Catalyst for Fischer-Tropsch reaction and method for producing the same

Abstract

To provide a catalyst for the FT (Fischer-Tropsch) reaction and a method for producing the same. [Solution] This disclosure provides a catalyst for an FT reaction, comprising a composite support containing uniformly distributed alumina and zeolite, and a metal uniformly supported on the composite support, wherein the metal is Co, and also provides a method for producing the catalyst.

Description

[Technical Field]

[0001] This disclosure relates to a catalyst for the FT (Fischer-Tropsch) reaction and a method for producing the same. [Background technology]

[0002] Synthetic fuel (or synfuel) is generally defined as hydrocarbons produced from synthesis gas, a mixture of carbon monoxide and hydrogen, through a series of chemical reactions, and is distinct from hydrocarbons selected by distillation from crude oil. A typical reaction for synthesizing liquid hydrocarbons from synthesis gas using a catalytic reaction is the FT reaction.

[0003] Aviation oil is fuel used in aircraft engines. Sustainable aviation fuel (SAF) refers to aviation fuel made from sustainable and renewable raw materials. These raw materials may be bio-derived, such as seaweed, animals and plants, or edible oils, or they may be synthetic raw materials produced using carbon dioxide from the air or hydrogen derived from water.

[0004] SAF can replace conventional aviation oil without modifying existing aircraft. SAF has the advantage of reducing carbon emissions by up to 80% compared to conventional aviation oil, which is produced using fossil resources such as petroleum and coal. SAF is attracting attention not only from the perspective of the depletion of existing fossil resources and rising crude oil prices, but also from the perspective of preventing global warming and reducing carbon dioxide emissions. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Korean Published Patent Publication No. 10-2018-0125087 [Overview of the project] [Problems that the invention aims to solve]

[0006] According to one aspect of this disclosure, a novel catalyst that can be used in FT reactions can be provided. According to another aspect of this disclosure, a method for producing the catalyst can be provided.

[0007] The catalyst of this disclosure can be widely applied in SAF manufacturing technology and can therefore contribute to preventing global warming by reducing carbon emissions. [Means for solving the problem]

[0008] One aspect of the present disclosure is a catalyst for an FT reaction, comprising a composite support containing uniformly distributed alumina and zeolite, and a metal supported on the composite support, wherein the metal includes Co.

[0009] According to one embodiment, the catalyst has a compositional uniformity of 5.0 or less as defined in the UN of Formula 1,

number

[0010] According to one embodiment, the zeolite has an MRE or MFI structure.

[0011] According to one embodiment, the zeolite includes EU-2, ZSM-5, ZSM-48, or a combination thereof.

[0012] According to one embodiment, the weight ratio of alumina to zeolite in the composite support is 1:1 to 1:5.

[0013] According to one embodiment, the content of the composite support in the catalyst is at least 80 wt%.

[0014] According to one embodiment, the metal further includes Fe.

[0015] According to one embodiment, the content of the metal in the catalyst is at least 5 wt%.

[0016] According to one embodiment, the catalyst further includes a promoter metal.

[0017] According to one embodiment, the promoter metal includes Y, Ce, La, W, Mo, or a combination thereof.

[0018] According to one embodiment, the content of the promoter metal in the catalyst is at least 1 wt%.

[0019] According to one embodiment, when the catalyst is measured by temperature-programmed reduction (H2-TPR), it includes a reduction peak at 600 °C or higher.

[0020] Another aspect of the present disclosure is a method for manufacturing a catalyst for the FT reaction, including the steps of preparing a composite support mixture including an alumina hydrate and zeolite, preparing a metal precursor solution including Co, mixing the composite support mixture and the precursor solution to manufacture a catalyst mixture, and firing the catalyst mixture.

[0021] According to one embodiment, the step of manufacturing the catalyst mixture further includes the step of adding an acid to the precursor solution.

[0022] According to one embodiment, the step of manufacturing the catalyst mixture includes mixing the composite support mixture and the precursor solution to produce a paste, and extruding the paste to produce an extrudate, and the step of firing the catalyst mixture is the step of firing the extrudate.

Advantages of the Invention

[0023] According to one embodiment, the use of the catalyst in the Fischer-Tropsch reaction can increase the selectivity of the fraction below the diesel boiling range in the Fischer-Tropsch reaction product. According to one embodiment, the use of the catalyst can increase the contents of olefins and iso-paraffins in the Fischer-Tropsch reaction product. According to one embodiment, the Fischer-Tropsch process using the catalyst can increase the yield of aviation fuel in cooperation with a subsequent fuel oil production process.

Brief Description of the Drawings

[0024] [Figure 1] An SEM image of a cross-section of a catalyst support according to one embodiment is shown. [Figure 2] The distribution of each element by EDS analysis in the cross-section of a catalyst support according to one embodiment is shown. [Figure 3] A line profile of the composition of Al and Si on a reference line which is a straight line crossing the center of a catalyst support according to one embodiment is shown. [Figure 4] The H2-TPR analysis results of catalysts according to some examples and comparative examples are shown. [Figure 5] The results of performance experiments of catalysts in the Fischer-Tropsch reaction according to some examples and comparative examples are shown. [Figure 6] The results of performance experiments of catalysts in the Fischer-Tropsch reaction according to some examples and comparative examples are shown.

Modes for Carrying Out the Invention

[0025] Hereinafter, the present disclosure will be described in detail with reference to the accompanying drawings. However, this is merely exemplary, and the present disclosure is not limited to the specific embodiments described by way of example.

[0026] Catalyst for FT reaction One aspect of the present disclosure provides a catalyst for FT reactions. The FT reaction product, a liquid hydrocarbon or synthetic oil (syncrude), can be used as a starting material for fuel oil production. Among the fuel oils, aviation oil can be obtained by isomerizing a fraction in the kerosene boiling point range of the synthetic oil, or by alkylating and / or polymerizing a fraction in the naphtha boiling point range of the synthetic oil, and / or by cracking a fraction above the diesel boiling point range.

[0027] In this disclosure, the terms naphtha fraction, kerosene fraction (also referred to as SAF fraction), and diesel+ fraction are used in relation to synthetic oils. The naphtha fraction refers to a fraction within the naphtha boiling point range or the naphtha carbon number range, and these can be used interchangeably. This also applies to the kerosene fraction and the diesel+ fraction. In this disclosure, the naphtha fraction contains hydrocarbons having 5 to 8 carbon atoms, the kerosene fraction contains hydrocarbons having 9 to 15 carbon atoms, and the diesel+ fraction contains hydrocarbons having 16 or more carbon atoms.

[0028] Taking into consideration the coordination between the FT process and the aviation oil manufacturing process described above, the catalyst of this disclosure is a catalyst designed to produce a synthetic oil having a composition that can increase the production efficiency of aviation oil.

[0029] The catalyst comprises a composite support and a metal supported on the composite support. The composite support comprises alumina and zeolite. The metal also comprises Co.

[0030] The alumina and zeolite are uniformly distributed within the composite carrier. In this disclosure, "uniformly distributed" means that the alumina and / or zeolite are not concentrated in any particular region within the composite carrier.

[0031] In some embodiments of this disclosure, the uniform distribution of alumina and zeolite can be defined by the UN of the following formula 1.

[0032]

number

[0033] According to one embodiment, the UN of the catalyst may be 5.0 or less. Specifically, the UN of the catalyst may be 3.3 or less, more specifically 2.5 or less, more specifically 2.3 or less, and still more specifically 2.1 or less. In this case, UN may be greater than 0 and substantially 0.01 or more, but is not limited thereto.

[0034] In equation 1, C Al (i) (where i is a natural number from 1 to M), at least one of these may be the alumina composition at a location belonging to the central region of the cross-section of the support (hereinafter referred to as the support cross-section), and at least one may be the alumina composition at a location belonging to the edge region of the cross-section of the support.

[0035] The central region can be defined as the area within 0.01 to 0.20 Rr, specifically within 0.05 to 0.15 Rr, of the center of the carrier cross-section, based on the radius Rr of the carrier cross-section in the radial direction at the center of the carrier. In such cases, the shape of the central region can correspond to the shape of the carrier cross-section. That is, the central region may be a shape that is 0.01 to 0.20 Rr smaller than the shape of the carrier cross-section, specifically a shape that is 0.05 to 0.15 Rr smaller, based on length.

[0036] Since the carrier is porous, there is a risk that mounting material may penetrate into the edge during mounting to fix the carrier, and accurate composition analysis may not be performed due to such mounting material. Therefore, the edge region should be as adjacent as possible to the edge of the carrier cross-section while excluding the edge of the carrier cross-section contaminated by the mounting material and being free from contamination by the mounting material, so that it can show the uniformity of the composition in substantially the entire region of the carrier cross-section. From such a perspective, the edge region can mean a region from 0.70Rr to 0.95Rr, specifically a region from 0.75Rr to 0.85Rr, from the center of the carrier cross-section in the radial direction based on the radius Rr of the carrier cross-section in the radial direction at the center of the carrier.

[0037] Also, the constant interval between positions (positions where the composition is measured) separated at a constant interval on the reference line can correspond to the value obtained by dividing the distance between the edge region and the central region by M. According to one embodiment, the constant interval can be 1 to 20 μm, more specifically 1 to 10 μm, and even more specifically 2 to 8 μm, but is not necessarily limited thereto.

[0038] Also, UN relates to the compositional uniformity of alumina. However, since the carrier is a composite carrier of alumina and zeolite, and the alumina composition has a composition with the content (wt%) of alumina as the numerator and the total content (wt%) of alumina and zeolite as the denominator, the compositional uniformity of alumina can correspond to the compositional uniformity of zeolite. Therefore, a low numerical value of UN can mean not only that alumina is uniformly distributed but also that zeolite is uniformly distributed.

[0039] Experimentally, in Equation 1, the alumina composition (C Al ) can be calculated based on the results of energy dispersive spectrometry (EDS). Specifically, C Al(ave) is a value calculated by elemental mapping covering the entire cross-sectional area of ​​the carrier (including the edge and central regions mentioned above, but excluding parts contaminated by the mounting material), and C Al (i) may be calculated based on the measurement results at positions spaced at regular intervals in the line profile of the alumina composition on the cross-section of the support. The working distance (WD) during energy-dispersive spectroscopy was 12.7 mm, the acceleration voltage was 15 kV, the electron beam size was 0.4 nA, and the scan speed was 0.2 mm / msec. The result may be the result of repeated measurements tens to hundreds of times.

[0040] The metal can be uniformly supported on the composite support. In this disclosure, “uniformly supported” means that the metal is not concentrated in any particular region of the composite support. Specifically, the metal can be uniformly supported on both the alumina and the zeolite, rather than being supported primarily on alumina or primarily on the zeolite. In other words, the catalyst of this disclosure may be a composite catalyst in which a first catalyst, on which the metal is supported on alumina, and a second catalyst, on which the metal is supported on the zeolite, are uniformly distributed. The composite support includes alumina. The first catalyst (on which the metal is supported on alumina) facilitates the conversion of the synthesis gas into a liquid hydrocarbon having a relatively high carbon content (e.g., a fraction greater than diesel) in the FT reaction. According to one embodiment, the alumina may be derived from an alumina hydrate. The alumina hydrate may include boehmite, pseudo-boehmite, and combinations thereof. As described later, alumina hydrate can be calcined during catalyst production and ultimately converted to alumina. Since the alumina hydrate also functions as a binder, it can help the metal be better supported on the composite support during catalyst production. If alumina is used directly instead of alumina hydrate during catalyst production, the lack of binder function may lead to a problem where the adhesion between the metal and the composite support is not maintained.

[0041] The composite support also includes zeolite. The second catalyst (in which a metal is supported on zeolite) can increase the yield of the kerosene- and lower fractions in the FT reaction product. More specifically, the use of the second catalyst can increase the yield of the naphtha fraction. Furthermore, the use of the second catalyst can improve the selectivity of olefins and iso-paraffins in the synthetic oil.

[0042] According to one embodiment, the zeolite may have an MRE or MFI structure. Specifically, the zeolite may include EU-2, ZSM-5, ZSM-48, or a combination thereof. Furthermore, the zeolite may have a SAR (silica-alumina ratio) of 20 to 200. If the SAR is less than 20, the acid sites may be too strong, potentially leading to the production of very hard hydrocarbons mainly through the cracking reaction. Conversely, if the SAR exceeds 200, the acid sites may be too weak, potentially leading to the isomerization and cracking reactions being too inactive.

[0043] In the catalyst of this disclosure, the first catalyst and the second catalyst are uniformly distributed throughout the entire surface of the catalyst, closely located within, for example, a distance of several micrometers. Such close and uniform distribution of the first and second catalysts can increase the yield of the kerosene fraction as the FT reaction product.

[0044] Furthermore, the use of the catalyst of this disclosure allows for the control of the content ratio of n-paraffin to iso-paraffin in the kerosene fraction to a range of 1:1 to 1:2. In the subsequent process of producing aviation oil from the kerosene fraction, an isomerization step is required to meet the specifications of the aviation oil, such as the freezing point. However, the use of the catalyst of this disclosure allows for the presence of a sufficient amount of iso-paraffin in the kerosene fraction, thus eliminating the need for the isomerization step.

[0045] On the other hand, while alumina and zeolite are uniformly distributed within the composite carrier, it should be noted that such uniform distribution does not mean that the content of alumina and zeolite are equal to each other. Within the composite carrier, the zeolite content is equal to or greater than that of alumina. According to one embodiment, the weight ratio of alumina to zeolite in the composite carrier may be 1:1 to 1:5. Specifically, the weight ratio may be 1:1 to 1:4, more specifically 1:2 to 1:4, and even more specifically 1:2 to 1:3. If the ratio is less than 1:1, there is a risk that the function of the zeolite within the catalyst will be reduced. On the other hand, if the ratio exceeds 1:5, the amount of alumina hydrate may be insufficient, which may reduce the adhesive strength between the catalyst components and weaken the strength of the catalyst extruded after firing.

[0046] The composite support accounts for the majority of the catalyst weight. According to one embodiment, the content of the composite support in the catalyst may be at least 75 wt%. Specifically, the content may be 75-94 wt%, more specifically 75-92 wt%, even more specifically 75-89 wt%, and even more specifically 75-87 wt%. If the content is less than 75 wt%, the relative content of the metal component in the catalyst may become too high, resulting in insufficient support of the metal component, larger particles, and a decrease in catalyst efficiency. On the other hand, from the viewpoint of FT reaction efficiency and / or catalyst durability, the content may be 90 wt% or less.

[0047] The catalyst contains a metal including Co. The metal content in the catalyst may be at least 5 wt%. Specifically, the content may be 5 to 20 wt%, more specifically 7 to 20 wt%, even more specifically 8 to 20 wt%, and even more specifically 10 to 20 wt%. According to some embodiments, the particle size of the metal may be 1 μm or less. Here, particle size means the longest length of the particle. Also, according to some embodiments, the metal may further contain Fe.

[0048] The catalyst may further contain a co-catalyst metal. The co-catalyst metal can adjust the reaction rate of Co, thereby adjusting the chain length of the FT reaction product and contributing to increasing the selectivity of olefins. For example, the olefin content in the naphtha fraction of the FT reaction product using the catalyst of this disclosure containing a co-catalyst metal may be 50 wt% or more. Since olefins are required for oligomerization in the subsequent process of producing aviation oil from the naphtha fraction, increasing the olefin content in the naphtha fraction can increase the efficiency of aviation oil production without the need for additional olefin supply.

[0049] The metals that can be used as the co-catalyst metals are not particularly limited, as long as they are effective in achieving the above-mentioned objectives. For example, the co-catalyst metals may include Y, Ce, La, W, Mo, or combinations thereof.

[0050] According to one embodiment, the content of the co-catalyst metal in the catalyst may be at least 1 wt%. Specifically, the content may be 1 to 5 wt%, more specifically 1 to 4 wt%, and even more specifically 1 to 3 wt%. A co-catalyst metal content below the above range may not be sufficient to control the properties of metals such as Co in the catalyst. On the other hand, a co-catalyst metal content exceeding the above range may cause the problem of excessively reducing the activity of the metal. According to some embodiments, the weight ratio of metal to co-catalyst metal may be 3:1 to 10:1.

[0051] When the catalyst of this disclosure is inactive, the metal and co-catalyst metal can exist in the form of metal oxides. Activation of the catalyst can be performed by reducing the metal oxide with hydrogen. According to one embodiment, the catalyst may include a reduction peak at 600°C or above when measured by temperature-programmed reduction (H2-TPR). Specifically, the catalyst may include a maximum reduction peak at 600°C or above when measured by H2-TPR. While we do not wish to be bound by any particular theory, the presence of such reduction peaks is thought to be due to a strong interaction between the metal component and the composite support. Such a strong interaction can control the selectivity of the FT reaction products by somewhat inhibiting the activity of the metal component, and as a result, the generation of diesel+ fraction as FT reaction products can be reduced and the generation of iso-paraffin and olefins can be increased.

[0052] When used in a FT reaction, the catalyst of this disclosure can increase the conversion rate to liquid hydrocarbons, increase the yield of fractions with boiling points below kerosene relative to the diesel fraction, and in particular increase the yield of the kerosene fraction, thereby enhancing the selectivity of the olefin and iso-paraffin products. Of the FT reaction products thus produced, the kerosene fraction can be used as an aviation oil product without further isomerization steps, and the naphtha fraction can be converted to an aviation oil product via a conversion reaction without further olefin supply. The catalyst of this disclosure is expected to improve the overall aviation oil yield in conjunction with the aviation oil production process downstream of the FT process.

[0053] Method for producing a catalyst for FT reaction Other aspects of this disclosure provide methods for producing the FT reaction catalyst described above. Unless otherwise specified, it should be noted that the detailed descriptions of each component described in the "FT reaction catalyst" above are similarly applicable to the common components described in the "Method for Producing the FT reaction catalyst" below.

[0054] The method includes the steps of: preparing a composite support mixture containing alumina hydrate and zeolite; preparing a metal precursor solution containing Co; mixing the composite support mixture and the precursor solution to produce a catalyst mixture; and calcining the catalyst mixture.

[0055] In this disclosure, the metal precursor is not particularly limited as long as it can provide the metal atoms during the production of the catalyst mixture. In particular, considering the addition of acid as described later, the metal precursor may be a salt of the metal and the acid. According to one embodiment, the salt may specifically include a nitrate, a sulfate, a chloride, an acetate, or a combination thereof.

[0056] According to one embodiment, the precursor solution may be a mixed solution of a metal precursor and a co-catalyst metal precursor. The metal precursor and co-catalyst metal precursor in the precursor solution can be converted to the metal and co-catalyst metal, respectively, before mixing with the composite carrier mixture. According to one embodiment, the step of producing the catalyst mixture may further include the step of adding an acid to the precursor solution. The step of adding the acid can be performed before the precursor solution and the composite carrier mixture are mixed. The addition of such an acid can cause the metal in the precursor solution to dissociate and be converted into an ionic form.

[0057] The acid can be nitric acid, sulfuric acid, hydrochloric acid, acetic acid, or a combination thereof. From the viewpoint of preventing poisoning by residual salts, the acid may include nitric acid, acetic acid, or a combination thereof. Furthermore, from the viewpoint of the strength of the catalyst paste, the acid may include nitric acid.

[0058] The catalyst mixture can be manufactured by impregnation or co-mulling. Specifically, from the viewpoint of simplifying the work steps and maintaining the strength of the extruded product, the catalyst mixture can be manufactured by co-mulling. According to one embodiment, the step of manufacturing the catalyst mixture may include the step of mixing the composite carrier mixture and the precursor solution to manufacture a paste, and the step of extruding the paste to manufacture an extruded product. In this case, the subsequent step of calcining the catalyst mixture is replaced by the step of calcining the extruded product.

[0059] For paste production, the composite carrier mixture can be mixed by adding the precursor solution in several small portions. The produced paste can be manufactured into an extruder using a known extruder. The extruder can be cut to an appropriate length as needed.

[0060] The catalyst mixture or extruded material is subjected to a calcination treatment. According to one embodiment, the catalyst mixture or extruded material may be subjected to primary calcination at a temperature of 80 to 200°C for 1 to 10 hours, and secondary calcination at a temperature of 400 to 700°C for 1 to 10 hours. Specifically, the primary calcination may be carried out at a temperature of 100 to 150°C for 3 to 8 hours. If the temperature of the primary calcination is below the above range, there is a risk that moisture in the catalyst mixture or extruded material will not be sufficiently removed. On the other hand, if the temperature of the primary calcination exceeds the above range, the secondary calcination reaction may be carried out with moisture still present. In this case, there is a risk that the structure of the composite carrier may become easily disintegrated.

[0061] Specifically, the secondary firing can be carried out at a temperature of 500-600°C for 3-8 hours. If the temperature of the secondary firing is below the above range, there is a risk that problems may occur in which residual metal salt components in the catalyst mixture or extruded material, structural changes of alumina hydrate to alumina, and removal of ammonia in the zeolite components are not sufficiently performed. On the other hand, if the temperature of the secondary firing exceeds the above range, there is a risk that problems such as structural changes of alumina (e.g., γ-alumina) and structural collapse of zeolite may occur.

[0062] The catalyst of this disclosure can be manufactured by following the steps described above.

[0063] The embodiments of the present invention will be further described below with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope of the present invention and the technical concept, and that such variations and modifications will naturally fall within the scope of the appended claims.

[0064] Examples 1. Catalyst manufacturing (1) Example 1A-1F 16.1 g of MFI zeolite (SiO2 / Al2O3=30) and 7.9 g of pseudo-boehmite were mixed using a roller for 12 hours. A 1 M nitric acid (HNO3) solution was prepared and added to the zeolite-pseudo-boehmite mixture while mixing to form a composite carrier paste. The paste was extruded using an extruder, and the extruded material was cut to a size of 2 mm in diameter and 10 mm in length. The extruded material was calcined in an air atmosphere at 120°C for 5 hours and then at 550°C for 5 hours. The heating rate was 2°C / min. The calcined extruded material was crushed and meshed to produce MFI composite carriers as particles with a diameter of 0.4 to 1.2 mm.

[0065] Cobalt nitrate and a nitrate compound of the co-catalyst metal were quantitatively added to 10 g of distilled water and then dissolved. The nitrate compounds were quantitatively determined so that their content in the final catalyst was 10 wt% and 3 wt%, respectively. The metal mixture solution was added to 1.43 g of the previously prepared MFI composite carrier and mixed for 30 minutes. The mixture was placed in an oven set to 80°C to evaporate the water. The dried sample was calcined and meshed to produce the catalyst of Example 1. The calcination and meshing process was the same as the calcination process for the MFI composite carrier extruded described above. The components of the catalyst of Example 1 are shown in Table 1 below.

[0066] [Table 1] (2) Example 2A-2F 16.1 g of MFI zeolite (SiO2 / Al2O3=30), 14.7 g of MRE zeolite, or 14.8 g of Hierarchical MRE zeolite were prepared. One type of zeolite selected from the above was mixed with 7.9 g of pseudo-boehmite using a roller for 12 hours to prepare a composite carrier mixture.

[0067] A catalyst precursor mixed solution was prepared by dissolving cobalt nitrate and the nitrate of a co-catalyst metal in a 1M nitric acid (HNO3) solution. The metal and co-catalyst metal were quantified using the same method as in Example 1. The catalyst precursor mixed solution was added to the zeolite and boehmite composite carrier mixture and mixed to produce a paste. The paste was extruded using an extrusion device, and the extruded material was cut to a size of 2 mm in diameter and 10 mm in length. The extruded material was calcined and meshed to produce the catalyst of Example 2. The calcination and meshing were carried out under the same conditions as the calcination and meshing in Example 1. Table 2 shows the components of the catalyst of Example 2. h-MRE stands for hyaluranical MRE zeolite.

[0068] [Table 2] (3) Comparative Example A Co precursor solution was prepared by dissolving 27.4 g of cobalt nitrate (Co(NO3)2-6H2O) in 100 g of distilled water at room temperature. 50 g of Al2O3 extruded material was added to the Co precursor solution and mixed. The mixed solution was then placed in a rotary evaporator. A Co-supported extruded material (wet-extrudate) was prepared by evaporating the distilled water in the rotary evaporator (Rotary Bath temperature 80-95°C, pressure 100-200 mmHg, rpm 40-100). The extruded material (wet-extrudate) was placed in an oven and dried at 80°C for 12 hours. The dried sample was calcined and meshed to produce the catalyst of the comparative example. The calcination and meshing were carried out under the same conditions as in Example 1.

[0069] 2. Confirmation of SEM images of the manufactured catalyst and confirmation of component distribution. Figure 1 shows an SEM image of the cross-section of the catalyst extruded in Example 1E.

[0070] Figure 2 shows the distribution of each element in the aforementioned cross-section as determined by EDS analysis. Here, Al represents the distribution of alumina and zeolite, and Si represents the distribution of zeolite.

[0071] The line profiles of aluminum and silicon compositions along a reference line crossing the center of the cross-section of the extruded material of Example 1E (Figure 1) were calculated based on energy dispersive spectrometry (EDS) results and are shown in Figure 3. The UN values ​​for the two samples were calculated using Equation 1, yielding 2.42 and 3.24, respectively.

[0072] Figures 1 to 3 show that in the catalyst of the example, the composite support is uniformly dispersed within a few micrometers, and the metal and co-catalyst metal are also uniformly supported on the composite support.

[0073] 3.H2-TPR analysis Hydrogen-temperature-reduced reduction (H2-TPR) analysis was performed using an AutoChemII system from Micromeritics. 100 mg of sample was used. Prior to measurement, each sample was heated to 150°C under nitrogen (N2) conditions and maintained for 2 hours, then cooled to room temperature. After stabilizing the TCD detector signal (baseline), measurements were performed in a 50 sccm (cc / min) flowing gas atmosphere (6.82% hydrogen, balance helium (He)), while increasing the temperature from room temperature to 800°C at a gradient rate of 10°C / min.

[0074] Figure 4 shows the H2-TPR results for Examples 1A, 1E, 2B and the Comparative Example. From Figure 4, it can be seen that the catalysts of the Examples show a maximum reduction peak at 600°C or higher compared to the Comparative Example. The presence of such a high-temperature reduction peak is thought to be due to the strong interaction between the metal component of the catalyst in the Examples and the composite support.

[0075] 4. Catalyst performance experiment The catalyst performance of the previously manufactured catalysts in the examples and comparative examples was experimentally evaluated using the following procedure.

[0076] After mixing 1.43 g of catalyst with 10 g of SiC, the mixture was mounted in a fixed-bed reactor. In the pretreatment process, the temperature was raised to 420°C at a rate of 2°C / min while flowing hydrogen at atmospheric pressure at a flow rate of 20 cc / min for 12 hours to reduce and activate the catalyst metal, and then cooled to room temperature. The hydrogen was replaced with a reaction gas (Syngas, H260% + CO30% + Ar10%), the reaction pressure was adjusted to 20 Bar, and the temperature was raised to 250°C at a rate of 2°C / min while flowing 50 cc / min to start the reaction. After 100 hours of reaction, the mixture was cooled to room temperature. The reaction liquid product was recovered using a hot trap and a cold trap.

[0077] The recovered liquid product was subjected to 2D-GC analysis and separated and quantified according to carbon number into n-paraffins, iso-paraffins, olefins, naptenes, aromatics, etc. Specifically, an Agilent 7890A equipped with two columns (DB-5, DB-Wax) and a modulator was used. The liquid product was mixed with 10% methylene chloride solvent and injected in 1 μL (Split Ratio 100:1). The GC oven was heated from 40°C to 250°C at a rate of 2°C / min.

[0078] Figures 5 and 6 show the results of the component analysis of the liquid products recovered in catalyst performance experiments for each catalyst produced in Examples 1-2 and the Comparative Example. The proportions of naphtha, SAF, and diesel fractions in the liquid product for each catalyst, as well as the olefin content in the naphtha, are shown. All of the proportions and contents are based on weight.

[0079] Experimental results using the catalysts of the examples show that, compared to the comparative example, the production volume of the diesel fraction decreased and the olefin content in the naphtha increased. In particular, among the examples, the catalysts containing co-catalyst metals showed that the olefin content in the naphtha was 40 wt% or more.

[0080] In summary, the catalyst of this disclosure can reduce the production of the diesel fraction in the FT reaction product and increase the production of iso-paraffin and olefin components by inducing strong interactions with metal using a composite support. The use of the catalyst of this disclosure in the FT reaction process is expected to provide synergistic effects that can increase the production of aviation oil in conjunction with subsequent processes that convert the naphtha fraction into aviation oil products.

[0081] The above description is merely an example of applying the principles of this disclosure, and other configurations may be included without exceeding the scope of the present invention.

Claims

1. A catalyst for the FT (Fischer-Tropsch) reaction, A composite carrier containing uniformly distributed alumina and zeolite, The composite carrier includes a metal supported on the composite carrier, The aforementioned metal is a catalyst for the FT reaction, containing Co.

2. The catalyst has a compositional uniformity of 5.0 or less as defined by the UN in Formula 1, [Math 1] In Equation 1, UN is the degree of compositional uniformity, and C Ａｌ This is the alumina composition in which the total content (wt%) of alumina and zeolite is the denominator and the alumina content (wt%) is the numerator, C Ａｌ (ave) is the average alumina composition in the cross-section of the support crossing the center of the composite support, C Ａｌ (i) is the alumina composition at the i-th position, where positions are sequentially numbered at regular intervals along a reference line, which is a straight line crossing the center of the cross-section of the carrier, and M is the total number of positions on the reference line where the alumina composition is measured, and is a natural number between 20 and 500, as described in claim 1.

3. The FT reaction catalyst according to claim 1, wherein the zeolite has an MRE or MFI structure.

4. The FT reaction catalyst according to claim 1, wherein the zeolite comprises EU-2, ZSM-5, ZSM-48, or a combination thereof.

5. The catalyst for FT reaction according to claim 1, wherein the weight ratio of alumina to zeolite in the composite support is 1:1 to 1:

5.

6. The catalyst for FT reaction according to claim 1, wherein the content of the composite support in the catalyst is at least 80 wt%.

7. The catalyst for the FT reaction according to claim 1, further comprising Fe as the metal.

8. The catalyst for FT reaction according to claim 1, wherein the metal content in the catalyst is at least 5 wt%.

9. The catalyst for FT reaction according to claim 1, wherein the catalyst further comprises a co-catalyst metal.

10. The FT reaction catalyst according to claim 9, wherein the co-catalyst metal includes Y, Ce, La, W, Mo, or a combination thereof.

11. The catalyst for the FT reaction according to claim 9, wherein the content of the co-catalyst metal in the catalyst is at least 1 wt%.

12. The catalyst is used in hydrogen temperature-programmed reduction (H ２ The FT reaction catalyst according to claim 1, which includes a reduction peak at 600°C or higher when measured by -TPR.

13. A method for producing a catalyst for the FT reaction, The steps include preparing a composite support mixture containing alumina hydrate and zeolite, The steps include preparing a metal precursor solution containing Co, The steps include: mixing the composite carrier mixture and the precursor solution to produce a catalyst mixture; A method for producing a catalyst for an FT reaction, comprising the step of calcining the catalyst mixture.

14. A method for producing a catalyst for an FT reaction according to claim 13, wherein the step of producing the catalyst mixture further comprises the step of adding an acid to a precursor solution.

15. The step of producing the catalyst mixture is, The steps include: mixing the composite carrier mixture and the precursor solution to produce a paste; The step of extruding the paste to produce an extruded product is included, The method for producing a catalyst for an FT reaction according to claim 13, wherein the step of calcining the catalyst mixture is the step of calcining the extruded material.

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