Catalyst system for carbon dioxide conversion with improved selectivity of reaction product using zeolite

Abstract

The present invention relates to a catalyst system for carbon dioxide conversion with improved selectivity of a reaction product by utilizing zeolite and, more specifically, to a catalyst system with improved selectivity of a reaction product (C5-C12) by sequentially introducing zeolite (ZSM-5) into an Fe-based catalyst that is suitable for producing olefins (C2-C4) through a carbon dioxide hydrogenation reaction.

Description

Catalytic system for carbon dioxide conversion with improved selectivity of reaction products using zeolite

[0001] The present invention is a catalyst system for carbon dioxide conversion with improved selectivity of reaction products by utilizing zeolite, and specifically, zeolite (ZSM-5) is continuously introduced into an Fe-based catalyst that is easy to produce olefins (C2~C4) through carbon dioxide hydrogenation reaction to produce reaction products (C5~C 12 ) is related to a catalyst system that improves the selectivity.

[0002]

[0003] Since the Industrial Revolution, the increased use of fossil fuels like coal and oil has led to an excessive increase in carbon dioxide emissions. Carbon dioxide absorbs excessive radiant energy, raising the Earth's temperature, a phenomenon known as global warming. Global warming is causing rising temperatures, rising sea levels, droughts, floods, heat waves, heavy snowfall, and earthquakes, and is also causing physical environmental changes such as ecosystem disruption. It is also having a wide-ranging negative impact on our surroundings, including agriculture, livestock farming, and industrial activities, as well as human health and the living environment.

[0004] Recently, with the global interest in "carbon neutrality," a low-carbon, eco-friendly economy, technologies for capturing and processing carbon dioxide emitted from the atmosphere have been attracting attention from both academia and industry. Consequently, there is growing interest in developing new technologies that separate and recover carbon dioxide, allowing it to be recycled and reincorporated into the current energy and chemical industry systems. One such technology, hydrogenation, has been studied to convert carbon dioxide into alternative petroleum chemicals.

[0005] The applicant of the present invention has conducted research to convert excess carbon dioxide, hydrogen and some carbon monoxide in the process exhaust gas (HMP Purge gas), and through carbon dioxide hydrogenation reaction, converts C2~C4 base oil and C5~C 12 We developed an Fe-based FeCuKCeAl catalyst (application number 10-2023-0126884) that can be converted to a naphtha-range fuel.

[0006] Accordingly, in the present invention, zeolite is continuously introduced into a FeCuKCeAl catalyst that is easy to produce C2~C4 olefins, and C5~C is produced through oligomerization and aromatization. 12 We wanted to improve selectivity.

[0007]

[0008] The present invention additionally links zeolite to a carbon dioxide hydrogenation reaction using an Fe-based catalyst to produce a reaction product (C5~C 12 ) to provide a catalyst system with improved selectivity.

[0009]

[0010] A catalyst system for carbon dioxide conversion with improved selectivity of reaction products by utilizing zeolite according to the present invention comprises an Fe-based catalyst prepared through mixing and diffusion reaction by mechanical shear force of metal precursors under solvent-free conditions; and a zeolite; to convert carbon dioxide to C. 5+ It can produce hydrocarbons.

[0011] The above Fe-based catalyst may be a compound represented by the following [chemical formula 1].

[0012] [Chemical Formula 1]

[0013] Fe a Cu b K c Al d (M) e

[0014] The above M includes at least one selected from rare earth metals including cerium (Ce), lanthanum (La) and praseodymium (Pr), and the a, b, c, d and e have a total of 1 and are independently 0.01 to 0.7.

[0015] The above Fe-based catalyst can be manufactured by mixing each constituent metal precursor in an equivalent ratio according to the above chemical formula 1 and applying mechanical shear force.

[0016] The metal precursor may be a metal salt comprising at least one selected from the group consisting of nitrate, ammonium nitrate, carbonate, bicarbonate, hydroxide, oxide, oxyhydrate, acetate, and sulfate.

[0017] The above Fe-based catalyst may include a peak having a 2θ value of XRD of 35.85 to 35.95.

[0018] The above Fe-based catalyst may have a particle size (crystallite size) of 10 to 20 nm.

[0019] The above Fe-based catalyst has a BET surface area of ​​50 to 200 m 2 / g may be.

[0020] The above Fe-based catalyst has a pore volume of 0.01 to 0.5 cm 3 / g may be.

[0021] The above zeolite may be ZSM-5 (Zeolite Socony Mobil-5).

[0022] The SiO2 / Al2O3 ratio of the above ZSM-5 may be 20 to 600.

[0023] The above Fe-based catalyst and zeolite can be arranged in a dual bed (2-bed) in a single catalytic reactor or sequentially in different catalytic reactors.

[0024] The above Fe-based catalyst and zeolite can be arranged to sequentially contact the introduced gas containing carbon dioxide.

[0025] The above Fe-based catalyst and zeolite may be granules having a size of 0.3 to 2 mm.

[0026] The mass ratio of the above Fe-based catalyst and zeolite may be 1:0.1 to 5.

[0027] The carbon dioxide conversion method according to the present invention sequentially contacts a gas containing carbon dioxide with the Fe-based catalyst and zeolite in the carbon dioxide conversion catalyst system to produce C 5+ It can produce hydrocarbons.

[0028] The molar ratio of H2 and CO2 in the gas containing the above carbon dioxide may be 1 to 3:1.

[0029] The GHSV (Gas Hourly Space Velocity) of the gas containing the above carbon dioxide may be 1,000 to 10,000 mL / gcat·h.

[0030] In the above carbon dioxide conversion method, the pressure may be 1 to 50 bar.

[0031] In the above carbon dioxide conversion method, the temperature may be 100 to 1000°C.

[0032] In the above carbon dioxide conversion method, C5~C in the liquid product 12 The selectivity can be from 30 to 100%.

[0033]

[0034] According to the present invention, zeolite (ZSM-5) was continuously introduced to an Fe-based catalyst that is easy to produce olefins (C2~C4) through carbon dioxide hydrogenation reaction, and carbon dioxide conversion is easy even at a low hydrogen fraction (H2 / CO2=2 or less), so that reaction products such as naphthene, paraffin, and aromatics (C5~C) are produced. 12 ) improved the selectivity. In addition, depending on the catalyst composition, mass ratio, acidity point of zeolite, etc., the reaction product (C5~C 12 ) can be adjusted for yield and selectivity.

[0035]

[0036] Figure 1 shows the composition of an Fe-based catalyst and zeolite according to one embodiment of the present invention.

[0037] Figure 2 shows SEM and EDS mapping images of an Fe-based catalyst according to one embodiment of the present invention.

[0038] Figure 3 shows the XRD results of an Fe-based catalyst according to one embodiment of the present invention.

[0039] Figure 4 shows the XPS results of an Fe-based catalyst according to one embodiment of the present invention.

[0040] Figure 5 shows the XRD analysis results according to the zeolite acid point of the present invention.

[0041] Figure 6 shows the BET analysis results according to the zeolite acid point of the present invention.

[0042] Figure 7 shows the NH3-TPD analysis results according to the zeolite acid point of the present invention.

[0043] Figures 8 to 11 show the catalytic activity according to the catalyst composition of the present invention.

[0044] Figures 12 and 13 show the catalytic activity according to the zeolite acid site of the present invention.

[0045] Figures 14 and 15 show the catalytic activity according to the zeolite content of the present invention.

[0046] Figures 16 and 17 show the catalytic activity according to the zeolite acid site and content of the present invention.

[0047] Figure 18 shows C5~C among the entire products according to one embodiment of the present invention. 12 It shows the selectivity of .

[0048] Figures 19 and 20 show the catalytic activity according to the type of zeolite of the present invention.

[0049]

[0050] The embodiments described herein may be modified in various different forms, and the technology according to one embodiment is not limited to the embodiments described below. In addition, the embodiments of one embodiment are provided to more completely explain the present disclosure to a person with average knowledge in the relevant technical field. In this case, unless there is a different definition for the technical and scientific terms used, they have the meaning commonly understood by a person with ordinary skill in the technical field to which this invention belongs, and in the following description and the attached drawings, descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted.

[0051] Additionally, the singular forms used in this specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0052] Additionally, in this specification and the appended claims, the terms first, second, etc. are not used in a limiting sense but are used for the purpose of distinguishing one component from another.

[0053] Additionally, in this specification and the appended claims, when a part such as a film (layer), region or component is said to be located “on,” “above,” “upper,” “below,” “lower,” or “lower” another part, this includes not only cases where one part is in contact with another part, but also cases where another part exists between the two parts.

[0054] In addition, the terms "about," "substantially," and the like used in this specification and the appended claims are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings stated are presented, and are used to prevent unscrupulous infringers from unfairly utilizing the disclosure in which exact or absolute values ​​are stated to aid in the understanding of this specification and the appended claims.

[0055] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes.

[0056] Furthermore, terms such as “include” or “have” in this specification and the appended claims mean that a feature or component described in the specification is present, and unless specifically limited, do not preclude the possibility that one or more other features or components may be added.

[0057] Hereinafter, a catalyst system for converting carbon dioxide with improved selectivity of reaction products by utilizing the zeolite of the present invention will be described in detail with reference to the attached drawings.

[0058]

[0059] Hydrogenation is a metal-catalyzed reaction in which hydrogen molecules are added to a compound containing an unsaturated functional group, such as a double or triple bond. This reaction requires an unsaturated compound, hydrogen, and a catalyst. The reaction proceeds at various temperatures and pressures, depending on the activity of the catalyst and the type of reactant (unsaturated compound).

[0060] Table 1 shows the applications of products obtained through the hydrogenation reaction of carbon dioxide according to their carbon number range.

[0061]

[0062] Carbon number range classification application C1-C4 gaseous fuel, plastic synthetic raw material C5-C 12 Gasoline car fuel C 12 -C 16 Kerosene jet fuel, diesel oil C 16 -C 18 Diesel fuel, pyrolysis raw material C 18 -C 20 LubricantsLubricants, pyrolysis raw materialsC 20 -C 40 Paraffin Wax Wax C 40 Excess asphalt, asphalt, tar

[0063]

[0064] A crucial element in the carbon dioxide hydrogenation reaction is the catalyst. Without a metal catalyst, hydrogen gas itself barely reacts with organic compounds. Cobalt- and iron-based catalysts are commonly used. Iron-based catalysts are relatively inexpensive, offer a wide range of reactor operating conditions, and produce a high proportion of higher-grade products, such as branched hydrocarbons and lower olefins, making them widely used.

[0065] However, the FeCuKAl catalyst, which is widely known as a conventional Fe-based catalyst, had the problem of relatively low carbon dioxide conversion. Therefore, the applicant of the present invention developed an Fe-based FeCuKCeAl catalyst (application number 10-2023-0126884) by applying a rare earth metal as a cocatalyst that facilitates carbon dioxide adsorption and desorption to compensate for the shortcomings of conventional Fe-based catalysts.

[0066] Meanwhile, zeolites are natural and synthetic silicate minerals. Due to the porous structure of zeolites, in which cavities large enough to adsorb molecules exist regularly within the crystal, zeolites exhibit excellent interfacial activity and possess outstanding catalytic properties. The catalytic properties of zeolites vary depending on the zeolite structure, the nature and structural position of cations, the Si / Al content ratio, and the presence of active metal elements. The catalytic properties of zeolites are utilized in the fields of petroleum refining and petrochemicals, and when long-chain hydrocarbons and light olefins are supplied as reactants, they can control the carbon chain through cracking and oligomerization, thereby improving the yield of naphtha and gasoline.

[0067] Among zeolites, ZSM-5 (Zeolite Socony Mobil-5) has a high SiO2 / Al2O3 ratio, which generally results in excellent thermal stability, hydrophobicity, and a large Lewis acid site and small Brønsted acid site. It forms uniform three-dimensional channel-shaped pores with a diameter of approximately 5 to 6 Å, and due to its large pore size, more aromatic hydrocarbons are formed than linear hydrocarbons.

[0068] Accordingly, the present invention additionally links zeolite to the carbon dioxide hydrogenation reaction using an Fe-based catalyst to produce a reaction product (C5~C 12 ) provides a catalyst system with improved selectivity.

[0069]

[0070] The present invention comprises an Fe-based catalyst manufactured through a mixing and diffusion reaction by mechanical shearing of a metal precursor under solvent-free conditions; and a zeolite; which produces C from carbon dioxide. 5+ A catalyst system for converting carbon dioxide to produce hydrocarbons can be provided.

[0071] As an example, the Fe-based catalyst is a compound represented by the following chemical formula 1, which produces C2~C4 base oil and C5~C through carbon dioxide hydrogenation reaction. 12 It can be converted to a naphtha-range fuel. The previously filed FeCuKCeAl catalyst is described in detail in Korean Patent Application No. 10-2023-0126884.

[0072] [Chemical Formula 1]

[0073] Fe a Cu b K c Al d (M) e

[0074] The above M may include one or more selected from rare earth metals including cerium (Ce), lanthanum (La), and praseodymium (Pr). The above a, b, c, d and e have a total of 1 and are independently 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7 or a range between any two of the values ​​described herein, but is not limited thereto.

[0075] As an example, the Fe-based catalyst can be prepared by mixing each constituent metal precursor in an equivalent ratio according to the chemical formula 1 and applying mechanical shear force. Preferably, the catalyst can be prepared through mixing and diffusion reaction of each constituent metal precursor by mechanical shear force under solvent-free conditions, and this is called a solid state reaction (SSR) or solid-state reaction method.

[0076] The solid-state method is a reaction in which substances mixed in a pure solid state are converted into new compounds by temperature, pressure, etc., and is simpler to manufacture than the conventional co-precipitation (CP) or impregnation (IMP) method, and can produce catalysts with uniform particles.

[0077] As an example, the metal precursor may be a metal salt comprising at least one selected from the group consisting of nitrate, ammonium nitrate, carbonate, bicarbonate, hydroxide, oxide, oxyhydrate, acetate, and sulfate. Preferably, the metal precursor may be a metal nitrate, and a hydrate, anhydride, or a mixture thereof may also be used, but is not limited thereto.

[0078] As an example, the catalyst for carbon dioxide conversion may include a peak having an XRD 2θ value of 35.85, 35.86, 35.87, 35.88, 35.89, 35.90, 35.91, 35.92, 35.93, 35.94, 35.95, or a range between any two of the values ​​described herein. For example, the XRD 2θ value of the peak may be, but is not limited to, 35.85 to 35.95, 35.89 to 35.95, or 35.89 to 35.93.

[0079] As an example, the catalyst for carbon dioxide conversion may have a crystallite size of 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, or a range between any two of the values ​​described herein. For example, the particle size may be, but is not limited to, 10 to 20 nm, 10 to 15 nm, or 12 to 14 nm.

[0080] As an example, the above carbon dioxide conversion catalyst has a BET surface area of ​​50 m 2 / g, 60 m 2 / g, 70 m 2 / g, 80 m 2 / g, 90 m2 / g, 100 m 2 / g, 110 m 2 / g, 120 m 2 / g, 130 m 2 / g, 140 m 2 / g, 150 m 2 / g, 160 m 2 / g, 170 m 2 / g, 180 m 2 / g, 190 m 2 / g, 200 m 2 / g or may be within a range between any two values ​​described herein. For example, the BET surface area may be from 50 to 200 m 2 / g, 60 to 150 m 2 / g or 65 to 100 m 2 / g may be, but is not limited to, this.

[0081] As an example, the catalyst for converting carbon dioxide has a pore volume of 0.01 cm 3 / g, 0.02 cm 3 / g, 0.03 cm 3 / g, 0.04 cm 3 / g, 0.05 cm 3 / g, 0.06 cm 3 / g, 0.07 cm 3 / g, 0.08 cm 3 / g, 0.09 cm 3 / g, 0.1 cm 3 / g, 0.11 cm 3 / g, 0.12 cm 3 / g, 0.13 cm 3 / g, 0.14 cm 3 / g, 0.15 cm 3 / g, 0.16 cm 3 / g, 0.17 cm 3 / g, 0.18 cm 3 / g, 0.19 cm 3 / g, 0.2 cm 3 / g, 0.21 cm 3 / g, 0.22 cm 3 / g, 0.23 cm 3 / g, 0.24 cm 3 / g, 0.25 cm 3 / g, 0.26 cm 3 / g, 0.27 cm 3 / g, 0.28 cm 3 / g, 0.29 cm 3 / g, 0.3 cm 3 / g, 0.31 cm 3 / g, 0.32 cm 3 / g, 0.33 cm 3 / g, 0.34 cm 3 / g, 0.35 cm 3 / g, 0.36 cm 3 / g, 0.37 cm 3 / g, 0.38 cm 3 / g, 0.39 cm 3 / g, 0.4 cm 3 / g, 0.41 cm 3 / g, 0.42 cm 3 / g, 0.43 cm 3 / g, 0.44 cm 3 / g, 0.45 cm 3 / g, 0.46 cm 3 / g, 0.47 cm 3 / g, 0.48 cm 3 / g, 0.49 cm 3 / g, 0.5 cm 3 / g or may be within a range between any two values ​​described herein. For example, the volume of the void may be between 0.01 and 0.5 cm 3 / g, 0.05 to 0.5 cm 3 / g or 0.05 to 0.25 cm 3 / g may be, but is not limited to, this.

[0082] As an example, the zeolite may include a Si-Al zeolite, a Si-P-Al zeolite, or a mixture thereof, and may preferably be ZSM-5 (Zeolite Socony Mobil-5), but is not limited thereto.

[0083] As an example, the SiO2 / Al2O3 ratio of the ZSM-5 is 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, It may be within a range of 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600 or any two values ​​described herein. For example, the SiO2 / Al2O3 ratio may be, but is not limited to, 20 to 600, 20 to 400 or 30 to 400.

[0084] Figure 1 shows the composition of an Fe-based catalyst and zeolite according to one embodiment of the present invention.

[0085] As one embodiment, the Fe-based catalyst and zeolite may be arranged in a dual bed (2-bed) within a single catalytic reactor, and as another embodiment, the Fe-based catalyst and zeolite may be arranged sequentially in separate catalytic reactors. Preferably, the zeolite may be arranged in a dual bed within a single catalytic reactor, but is not limited thereto.

[0086] As an example, the Fe-based catalyst and zeolite may be arranged to sequentially contact the introduced gas containing carbon dioxide. Preferably, the gas containing carbon dioxide first reacts on the Fe-based catalyst and then secondarily undergoes oligomerization on the zeolite to form C 5+ It can produce hydrocarbons.

[0087] As an example, the Fe-based catalyst and zeolite are not particularly limited, but may preferably be granules, but are not limited thereto.

[0088] As an example, the size of the Granule may be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 0.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2 mm or within a range between any two of the values ​​described herein. For example, the size of the Granule may be, but is not limited to, 0.3 to 2 mm, 0.5 to 2 mm or 1 to 2 mm.

[0089] As an example, the mass ratio of the Fe-based catalyst and the zeolite may be 1:0.1, 1:02, 1:03, 1:04, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or within a range between any two of the values ​​described herein. For example, the mass ratio may be, but is not limited to, 1:0.1 to 5, 1:0.5 to 3, or 1:1 to 2.

[0090] In addition, the present invention sequentially contacts a gas containing carbon dioxide with the Fe-based catalyst and zeolite in the carbon dioxide conversion catalyst system to produce C 5+ A method for converting carbon dioxide to produce hydrocarbons can be provided.

[0091] As an example, the molar ratio of H2 and CO2 of the gas containing the carbon dioxide may be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, or within a range between any two of the values ​​described herein. For example, the molar ratio may be, but is not limited to, 1 to 3:1, 1.5 to 2.5:1, or 1.5 to 2:1.

[0092] As an example, the GHSV (Gas Hourly Space Velocity) of the gas containing the carbon dioxide may be 1,000 mL / gcat·h, 2,000 mL / gcat·h, 3,000 mL / gcat·h, 4,000 mL / gcat·h, 5,000 mL / gcat·h, 6,000 mL / gcat·h, 7,000 mL / gcat·h, 8,000 mL / gcat·h, 9,000 mL / gcat·h, 10,000 mL / gcat·h, or within a range between any two of the values ​​described herein. For example, the GHSV may be 1,000 to 10,000 mL / gcat·h, 3,000 to 8,000 mL / gcat·h, or 6,000 to 7,000 mL / gcat·h, but is not limited thereto.

[0093] In the above carbon dioxide conversion method, if the pressure and temperature are too low, the reaction is insufficient and the amount of reaction product produced is small, and if the pressure and temperature are too high, there is a problem of reduced energy efficiency.

[0094] As an example, in the carbon dioxide conversion method, the pressure is 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, 10 bar, 11 bar, 12 bar, 13 bar, 14 bar, 15 bar, 16 bar, 17 bar, 18 bar, 19 bar, 20 bar, 21 bar, 22 bar, 23 bar, 24 bar, 25 bar, 26 bar, 27 bar, 28 bar, 29 bar, 30 bar, 31 bar, 32 bar, 33 bar, 34 bar, 35 bar, 36 bar, 37 bar, 38 bar, 39 bar, 40 bar, 41 bar, 42 bar, 43 bar, 44 bar, 45 bar, 46 bar, 47 bar, 48 bar, The pressure may be within a range of 49 bar, 50 bar, or any two of the values ​​described herein. For example, the pressure may be, but is not limited to, 1 to 50 bar, 10 to 30 bar, or 15 to 25 bar.

[0095] As an example, in the carbon dioxide conversion method, the temperature may be 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, 800°C, 850°C, 900°C, 950°C, 1000°C, or within a range between any two of the values ​​described herein. For example, the temperature may be, but is not limited to, 100 to 1000°C, 200 to 500°C, or 250 to 350°C.

[0096] As an example, in the above carbon dioxide conversion reaction, C5~C in the liquid product 12 The selectivity may be within a range of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% or any two of the values ​​described herein. For example, C5~C in the liquid product 12 The selectivity may be, but is not limited to, 30 to 100%, 50 to 100%, or 90 to 100%.

[0097] According to the present invention, zeolite (ZSM-5) was continuously introduced to an Fe-based catalyst that is easy to produce olefins (C2~C4) through carbon dioxide hydrogenation reaction, and carbon dioxide conversion is easy even at a low hydrogen fraction (H2 / CO2=2 or less), so that reaction products such as naphthene, paraffin, and aromatics (C5~C) are produced. 12 ) improved the selectivity. In addition, depending on the catalyst composition, mass ratio, acidity point of zeolite, etc., the reaction product (C5~C 12 ) can be adjusted for yield and selectivity.

[0098]

[0099] Hereinafter, specific examples and experimental examples will be described. However, the examples and experimental examples described below are only illustrative, and the technology described in this specification is not limited thereto.

[0100]

[0101] <Manufacturing Example> Manufacturing of Fe-based catalyst (FeCuK20CeAl)

[0102] 15.1 g of Fe(NO3)3·9H2O, 18.0 g of Al(NO3)3·9H2O, 0.98 g of Cu(NO3)2·3H2O, 0.93 g of KNO3, 1.5 g of Ce(NO3)3·6H2O, and 22.4 g of NH4NO3 were placed in a mortar and mixed at room temperature for 20 minutes. During mixing, the mixture changed phases from solid to liquid to solid, and was mixed until it finally became a gel, and then calcined at 400°C for 5 hours to obtain an Fe-based catalyst (Fe 0.37 Cu 0.04 K 0.09 Ce 0.034 Al 0.47 ) was synthesized.

[0103]

[0104] <Reaction driving conditions>

[0105] After reduction treatment at atmospheric pressure 350 ℃ with a heating rate of 10 ℃ / min and a flow rate of H2 / CO=60 / 30 sccm for 5 hours, feed was supplied after pressurizing up to 20 bar with N2 at room temperature. Carbon dioxide hydrogenation reaction was performed at 300 ℃, 20 bar, and a space velocity of 6250 mL / gcat·h under the conditions of H2 / CO2 / CO=32 / 20 / 5 sccm. The reactants and products were analyzed online by a gas chromatograph (Agilent Instruments 8890) using a FID column GS-KCl / AL and a TCD column Porapak Q.

[0106]

[0107] <Example 1>

[0108] 0.6 g of powdered Fe-based catalyst (FeCuK20CeAl) and 0.6 g of powdered zeolite (ZSM-5(400)) were physically mixed in a mortar for 1 minute and charged into a down flow stainless steel fixed bed reactor with an inner diameter of 3 / 8” and a length of 40.7 mm (mass ratio 1:1).

[0109]

[0110] <Example 2>

[0111] In a down flow stainless steel fixed bed reactor with an inner diameter of 3 / 8" and a length of 40.7 mm, 0.6 g of powdered zeolite (ZSM-5(400)) was first charged into the lower bed, and then 0.6 g of powdered Fe-based catalyst (FeCuK20CeAl) was sequentially charged into the upper bed (mass ratio 1:1).

[0112]

[0113] <Example 3>

[0114] The same procedure as in Example 1 was performed, except that 0.6 g of a powdered Fe-based catalyst (FeCuK20CeAl) and 0.6 g of a powdered zeolite (ZSM-5(400)) were each manufactured into granules and mixed (mass ratio 1:1).

[0115] Using PIKE IR equipment, the catalyst in powder form was maintained at 3.5 intensity for 3 minutes to make pellets with a thickness of 0.1 mm, and then a 300 μm sieve was used to manufacture granules of 300 μm to 2 mm.

[0116]

[0117] <Example 4>

[0118] The same procedure as in Example 2 was followed, except that the Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(400)) were prepared in the form of granules rather than powders and filled (mass ratio 1:1).

[0119]

[0120] <Example 5>

[0121] The same procedure was followed as in Example 4 above, except that ZSM-5 (80) was used as the zeolite (mass ratio 1:1).

[0122]

[0123] <Example 6>

[0124] The same procedure was followed as in Example 4 above, except that ZSM-5 (30) was used as the zeolite (mass ratio 1:1).

[0125]

[0126] <Example 7>

[0127] The same procedure as in Example 5 was performed except that 1.2 g of zeolite (ZSM-5(80)) was charged (mass ratio 1:2).

[0128]

[0129] <Example 8>

[0130] The same procedure as in Example 5 was performed except that 1.8 g of zeolite (ZSM-5(80)) was charged (mass ratio 1:3).

[0131]

[0132] <Example 9>

[0133] The same procedure as in Example 4 was performed except that 1.8 g of zeolite (ZSM-5 (400)) was charged (mass ratio 1:3).

[0134]

[0135] <Example 10>

[0136] The same procedure as in Example 6 was performed except that 1.8 g of zeolite (ZSM-5(30)) was charged (mass ratio 1:3).

[0137]

[0138] <Example 11>

[0139] 0.6 g of Fe-based catalyst (FeCuK20CeAl) and 0.18 g of zeolite (ZSM-5(80)), each manufactured in the form of granules, were charged into a down flow stainless steel fixed bed reactor with an inner diameter of 3 / 8” and a length of 40.7 mm (mass ratio 1:0.3).

[0140] After reduction treatment with only H2 at atmospheric pressure 350 ℃ for 5 hours at a heating rate of 10 ℃ / min as a catalyst pretreatment, the feed was supplied after pressurizing up to 20 bar with N2 at room temperature. Carbon dioxide hydrogenation reaction was performed at 320 ℃, 30 bar, and 4000 mL / gcat·h space velocity with H2 / CO2 = 3. The reactants and products were analyzed online through a gas chromatograph (Agilent Instruments 8890) using a FID column GS-KCl / AL and a TCD column Porapak Q.

[0141]

[0142] <Example 12>

[0143] The same procedure was followed as in Example 11 above, except that ZSM-5 (400) was filled with zeolite (mass ratio 1:0.3).

[0144]

[0145] <Comparative Example 1>

[0146] The same procedure was followed as in Example 11 above, except that Beta was filled with zeolite (mass ratio 1:0.3).

[0147]

[0148] Comparative Example 2

[0149] The same procedure was followed as in Example 11 above, except that FAU (Zeolite Y) was filled with zeolite (mass ratio 1:0.3).

[0150]

[0151] <Comparative Example 3>

[0152] The same procedure was followed as in Example 11 above, except that FER was filled with zeolite (mass ratio 1:0.3).

[0153]

[0154] <Experimental Example 1> Analysis of Fe-based catalysts

[0155] The Fe-based catalyst (FeCuK20CeAl) manufactured in the above manufacturing example was analyzed.

[0156] Figure 2 shows SEM and EDS mapping images of an Fe-based catalyst according to one embodiment of the present invention. It was confirmed that the Fe-based catalyst had a high metal dispersion and a small particle size.

[0157]

[0158] Catalyst nameCatalyst2θFWHMCrystallite size (nm)CeO2 / Fe2O3Peak intensity ratioFeCuK20CeAlFe 0.37 Cu 0.04 K 0.09 Ce 0.034 Al 0.47 35.910.67121.74

[0159]

[0160] Figure 3 and Table 2 show the XRD results of an Fe-based catalyst according to one embodiment of the present invention. A peak corresponding to CeO2 was confirmed at 33.3°, and a peak corresponding to Fe2O3 was confirmed at 35.9°. The 2θ of the Fe-based catalyst was measured to be 35.91, the FWHM (full width at half maximum) was 0.67, the crystallite size was 12 nm, and the CeO2 / Fe2O3 peak intensity ratio was 1.74.

[0161] Figure 4 shows the XPS results of an Fe-based catalyst according to one embodiment of the present invention. The influence of the dispersion state of each metal is Fe. 2+ Wow Fe 3+ It is a mixed form. The Fe of the above Fe-based catalyst 2+ / Fe 3+ The ratio was measured as 1.2.

[0162]

[0163] Catalyst NameCatalyst X CO+CO2 (%)Yield (%)C 5~12 / CH4yield ratioCH4C 2~4C 5~12 C 13+ FeCuK20CeAlFe 0.37 Cu 0.04 K 0.09 Ce 0.034 Al 0.47 36.81.510.618.06.012.0

[0164]

[0165] Table 3 shows the reaction activity of an Fe-based catalyst according to one embodiment of the present invention. Yield represents the yield according to CO+CO2 conversion. The CO2 conversion rate of the Fe-based catalyst is 25.9%, and C 5~12 / CH4yield ratio was measured as 12.0.

[0166]

[0167] <Experimental Example 2> Zeolite acid site analysis

[0168] The acid point of zeolite (ZSM-5(x), x=SiO2 / Al2O3ratio) was analyzed. Table 4 shows the analysis results according to the acid point of the zeolite of the present invention.

[0169] Zeolite was maintained at 500 ℃ (heating rate 10 ℃ / min) in a He atmosphere for 1 hour to remove impurities and moisture, then cooled to 100 ℃ and adsorbed at 15% NH3 / He 50 mL / min for 30 minutes. After purging with He atmosphere for 1 hour and when the baseline stabilized, a Thermal Conductivity Detector (TCD) signal was obtained from NH3 desorbed at 500 ℃ (heating rate 10 ℃ / min).

[0170]

[0171] BET Surface Area (m 2 / g)t-plot micropore area (m 2 / g)Pore volume (ml / g)Amount of Acid Sites (mmol NH3 / g)N2PhysisorptionNH3-TPDTotalZSM-5(30)3772510.23480.439 (211 ℃)0.330 (410 ℃)0.769ZSM-5(80)3742550.23280.168 (192 ℃)0.098 (374 ℃)0.266ZSM-5(400)3682300.21530.041 (173 ℃)0.046 (351 ℃)0.087

[0172]

[0173] Figure 5 shows the XRD analysis results according to the zeolite acid point of the present invention, and it was confirmed in X-Ray Diffraction that ZSM-5 had a good crystal structure.

[0174] Figure 6 shows the BET analysis results according to the zeolite acid site of the present invention. From the BET analysis, there was no significant difference in the surface area and pore volume of ZSM-5 (30), ZSM-5 (80), and ZSM-5 (400).

[0175] Figure 7 shows the NH3-TPD analysis results according to the zeolite acid site of the present invention, and the acid site of each ZSM-5 was confirmed through NH3Temperature programmed Desorption (TPD) analysis. The acid site of ZSM-5 (30), which has the lowest SiO2 / Al2O3 ratio, was measured to be 0.769 mmol / g, that of ZSM-5 (80) to be 0.266 mmol / g, and that of ZSM-5 (400), which has the lowest acid site, to be 0.087 mmol / g.

[0176]

[0177] <Experimental Example 3> Catalytic activity according to composition

[0178] The catalytic activity according to the composition of Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(x), x=SiO2 / Al2O3ratio) was compared. Example 1 is Powder Mixing, Example 2 is Powder 2-bed, Example 3 is Granule Mixing, and Example 4 is Granule 2-bed.

[0179]

[0180] Catalyst X CO+CO2 (%)Selectivity (%)CH4C 2~4 =C 2~4 C 5~6 C 6+ FeCuK20CeAl36.84.124.44.71.165.7Example 124.310.316.272.963.6Example 234.94.411.74.11.478.4Example 336.34.87.47.34.675.9Example 435.84.17.26.34.577.9

[0181]

[0182] Figures 8, 9 and Table 5 show the catalytic activity according to the catalyst composition of the present invention. In Example 1, the CO+CO2 conversion rate decreased, CH4 selectivity improved, and C5~C in the liquid phase 10 mol% decreased. This is thought to be due to the transfer of alkali metal K on the Fe-based catalyst to the zeolite with acid sites during physical mixing with a mortar, which adversely affects the catalytic activity. In Examples 2 to 4, there was no change in the conversion rate, but C5~C in the liquid phase 10 mol% has been improved.

[0183] Among these, Example 4 is considered to be the most suitable in terms of reaction conditions and ease of continuous reaction according to each catalyst. Therefore, in the experimental examples described below, the composition of the Fe-based catalyst and zeolite was performed in the Granule 2-bed format of Example 4.

[0184] The activities of Fe-based catalyst (FeCuK20CeAl), zeolite (ZSM-5(80)) and Example 5 were compared.

[0185]

[0186] Catalyst X CO+CO2 (%)Selectivity (%)CH4C 2~4 =C 2~4 C 5~6 C 6+ FeCuK20CeAl36.84.124.44.71.165.7ZSM-5(80)3.000000Example 536.942.711.46.775.2

[0187]

[0188] Figures 10, 11, and Table 6 show the catalytic activity according to the catalyst composition of the present invention. The CO+CO2 conversion rate was measured to be 36.8% for FeCuK20CeAl, 3.0% for ZSM-5(80), and 36.9% for Example 5. Therefore, it was confirmed that ZSM-5(80) does not significantly participate in the CO+CO2 conversion.

[0189] However, Example 5 shows that C in the total product is introduced by zeolite. 2~4 = Olefins are converted to paraffins, etc., and C5~C in the liquid phase 10 mol% was improved from 65.3% to 90.4% for FeCuK20CeAl. This means that the introduction of zeolite resulted in a significant change in the CO+CO2 conversion rate without significant changes in C 5+ This means that improved selectivity is possible.

[0190]

[0191] <Experimental Example 4> Catalytic activity according to zeolite acid site

[0192] The catalytic activity of zeolite (ZSM-5(x), x=SiO2 / Al2O3ratio) was confirmed according to the acid site. As the SiO2 / Al2O3 ratio of zeolite increases, the number of Al sites decreases, resulting in fewer acid sites and stronger acid strength. On the other hand, as the SiO2 / Al2O3 ratio decreases, the number of acid sites increases and the acid strength decreases.

[0193] In Example 4, the zeolite is ZSM-5 (400), in Example 5, the zeolite is ZSM-5 (80), and in Example 6, the zeolite is ZSM-5 (30).

[0194]

[0195] Catalyst X CO+CO2 (%)Selectivity (%)CH4C 2~4 =C 2~4 C 5~6 C 6+ FeCuK20CeAl36.84.124.44.71.165.7Example 435.84.17.26.34.577.9Example 536.942.711.46.775.2Example 636.73.41.314.75.974.7

[0196]

[0197] Figures 12, 13, and Table 7 show the catalytic activity according to the acid sites of the zeolite of the present invention. There was no change in the conversion rate according to the acid sites of the zeolite, but the selectivity for CH4 decreased as the acid sites increased. In addition, the more acid sites of the zeolite, the higher the C5~C content in the liquid phase. 10 mol% increased, and C5~C in the liquid phase 10 The amount of aromatics in mol% also increased.

[0198]

[0199] <Experimental Example 5> Catalytic activity according to zeolite content

[0200] The catalytic activity was confirmed according to the mass ratio of the Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(80)). The mass ratio of Example 5 was 1:1, the mass ratio of Example 7 was 1:2, and the mass ratio of Example 8 was 1:3.

[0201]

[0202] Catalyst X CO+CO2 (%)Selectivity (%)CH4C 2~4 =C 2~4 C 5~6 C 6+FeCuK20CeAl36.84.124.44.71.165.7Example 536.942.711.46.775.2Example 736.34.80.814.25.374.9Example 836.140.614.77.872.9

[0203]

[0204] Figures 14, 15 and Table 8 show the catalytic activity according to the zeolite content of the present invention. As the content of ZSM-5 (80) increases, olefins in the total product are converted to paraffins, cycloparaffins and aromatics, and C5~C in the liquid phase 10 mol% gradually increased. In addition, as the content of ZSM-5(80) increased, C5~C in the liquid phase 10 The amount of aromatics in mol% also increased.

[0205]

[0206] <Experimental Example 6> Catalytic activity according to zeolite acid site and content

[0207] The activity of the catalyst was confirmed according to the acid site of zeolite (ZSM-5(x), x=SiO2 / Al2O3ratio) and the mass ratio with Fe-based catalyst (FeCuK20CeAl).

[0208] Example 4 has a mass ratio of Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(400)) of 1:1, Example 5 has a mass ratio of Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(80)) of 1:1, and Example 6 has a mass ratio of Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(30)) of 1:1.

[0209] Example 8 has a mass ratio of Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(80)) of 1:3, Example 9 has a mass ratio of Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(400)) of 1:3, and Example 10 has a mass ratio of Fe-based catalyst (FeCuK20CeAl) and zeolite (ZSM-5(30)) of 1:1.

[0210]

[0211] Catalyst X CO+CO2 (%)Selectivity (%)CH4C 2~4 =C 2~4 C 5~6 C 6+ FeCuK20CeAl36.84.124.44.71.165.7Example 435.84.17.26.34.577.9Example 536.942.711.46.775.2Example 636.73.41.314.75.974.7Example 836.140.614.77.872.9Example 935.34.42.38.45.779.2Example 1034.54.70166.373.0

[0212]

[0213] Figures 16, 17, and Table 9 show the catalytic activity according to the zeolite acid site and content of the present invention. When the mass ratio of FeCuK20CeAl and ZSM-5(x) is 1:3, the mass ratio is 1:1 compared to C 2~4 = Selectivity decreases and C 5+ Selectivity has been improved. C5~C in liquid phase 10 In mol%, FeCuK20CeAl is 66.0%, while C5~C in the liquid phase with the introduction of zeolite 10 The mol% was significantly improved to 93.2%.

[0214] In addition, as the acidity and content increase, the olefin content in the total product decreases to less than 1%, and C5~C in the liquid phase 10 The amount of aromatics in mol% increased significantly.

[0215] Figure 18 shows C5~C among the entire products according to one embodiment of the present invention. 12 It shows the selectivity of C5~C among all gaseous and liquid products generated during the entire reaction time. 12 The products were in the range of C5~C. In the Fe-based catalyst (FeCuK20CeAl), 36.7% of the products were in the C5~C 12, and when zeolite (ZSM-5(x), x=SiO2 / Al2O3ratio) was introduced, C5~C of the total product 12 This overall increase was as high as 67.3%. Therefore, by introducing zeolite, the target product (C5~C 12 ) can improve the selectivity, and the yield of the entire product can be controlled according to process variables such as the acidity and content of the zeolite.

[0216]

[0217] Experimental Example 7

[0218] The activity of the catalyst was confirmed according to the type of zeolite. Example 11 is ZSM-5 (80), Example 12 is ZSM-5 (400), Comparative Example 1 is Beta, Example 2 is FAU, and Example 3 is FER.

[0219]

[0220] Catalyst X CO2 (%)Selectivity (%)COC1C 2~4 =C 2~4 C 5~6 C 6+ FeCuK20CeAl39.817.810.920.45.41.661.6Example 1139.617.513.78.414.05.158.8Example 1240.516.51111.28.03.866Comparative Example 140.815.68.420.35.21.664.5Comparative Example 237.115.29.6215.11.662.7Comparative Example 340.215.98.724.86.41.858.3

[0221]

[0222] Figures 19, 20, and Table 10 show the catalytic activity according to the type of zeolite of the present invention. In Examples 11 and 12, it was confirmed that the C5-C10 mol% in the liquid phase increased, and the olefin decreased, resulting in the production of paraffin and aromatic. However, Comparative Examples 1 to 3 showed the same activity as FeCuK20CeAl without introducing zeolite, and did not show any effect due to the introduction of zeolite.

[0223]

[0224] Although the present invention has been described in this specification with specific details and limited examples, these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on these descriptions. Therefore, the ideas described in this specification should not be limited to the described examples, and all things that are equivalent or equivalent to the claims below, as well as the claims, are considered to fall within the scope of the ideas described in this specification.

Claims

1. Fe-based catalysts prepared through mixing and diffusion reactions of metal precursors under solvent-free conditions by mechanical shearing; and zeolites; including carbon dioxide to C 5+ A catalyst system for converting carbon dioxide to produce hydrocarbons.

2. In paragraph 1, The above Fe-based catalyst is a catalyst system for carbon dioxide conversion, which is a compound represented by the following [chemical formula 1]. [Chemical Formula 1] Fe a With b K c the d (M) e The above M includes at least one selected from rare earth metals including cerium (Ce), lanthanum (La) and praseodymium (Pr), and the a, b, c, d and e have a total of 1 and are independently 0.01 to 0.

7.

3. In paragraph 2, The above Fe-based catalyst is a catalyst system for carbon dioxide conversion manufactured by mixing each component metal precursor in an equivalent ratio according to the above chemical formula 1 and applying mechanical shear force.

4. In paragraph 3, A catalyst system for carbon dioxide conversion, wherein the metal precursor is a metal salt comprising at least one selected from the group consisting of nitrate, ammonium nitrate, carbonate, bicarbonate, hydroxide, oxide, oxyhydrate, acetate, and sulfate.

5. In paragraph 2, The above Fe-based catalyst is a catalyst system for carbon dioxide conversion, which includes a peak having an XRD 2θ value of 35.85 to 35.

95.

6. In paragraph 2, The above Fe-based catalyst is a catalyst system for carbon dioxide conversion having a particle size (crystallite size) of 10 to 20 nm.

7. In paragraph 2, The above Fe-based catalyst has a BET surface area of ​​50 to 200 m 2 Catalytic system for carbon dioxide conversion of / g.

8. In paragraph 2, The above Fe-based catalyst has a pore volume of 0.01 to 0.5 cm 3 Catalytic system for carbon dioxide conversion of / g.

9. In paragraph 1, The above zeolite is a catalyst system for carbon dioxide conversion, which is ZSM-5 (Zeolite Socony Mobil-5).

10. In paragraph 9, A catalyst system for carbon dioxide conversion wherein the SiO2 / Al2O3 ratio of the above ZSM-5 is 20 to 600.

11. In paragraph 1, A catalyst system for carbon dioxide conversion in which the above Fe-based catalyst and zeolite are sequentially arranged in a dual bed (2-bed) in a single catalyst reactor or in different catalyst reactors.

12. In paragraph 11, A catalyst system for carbon dioxide conversion, wherein the above Fe-based catalyst and zeolite are arranged to sequentially contact a gas containing introduced carbon dioxide.

13. In paragraph 1, The above Fe-based catalyst and zeolite are a catalyst system for carbon dioxide conversion in the form of granules having a size of 0.3 to 2 mm.

14. In paragraph 1, A catalyst system for carbon dioxide conversion wherein the mass ratio of the Fe-based catalyst and zeolite is 1:0.1 to 5.

15. In any one of the carbon dioxide conversion catalyst systems of clauses 1 to 14, a gas containing carbon dioxide is sequentially brought into contact with the Fe-based catalyst and zeolite to form C 5+ A method for converting carbon dioxide to produce hydrocarbons.

16. In paragraph 15, A method for converting carbon dioxide, wherein the molar ratio of H2 and CO2 in the gas containing the carbon dioxide is 1 to 3:

1.

17. In paragraph 15, A method for converting carbon dioxide, wherein the GHSV (Gas Hourly Space Velocity) of the gas containing the carbon dioxide is 1,000 to 10,000 mL / gcat·h.

18. In paragraph 15, A carbon dioxide conversion method in which the pressure is 1 to 50 bar.

19. In paragraph 15, A carbon dioxide conversion method in which the temperature is 100 to 1000°C.

20. In paragraph 15, In the above carbon dioxide conversion method, C5~C in the liquid product 12 A carbon dioxide conversion method having a selectivity of 30 to 100%.

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