0.9:100. When the catalyst was produced under this ratio, the concentration of tungsten (W) confirmed in the catalyst by the ICP-OES method was approximately 1 wt%.

[0187]

[0188] Example 2.

[0189] A catalyst (2WZ) was prepared in the same manner as in Example 1, except that the concentration of tungsten (W) in the aqueous solution of ammonium metatungstate hydrate was set to approximately 1.6 wt%, and the weight ratio (A:Z) of ammonium metatungstate hydrate (A) and zirconia (IV) hydroxide (Z) was set to approximately 1.9:100 during the mixing process for catalyst synthesis. When the catalyst was synthesized under these ratios, the concentration of tungsten (W) in the catalyst confirmed by the ICP-OES method was approximately 2 wt%.

[0190]

[0191] Example 3.

[0192] A catalyst (5WZ) was prepared in the same manner as in Example 1, except that the concentration of tungsten (W) in the aqueous solution of ammonium metatungstate hydrate was set to about 3.8 wt%, and the weight ratio (A:Z) of ammonium metatungstate hydrate (A) and zirconia (IV) hydroxide (Z) was set to about 4.9:100 during the mixing process for catalyst synthesis. When the catalyst was synthesized under these ratios, the concentration of W in the catalyst confirmed by ICP-OES was about 5 wt%.

[0193]

[0194] Example 4.

[0195] A catalyst (10WZ) was prepared in the same manner as in Example 1, except that the concentration of tungsten (W) in the aqueous solution of ammonium metatungstate hydrate was set to about 7.3 wt%, and the weight ratio (A:Z) of ammonium metatungstate hydrate (A) and zirconia (IV) hydroxide (Z) was set to about 10:100 during the mixing process for catalyst synthesis. When the catalyst was synthesized under these ratios, the concentration of W in the catalyst confirmed by ICP-OES was about 10 wt%.

[0196]

[0197] Example 5.

[0198] A catalyst (15WZ) was prepared in the same manner as in Example 1, except that the concentration of tungsten (W) in the aqueous solution of ammonium metatungstate hydrate was set to about 10.6 wt%, and the weight ratio (A:Z) of ammonium metatungstate hydrate (A) and zirconia (IV) hydroxide (Z) was set to about 16:100 during the mixing process for catalyst synthesis. When the catalyst was synthesized under these ratios, the concentration of W in the catalyst confirmed by ICP-OES was about 15 wt%.

[0199]

[0200] Example 6.

[0201] A catalyst in which platinum and tungsten are supported on a support (zirconia) was prepared. The catalyst was prepared by introducing Pt into the catalyst (5WZ) of Example 3. A precursor was prepared by mixing chloroplatinic acid (H2PtCl6, 8 weight% in H2O, Sigma-Aldrich) and the catalyst (5WZ) of Example 3 through impregnation, and after drying the precursor at 110°C, the catalyst (0.01-PtWZ) was prepared by calcining the mixture while exposing it to air and increasing the temperature to 500°C at a rate of 2°C / min for about 3 hours. During the preparation process, the mixing weight ratio (5WZ:Pt) of the catalyst (5WZ) of Example 3 and chloroplatinic acid (Pt) was controlled to be approximately 100:0.01. The amount of platinum confirmed by ICP-OES analysis in the catalyst obtained through the above process was approximately 0.01 wt%.

[0202]

[0203] Example 7.

[0204] A catalyst (0.1-PtWZ) was prepared in the same manner as in Example 6, except that the mixing weight ratio (5WZ:Pt) of the catalyst (5WZ) of Example 3 and chloroplatinic acid (Pt) was controlled to approximately 100:0.1 during the manufacturing process. The amount of platinum in the catalyst was confirmed to be approximately 0.1 wt% through ICP-OES analysis.

[0205]

[0206] Example 8.

[0207] A catalyst (0.5-PtWZ) was prepared in the same manner as in Example 6, except that the mixing weight ratio (5WZ:Pt) of the catalyst (5WZ) of Example 3 and chloroplatinic acid (Pt) was controlled to approximately 100:0.5 during the manufacturing process. The amount of platinum in the catalyst was confirmed to be approximately 0.5 wt% through ICP-OES analysis.

[0208]

[0209] Example 9.

[0210] A catalyst (1-PtWZ) was prepared in the same manner as in Example 6, except that the mixing weight ratio (5WZ:Pt) of the catalyst (5WZ) of Example 3 and chloroplatinic acid (Pt) was controlled to approximately 100:1 during the manufacturing process. The amount of platinum in the catalyst was confirmed to be approximately 1 wt% through ICP-OES analysis.

[0211]

[0212] Analysis Example 1. Catalyst Analysis

[0213] The characteristics of the catalysts of Examples 1 to 5 are summarized and described in Table 1 below. Figures 1 to 5 are N2 adsorption-desorption isotherms confirmed for the catalysts of Examples 1 to 5. Figure 1 shows the results for the catalyst of Example 1, Figure 2 shows the results for the catalyst of Example 2, Figure 3 shows the results for the catalyst of Example 3, Figure 4 shows the results for the catalyst of Example 4, and Figure 5 shows the results for the catalyst of Example 1.

[0214] In Table 1, WO3nominal loading is the nominal loading (weight%) of WO3 in the catalyst confirmed by ICP-OES analysis, and S BET is the BET surface area (m) of each catalyst. 2 / g), and V p is the pore volume (cm) of each catalyst 3 / g), MPD is the mean pore diameter (nm) of each catalyst, and (W / Zr) surf is the ratio of W to Zr on the surface of each catalyst as confirmed by XPS analysis.

[0215] In Table 1, Reference is the value for zirconia used as a carrier in the examples.

[0216] WO3nominal loadingS BET VpMPD(W / Zr) surfReference-3.60.0232.1-Example 11.19.30.0523.27.48Example 22.113.90.0618.69.75Example 35.121.90.0713.612.17Example 410.324.00.0712.416.38Example 515.120.50.0714.819.83

[0217]

[0218] Through the above, it was confirmed that the synthesized catalyst exhibited a relatively large specific surface area and small pore size compared to pure zirconia (ZrO2) (Reference), and it was confirmed that there was a tendency for the specific surface area to increase and the pore size to decrease as the amount of tungsten (W) in the catalyst increased.

[0219] The WOx structure on the catalyst surface was confirmed according to the content of tungsten (W) in the catalyst. The state of WOx was classified through the surface density of WOx on ZrO2, which acts as a carrier (Fig. 6).

[0220] Surface density of 0 to 4 W / nm 2 In this case, it is classified as a sub-monolayer region, and the surface density is 4 to 8 W / nm. 2 In this case, it is classified as a polytungsten growth region, and the surface density is 8 W / nm. 2 In case of excess, it was classified as a crystalline WO3coexistence region.

[0221] The surface density of the catalyst (1WZ) of Example 1 is 3.52 W / nm 2 The surface density of the catalyst (2WZ) of Example 2 was 4.71 W / nm. 2 The surface density of the catalyst (5WZ) of Example 3 was 7.48 W / nm. 2 The surface density of the catalyst (10WZ) of Example 4 was 13.65 W / nm. 2The surface density of the catalyst (15WZ) in Example 5 was about 15 W / nm. 2 degree. Figure 7 shows the XRD analysis results for the catalysts. As the concentration of W increased, the monoclinic phase of ZrO2, which was initially dominant, gradually converted to a tetragonal phase. In the catalysts of Examples 1 to 3 (1WZ, 2WZ, 5WZ), no diffraction peak corresponding to monoclinic WO3 was observed. This confirms that in the cases of Examples 1 to 3, WOx on the ZrO2 carrier was amorphous. For the catalysts of Examples 4 and 5 (10WZ, 15WZ), diffraction peaks at 23.6° and 33.5° were confirmed, respectively, and these diffraction peaks correspond to monoclinic WO3.

[0222] To investigate the dispersion of tungsten (W) within the catalyst in the region below 100 nm, HAADF-STEM and EDS mapping were analyzed. The STEM image showed the distribution of WOx species on the surface (Fig. 10).

[0223] FIG. 3a is a HAADF-STEM image of the catalyst of Example 1, FIG. 3b is a HAADF-STEM image of the catalyst of Example 2, FIG. 3c is a HAADF-STEM image of the catalyst of Example 3, FIG. 3d is a HAADF-STEM image of the catalyst of Example 4, and FIG. 3e is a HAADF-STEM image of the catalyst of Example 5.

[0224] EDS mapping showed that the W atom intensity increased with the W content in the catalyst (Fig. 11). Figures a, f, and k of Figure 11 represent the results for the catalyst of Example 1, b, g, and l represent the results for the catalyst of Example 2, c, h, and m represent the results for the catalyst of Example 3, d, i, and n represent the results for the catalyst of Example 4, and e, j, and o represent the results for the catalyst of Example 5. Figures a to e of Figure 11 represent the results for total elements overlapped for all elements in the catalyst, f to j represent the results for which tungsten is indicated in yellow, and k to o represent the results for which zirconium (Zr) is indicated in blue. When the W loading amount was high, polymeric tungsten oxides forming WOx domains were generated.

[0225] The structures of WOx and ZrO2 were confirmed through Raman and UV-vis spectroscopy. In the Raman spectra (Fig. 2c) of the catalysts (1WZ, 2WZ, 5WZ) of Examples 1 to 3, the peak at 330 cm -1 , 414 cm -1 , 464 cm -1 , 480 cm -1 , 570 cm -1 , and 648 cm -1 Bands were identified in . These bands represent the presence of monoclinic zirconia (m-ZrO2). In addition, in the Raman spectra (Fig. 8) of the catalysts of Examples 1 to 3 (1WZ, 2WZ, 5WZ), bands were detected at 700 to 850 cm -1 No bands were identified within the range, indicating that virtually no crystalline WO3 was present.

[0226] On the other hand, for the catalysts of examples 4 and 5 (10WZ, 15WZ), 717 and 805 cm -1The WO3 phase was confirmed in .

[0227] Figure 9 shows the Eg (optical absorption edge energy) value calculated from the UV-Vis spectroscopy analysis results, and the type of tungsten (W species) can be identified through this Eg value. Figure 9 shows [F(R∞)hν] 2 The results of inferring the straight lines in the plot are also shown. Sodium tungstate dihydrate (Na2WO4·H2O, 4.89 eV) and ammonium metatungstate ((NH4)6H2W 12 O 40 , 3.23 eV) were used as references for isolated tungsten oxide and clusters, respectively. Monoclinic WO3 (2.59 eV) served as reference for Eg values.

[0228] As the size of the tungsten domain (W domain) increased, the Eg value decreased. Based on the Eg value, a single line was drawn for the catalysts of Examples 1 to 3, and two lines were obtained for the catalysts of Examples 4 and 5 (Fig. 9). The catalyst of Example 1 (1WZ) showed the highest Eg value (3.42 eV). As the amount of tungsten increased, the Eg values ​​of the catalysts of Example 2 (2WZ) and Example 3 (5WZ) decreased to 3.35 eV and 3.26 eV, respectively. These results suggest that the Eg values ​​of the catalysts of Examples 1 to 3 are located between those of clusters and isolated sites.

[0229] The results for the catalyst of Example 4 (10WZ) and Example 5 (15WZ) are represented by dashed and solid lines, respectively. The value of the dashed line was approximately 2.63 eV, which is similar to the Eg value of WO3. The Eg values ​​of the catalyst of Example 4 (10WZ) and Example 5 (15WZ) were 3.10 eV and 2.92 eV, respectively, indicating cluster characteristics. These values ​​are lower than the Eg value of ammonium metatungstate (3.23 eV).

[0230] The trend of W surface density determined by UV-Vis analysis corresponded to the results of Raman and XRD analyses.

[0231] Considering that the isomerization effect of hydrocarbons generated during the CO2 hydrogenation reaction is affected by the number and strength of acid sites of the tungsten species of the catalyst, the dependence on the number and strength of acid sites was investigated through Py-DRIFT and NH3-TPD analyses (Figs. 12 and 13).

[0232] Figure 12 shows the results of Py-DRIFT analysis, and Figure 13 shows the results of NH3-TPD analysis. In Figures 12 and 13, 1WZ is the result for Example 1, 2WZ is the result for Example 2, 5WZ is the result for Example 3, 10WZ is the result for Example 4, and 15WZ is the result for Example 5.

[0233] Py-DRIFT can distinguish BrØnsted acid sites and Lewis acid sites. 1,543 cm -1 The characteristic band observed in corresponds to the Bronsted acid point and the N of the pyridinium ion. + It is due to the single bond between the hydrogens of the acid site. 1,489 cm -1 and 1,640 cm-1 This peak, along with an additional peak at 1,440 cm, is used to identify hydrogen within the Bronsted acid point. -1 The peaks observed at 1,570 and 1,600 cm- represent pyridine-coordinated electron pairs. Additionally, 1 The peaks in represent Lewis acid sites. The ratio of Bronsted acid sites to Lewis acid sites determined by Py-DRIFT analysis is related to the density and local structure of tungsten (W).

[0234] The DRIFT spectrum of the catalyst of Example 1 (1WZ) having isolated WO3 showed distinct bands corresponding to Lewis acid sites. The catalysts of Example 4 (10WZ) and Example 5 (15WZ) showed bands corresponding to both Lewis acid sites and Bronsted acid sites. The catalyst of Example 3 (5WZ) showed the highest Bronsted acid site concentration. The overall acid strength can be determined by NH3-TPD analysis. In NH3-TPD analysis, the NH3 desorption peak can be classified into a "weak" acid site associated with NH3 desorption between 50°C and 210°C and a "moderate" acid site associated with NH3 desorption between 210°C and 400°C. Weak acid sites were identified for the catalysts of Examples 1 to 5, and slight variability was observed depending on the tungsten (W) content. NH3 desorption at weak acid sites was highest in 5WZ (Fig. 13).

[0235]

[0236] Test Example 1.

[0237] The catalytic performance of the catalyst (NaFe) of Manufacturing Example 1 was evaluated in a single bed catalyst system. 0.5 g of the catalyst of Manufacturing Example 1 was charged into a tubular reactor and evaluated (evaluation conditions: 340°C, 20 bar, 48 hours, WHSV (weight hourly space velocity) = 9,000 mL·h). -1 ·g cat -1 , and H2 / CO2= 3:1).

[0238] The CO2 conversion rate (X in Equation A) as a result of the hydrogenation reaction in the above single bed catalyst system CO2 ) was confirmed to be about 42%, and the CO selectivity (S in Eq. E) CO ) was confirmed to be about 10%, and CH4 selectivity (S in formula B) CH4 ) was found to be 15.6%, and the product contained about 31.1% of C2 to C4 light olefins, about 4.5% of light paraffins, and 48.8% of C5+ hydrocarbons.

[0239] A hydrogenation reaction was carried out using a dual-bed catalyst system. The reactor includes a first bed and a second bed, the first bed being filled with the Fe catalyst of Preparation Example 1, and the second bed being filled with an isomerization catalyst (zeolite or the catalyst of the example). 0.5 g of the catalyst of Preparation Example 1 and 0.5 g of the isomerization catalysts were each filled in a tubular reactor, and the two catalyst layers were separated using a separation membrane (a separation layer of sand) to construct the dual-bed catalyst system.

[0240] The catalyst in the reactor was reduced before the reaction through H2 flow under ambient pressure and 400°C. After reduction, the temperature was lowered to 340°C and 4,500 mL·h -1 ·g cat -1 A mixed gas (H2 / CO2 / N2= 72:24:4) was injected into the reactor at 20 bar with a WHSV (weight hourly space velocity). N2 was injected as an internal standard for GC (gas chromatography).

[0241] Table 2 below and Figures 14 to 20 show the results of the hydrogenation reaction.

[0242] Hydrocarbon distribution results in Table 2 below are CO free hydrocarbon selectivity (Reaction condition: H2 / CO2=3, 340℃, 20 bar, catalyst (NaFe)=0.5g, isomerization catalyst=0.5g, flow=4,500 ml h -1 gcat -1 ), C1 represents a hydrocarbon having 1 carbon number, C2-4(=) represents an olefin having 2 to 4 carbon numbers, C2-4(0) represents a paraffin having 2 to 4 carbon numbers, and C5+ represents a hydrocarbon having 5 or more carbon numbers.

[0243] CO2ConversionCOSelectivityHydrocarbon distributionC1C2-4(=)C2-4(0)C5+w / o4210.015.631.14.548.8Example 143.210.416.830.95.047.4Example 241.411.317.732.36.643.4Example 341.610.314.829.88.447.0Example 440.69.913.729.79.247.4Example 542.110.615.430.08.246.5

[0244]

[0245] From the results in Table 2 and Figures 6 and 7, no significant changes in CO2 conversion or CO and CH4 selectivity were observed upon addition of the isomerization catalyst. However, significant changes were observed in the distribution of gaseous products, indicating that the introduction of the isomerization catalyst alleviated the production of light hydrocarbons.

[0246] By examining the isomer fractions within C4 hydrocarbon compounds (1-butene, 2-butene, and isobutene), it was confirmed that the selectivity toward linear alpha C4 olefin products increased for catalysts with low tungsten (W) content. The isomer fractions of 2-butene and isobutene increased with increasing tungsten (W) content, and a similar trend was observed for the liquid products.

[0247] In the liquid hydrocarbon composition analyzed using GC (MS and GC), olefins were the most dominant, and the production of aromatic compounds and cyclic compounds slightly increased in the presence of an isomer catalyst.

[0248] This isomerization effect can also be confirmed by the olefin-isomer ratio of the produced hydrocarbon compound. In a single-bed reactor, the isomer ratio was approximately 30%, but in the presence of the catalyst of Example 3, the fraction of isomerized olefin increased to 82% (Fig. 14). The catalytic performance tended to saturate after the tungsten (W) concentration exceeded a certain critical point. When the tungsten (W) concentration increased, the change in the carbon chain length of the liquid product was not significant (Fig. 21).

[0249] 1 H-NMR and 13The results of C-NMR analysis are shown in Figures 16 and 17. 1 A distinct peak pattern was identified in the olefin region between 4 ppm and 7 ppm in the H-NMR spectrum (Fig. 16). Olefin isomers exhibited a dominant peak at approximately 5.4 ppm, while linear alpha olefins exhibited dominant peaks at 5 ppm and 5.8 ppm. The peak intensity of the isomerized olefin at 5.4 ppm increased as the tungsten (W) content increased up to 5 wt%. The peak decreased as the W content exceeded 5 wt%. 13 C-NMR spectra further confirmed the presence of C-C bonds within the molecule (Fig. 17). Irregular peaks at 120 to 140 ppm indicated the mixing of other hydrocarbon components, and the production of linear alpha olefins decreased due to catalytic isomerization. In the catalysts of Examples 1 to 3, the corresponding peaks were further split as the tungsten (W) content increased, but the effect in the catalysts of Examples 4 and 5 decreased due to the formation of crystalline WO3 domains. This trend is 1 H-NMR and 13 As confirmed by C-NMR analysis, this is consistent with the selectivity of the liquid product. The overall hydrocarbon distribution from C1 to C22 was determined by GC, and the amount of paraffins increased with increasing tungsten concentration in the catalyst. However, olefins still predominate in the produced hydrocarbons (Figs. 22-27).

[0250]

[0251] Analysis Example 2. Catalyst Analysis

[0252] The catalysts of Examples 6 to 9 were analyzed. Figure 28 shows the EDS mapping results for the catalysts of Examples 6 to 9. Figures a, e, i, and m of Figure 28 are the analysis results for the catalyst of Example 6, b, f, j, and n are the results for the catalyst of Example 7, c, g, k, and o are the results for the catalyst of Example 8, and d, h, l, and p are the results for the catalyst of Example 9.

[0253] In Table 4 below, Pt nominal loading is the nominal loading (weight%) of Pt in the catalyst confirmed through ICP-OES analysis, and Pt surf is the amount (weight %) of Pt in the catalyst confirmed through XPS analysis. As confirmed in Table 3 and Figure 28 below, the presence of Pt was not confirmed in the XPS analysis of the catalyst of Example 6 (0.01 Pt), but the presence of evenly dispersed Pt species was confirmed in the EDS mapping.

[0254] Pt nominal loadingPt surf Example 3 Not detected Not detected Example 60.02 Not detected Example 70.090.09 Example 80.450.42 Example 91.011.04

[0255]

[0256] Fig. 29 is an XRD analysis pattern for the catalysts of Examples 6 to 9, and the absence of a Pt(111) XRD peak at 38.7° in Fig. 29 shows that Pt is not aggregated but well distributed within the catalyst (Fig. 29). The change in the number and intensity of acid sites according to the addition of Pt was confirmed through NH3-TPD and Py-DRIFT analyses (Figs. 30 and 31). Fig. 30 shows the NH3-TPD analysis result for the catalysts of Examples 6 to 9, and Fig. 31 shows the Py-DRIFT analysis result. Regardless of the Pt concentration, the weak acid sites of the catalysts showed a similar trend (Fig. 30). However, as the Pt concentration increased, the intensity of the acid sites confirmed within the intermediate temperature range decreased along with the increase in the number of acid sites. Unlike NH3-TPD, no distinct trend was observed in the Py-DIRFT results.

[0257]

[0258] Test Example 2.

[0259] In the second bed of a dual bed catalyst system constructed in the same manner as in Test Example 1, one of the catalysts of Examples 6 to 9 was introduced as an isomerization catalyst, and the reaction was performed. Referring to Table 4 and FIG. 32 below, compared to the case of Test Example 1, that is, compared to when the catalysts of Examples 1 to 5 were present, no significant changes in the CO2 conversion rate, CO, and CH4 selectivity were observed, but the overall selectivity of C2 to C4 hydrocarbons (mainly paraffins) increased, and the fraction of C5+ hydrocarbons decreased as the concentration of Pt increased.

[0260] Hydrocarbon distribution results in Table 4 below are CO free hydrocarbon selectivity (Reaction condition: H2 / CO2=3, 340℃, 20 bar, catalyst (NaFe)=0.5g, isomerization catalyst=0.5g, flow=4,500 ml h -1 gcat- 1 ), C1 represents a hydrocarbon having 1 carbon number, C2-4(=) represents an olefin having 2 to 4 carbon numbers, C2-4(0) represents a paraffin having 2 to 4 carbon numbers, and C5+ represents a hydrocarbon having 5 or more carbon numbers.

[0261] CO2ConversionCOSelectivityHydrocarbon distributionC1C2-4(=)C2-4(0)C5+Example 341.610.314.829.88.447.0Example 642.110.216.12.541.639.7Example 741.910.116.23.441.938.6Example 842.510.816.11.845.436.7Example 942.611.216.80.316.136.7

[0262]

[0263] Looking at the distribution of gaseous products, paraffins were primarily produced for all catalysts, and olefins were hardly observed for the catalyst of Example 9, which had a high Pt concentration (Fig. 37). As the Pt concentration increased, the production of olefin products gradually decreased.

[0264] Although the isomerization effect was confirmed in the catalysts of Examples 6 to 9, as the concentration of Pt increased, n-paraffins were predominantly present in the gaseous product, and the isoparaffin selectivity decreased (Fig. 37).

[0265] The isoparaffin / n-paraffin ratios obtained using the catalysts of Examples 6 to 9 were higher than the corresponding ratios obtained using the catalysts of Examples 1 to 5. 1H-NMR and 13 C-NMR analysis confirmed changes in the types of hydrocarbons present in the liquid products. Compared to the catalysts of Examples 1 to 5, peaks corresponding to the saturated hydrocarbon region (0 ppm to 3 ppm) were clearly observed in the catalysts of Examples 6 to 9, and compared to the catalysts of Examples 1 to 5, the intensity of the peaks corresponding to the unsaturated hydrocarbon region (4.5 ppm to 8 ppm) was not as high.

[0266] GC-MS and GC analyses showed that paraffins were the predominant hydrocarbon in the liquid hydrocarbon, with aromatic compounds being reduced by hydrogenation and isomerization by Pt (Fig. 33). The addition of Pt to the catalyst dramatically increased the distribution ratio of isoparaffins in the liquid hydrocarbon, with the catalyst of Example 6 recording a maximum isoparaffin ratio of 42%.

[0267] 13 In the C-NMR spectrum, the intensity of the C=C peak was significantly reduced, indicating that unsaturated hydrocarbons were efficiently saturated by Pt (Fig. 39). The paraffin isomer ratio was highest in the catalyst of Example 6. The catalysts of Examples 6 to 9 showed a predominant paraffin production effect over the entire hydrocarbon range from C1 to C22 (Figs. 40 to 43). The addition of Pt reduced the overall hydrocarbon chain length, and this effect became greater as the Pt concentration increased (Fig. 44).

[0268] By applying the catalyst disclosed herein (Pt / WO3-ZrO2 catalyst with controlled Pt and W contents) subsequent to a bed applying a Na-Fe3O4 catalyst, a paraffin content exceeding 70%, a very low olefin selectivity of less than 5%, and a suitable aromatic selectivity of approximately 15% are achieved.

[0269] The presence of high C12+ hydrocarbons was confirmed by the catalyst (Pt / WO3-ZrO2) (7%) disclosed herein along with lower coke formation. The catalyst exhibited excellent stability with almost no deactivation observed even after a 100-hour stability test (Figs. 45 and 46).

[0270] Light olefins and liquid hydrocarbons produced by the Na-Fe3O4 catalyst were further isomerized by the catalyst disclosed herein, and as a result, converted into isoparaffins. That is, as exemplarily shown in Fig. 47, it can be seen that linear olefins are mainly produced by the Fe catalyst (Na-Fe3O4 catalyst), and such olefins are converted into isoparaffins by the catalyst disclosed herein.

[0271] These isoparaffins can be used as liquid E-fuel without additional hydrogen consumption.

Claims

1. An oxide of the first metal as a carrier; and Containing an oxide of a second metal present together with the carrier, The oxide of the above first metal comprises a monoclinic or tetragonal crystal, The oxide of the second metal is an isomerization catalyst comprising an amorphous or monoclinic crystal.

2. An isomerization catalyst in the first paragraph, wherein the oxide of the first metal is zirconia, alumina, titania or silica, and the oxide of the second metal is tungsten oxide.

3. An isomerization catalyst according to claim 1 or 2, wherein the oxide of the first metal comprises a monoclinic crystal and the oxide of the second metal is an amorphous crystal.

4. An isomerization catalyst according to any one of claims 1 to 3, wherein the oxide of the first metal comprises a tetragonal crystal, and the oxide of the second metal comprises a monoclinic crystal.

5. In any one of paragraphs 1 to 4, the surface density of the oxide of the second metal is 1 to 30 W / m 2 Isomerization catalyst within the range of .

6. In any one of paragraphs 1 to 5, the specific surface area is 1 to 50 m 2 Isomerization catalyst within the range of / g.

7. In any one of paragraphs 1 to 6, the volume of the pores is 0.001 to 0.5 cm 3 Isomerization catalyst within the range of / g.

8. An isomerization catalyst according to any one of claims 1 to 7, wherein the average pore diameter is in the range of 1 to 60 nm.

9. An isomerization catalyst according to any one of claims 1 to 8, comprising at least one acid site selected from the group consisting of a Bronsted acid site and a Lewis acid site.

10. An isomerization catalyst according to any one of claims 1 to 9, wherein NH3 desorption from NH3-TPD occurs within a range of 50°C to 210°C.

11. An isomerization catalyst according to any one of claims 1 to 10, wherein the weight ratio of the second metal to the first metal on the surface confirmed by XPS analysis is in the range of 3 to 50.

12. An isomerization catalyst according to any one of claims 1 to 11, wherein the content of the second metal confirmed by ICP-OES is in the range of 0.5 to 20 wt%.

13. An isomerization catalyst according to any one of claims 1 to 12, further comprising a third metal.

14. An isomerization catalyst in claim 13, wherein the third metal is platinum.

15. An isomerization catalyst in which platinum is not detected in XPS or XRD analysis in paragraph 14, but platinum is confirmed in EDS mapping analysis.

16. An isomerization catalyst according to claim 13, wherein the content of the third metal confirmed by ICP-OES is in the range of 0.001 to 2 wt%.

17. An isomerization catalyst according to claim 13, wherein the second metal is tungsten and the third metal is platinum.

18. A method comprising a step of obtaining a product by subjecting a raw material containing a hydrocarbon compound to an isomerization reaction in the presence of an isomerization catalyst according to any one of claims 1 to 17.

19. A method according to claim 18, wherein the product comprises a branched olefin or isoparaffin.

20. A first step of obtaining a first product by reacting a raw material including at least one selected from the group consisting of CO and CO2 in the presence of an Fe-based catalyst; and A method comprising a second step of obtaining a second product by reacting the first product in the presence of a catalyst according to any one of claims 1 to 17.

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