Supported catalyst, its preparation method and its application

Abstract

The present invention relates to a supported catalyst, its preparation method, and its applications. The supported catalyst provided by the present invention comprises a support and a metal active component supported on the support, the metal active component being at least one selected from the group consisting of Group VIB metal elements and Group VIII metal elements. The support contains at least one of a heat-resistant inorganic oxide and a molecular sieve. The support has internal channels penetrating the support, the ratio of the cross-sectional area of ​​the channels to the cross-sectional area of ​​the support being 0.05 to 3:100, and the difference R between the water absorption and BET pore volume of the support is 0.2 mL / g or more. The supported catalyst provided by the present invention may be used as a hydrogenation catalyst. When used in the hydrocracking of hydrocarbon oils, the supported catalyst can achieve both high catalytic activity and high jet fuel yield. The supported catalyst provided by the present invention may also be used as a Fischer-Tropsch synthesis catalyst. When used in Fischer-Tropsch synthesis, the catalyst exhibits high strength and high activity efficiency. Furthermore, because high radial crushing strength is achieved without compromising catalytic activity, the supported catalysts provided by the present invention are particularly suitable for use in fixed bed reactions.

Description

Detailed Description of the Invention

[0001] [Technical field] The present disclosure relates to supported catalysts, and more particularly to supported catalysts having internal channels axially penetrating the support and exhibiting both high strength and high catalytic activity, as well as methods for preparing and applying the same.

[0002] [background] Increasing environmental awareness and stricter environmental regulations are forcing the petroleum refining industry to pay more attention to the development of clean fuel production technologies. In the future, automotive fuels on the market will tend to be "ultra-low sulfur," and as a result, fuels that cannot meet emission standards will be barred from the market. As an effective desulfurization method, hydrogenation technology plays an increasingly important role in the production of clean automotive fuels. High-efficiency hydrogenation catalysts are particularly key to hydrogenation technology. Therefore, the development of new hydrocracking catalysts with higher activity and selectivity has become one of the most pressing needs in the petroleum refining industry.

[0003] The Fischer-Tropsch synthesis process, also known as FT synthesis, is a process that uses synthesis gas (a mixture of carbon monoxide and hydrogen) as a feedstock to synthesize liquid hydrocarbons, or hydrocarbons, under appropriate conditions in the presence of a catalyst. It is a key step in the indirect conversion of non-petroleum resources, such as coal, natural gas, and biomass, into pure liquid fuels and chemical feedstocks.

[0004] Hydrocracking catalysts and Fischer-Tropsch synthesis catalysts are typically prepared by impregnation. That is, a solution containing the required active components (e.g., Ni, Mo, Co, W, etc.) is impregnated into a support, followed by drying and, with or without calcination. The active components and support are key components of supported catalysts. The active components are supported on the surface of the support. The support is primarily used to support the active components and impart specific physical properties to the catalyst. The support itself generally does not have catalytic activity. However, the support has many effects on the performance of supported catalysts. For example, it can affect catalyst performance and product distribution. For example, the performance of Fischer-Tropsch synthesis catalysts can vary significantly if different support shapes are used. Since the Fischer-Tropsch synthesis is a reaction that suffers from serious problems in diffusion and mass transfer, a support with a large macroscopic external surface area and a short macroscopic diffusion distance can be advantageous in increasing the Fischer-Tropsch synthesis reaction activity and reducing the selectivity to methane.

[0005] Identifying the geometric shape and size of industrial catalysts often requires balancing multiple aspects while considering the catalyst's multiple properties. Many catalyst shapes have been developed to achieve different goals. The most commonly used shape is the sphere, which is often used for fluidized catalysts or catalysts with special fluidity requirements. Strips are also used for fixed-bed catalysts. Based on the strip, this has been further expanded to include cylindrical strips, trilobe strips, tetralobe strips, other multilobe strips, and modified multilobe strips. Barrel-shaped strips, i.e., strips with multiple holes within a cylinder, such as the classic Raschig ring, cross ring, pall ring, and step ring, also exist. Honeycomb carriers, i.e., cordierite or alumina matrices with uniformly distributed channels, also exist, and are often used in SCR and automobile exhaust gas treatment.

[0006] Several methods for improving catalyst diffusion performance have been disclosed in the prior art. CN1859975A discloses a modified three-lobe strip catalyst. CN101134173A proposes a carrier and catalyst with a special ellipsoidal shape, with one or more grooves opening on the ellipsoid. It is said that the catalyst has a larger external surface area and good mass transfer performance, making it suitable for wide use in, for example, heavy oil processing reactions. CN103269798A proposes a shaped catalyst body having a base surface, a cylindrical surface, a cylindrical axis, and at least one fully penetrating cylindrical opening running parallel to the cylindrical axis, with the base surface of the cylinder having at least four corners. It is used as a carrier with a low surface area. CN105233880A discloses an inner-core cloverleaf-shaped catalyst carrier, its preparation method, and its application. The carrier is composed of two layers, with the outer shell made of a porous structural material and the inner core made of a dense structural material. The inner core is 1 mm thick. 2 The catalyst has a specific surface area of ​​less than 1 / g. The catalyst has high compressive strength and exhibits low diffusion effects when used in Fischer-Tropsch synthesis catalysts.

[0007] In terms of catalyst and active metal utilization, catalysts with central channels, such as Raschig rings or cross rings, have the highest activity utilization, followed by honeycomb supports, strip supports, and then spherical supports. However, the order of strength of these catalysts is the exact opposite. To balance catalyst utilization and strength, hollow supports or hollow catalysts with morphologies such as Raschig rings and honeycomb supports are commonly used. In such cases, ceramics are often used as the matrix. Due to the fact that the matrix itself has high strength, even if voids remain in the center, the overall strength remains high. For support or catalyst materials with insufficient matrix strength, spherical or strip shapes are considered to avoid the sudden deterioration in overall strength and even collapse of the support caused by central voids. In the case of strip shapes, it has been proposed to increase the twist of the outer interface of the strip to increase the contact area with the outside, further improving the catalyst activity while minimizing changes in strength.

[0008] Furthermore, methods have been proposed for increasing the amount of macropores or ultramacropores by adding shaping aids to improve the catalyst's diffusion performance. CN103418441B discloses a hydrorefining catalyst, the support of which is a molded body containing carbon, cellulose ether, and hydrated alumina. The disclosed hydrorefining catalyst not only exhibits excellent performance in the hydrorefining of hydrocarbon oils, but also requires a simple preparation method and low production costs. CN1115388C proposes a hydrogenation protectant and its preparation method. It uses carbon black or an organic pore expander as a pore expander. It is said to achieve higher catalytic activity, lower carbon deposition, better activity stability, and higher strength. CN101890382B proposes a method for preparing a catalyst containing rod-shaped nanooxides in addition to an alumina material. The catalyst prepared by the disclosed method has a large pore volume, large pore size, and good pore permeability, making it particularly suitable for the hydrogenation of residual oils in a fixed bed.

[0009] As mentioned above, methods for improving diffusion disclosed in the prior art include introducing channels into the support, using modifiers to optimize pores, and increasing the contact area through special shapes. The channel introduction method is generally suitable for supports with high matrix strength or small specific surface areas, but not for supports with low matrix strength or large specific surface areas. The pore optimization method using modifiers is primarily based on forming pores through fillers. Pores are optimized by improving the bonding between basic units by adding additives or using hydrated alumina precursors with different properties. Such methods require a large amount of additives and generally result in smaller pores.

[0010] From the above, it can be seen that the catalysts and supports in the prior art still have many deficiencies. There is a need for catalysts that exhibit both high strength and high catalytic activity.

[0011] [Summary of the Invention] The present disclosure aims to solve the above-mentioned shortcomings in the prior art by providing a supported catalyst and its preparation and application methods. The supported catalyst of the present disclosure can be used as a hydrogenation catalyst. When used in the hydrocracking of hydrocarbon oils, it can simultaneously achieve high catalytic activity and a high jet fuel yield. The supported catalyst of the present disclosure can also be used as a Fischer-Tropsch synthesis catalyst. When used in Fischer-Tropsch synthesis, the catalyst exhibits the advantages of high strength and high activity efficiency.

[0012] In order to achieve the above object, a first aspect of the present disclosure includes a support and a metal active component supported on the support, The metal active component is at least one selected from the group consisting of Group VIB metal elements and Group VIII metal elements, the support contains at least one of a heat-resistant inorganic oxide and a molecular sieve; The carrier includes an internal channel penetrating the carrier, and the ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the carrier is 0.05 to 3:100; The supported catalyst has a difference R between the water absorption rate and the BET pore volume of the support of 0.2 mL / g or more.

[0013] A second aspect of the present disclosure is (I) mixing a precursor of the carrier, water, an optional foaming agent, an optional extrusion aid, and an optional binder to obtain a mixture; (II) molding the mixture to obtain a compact, wherein an internal channel extends through the compact; (III) subjecting the molded body obtained in step (II) to a first firing to obtain a carrier; (IV) impregnating the support obtained in step (III) with a solution containing a precursor of a metal active component, followed by drying and a second calcination.

[0014] A third aspect of the present disclosure provides the use of the above-described supported catalyst in hydrocracking.

[0015] A fourth aspect of the present disclosure provides a hydrocracking method, comprising contacting a hydrocarbon oil with a hydrocracking catalyst under hydrocracking conditions, wherein the hydrocracking catalyst is the supported catalyst of the present disclosure.

[0016] A fifth aspect of the present disclosure provides use of the above-described supported catalyst in a Fischer-Tropsch synthesis reaction.

[0017] A sixth aspect of the present disclosure provides a Fischer-Tropsch synthesis method comprising contacting CO and H2 with a supported catalyst of the present disclosure under conditions for a Fischer-Tropsch synthesis reaction.

[0018] The present disclosure may take the form of the following items.

[0019] 1. A hydrogenation catalyst comprising a support and a Group VIB metal element and a Group VIII metal element supported on the support, The support contains at least one of a heat-resistant inorganic oxide and a molecular sieve, the support includes internal channels penetrating the support, the ratio of the cross-sectional area of ​​the channels to the cross-sectional area of ​​the support is 0.05 to 30:100, and the difference R between the water absorption rate and the BET pore volume of the support is 0.2 mL / g or more.

[0020] 2. The catalyst according to item 1, wherein the Group VIB metal element is present in an amount of 10 to 35 wt. %, the Group VIII metal element is present in an amount of 2 to 15 wt. %, and the support is present in an amount of 50 to 88 wt. %, all on an oxide basis, based on the total amount of the catalyst.

[0021] 3. The Group VIB metal element is Mo and / or W, and the Group VIII metal element is Co and / or N; Preferably, the heat-resistant inorganic oxide is at least one selected from the group consisting of alumina, silica, titania, magnesium oxide, zirconia, thorium oxide, and beryllium oxide, and is preferably at least one of alumina, silica, titania, and zirconia; Preferably, the heat-resistant inorganic oxide is present in an amount of 1 to 99% by weight, and the molecular sieve is present in an amount of 1 to 99% by weight, based on the total amount of the support.

[0022] 4. The ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the carrier is 0.1 to 20:100, preferably 0.2 to 10:100; Preferably, the difference R between the water absorption rate and the BET pore volume of the carrier is 0.2 to 0.8 mL / g, more preferably 0.2 to 0.5 mL / g; Preferably, the difference R between the water absorption rate and the BET pore volume of the support accounts for 10 to 50%, preferably 15 to 35%, of the water absorption rate of the support.

[0023] 5. The carrier is in the form of a sphere and / or a strip, preferably a strip, more preferably a multi-lobed strip, Preferably, the carrier has an equivalent diameter of 5 mm or less, preferably 3 mm or less, more preferably 2 mm or less, even more preferably between 0.8 and 2 mm; Preferably, the channels are passages of uniform cross section, more preferably the channels are in the shape of cylinders and / or regular polygonal prisms; More preferably, the diameter of the cylinder and the diameter of the circumscribing circle of the regular polygonal prism are independently 5 μm or more, preferably 0.01 to 0.5 mm, and more preferably 0.05 to 0.3 mm.

[0024] 6. The catalyst according to any one of items 1 to 5, wherein the support has a radial crushing strength of 14 to 30 N / mm, preferably 18 to 26 N / mm, and preferably the catalyst has a bulk density of 0.5 to 1 g / mL, more preferably 0.6 to 0.9 g / mL.

[0025] 7. The number of the channels is 1 to 10, preferably 1 to 6; Preferably, the support has a circular cross section, and the channels extend along a central axis of the circle and / or are equally spaced circumferentially along the central axis; preferably, the support has a multi-lobed cross section, and the channels extend along a central axis of a circumscribing circle of the multi-lobed shape and / or extend along a central axis of a circumscribing circle of each lobe of the multi-lobed shape.

[0026] 8. The carrier is (I) mixing a precursor of the carrier, a foaming agent, water, optionally an extrusion aid, and optionally a binder to obtain a mixture; (II) molding the mixture to obtain a compact, wherein an internal channel extends through the compact; (III) a step of calcining the molded body obtained in step (II).

[0027] 9. The foaming agent is an animal protein-based foaming agent and / or a plant-based foaming agent, preferably an animal protein-based foaming agent; Preferably, the animal protein-based foaming agent is at least one selected from the group consisting of an animal hoof-based foaming agent, an animal hair-based foaming agent, and an animal blood gel-based foaming agent; 9. The catalyst according to item 8, wherein the foaming agent is present in an amount of 0.1 to 50 mL, preferably 0.5 to 20 mL, per 100 g of the precursor of the support, on a dry basis.

[0028] 10. The extrusion aid is at least one selected from the group consisting of sesame powder, cellulose and its derivatives, starch and its derivatives, ethylene glycol, and diethylene glycol; the binder is at least one selected from the group consisting of hydroxymethyl cellulose, inorganic acid, starch and its derivatives, silica sol, and aluminum sol; The extrusion aid is present in an amount of 0.1 to 6 g per 100 g of the carrier precursor on a dry basis; 9. The catalyst according to item 8, wherein the binder is present in an amount of 0.1 to 10 g per 100 g of the precursor of the support on a dry basis.

[0029] 11. The catalyst according to item 8, wherein the mixing in step (I) comprises mixing a precursor of the support and the extrusion aid, and then adding the foaming agent, the binder, and water to obtain a mixture; and preferably, the calcination in step (II) is carried out at a temperature of 350 to 700°C, preferably 450 to 650°C, for 1 to 10 hours, preferably 2 to 6 hours.

[0030] 12. The shaping in step (II) is carried out in an extruder, the extruder including a body and an orifice plate, the body configured to allow the mixture to pass through the orifice plate and be shaped; The orifice plate includes a base (1) having a forming hole (2), a bracket (3) having at least one feed hole (6), and at least one forming rod (4); Item 9. The catalyst according to item 8, wherein the bracket (3) is disposed on the base (1), the molding hole (2) is connected to the supply hole (6), the bracket (3) further comprises at least one mounting hole (5) through which a molding rod (4) passes, and the molding rod (4) is disposed so as to pass through the molding hole (2).

[0031] 13. The ratio of the cross-sectional area of ​​the forming rod (4) to the cross-sectional area of ​​the forming hole (2) in the orifice plate is 0.05 to 30:100, preferably 0.1 to 20:100, and more preferably 0.2 to 10:100; Preferably, the forming holes (2) have an equivalent diameter of 5 mm or less, preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 0.8 to 2 mm; preferably, the forming holes (2) have a circular, elliptical, or multi-lobed cross section; preferably, the multi-lobed shape is tri-, tetra-, or pentapelobate; preferably, the number of the forming rods (4) is 1 to 10, preferably 1 to 6; preferably, the forming holes (2) have a multi-lobed cross section; and the forming rods (4) extend along the central axis of the circumscribing circle of the multi-lobed shape and / or extend along the central axis of each lobe of the multi-lobed shape; preferably, the number of the mounting holes (5) is equal to the number of the forming rods (4); and preferably, the forming rods (4) are detachably connected to the bracket (3) via the mounting holes (5).

[0032] 14. The number of the supply holes (6) is 1 to 20, preferably 2 to 20, Item 14. The catalyst according to Item 13, wherein a plurality of supply holes (6) are arranged at equal intervals along the shaping rod (4) in the circumferential direction, preferably, the portion of the shaping rod (4) extending into the shaping hole (2) is configured to have a uniform cross section, preferably, the portion of the shaping rod (4) extending into the shaping hole (2) is configured as a cylinder, preferably, the cylinder has a diameter of 5 μm or more, preferably 0.01 to 0.5 mm, more preferably 0.05 to 0.3 mm, preferably, the portion of the shaping rod (4) extending into the shaping hole (2) is configured as a regular polygonal prism, preferably, the regular polygonal prism has a circumscribed circle with a diameter of 5 μm or more, preferably 0.01 to 0.5 mm, more preferably 0.05 to 0.3 mm, preferably, the base (1) and the bracket (3) together form an outer contour, preferably, the base (1) and the bracket (3) are configured to be detachably connected.

[0033] 15. Use of the hydrogenation catalyst according to any one of items 1 to 14 in hydrocracking.

[0034] 16. A hydrocracking method comprising a step of contacting a hydrocarbon oil with a hydrocracking catalyst under hydrocracking conditions, wherein the hydrocracking catalyst is the hydrogenation catalyst according to any one of items 1 to 14.

[0035] The present disclosure may also be in the form of the following items.

[0036] 1. A catalyst comprising a carrier, a metal active component supported on the carrier, and optionally a first metal promoter, wherein the first metal promoter is at least one selected from the group consisting of transition metals; The carrier includes an internal channel penetrating the carrier, and the ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the carrier is 0.05 to 25:100; The support contains at least one of a heat-resistant inorganic oxide and a molecular sieve, and 1. A Fischer-Tropsch synthesis catalyst, wherein the metal active component is Co.

[0037] 2. The ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the carrier is 0.1 to 20:100, more preferably 0.2 to 9:100; Preferably, the channels are passages of uniform cross section, more preferably the channels are in the shape of cylinders and / or regular polygonal prisms; Further preferably, the diameter of the cylinder and the diameter of the circumscribing circle of the regular polygonal prism are independently 6 μm or more, preferably 0.01 to 0.5 mm, and more preferably 0.05 to 0.3 mm.

[0038] 3. The carrier is in the form of a sphere and / or a strip, preferably a strip, even more preferably a multilobal strip, more preferably a trilobal, tetralobal or pentalobal strip; 3. The Fischer-Tropsch synthesis catalyst according to item 1 or 2, wherein the support has an equivalent diameter of 5 mm or less, preferably 0.05 mm to 5 mm, further preferably 0.1 mm to 3 mm, and more preferably 0.5 mm to 2 mm.

[0039] 4. The number of the channels is 1 to 9, preferably 1 to 5; Preferably, the carrier has a circular cross section, the channels extending along a central axis of the circle and / or being equally spaced circumferentially along the central axis; 4. The Fischer-Tropsch synthesis catalyst according to any one of items 1 to 3, wherein the support preferably has a multi-lobed cross section, and the channels extend along a central axis of a circumscribing circle of the multi-lobed shape and / or along a central axis of a circumscribing circle of each lobe of the multi-lobed shape.

[0040] 5. The heat-resistant inorganic oxide contains at least one of alumina, silica, titania, magnesium oxide, zirconia, thorium oxide, and beryllium oxide, and preferably contains at least one of alumina, silica, titania, and zirconia; Preferably, the molecular sieve comprises at least one of a 10-ring silica-alumina molecular sieve, a 12-ring silica-alumina molecular sieve, a 14-ring silica-alumina molecular sieve, and an 18-ring silica-alumina molecular sieve; 5. The Fischer-Tropsch synthesis catalyst according to any one of items 1 to 4, wherein the molecular sieve is at least one selected from the group consisting of ZRP molecular sieves, Y molecular sieves, beta molecular sieves, mordenite, ZSM-5 molecular sieves, MCM-41 molecular sieves, Ω molecular sieves, ZSM-12 molecular sieves, and MCM-22 molecular sieves, and further preferably at least one of Y molecular sieves, beta molecular sieves, ZSM-5, and mordenite. Preferably, the support is a refractory inorganic oxide. 6. On an oxide basis, the metal active component is present in an amount of 5 to 80 wt. %, preferably 20 to 40 wt. %, based on the total amount of the catalyst; Preferably, the first metal promoter is at least one selected from the group consisting of Ni, Fe, Cu, Ru, Rh, Re, Pd and Pt; 6. The Fischer-Tropsch synthesis catalyst according to any one of items 1 to 5, wherein the first metal promoter is present in an amount of 0 to 40 wt. %, more preferably 0.1 to 20 wt. %, based on the total amount of the catalyst, on an oxide basis.

[0041] 7. The catalyst further comprises a second metal promoter supported on the support, wherein the second metal promoter is at least one selected from the group consisting of alkali metals and alkaline earth metals, preferably at least one of Na, K, Mg, and Ca; 7. The Fischer-Tropsch synthesis catalyst according to any one of items 1 to 6, wherein the second metal promoter is present in an amount of 1 to 20 wt. %, more preferably 2 to 10 wt. %, based on the total amount of the catalyst, on an oxide basis.

[0042] 8.(1) mixing a precursor of the support, water, optionally an extrusion aid, and optionally a deflocculating agent to obtain a mixture, and subjecting the mixture to shaping and a first firing to obtain the support, wherein shaping produces internal channels through the support; (2) impregnating the support obtained in step (1) with a solution containing a precursor of the metal active component and optionally a precursor of the first metal promoter, followed by drying and a second calcination.

[0043] 9. In the step (1), the extrusion aid is at least one selected from the group consisting of sesban powder, cellulose and its derivatives, starch and its derivatives, ethylene glycol, and diethylene glycol; the peptizing agent is at least one selected from inorganic acids (preferably nitric acid); 9. The method according to item 8, wherein the first firing is preferably carried out at a temperature of 350 to 700°C, preferably 450 to 650°C, for 1 to 10 hours, preferably 2 to 6 hours.

[0044] 10. In the step (2), the drying is carried out at a temperature of 80 to 140°C for 1 to 10 hours; Preferably, the second firing is carried out at a temperature of 350 to 750°C for 1 to 10 hours; Preferably, the solution in step (2) further contains a precursor of the second metal promoter.

[0045] 11. A Fischer-Tropsch synthesis catalyst prepared by the method according to any one of items 8 to 10.

[0046] 12. Use of a Fischer-Tropsch synthesis catalyst according to any one of items 1 to 7 and 11 in a Fischer-Tropsch synthesis reaction. 13. A method for Fischer-Tropsch synthesis, comprising the step of contacting CO and H2 with a catalyst under conditions for a Fischer-Tropsch synthesis reaction, wherein the catalyst is a Fischer-Tropsch synthesis catalyst according to any one of items 1 to 7 and 11.

[0047] The catalyst of the present invention employs a one-step process to form a support with internal channels. The support has internal channels penetrating the support, which is beneficial for improving the effective utilization of the active components of the catalyst. It is also preferable to add a foaming agent when forming the support. The addition of the foaming agent allows gas components to be entrapped within the shaped body, thereby increasing the proportion of macropores and ultramacropores in the pore volume of the support and increasing the permeation of the support. The supported catalyst of the present disclosure employs a support structure with both pores and channels. This can improve the diffusion of polymers, which can be beneficial for improving the activity of the catalyst and the accessibility of active centers. When used in the hydrocracking of hydrocarbon oils, it can simultaneously achieve high jet fuel yields and high catalytic activity. When used in the Fischer-Tropsch synthesis reaction, the supported catalyst of the present disclosure offers the advantage of further improving Fischer-Tropsch synthesis activity and selectivity to C5+ hydrocarbons, while reducing selectivity to methane. In addition, the supported catalyst of the present disclosure employs a support with an optimized channel structure, thereby providing higher radial crushing strength. Therefore, the supported catalyst of the present disclosure is particularly suitable for use in fixed-bed reactors, such as microreactors, microchannel reactors, microchemical reactors, or mesoscopic reactors. These reactors require catalysts with high strength, high porosity, and low pressure drop characteristics.

[0048] [Drawing Description] FIG. 1 is a schematic diagram showing the structure of a base of an orifice plate according to an embodiment of the present disclosure.

[0049] FIG. 2 is a schematic diagram showing the structure of a bracket of an orifice plate according to an embodiment of the present disclosure.

[0050] FIG. 3 is a schematic diagram showing the structure of a molding rod of an orifice plate according to an embodiment of the present disclosure.

[0051] FIG. 4 is a schematic diagram showing a cross section of the carrier SA of Example 1 according to the present disclosure.

[0052] FIG. 5 is a schematic diagram showing the structure of a bracket of an orifice plate according to an embodiment of the present disclosure.

[0053] FIG. 6 is a schematic diagram showing a cross section of the carrier DA of Comparative Example 1. As shown in FIG.

[0054] FIG. 7 is a schematic diagram showing a cross section of a carrier SB of Example 2 according to the present disclosure.

[0055] FIG. 8 is a schematic diagram showing a cross section of a carrier SC according to a third embodiment of the present invention.

[0056] FIG. 9 is a schematic diagram showing a cross section of the carrier SD of Example 4 according to the present invention.

[0057] FIG. 10 is a schematic diagram showing a cross section of a carrier ZA according to Example 10 of the present invention.

[0058] FIG. 11 is a schematic diagram showing a cross section of the carrier ZB of Example 11 according to the present invention.

[0059] FIG. 12 is a schematic diagram showing a cross section of the carrier ZC of Example 12 according to the present invention.

[0060] FIG. 13 is a schematic diagram showing a cross section of the carrier ZD of Example 13 according to the present invention.

[0061] FIG. 14 is a schematic diagram showing a cross section of a carrier ZE according to Example 14 of the present invention.

[0062] FIG. 15 is a schematic diagram showing a cross section of the carrier ZF of Example 15 according to the present invention.

[0063] FIG. 16 is a schematic diagram showing a cross section of the carrier DA-2 of Comparative Example 2.

[0064] FIG. 17 is a graph showing the relationship between the channel size of the carrier and the radial crushing strength.

[0065] [Reference symbol explanation] 1. Bass 2. Molding hole 3. Bracket 4. Forming rod 5. Mounting holes 6. Supply hole 7. First installation structure 8. Second installation structure 13. Head 14. Rod part [Detailed explanation] It should be understood that the endpoints and any values ​​in the ranges of values ​​disclosed herein are not limited to the exact range or value, but encompass values ​​close to those ranges or values. With respect to ranges of values, it is possible to combine the endpoints of each range, the endpoints of each range and each individual point, and the individual points to provide one or more new ranges of values, as if these ranges of values ​​were specifically disclosed herein. Except as described in the examples, all numerical values ​​of parameters herein should be understood to be modified in all cases by the word "about", regardless of whether "about" actually appears before the numerical value.

[0066] Unless otherwise taught below, directional terms such as "up, down, left, right" used herein generally refer to "up, down, left, right" as shown with reference to the drawings, and directional terms such as "inside and outside" used herein refer to the inside and outside relative to the outer shape of each component itself.

[0067] In this disclosure, items defined by "at least one," "one or more," and "and / or" refer to the presence of the listed items or any combination thereof.

[0068] A first aspect of the present disclosure provides a supported catalyst comprising: a support; and a metal active component supported on the support, wherein the metal active component is at least one selected from the group consisting of Group VIB metal elements and Group VIII metal elements; the support contains at least one of a heat-resistant inorganic oxide and a molecular sieve; the support comprises internal channels penetrating the support, wherein the ratio of the cross-sectional area of ​​the channels to the cross-sectional area of ​​the support is 0.05 to 3:100; and the difference R between the water absorption and BET pore volume of the support is 0.2 mL / g or more.

[0069] As used herein, an "internal channel through a carrier" refers to a channel present within the carrier that provides the carrier with a well-permeable structure. The channel extends through the carrier. In a variant, the channel in the carrier extends along the longitudinal axis of the carrier and connects two ends of the carrier.

[0070] According to a preferred embodiment of the present disclosure, the Group VIB metal element is Mo and / or W, and the Group VIII metal element is Co and / or Ni. Thus, the metal active component may be one or more of Mo, W, Co, and Ni.

[0071] The Group VIB metal element and the Group VIII metal element may each be supported on a support in various forms commonly used in the art. For example, the Group VIB metal element and the Group VIII metal element may each be in the form of an oxide and / or sulfide supported on a support. That is, the supported catalyst of the present disclosure includes both the oxidized catalyst before sulfurization and the sulfided catalyst after sulfurization.

[0072] The contents of Group VIB and Group VIII metal elements in the supported catalyst may be selected within wide ranges, with the Group VIB metal element being present in an amount of 10 to 35 wt. %, preferably 15 to 30 wt. %, the Group VIII metal element being present in an amount of 2 to 15 wt. %, preferably 2.5 to 10 wt. %, and the support being present in an amount of 50 to 88 wt. %, preferably 60 to 82.5 wt. %, all on an oxide basis, based on the total amount of catalyst.

[0073] According to another preferred embodiment of the present disclosure, the metal active component is at least one of Group VIII metal elements, preferably at least one of Ni, Fe, and Co, more preferably Co. In a variant, the catalyst further comprises a first metal promoter supported on a support, the first metal promoter being at least one of transition metals. The metal active component and the first metal promoter are different elements. Preferably, the first metal promoter is at least one selected from the group consisting of Cu, Ru, Rh, Re, Pd, and Pt.

[0074] The contents of Co and the first metal promoter in the catalyst may be selected within wide ranges within the present disclosure. Preferably, Co is present in an amount of 5 to 80 wt %, more preferably 20 to 40 wt %, based on the total amount of the catalyst, on an oxide basis. The first metal promoter is present in an amount of 0 to 40 wt %, more preferably 0.1 to 20 wt %, based on the total amount of the catalyst, on an oxide basis.

[0075] In one variation, the supported catalyst further comprises a second metal promoter supported on the support, the second metal promoter being at least one selected from the group consisting of alkali metals and alkaline earth metals. Alkali metals include, but are not limited to, Li, Na, and K. Alkaline earth metals include, but are not limited to, Mg and Ca. Preferably, the second metal promoter is at least one of Na, K, Mg, and Ca, e.g., K and / or Mg.

[0076] The content of the second metal promoter may be selected within a wide range within the present disclosure. Preferably, on an oxide basis, the second metal promoter is present in an amount of 0 to 20 wt %, preferably 1 to 20 wt %, more preferably 2 to 10 wt %, based on the total amount of the catalyst.

[0077] In one variation, the supported catalyst comprises a support and a metal active component, wherein the first metal promoter and the second metal promoter are supported on the support, the metal active component being at least one selected from the group consisting of Ni, Fe, and Co, the first metal promoter being at least one selected from the group consisting of Cu, Ru, Rh, Re, Pd, and Pt, and the second metal promoter being K and / or Mg, all on an oxide basis, based on the total amount of catalyst, the support being present in an amount of 30-75 wt %, the metal active component being present in an amount of 20-40 wt %, the first metal promoter being present in an amount of 0.1-20 wt %, and the second metal promoter being present in an amount of 2-10 wt %, all on a catalyst oxide basis.

[0078] In this disclosure, the water absorption rate refers to the water absorption rate after wiping. They are used interchangeably in this specification. Unless otherwise specified, the water absorption rate after wiping is obtained by soaking the dry carrier of this disclosure in deionized water at room temperature (20 to 25°C) for 30 minutes or more, filtering, wiping with filter paper, and obtaining the mass of the carrier after water absorption. The ratio of the difference between the obtained mass and the mass of the carrier before water absorption to the mass of the carrier before water absorption is the water absorption rate after wiping.

[0079] According to one embodiment of the present disclosure, the water absorption rate of the carrier after wiping is in the range of 0.8 to 2 mL / g, preferably 0.9 to 1.5 mL / g.

[0080] According to one embodiment of the present disclosure, the BET pore volume of the support is 0.62 to 1.3 mL / g, preferably 0.7 to 1.1 mL / g.

[0081] In this disclosure, unless otherwise specified, BET pore volume is measured according to the method defined in RIPP151-190.

[0082] According to the present disclosure, the difference R between the water absorption rate and the BET pore volume of the support is preferably 0.2 to 0.8 mL / g, more preferably 0.2 to 0.5 mL / g.

[0083] According to the present disclosure, the difference R between the water absorption rate and the BET pore volume of the support preferably accounts for 10 to 50%, preferably 15 to 35%, of the water absorption rate of the support. A larger value for the support of the present disclosure indicates that macropores or ultramacropores account for a larger proportion of the total pore volume within the support of the present disclosure. As mentioned above, in the present disclosure, unless otherwise specified, the pore volume of the support is measured according to the BET method, and the water absorption rate (water absorption rate after wiping) is measured according to the water absorption method. Therefore, the difference R between the water absorption rate and the BET pore volume is used to indicate the pore volume of the macropores or ultramacropores, and the water absorption rate is used to indicate the total pore volume of the support.

[0084] According to the present disclosure, the ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the support is preferably 0.1 to 3: 100, and more preferably 0.2 to 3: 100. The catalyst of the present disclosure employs a support having a structure including channels as well as pores, which allows the active components of the catalyst to be effectively utilized, thereby improving the activity of the catalyst while ensuring the strength of the catalyst.

[0085] According to the present disclosure, the carrier preferably has a radial crushing strength of 14-30 N / mm, preferably 18-26 N / mm. Unless otherwise specified, the radial crushing strength of the carrier in the present disclosure is measured on a QCY-602 compressive strength tester (manufactured by the Soda Research Institute of the Ministry of Chemical Industry) according to the method specified in GB3635-1983.

[0086] The carrier used in the catalyst of the present disclosure has channels with an optimized structure, thereby having higher mechanical strength, which further improves the mechanical strength of the corresponding supported catalyst. Furthermore, the carrier used in the catalyst of the present disclosure has a structure including channels as well as pores, which can effectively improve the activity of the catalyst and the accessibility to the active centers, and is very suitable for the diffusion of macromolecules.

[0087] In the present disclosure, the shape of the carrier can be selected within a wide range. The shape of the carrier may be any of various shapes commonly used in the art. The shape of the carrier may be regular or irregular, preferably regular. For example, the carrier may have the shape of a sphere, a strip, a ring, a honeycomb, or a butterfly. The strip referred to in the present disclosure may be a cylindrical strip, an elliptical strip (equivalent to a bilobal strip), or a multilobal strip. In the present disclosure, the shape of the strip is not limited. The sphere referred to in the present disclosure may be a regular sphere or an irregular sphere. That is, the outer curve of the cross section of the carrier may be circular or imperfect circular. In the present disclosure, the length and distribution of the carrier in the shape of a strip are not limited.

[0088] Preferably, the carrier is in the form of a sphere and / or a strip, more preferably in the form of a strip, more preferably a multi-lobed strip.

[0089] The term "strip" as used herein refers to a material that is produced by extrusion or press molding, has a length of 50% or more of the diameter of its circumscribing circle, and has a three-dimensional structure. In the present disclosure, the length and distribution of the carrier in the form of a strip are not limited.

[0090] In the present invention, a carrier in the shape of a multi-lobed strip means that the cross section of the carrier is multi-lobed. In the present disclosure, the size of each lobe of the multi-lobed shape and the ratio of the size of one lobe to the other lobes are not limited. That is, the multi-lobed shape may be a regular multi-lobed shape, an irregular multi-lobed shape, or a deformed multi-lobed shape. In the present disclosure, the number of lobes, the shape of the lobes, and the ratio between the lobes of the multi-lobed shape are not limited. According to the present disclosure, the multi-lobed strip shape may be at least one of a three-lobe strip shape, a four-lobe strip shape, a five-lobe strip shape, a six-lobe strip shape, etc.

[0091] According to one preferred embodiment of the present disclosure, the carrier is in the shape of a sphere and / or strip, and the carrier has an equivalent diameter of 5 mm or less, preferably 3 mm or less, more preferably 2 mm or less, even more preferably 0.8 to 2 mm.

[0092] According to one embodiment of the present disclosure, when the carrier has a shape other than those mentioned above, the carrier may have an outer shape with a minimum cross-sectional dimension of 5 mm or less, preferably 3 mm or less, more preferably 2 mm or less.

[0093] According to a preferred embodiment of the present disclosure, the catalyst has a bulk density of 0.5 to 1 g / mL, more preferably 0.6 to 0.9 g / mL. The catalyst of the present disclosure has a lower bulk density.

[0094] In the present disclosure, the bulk density of the catalyst is measured by a conventional method. In particular, the method may include crushing the catalyst, sieving the particles to 16-20 mesh, adding the sieved particles to a 500 mL graduated cylinder, and obtaining the weight G and visual volume V. The bulk density of the catalyst = G / V.

[0095] In the present disclosure, the channels may be formed in various reasonable shapes, and may be regular or irregular. From the viewpoint of ease of processing, it is preferable that the channels have regular shapes. The cross-sectional area of ​​the channels along the flow direction may be the same or may be different (gradually increasing or gradually decreasing). When the cross-sectional area of ​​the channel gradually increases along the flow direction, the channel may have a shape including, but not limited to, a cone. When the cross-sectional area of ​​the channel gradually decreases along the flow direction, the channel may have a shape including, but not limited to, an inverted cone.

[0096] Preferably, the channel is a passageway of uniform cross section. The cross section of the channel may be regular or irregular, preferably a regular shape. The preferred configuration can facilitate processing, and at the same time, a support having a through-channel structure with a corresponding shape can be more favorable for the diffusion of macromolecules.

[0097] The channels may have various processable shapes. From the viewpoint of ease of processing, the channels are preferably in the shape of a cylinder and / or a regular polygonal prism. Correspondingly, the cross section of the channel is a circle and / or a regular polygon. The above-mentioned preferred configuration not only facilitates processing but also effectively ensures the stability of the support. In this case, the inner surface of the catalyst is more regular, which avoids stress accumulation caused by the presence of sharp walls in the channel structure, reduces the probability of catalyst collapse, and improves the compactness and strength of the support. It should be noted that the circles and regular polygons in the present disclosure also include incomplete circles and / or regular polygons.

[0098] More preferably, when the channel is cylindrical in shape, its circular cross section has a diameter of 5 μm or more, preferably 0.01 to 0.5 mm, more preferably 0.05 to 0.3 mm.

[0099] More preferably, when the channel has the shape of a regular polygonal prism, the circumscribed circle of the regular polygonal cross section has a diameter of 5 μm or more, preferably 0.01 to 0.5 mm, and more preferably 0.05 to 0.3 mm.

[0100] In the present disclosure, a regular polygonal prism may be a triangular prism, a quadrangular prism, a pentagonal prism, etc. Accordingly, the cross section of the channel of the support is a regular triangle, a square, a regular pentagon, etc., correspondingly.

[0101] The number of channels can be selected within a wide range within the present disclosure. It can be selected by those skilled in the art by comprehensively considering strength and bulk density. It can be one, or two or more, and can be appropriately selected according to the actual requirements for the number of channels. Preferably, the number of channels is 1 to 10, preferably 1 to 6.

[0102] It should be noted that when the number of channels is two or more, the ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the support refers to the ratio of the total cross-sectional area of ​​all channels to the cross-sectional area of ​​the support, as defined above.

[0103] The specific location of the channel may be selected within a wide range within the present disclosure, as long as the channel can penetrate the carrier. When the number of channels is 1, the channel preferably extends along the central axis of the carrier. In this case, when the cross section of the carrier is circular, the channel extends along the central axis of the carrier in a cylindrical shape, and when the cross section of the carrier is multilobed, the channel extends along the central axis of the circumscribing cylinder of the multilobed shape.

[0104] When the number of channels is two or more, the relative positions of the channels are not particularly limited. Preferably, the channels are uniformly distributed. This preferred configuration is more advantageous in ensuring a more balanced distribution of forces on the support and further optimizing the overall strength of the support. Preferably, uniform distribution means that the distance from each channel to the center of the circumscribing circle of the cross section of the support is equal, more preferably, the distance between each channel is equal, and more preferably, the distance from each channel to the center of the circumscribing circle of the cross section of the support is equal to the distance from each channel to the edge of the support.

[0105] According to a preferred embodiment of the present disclosure, the cross section of the support is circular, and the channels extend along the central axis of the cylindrical support and / or are equally spaced circumferentially along the central axis. This preferred configuration provides a uniform distribution of the channels, which effectively avoids a sharp decrease in strength in the portion of the support associated with the incorporation of the channels within the support, thereby ensuring the mechanical strength of the support.

[0106] According to another preferred embodiment of the present disclosure, the cross section of the support is multilobal, and the channels extend along the central axis of the circumscribing cylinder of the multilobal shape and / or along the central axis of the circumscribing cylinder of each lobe of the multilobal shape. This preferred configuration results in a uniform distribution of the channels, which effectively avoids a sharp decrease in strength in parts of the support associated with the incorporation of channels within the support, thereby ensuring the mechanical strength of the support.

[0107] In the present disclosure, the support may have a composition commonly used in the art, and may contain at least one of a heat-resistant inorganic oxide and a molecular sieve.

[0108] The type of heat-resistant inorganic oxide in the present disclosure is not particularly limited. It may be a heat-resistant inorganic oxide commonly used in the art. For example, the heat-resistant inorganic oxide may be at least one selected from the group consisting of alumina, silica, titania, magnesium oxide, zirconia, thorium oxide, and beryllium oxide. Specific examples include, but are not limited to, alumina, silica, zirconia, titania, magnesium oxide, thorium oxide, beryllium oxide, alumina-titania, alumina-magnesium oxide, silica-magnesium oxide, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, titania-zirconia, silica-alumina-zirconia, silica-alumina-thorium oxide, silica-alumina-titania, or silica-alumina-magnesium oxide. Preferably, the heat-resistant inorganic oxide is at least one of alumina, silica, titania, and zirconia. More preferably, the heat-resistant inorganic oxide is alumina.

[0109] As used herein, the term "alumina" refers to a compound having the chemical formula mAl2O3·nH2O, where m and n are any numbers and can be integers or fractions. The crystalline form of alumina is not limited in this disclosure.

[0110] The term "molecular sieve" as used herein refers to a material with a regular crystalline structure and pores, which has a framework formed from silicon and aluminum elements. It is also called zeolite. It may further contain other elements, such as at least one of P, Ti, Ge, and Ga. In the present disclosure, there is no limitation on the elements for forming the molecular sieve.

[0111] The molecular sieve in this disclosure may be one, two or more molecular sieves, or may be a mixed crystal or twin crystal of two molecular sieves. As used herein, the phrase "two molecular sieves" refers to two different types of molecular sieves, or two molecular sieves that belong to the same type but have different properties (e.g., different silicon to aluminum ratios).

[0112] As used herein, the phrase "more molecular sieves" refers to three or more molecular sieves, which may be of different types or may be molecular sieves of the same type but with different properties, each molecular sieve comprising 0.1 to 80% by weight of the carrier.

[0113] The ratio of the two molecular sieves may be 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1:1, etc. The ratio of the two molecular sieves may be any value.

[0114] According to the present disclosure, the molecular sieve may be at least one selected from the group consisting of 10-ring silica-alumina molecular sieves, 12-ring silica-alumina molecular sieves, 14-ring silica-alumina molecular sieves, and 18-ring silica-alumina molecular sieves. In the present disclosure, the opening size and pore size of the molecular sieve are not limited.

[0115] In the present disclosure, the silicon to aluminum ratio of the molecular sieve is not limited. The silicon to aluminum ratio referred to in this specification refers to the SiO2 / Al2O3 ratio.

[0116] According to a preferred embodiment of the present disclosure, the molecular sieve is at least one selected from the group consisting of ZRP molecular sieve, Y molecular sieve, beta molecular sieve, mordenite, ZSM-5 molecular sieve, MCM-41 molecular sieve, Ω molecular sieve, ZSM-12 molecular sieve, and MCM-22 molecular sieve, and preferably at least one of Y molecular sieve, beta molecular sieve, ZSM-5 molecular sieve, and mordenite.

[0117] The molecular sieves may be commercially available or may be prepared by any known method.

[0118] The Y molecular sieve described herein may be a Y molecular sieve having a unit cell constant in the range of 2.452 to 2.475 nanometers and a silica / alumina molar ratio in the range of 3.5 to 7. It may be an ultrastable Y molecular sieve prepared by exchanging the Y molecular sieve with ammonium ions followed by one or more hydrothermal treatments. The ultrastable Y molecular sieve may have a unit cell constant in the range of 2.420 to 2.455 nanometers, and the silica / alumina molar ratio in the framework may be up to 100, preferably up to 60. It may also be a phosphorus-containing ultrastable Y molecular sieve prepared by exchanging the Y molecular sieve with a solution of one or more inorganic ammonium phosphides followed by one or more hydrothermal treatments. It may also be a rare-earth-containing Y molecular sieve prepared by treating the Y molecular sieve with an aqueous solution of a rare-earth compound together with one or more hydrothermal treatments.

[0119] According to the present disclosure, preferably, the heat-resistant inorganic oxide is present in an amount of 1 to 99 wt % and the molecular sieve is present in an amount of 1 to 99 wt % based on the total amount of the support, and more preferably, the heat-resistant inorganic oxide is present in an amount of 70 to 97 wt % and the molecular sieve is present in an amount of 3 to 30 wt % based on the total amount of the support.

[0120] In the present disclosure, when the heat-resistant inorganic oxide and the metal promoter contain the same metal element, their amounts are taken into account as the amount of the metal promoter.

[0121] A second aspect of the present disclosure provides a method for preparing the above-described supported catalyst, comprising: (I) mixing a precursor of the carrier, water, an optional foaming agent, an optional extrusion aid, and an optional binder to obtain a mixture; (II) molding the mixture to obtain a compact, wherein an internal channel extends through the compact; (III) subjecting the molded body obtained in step (II) to a first firing to obtain a carrier; (IV) impregnating the support obtained in step (III) with a solution containing a precursor of a metal active component, followed by drying and a second calcination.

[0122] According to the present disclosure, the term "optionally" means that the relevant component may or may not be added. In the mixing of step (I) of the present disclosure, a foaming agent may or may not be added, an extrusion aid may or may not be added, and a binder may or may not be added. In a variant, it is preferable to add a foaming agent.

[0123] According to the present disclosure, the precursor of the support may be any substance that can be converted into a support by the first calcination in step (III). In particular, the precursor of the support may be at least one selected from the group consisting of a thermostable inorganic oxide, a precursor of a thermostable inorganic oxide, and a molecular sieve. Preferably, the precursor of the support may be a thermostable inorganic oxide and / or a precursor of a thermostable inorganic oxide. The precursor of a thermostable inorganic oxide may be any substance that can be converted into a thermostable inorganic oxide by the first calcination in step (III). The selection of the thermostable inorganic oxide has been described above, and will not be repeated here.

[0124] The selection of molecular sieves has been discussed above and will not be repeated here.

[0125] According to a preferred embodiment of the present disclosure, the precursor of the heat-resistant inorganic oxide may be a precursor of alumina, such as, but not limited to, hydrated alumina (e.g., aluminum hydroxide, pseudoboehmite), a gel containing hydrated alumina, and a sol containing hydrated alumina. For example, the precursor of alumina may be a dry powder of alumina sol. The dry powder of alumina sol may be commercially available (e.g., manufactured by Sinopec Catalyst Ltd. Co., Changling Company) or may be prepared by any known method. The present disclosure does not have any limitations in this regard.

[0126] In the preparation method of the present invention, the amount of thermotolerant inorganic oxide and / or precursor of thermotolerant inorganic oxide and molecular sieve may be selected within a wide range. Those skilled in the art can identify the appropriate amount for any specific condition. The possible ranges of amounts have been described above and will not be repeated here.

[0127] According to the present disclosure, the foaming agent has the ability to trap gas. It may be an organic or inorganic substance. It may be a pure substance or a mixture of multiple components. The foaming agent may be at least one selected from the group consisting of physical foaming agents, chemical foaming agents, synthetic surfactant foaming agents, animal protein-based foaming agents, and plant-based foaming agents. Preferably, the foaming agent is an animal protein-based foaming agent and / or a plant-based foaming agent. The animal protein-based foaming agent is preferably at least one selected from the group consisting of animal hoof-based foaming agents, animal hair-based foaming agents, and animal blood gel-based foaming agents. The plant-based foaming agent is preferably at least one selected from the group consisting of rosin soap-based foaming agents and tea saponin.

[0128] According to a preferred embodiment of the present disclosure, the foaming agent is an animal protein-based foaming agent, such as an animal hoof-based foaming agent and / or egg white. The inventors of the present invention have found through research that, compared with traditional physical foaming agents, chemical foaming agents and synthetic surfactant foaming agents, the animal protein-based foaming agent has a distinct advantage in more effectively forming bubbles with high tenacity and high stability during the preparation of the carrier.

[0129] According to the method of the present disclosure, the foaming agent may be introduced in the form of using water as a solvent or using other organic substances as a solvent, but the form of a solution using water is preferred.

[0130] According to a preferred embodiment of the present disclosure, the animal protein-based foaming agent is introduced in the form of a solution of animal protein-based foaming agent hydrolysate. When proteins are hydrolyzed, the longer peptide chain protein macromolecules become a mixture of shorter chain water-soluble medium-sized molecules and water-soluble small molecules. When dissolved in water, they can form a colloidal solution with a certain viscosity. The presence of strong hydrophilic groups, such as carboxyl groups and hydroxyl groups, and hydrophobic groups, such as long-chain hydrocarbon groups, as well as other factors, such as the asymmetric properties of the molecules, can reduce surface tension and thereby promote the formation of an interface. Furthermore, these small and medium-sized peptide chains can diffuse along the interface and form a protective network through intermolecular hydrogen bonds, which strengthens the interface and is therefore more favorable for the formation and stabilization of foam.

[0131] The present disclosure does not specifically limit the means for obtaining a solution of animal protein foaming agent hydrolysates by hydrolyzing the animal protein foaming agent. Based on the above description, those skilled in the art can prepare a solution of animal protein foaming agent hydrolysates by any means. For example, it may be carried out by the method disclosed in "Research on protein-type concrete foaming agent [J]: Ma Zhijun, Li Xiaoyun, Ma Xuelei et al., Building Science, 2009, 25(5):73-76".

[0132] To accelerate the hydrolysis of the animal protein, a hydrolysis promoter may be added during the hydrolysis, as appropriate, although the present disclosure is not particularly limited in this regard.

[0133] According to the method of the present disclosure, the extrusion aid is preferably at least one selected from the group consisting of sesban powder, cellulose and its derivatives, starch and its derivatives, ethylene glycol, and diethylene glycol. The starch derivative may be one or more of oxidized starch, esterified starch, carboxymethyl starch, cationic starch, hydroxyalkyl starch, and polymeric starch. The cellulose derivative may be one or more of cellulose ether, cellulose ester, and cellulose ether ester. The examples illustrate the use of sesban powder as the extrusion aid. However, the present disclosure is not limited thereto.

[0134] According to the method of the present disclosure, the type of binder may be selected within a wide range, including, for example, at least one of hydroxymethyl cellulose, inorganic acid, starch and its derivatives, silica sol, or aluminum sol.

[0135] According to the method of the present disclosure, the means for mixing the carrier precursor, the foaming agent, the water, the optional extrusion aid, and the optional binder is not particularly limited, as long as the carrier precursor, the foaming agent, the water, the optional extrusion aid, and the optional binder are mixed. Preferably, the mixing in step (I) includes mixing the carrier precursor and the extrusion aid, and then adding the foaming agent, the binder, and the water to obtain a mixture. In the preferred embodiment, the carrier precursor and the extrusion aid are first mixed to obtain a mixed powder, to which the foaming agent, the binder, and the water are added. This is more advantageous in improving the catalytic performance of the prepared catalyst.

[0136] More preferably, the mixing in step (I) comprises mixing the precursor of the support and the extrusion aid to obtain a mixed powder, foaming the foaming agent, the binder, and water to obtain a foaming liquid, and mixing the mixed powder and the foaming liquid. This preferred configuration is more advantageous in improving the catalytic performance of the catalyst prepared using the obtained support. In a variant, the foaming agent can be used in the presence of the mixed powder, and then water and the binder are introduced.

[0137] According to the present disclosure, the foaming agent is preferably an animal protein-based foaming agent. The amount of foaming agent may be selected within a wide range. For example, the foaming agent is present in an amount of 0 to 50 mL, preferably 0.1 to 50 mL, more preferably 0.5 to 20 mL, per 100 g of the carrier precursor, on a dry basis. This configuration is more advantageous in that the resulting carrier has both higher mechanical strength and a better pore structure.

[0138] According to the present disclosure, preferably the foaming agent is a botanical foaming agent and is present in an amount of 0-5g, preferably 0.1-5g.

[0139] According to the present disclosure, preferably the extrusion aid is present in an amount of 0-6 g, preferably 0.1-6 g, preferably 2-4 g, per 100 g of precursor of the carrier on a dry basis.

[0140] According to the present disclosure, the binder is preferably present in an amount of 0-10 g, preferably 0.1-10 g, preferably 0.5-6 g per 100 g of precursor of the support on a dry basis.

[0141] According to the present disclosure, water is used as a dispersion medium in the mixture, the amount of water being specified by the criteria for uniformly mixing the other ingredients.

[0142] According to the present disclosure, the mixture may optionally contain a deflocculating agent, but preferably does not contain a deflocculating agent. Existing methods for preparing carriers require the addition of a deflocculating agent, such as dilute nitric acid. However, in the method for preparing the carrier of the present disclosure, a deflocculating agent may or may not be added.

[0143] The conditions for the first firing of the molded body in the present disclosure are not particularly limited. Conditions commonly used in the art may be used. Generally, the first firing may be carried out at a temperature of 350 to 700°C, preferably 450 to 650°C, for 1 to 10 hours, preferably 2 to 6 hours. The first firing may be carried out in an oxygen-containing atmosphere (e.g., air) or in an inert atmosphere. An inert atmosphere refers to a gas that is inert under the drying or firing conditions, such as nitrogen or a rare gas (e.g., argon).

[0144] Before the first firing of the molded body, the method may further include drying the molded body. Drying may be carried out under conventional conditions in the art. For example, drying may be carried out at a temperature of 100 to 200°C for 2 to 12 hours. Drying may be carried out under normal pressure or under reduced pressure. There is no particular limitation in this regard. Drying may be carried out in an oxygen-containing atmosphere or in an inert atmosphere.

[0145] According to the present disclosure, the method for preparing a carrier may further include the steps of kneading the mixture and then shaping it. Specifically, the mixture can be fed to an extruder, kneaded therein, and then extruded to obtain a shaped body.

[0146] According to the present disclosure, a molded body is obtained by molding, and an internal channel penetrates the molded body. The molding method may be selected from a wide range, as long as a molded body having an internal channel penetrating the molded body can be obtained. Preferably, the molding in step (II) is performed in an extruder. The extruder includes a main body and an orifice plate for extruding a strip, and the main body is configured to allow the mixture to pass through the orifice plate and be molded. As shown in FIGS. 1-3 , the orifice plate has a base 1 having a molding hole 2, a bracket 3 having at least one feed hole 6, and at least one molding rod 4. The bracket 3 is disposed above the base 1. The molding hole 2 is in communication with the feed hole 6. The bracket 3 further has at least one mounting hole 5 through which the molding rod 4 can pass. The molding rod 4 is configured to penetrate the molding hole 2. In the preferred configuration, the molding hole 2 of the orifice plate and the molding rod 4 penetrating the molding hole 2 together form a molding cavity, through which the mixture is molded into a corresponding shape. The preferred configuration allows for the preparation of supports with internal channels via a one-step process that is not only easy to carry out, but also has both high strength and high utilization of active metals.

[0147] According to the present invention, the expression "for extruding a strip" means that the orifice plate is used to extrude a strip. However, the expression "for extruding a strip" does not limit the structure of the orifice plate of the present disclosure.

[0148] Based on this disclosure, one skilled in the art will understand that a forming hole 2 may penetrate the base 1 and a forming rod 4 may be fitted into (or passed through) the forming hole 2, thereby resulting in a carrier having an internal channel passing through the carrier.

[0149] According to the present disclosure, the shaped rod 4 is configured to pass through the shaped hole 2. This can be understood as the shaped rod 4 having a length such that one end of the shaped rod 4 is located at the end of the base 1 remote from the bracket, or the one end of the shaped rod 4 is outside the end of the base 1 remote from the bracket.

[0150] According to a preferred embodiment of the present disclosure, the ratio of the cross-sectional area of ​​the forming rod 4 to the cross-sectional area of ​​the forming hole 2 corresponds to the above-mentioned ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the support. For example, it may be 0.05 to 3:100, preferably 0.1 to 3:100, and more preferably 0.2 to 3:100. The above-mentioned preferred configuration may be more advantageous in ensuring that the prepared support has both high strength and high utilization of the active metal.

[0151] It should be understood that, according to the present disclosure, the shape of the forming hole 2 is actually the shape of the prepared carrier, and the shape of the forming hole 2 may be selected according to the above explanation regarding the shape of the carrier.

[0152] According to a preferred embodiment of the present disclosure, the cross section of the forming hole 2 is circular or multi-lobed. The circular and multi-lobed shapes are not particularly limited and may be selected according to the above description regarding the shape of the carrier.

[0153] The size of the forming hole 2 may be selected within a wide range within the present disclosure. Those skilled in the art can make an appropriate selection according to the size requirements of the carrier. The method for preparing a carrier of the present disclosure is particularly suitable for preparing small-sized carriers. Preferably, the equivalent diameter of the forming hole 2 is 5 mm or less, preferably 3 mm or less, even more preferably 2 mm or less, and more preferably 0.8 to 2 mm.

[0154] The number of shaped rods 4 may be selected within a wide range within the present disclosure. It may be one, two or more, and may be appropriately selected according to the requirement of the number of internal channels in the carrier. Preferably, the number of shaped rods 4 may be 1 to 10, more preferably 1 to 6. It should be understood that the number of shaped rods 4 corresponds to the number of the above-mentioned channels in the carrier.

[0155] According to the present disclosure, the positions of the forming rods correspond to the positions of the channels in the carrier. Based on the above description of the positions of the channels in the carrier, those skilled in the art will know how to set the forming rods. Preferably, if the cross section of the forming hole 2 is circular, the forming rods 4 may extend along the central axis of the circle. If the number of forming rods 4 is more than two, the forming rods 4 may be equally spaced circumferentially around the center of the circle. According to a preferred embodiment of the present disclosure, the cross section of the forming hole 2 is multi-lobed, and the forming rods 4 extend along the central axis of the circumscribing cylinder of the multi-lobed shape and / or along the central axis of the circumscribing cylinder of each lobe of the multi-lobed shape. The above preferred configuration allows for a more reasonable design of the positions of the internal channels in the carrier, resulting in a uniform distribution of the channels. This can effectively avoid a sudden decrease in the strength of parts of the carrier due to the incorporation of channels in the carrier. Furthermore, it can improve the mechanical strength of the carrier.

[0156] According to one embodiment of the present invention, the number of mounting holes 5 is equal to the number of forming rods 4 .

[0157] Preferably, the molding rod 4 is detachably connected to the bracket 3 via the mounting hole 5. In the present disclosure, the detachable connection satisfies the requirement that when the connection is functioning, one of the two connected parts does not move relative to the other, and when the functioning is terminated, they can be disassembled and replaced.

[0158] The forming rod 4 may be arranged in a variety of suitable configurations. For example, as shown in Figure 3, the head 13 of the forming rod 4 is placed in the mounting hole 5, and the rod portion 14 of the forming rod extends toward the discharge outlet of the forming hole and fits into (or passes through) the mounting hole 5 and the forming hole 2. This arrangement is easy and inexpensive to install.

[0159] According to the present disclosure, the number of feed holes 6 may be selected within a relatively wide range. For example, it may be 1 to 20, preferably 2 to 20. Preferably, as shown in FIG. 2, multiple feed holes 6 are equally spaced circumferentially arranged along the forming rod 4. This preferred configuration is more advantageous for uniformly supplying material around the forming rod 4, thereby uniformly distributing force around the forming rod 4 and thereby extending the life of the forming rod 4. Based on the above, those skilled in the art can select the number of feed holes 6 circumferentially arranged around each forming rod 4 according to actual conditions. It should be understood that the feed holes 6 may be arranged in various appropriate patterns. For example, as shown in FIG. 2, multiple feed holes may communicate with the mounting hole 5 or may be isolated from the mounting hole 5.

[0160] The forming rod 4 is placed in a mounting hole 5 formed in the support structure of the bracket 3, which in turn covers the distribution area of ​​the forming hole 2. In this regard, the bracket 3 is preferably configured to have a uniform cross-sectional structure to ensure uniform distribution of raw material and simplify processing of the bracket 3, thereby maximizing the thickness of the support structure (referring to the dimension along the discharge direction of the forming hole). This enhances the support structure's ability to bear the compressive action associated with the supply of material through the forming hole and improves the reliability of the fixing of the forming rod. Preferably, the distribution area of ​​the feed hole 6 at least partially overlaps the distribution area of ​​the forming hole 2 so that the bracket 3 can uniformly supply material directly to the region of the forming hole 2 in the base 1 through the feed hole 6. This can be advantageous for simultaneously supplying material to various areas of the entrance of the forming hole 2. In addition, the feed hole may be configured to have an overall multi-lobed outer contour having the same shape as the forming hole.

[0161] Preferably, as shown in Fig. 3, the portion of the forming rod 4 extending into the forming hole 2 is configured to have a uniform cross-sectional structure. The preferred configuration can effectively ensure the uniformity of the processed shape of the prepared carrier, and can be advantageous in obtaining a dense carrier having high density and strength.

[0162] In particular, the forming rod 4 may be formed into various suitable shapes to facilitate the preparation of a carrier having an internal channel with a corresponding shape. It should be understood that the portion of the forming rod 4 extending into the forming hole 2 corresponds to the internal channel in the carrier. Preferably, the portion of the forming rod 4 extending into the forming hole 2 is configured as a cylinder. In this case, the prepared carrier may have a corresponding cylindrical channel. This makes the inner surface of the carrier smooth and regular, avoids stress accumulation in the carrier caused by the presence of sharp walls in the channel structure, and reduces the probability of the carrier collapsing. More preferably, the cylinder is configured to have a diameter of 5 μm or more, preferably 0.01 to 0.5 mm, and even more preferably 0.05 to 0.3 mm.

[0163] More preferably, the portion of the forming rod 4 that extends into the forming hole 2 is configured as a regular polygonal prism. In this case, the prepared support may have corresponding channels of the regular polygonal prism, making the inner surface of the support more regular. This is advantageous in ensuring a more uniform distribution of forces on the support and further optimizing the overall strength of the support.

[0164] More preferably, the regular polygonal prism is configured to have a circumscribing cylinder, and the diameter of the circumscribing cylinder is 5 μm or more, preferably 0.01 to 0.5 mm, and more preferably 0.05 to 0.3 mm.

[0165] In the present disclosure, a regular polygonal prism may be configured as any regular polygonal prism, such as a triangular prism, a quadrangular prism, a pentagonal prism, etc. Accordingly, the prepared support has channels with cross sections of corresponding regular polygons, such as an equilateral triangle, a square, a regular pentagon, etc.

[0166] According to a preferred embodiment of the present disclosure, the base 1 and the bracket 3 are detachably connected. This detachable connection satisfies the requirement that one of the base 1 and the bracket 3 does not move relative to the other when the connection is functioning, and that they can be disassembled and replaced when the function is terminated. Preferably, the base 1 and the bracket 3 are arranged closely to each other to avoid leakage. For example, the base 1 may be provided with a first mounting structure 7 on its contact surface with the bracket 3, and the bracket 3 may be provided with a second mounting structure 8 corresponding to the first mounting structure 7 on its contact surface with the base 1. For example, one of the first mounting structure 7 and the second mounting structure 8 is configured as a mounting groove, and the other is configured as a mounting protrusion corresponding to the mounting groove. According to one embodiment of the present disclosure, the base 1 and the bracket 3 have the same overall outer contour. Said configuration may be more convenient for installation and operation.

[0167] According to the present disclosure, there are no particular limitations on the heights of the base 1 and the bracket 3. Preferably, the ratio between the height of the base 1 and the height of the bracket 3 is set to 1:(0.2 to 5.0).

[0168] For ease of understanding, a specific molding method is provided herein. The method includes the steps of feeding the mixture obtained in step (I) into an extruder, the extruder including a body and an orifice plate, the body configured to allow the mixture to pass through the orifice plate and be molded. The mixture is fed through the feed holes 6 of the bracket 3 into the molding cavity formed by the molding holes 2 and the molding rods 4 to obtain a molded body, with internal channels running through the molded body. The number and shape of the molding rods 4 correspond to the number and shape of the channels, and the shape and size of the molding holes 2 correspond to the shape and size of the molded body.

[0169] The extruder body may be any commonly used in the art and will not be repeated here.

[0170] In the present disclosure, step (IV) employs an impregnation method to introduce the metal active component onto the support. In one variation, the metal active component is one or more selected from Group VIB metal elements and Group VIII metal elements. The Group VIB metal elements and Group VIII metal elements can be added together onto the support by a co-impregnation method. Alternatively, the Group VIB metal elements and Group VIII metal elements can be added separately by stepwise impregnation. The order of addition of the Group VIB metal elements and Group VIII metal elements is not particularly limited. Specifically, the precursors of the metal active component used in step (IV) may be a compound of a Group VIB metal element and a compound of a Group VIII metal element. The compound of a Group VIB metal element and the compound of a Group VIII metal element may be selected individually depending on the type of Group VIB metal element and Group VIII metal element required. When the Group VIB metal element is molybdenum and / or tungsten, the compound of the Group VIB metal element may be a compound of tungsten and / or a compound of molybdenum. In the present disclosure, examples of the compound of the Group VIB metal element may include, but are not limited to, one or more of tungstic acid, molybdic acid, metatungstic acid, ethylmetatungstic acid, paramolybdic acid, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, and ammonium ethylmetatungstate. When the Group VIII metal element is cobalt and / or nickel, the compound of the Group VIII metal element is preferably one or more of a salt of an oxygen-containing acid having nickel as a cation, a salt of an oxygen-free acid having nickel as a cation, a salt of an oxygen-containing acid having cobalt as a cation, and a salt of an oxygen-free acid having cobalt as a cation. In the present disclosure, examples of compounds of Group VIII metal elements may include, but are not limited to, one or more of nickel nitrate, nickel sulfate, nickel acetate, nickel bicarbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt bicarbonate, nickel chloride, and cobalt chloride.

[0171] According to the present disclosure, various solvents commonly used in the art may be used to prepare a solution containing a precursor of a metal active component, as long as the precursor of the metal active component can be dissolved in the solvent to form a homogeneous and stable solution. For example, the solvent may be water.

[0172] In another variation, the catalyst contains Co as the metal active component and a first metal promoter. Correspondingly, according to a preferred embodiment of the present disclosure, the solution used in step (IV) further contains a precursor of the first metal promoter. As described above, the first metal promoter may be introduced together with the other components by co-impregnation, or may be introduced separately by stepwise impregnation. In a variation, the precursor of the metal active component may be any substance that can be converted to cobalt oxide by second calcination. For example, it may be one or more of cobalt hydroxide, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt bicarbonate, cobalt formate, cobalt acetate, cobalt oxalate, and cobalt naphthenate.

[0173] In a further variation, the catalyst may further contain a second metal promoter. Correspondingly, according to a preferred embodiment of the present disclosure, the solution used in step (IV) further contains a precursor of the second metal promoter. As mentioned above, the second metal promoter may be introduced together with the other components by co-impregnation, or may be introduced separately by stepwise impregnation.

[0174] The first metal promoter precursor and the second metal promoter precursor may be any material that can be converted to the corresponding first metal promoter oxide and second metal promoter oxide, respectively, by the second calcination. The first metal promoter precursor and the second metal promoter precursor may be those commonly used in the art, for example, one or more of their water-soluble salts, such as nitrates, acetates, bicarbonates, hydrochlorides, and soluble complexes thereof.

[0175] The concentrations of the metal active component precursor, the first metal promoter precursor and the second metal promoter precursor in the solution may be selected according to the desired water absorption rate of the support and the target content of each component in the catalyst, which is well known by those skilled in the art.

[0176] The impregnation method may be any impregnation method commonly used in the art. For example, it may be a pore saturation impregnation method. In the present disclosure, there is no particular limitation on the impregnation time or number of repetitions, as long as the amount of metal active component on the final catalyst can reliably meet the specific application requirements. Generally, impregnation may be carried out for 0.5 to 12 hours.

[0177] According to the present disclosure, the drying conditions for the impregnated carrier are not particularly limited. Generally, drying may be carried out at a temperature of 80 to 300°C, preferably 100 to 200°C, for 0.5 to 24 hours, preferably 1 to 12 hours.

[0178] In the present disclosure, the conditions for the second calcination of the dried and impregnated support are not particularly limited. Conditions commonly used in the art may be adopted. Generally, the second calcination may be carried out at a temperature of 350 to 700°C, preferably 400 to 650°C, for 0.2 to 12 hours, preferably 1 to 10 hours. The second calcination may be carried out in an oxygen-containing atmosphere.

[0179] The supported catalysts of the present disclosure can be used for various hydrocarbon feedstock hydrogenation reactions, including, but not limited to, hydrodesulfurization, hydrodenitrogenation, olefin saturation, aromatic saturation, hydrocracking, and hydroisomerization. The catalysts of the present disclosure may also be used as Fischer-Tropsch synthesis catalysts. The supported catalysts of the present disclosure may also be used as oxidation catalysts for aromatization reactions, photocatalysis, enzyme immobilization, etc.

[0180] The various hydrocarbon feedstocks may be various heavy mineral or synthetic oils or blends thereof, such as straight run gas oil, vacuum gas oil, demetallized oil, atmospheric resid, deasphalted vacuum resid, coker distillate, catalytic cracking distillate, shale oil, tar sands oil, coal liquids, etc.

[0181] The inventors of the present invention have found that the catalyst of the present disclosure is particularly suitable as a hydrocracking catalyst.Therefore, a third aspect of the present disclosure provides the use of the supported catalyst of the present disclosure in hydrocracking.The supported catalyst of the present disclosure can be used for hydrocracking various hydrocarbon oils to produce hydrocarbon fractions with lower boiling points and lower molecular weights.

[0182] According to a fourth aspect of the present disclosure, the present disclosure provides a hydrocracking method, the hydrocracking method comprising the step of contacting a hydrocarbon oil with a hydrocarbon cracking catalyst under hydrocracking conditions, wherein the hydrocracking catalyst is a supported catalyst of the present disclosure.

[0183] The supported catalyst, its preparation method, and the type of hydrocarbon oil have been described in detail above and will not be repeated here.

[0184] The remaining conditions for the hydrocracking method of the present disclosure are not particularly limited. Conditions commonly used in the art may be adopted. Generally, hydrocracking conditions include a temperature of 200 to 650°C, preferably 300 to 510°C, a gauge pressure of 3 to 24 MPa, preferably 4 to 15 MPa, a volume ratio of hydrogen to oil of 100 to 5000, preferably 200 to 1500, and a time of 0.1 to 30 h. -1 , preferably 0.2 to 5 hours -1 The liquid volume hourly space velocity may include

[0185] According to the present disclosure, the catalyst is preferably pre-vulcanized before use in hydrocracking. The conditions for pre-vulcanization may be those commonly used in the art. For example, the conditions for pre-vulcanization may include pre-vulcanization using sulfur, hydrogen sulfide, or a sulfur-containing substance in the presence of hydrogen at a temperature of 140 to 370°C. According to the hydrocracking method of the present disclosure, pre-vulcanization may be carried out outside the reactor or in situ within the reactor. Specific conditions for pre-vulcanization are well known to those skilled in the art and will not be repeated here. The catalyst of the present disclosure may be used directly without pre-treatment or after reduction treatment.

[0186] The present inventors have found that the supported catalyst of the present disclosure is particularly suitable as a Fischer-Tropsch synthesis catalyst. Accordingly, a fifth aspect of the present disclosure provides use of the above-described supported catalyst in a Fischer-Tropsch synthesis reaction.

[0187] A sixth aspect of the present invention provides a method of Fischer-Tropsch synthesis, the method comprising the step of contacting CO and H2 with a Fischer-Tropsch synthesis catalyst under conditions for a Fischer-Tropsch synthesis reaction, wherein the Fischer-Tropsch synthesis catalyst is the supported catalyst described above.

[0188] In the present disclosure, the catalyst may be activated before being used in the Fischer-Tropsch synthesis reaction. The conditions and operation of the activation treatment are not particularly limited and may be carried out according to those commonly used in the art. Preferably, the activation treatment includes carrying out reductive activation in the presence of hydrogen at a temperature of 120 to 500°C. The reductive activation may be carried out outside the reactor or in situ in the reactor to convert the catalyst into an elemental metal active material. The activation treatment may be carried out for 1 to 10 hours.

[0189] In the present disclosure, the conditions for the Fischer-Tropsch synthesis are preferably a temperature of 150 to 300°C, preferably 170 to 250°C, more preferably 190 to 230°C, a pressure of 0.2 to 16 MPa, preferably 1.0 to 10 MPa, and a reaction time of 200 to 400,000 hours. -1 , preferably 500 to 100,000 h -1 , more preferably 1000 to 50,000 h -1 and a volume ratio of H to CO of 0.8 to 3.6, preferably 1.5 to 2.5, and more preferably 1.8 to 2.2. In the contact, an inert gas may be introduced as a diluent gas such as nitrogen at a content of 0 to 50% by volume in the mixed gas.

[0190] Example The present disclosure will be described in detail below with reference to examples.

[0191] In the following examples, BET pore volume was measured according to the method defined in RIPP151-190; The water absorption rate is the water absorption rate after wiping, which is obtained by soaking a dried carrier in deionized water for 60 minutes at room temperature (20-25°C), filtering it, wiping it with filter paper, and then obtaining the mass of the carrier after water absorption. The ratio of the difference between the obtained mass and the mass of the carrier before water absorption to the mass of the carrier before water absorption was used as the water absorption rate after wiping; The radial crushing strength of the carrier was measured using a QCY-602 compressive strength tester (manufactured by the Soda Research Institute, Ministry of Chemical Industry) according to the method specified in GB3635-1983; The bulk density of the catalyst was measured according to the method defined in Industrial Catalyst Analysis, Testing and Characterization (edited by Liu Xiyao; China Petrochemical Press, Beijing, p. 29, April 1990). In particular, in this disclosure, the bulk density of the catalyst is determined by a method including the steps of crushing the catalyst, sieving the particles to 16-20 mesh, adding the sieved particles to a 500 mL graduated cylinder, and obtaining the weight G and visual volume V. The bulk density of the catalyst = G / V.

[0192] In the following Preparation Examples, Examples, and Comparative Examples, the pressure was gauge pressure, and the amount was measured on a dry basis after the sample was fired at 600° C. for 4 hours.

[0193] [Part I: Regarding supported catalysts used as hydrogenation catalysts] [Preparation Example 1] (1) 200.0 g of dried alumina sol powder (manufactured by Sinopec Catalyst Ltd. Co., Changling Company, 68 wt. % on a dry basis, pseudoboehmite as the main component, hereinafter the same), 19.2 g of HY molecular sieve (manufactured by Sinopec Catalyst Ltd. Co., Changling Company, 79 wt. % on a dry basis, FAU molecular sieve, hereinafter the same), and 8 g of sesban powder were uniformly mixed to obtain a mixed powder. 10 mL of egg white (from fresh eggs) and 1 g of hydroxymethylcellulose were mixed with water to make a total volume of 175 mL. This mixture was whipped in a whisk and mixed with the mixed powder to obtain a mixture.

[0194] (2) The above mixture was fed into an extruder, kneaded three times (15 minutes each), and extruded into a strip through a trilobe orifice plate with a diameter of 1.6 mm and a core, on which three shaped rods (three cylinders with a diameter of 0.1 mm) were provided. The extruded strip was dried at 120°C for 3 hours and then calcined in air at 600°C for 3 hours. Catalyst support SA was obtained.

[0195] The carrier was in the form of a trilobal strip, with a cross-sectional circumscribing circle having a diameter of 1.6 mm. The carrier contained three internal channels (three cylinders with a diameter of 0.1 mm) extending through the carrier, each extending along the central axis of the circumscribing circle of each trilobe. The cross-section of the carrier is shown schematically in Figure 4, and the strengths of the carrier are listed in Table 1.

[0196] The molding was carried out specifically as described in the detailed description above. In particular, the molding was carried out using an orifice plate including a bracket 3 having twelve feed holes 6, and the orifice plate was provided with three forming rods 4. As shown in FIG. 5, each of the four feed holes 6 was equally spaced circumferentially along one of the forming rods 4. The bracket 3 also had three mounting holes 5 through which the forming rods 4 could pass. Each of the three forming rods 4 extended along the central axis of the circumscribing circle of each of the three lobes, as shown in FIG. 5.

[0197] [Comparative Preparation Example 1] (1) 200.0 g of dried alumina sol powder, 19.2 g of HY molecular sieve, and 8 g of Sesban powder were uniformly mixed to obtain a mixed powder. 2.5 mL of nitric acid with a weight concentration of 68% was added with water to make 155 mL and mixed uniformly. The solution was added to the mixed powder to obtain a mixture. The mixture was fed into an extruder, kneaded three times (15 minutes each), and extruded into strips through a trilobe orifice plate with a diameter of 16 mm. The extruded strips were dried at 120°C for 3 hours and then calcined in air at 600°C for 3 hours. Carrier DA was obtained, which was solid (without internal channels).

[0198] The support was in the shape of a trilobe strip, and the diameter of the circumscribed circle of the cross section was 1.6 mm. The cross section of the support is shown schematically in FIG.

[0199] [Preparation Example 2] (1) 200.0 g of dried alumina sol powder, 19.2 g of HY molecular sieve, and 8 g of sesban powder were uniformly mixed to obtain a mixed powder. 10 mL (equivalent to 1.0 g of hoof meat) of animal protein foaming agent (Ma Zhijun, Li Xiaoyun, Ma Xuelei, Cui Yanling, Jia Yonghui, Building Science, 2009, 25(05), pp. 73-76, Study of protein concrete foaming agent [J], prepared by hydrolyzing 20 g of hoof meat, 6 g of Ca(OH)2, 2 g of NaHSO3, and 200 mL of water for 6 hours at 80°C to prepare a liquid foaming agent) and 1 g of hydroxymethylcellulose were added, and water was added to a total volume of 175 mL. The mixture was foamed in a foaming machine and mixed with the mixed powder to obtain a mixture.

[0200] (2) The above mixture was fed into an extruder, kneaded three times (15 minutes each), and extruded into a strip through a four-lobed orifice plate with a diameter of 1.6 mm and a core, on which four shaped rods (four cylinders with a diameter of 0.1 mm) were provided. The extruded strip was dried at 120°C for 3 hours and then calcined in air at 600°C for 3 hours. Carrier SB was obtained.

[0201] The support was in the shape of a four-lobed strip, with a 1.6 mm diameter circumscribed circle of the cross section. The support contained four internal channels (four cylinders with a diameter of 0.1 mm) extending through the support. Each of the four cylindrical channels extended along the central axis of the circumscribed circle of each of the four lobes. The cross section of the support is shown schematically in Figure 7, and the strengths of the support are listed in Table 1.

[0202] [Preparation Example 3] Preparation Example 1 was repeated, except that the egg white volume was 5 mL and a trilobe orifice plate with a diameter of 1.6 mm and a core was used for strip extrusion. The carrier was in the shape of a trilobe strip, with a cross-sectional circumscribed circle diameter of 1.6 mm. The carrier contained four internal channels (one equilateral triangular prism with a circumscribed circle diameter of 0.1 mm and three cylindrical prisms with a diameter of 0.1 mm) penetrating the carrier. The triangular prism-shaped channel extended along the central axis of the trilobe-shaped circumscribed circle, and each of the three cylindrical channels extended along the central axis of the trilobe-shaped circumscribed circle. Carrier SC was obtained. The cross-section of the carrier is shown in Figure 8, and the carrier strengths are listed in Table 1.

[0203] [Preparation Example 4] Preparation Example 2 was repeated, except that the animal protein-based foaming agent was used in a volume of 20 mL, and a trilobe orifice plate with a diameter of 1.6 mm and a core was used to extrude the strip. The carrier was in the shape of a trilobe strip, with a cross-sectional circumscribed circle diameter of 1.6 mm. The carrier contained three internal channels (three regular hexagonal prisms with a circumscribed circle diameter of 0.1 mm) penetrating the carrier, each extending along the central axis of the circumscribed circle of each of the trilobes. Carrier SD was obtained. The cross-section of the carrier is shown in Figure 9, and the strength of the carrier is listed in Table 1.

[0204] [Preparation Example 5] Preparation Example 1 was repeated, except that the amount of egg white was 20 mL. Carrier SE was obtained. The strength of the carrier is listed in Table 1.

[0205] [Preparation Example 6] Preparation 1 was repeated except that egg white was replaced by a vegetable-based foaming agent.

[0206] Specifically, (1) 200.0 g of dried alumina sol powder, 19.2 g of HY molecular sieve, and 8 g of sesban powder were uniformly mixed to obtain a mixed powder. 1.5 g of tea saponin (manufactured by Xinyi FEIHUANG Chemical Co., Ltd.) was mixed with 0.5 mL of nitric acid (concentration 68%), and water was added to make a total volume of 175 mL. The mixture was foamed in a foaming machine and mixed with the mixed powder to obtain a mixture.

[0207] (2) Step (2) of Preparation Example 1 was repeated to extrude the mixture into strips. The extruded strips were dried at 120°C for 3 hours and then calcined in air at 600°C for 3 hours. Support SF was obtained. The strength of the support is listed in Table 1.

[0208] [Preparation Example 7] Preparation Example 1 was repeated, except that a trilobe orifice plate having a core and a diameter of 1.6 mm was used to extrude the strip, and one molding rod (a cylinder with a diameter of 0.2 mm) was provided on the orifice plate. Carrier SG was obtained. The carrier was in the shape of a trilobe strip, the diameter of the circumscribed circle of the cross section was 1.6 mm, and the carrier contained one internal channel (a cylindrical channel with a diameter of 0.2 mm) penetrating the carrier, and the cylindrical channel extended along the central axis of the circumscribed circle of the trilobe shape. The strength of the carrier is listed in Table 1.

[0209] The physicochemical properties of the carriers prepared as above were characterized, and the results are listed in Table 1 below.

[0210] [Table 1] Note: The percentage refers to the ratio of the difference R to the water absorption rate of the carrier, and the strength refers to the radial crushing strength of the carrier.

[0211] [Examples 1-7 and Comparative Example 1] These examples were used to illustrate the catalytic performance of the catalysts of the present disclosure.

[0212] The water absorption of the above supports was measured. An aqueous solution of nickel nitrate (analytical grade, manufactured by Beijing Yili Chemical Reagent Factory) and ammonium metatungstate (industrial product, manufactured by Sinopec Catalyst Ltd. Co., Changling Company) was prepared, corresponding to 21.5 wt.% tungsten oxide and 2.5 wt.% nickel oxide in the catalyst. The supports of the Preparation Example and Comparative Preparation Example were impregnated with the aqueous solution via the pore saturation method. The impregnated supports were dried at 120°C for 5 hours and then calcined at 400°C for 3 hours to obtain catalysts CSA-CSG and CDA, respectively. The bulk density of each catalyst was measured, and the results are listed in Table 2.

[0213] The process was carried out in a continuous manner, with the feedstock having a viscosity of 0.9122 g / cm (at 20°C). 3 density, T IBP = 272℃, T 50% = 422°C and T FBP =536℃Maoming VGO(2011).

[0214] Each catalyst was divided into particles with a length of 3 to 5 mm. 100 g of catalyst was inserted into a 200 ml fixed-bed reactor, and the remaining space was filled with ceramic balls. Before passing the feed oil, the catalyst was gas-phase vulcanized for 28 hours under conditions of a hydrogen partial pressure of 15.0 MPa, a temperature of 300°C, and DMDS as a vulcanizing agent. Then, the catalyst was vulcanized under conditions of a hydrogen partial pressure of 14.7 MPa, a temperature of 320°C, a hydrogen-to-oil ratio of 1200 vol / vol, and a volumetric space velocity of 0.85 h. -1 The feed oil was passed through under the conditions of After 400 hours of reaction, a sample was taken.

[0215] The catalyst was detected for catalytic activity, jet fuel yield (distillation range of 160-250 °C), and temperature of 95% of the residual oil. The results are shown in Table 2.

[0216] The activity referred to the cracking reaction temperature at which the conversion to hydrocarbon oils having a distillation temperature higher than 350° C. was 60%. A lower cracking reaction temperature indicated a higher catalytic activity of the catalyst.

[0217] The 95% temperature of the residual oil refers to the distillation temperature at the 95% distillation point on the simulated distillation curve.

[0218] [Example 8] Example 1 was repeated, except that an aqueous solution of ammonium molybdate, nickel bicarbonate, and phosphoric acid was prepared, corresponding to 16.3 wt.% molybdenum oxide, 2.8 wt.% nickel oxide, and 1.1 wt.% phosphorus in the catalyst. Catalyst CSH was obtained. The performance data of the catalyst are listed in Table 2.

[0219] [Example 9] Example 1 was repeated, except that an aqueous solution of ammonium metatungstate and nickel nitrate was prepared in a manner corresponding to 17.0 wt. % tungsten oxide and 3.0 wt. % nickel oxide in the catalyst. Catalyst CSI was obtained. The performance data of the catalyst are listed in Table 2.

[0220] [Table 2] As can be seen from the data in Table 2, the catalyst of the present disclosure had the advantages of high activity, high jet fuel yield, and low bulk density.

[0221] [Part II: Supported catalysts used in Fischer-Tropsch synthesis] [Example 10] This example was used to illustrate the preparation of the support and catalyst of the present disclosure. (1) Preparation of the carrier S1: 200.0 g of dry powder of alumina sol (manufactured by Sinopec Catalyst Ltd. Co., Changling Company, 68 wt % on a dry basis) and 6 g of sesban powder were uniformly mixed to obtain a mixed powder. Water was added to 2.5 mL of nitric acid to make a total volume of 155 mL, and the mixture was uniformly mixed. The solution was added to the mixed powder to obtain a mixture.

[0222] S2: The above mixture was kneaded three times in an extruder and extruded into strips through a core-equipped trilobe orifice plate with a diameter of 1.6 mm. The extruded strips were dried at 120°C for 3 hours and then calcined in air at 600°C for 3 hours. Catalyst support ZA was obtained. The support was in the shape of a trilobe strip, the diameter of the circumscribed circle of the cross section was 1.6 mm, and the support contained an internal channel (which was a cylinder with a diameter of 0.1 mm) penetrating the support, and the channel extended along the central axis of the circumscribed circle. The cross section of catalyst support ZA is shown in Figure 10, and its radial crushing strength is listed in Table 3.

[0223] The molding was carried out as follows: The molding was carried out using an orifice plate including a base 1 having a molding hole 2 (as shown in FIG. 1, the molding hole 2 was trilobal and the diameter of its circumscribed circle was 1.6 mm), a bracket 3 having three feed holes 6, and one molding rod 4. As shown in FIG. 2, the three feed holes 6 were equally spaced circumferentially along the molding rod 4. As shown in FIGS. 1 and 2, the bracket 3 was placed on the base 1. The base 1 and the bracket 3 were provided with a first mounting structure 7 and a second mounting structure 8 on their contact surfaces, respectively, which were aligned to detachably connect the base 1 and the bracket 3.

[0224] The bracket 3 was further provided with a mounting hole 5 through which a forming rod 4 (shaped as shown in Figure 3) passed. The forming rod 4 was arranged to pass through the forming hole 2. The forming rod 4 extended along the central axis of the circumscribing circle of the trilobe shape. The head 13 of the forming rod 4 was installed in the mounting hole 5, and the rod portion 14 of the forming rod extended toward the discharge outlet of the forming hole and was fitted into (or passed through) the mounting hole 5 and the forming hole 2. The portion of the forming rod 4 located within the forming hole was configured as a cylinder with a diameter of 0.1 mm.

[0225] (2) Preparation of catalyst A solution of cobalt nitrate (analytical grade, manufactured by Beijing Yili Chemical Reagent Factory) was prepared corresponding to 30% by weight of cobalt oxide in the catalyst. The ZA support was impregnated twice with the cobalt nitrate solution by the pore saturation method. After each impregnation, the impregnated support was dried at 120°C for 3 hours and then calcined at 400°C for 3 hours. Catalyst ZAC was obtained.

[0226] [Example 11] This example was used to illustrate the preparation of the support and catalyst of the present disclosure. (1) Preparation of the carrier Example 10 was repeated, except that a trilobe orifice plate having a diameter of 1.6 mm and a core was used to extrude the strip, and three shaped rods were provided on the orifice plate. Catalyst support ZB was obtained. The support was in the form of a trilobe strip, the diameter of the circumscribed circle of its cross section was 1.6 mm, and the support contained three internal channels (which were cylindrical with a diameter of 0.1 mm) extending through the support, each extending along the central axis of the circumscribed circle of each of the trilobes. The cross section of catalyst support ZB is shown in Figure 11, and its radial crushing strength is listed in Table 3.

[0227] The molding of Example 10 was repeated, except that the bracket 3 was provided with 12 feed holes 6 and the orifice plate was provided with three forming rods 4. As shown in FIG. 6, each of the four feed holes 6 was equally spaced circumferentially along one of the forming rods 4. The bracket 3 was further provided with three mounting holes 5 to allow the forming rods 4 to pass through. Each of the three forming rods 4 extended along the central axis of the circumscribing circle of each of the trilobes.

[0228] (2) Preparation of catalyst The catalyst preparation outlined in Example 10 was repeated, except that the support ZA was replaced by catalyst support ZB. Catalyst ZBC was obtained.

[0229] [Example 12] This example was used to illustrate the preparation of the support and catalyst of the present disclosure. (1) Preparation of the carrier Example 11 was repeated, except that a trilobe orifice plate having a diameter of 1.6 mm and a core was used to extrude the strip, and three shaped rods were provided on the orifice plate. Catalyst support ZC was obtained. The support had the shape of a trilobe strip, the diameter of the circumscribed circle of its cross section was 1.6 mm, and the support contained three internal channels (regular hexagonal prisms with a circumscribed circle diameter of 0.1 mm) penetrating the support, each extending along the central axis of the circumscribed circle of each of the trilobes. The cross section of catalyst support ZC is shown in Figure 12, and the radial crushing strength of catalyst support ZC is listed in Table 3.

[0230] The molding of Example 11 was repeated, except that the three molded rods 4 were all in the shape of regular hexagonal prisms with a circumscribing circle diameter of 0.1 mm.

[0231] (2) Preparation of catalyst The catalyst preparation outlined in Example 10 was repeated, except that the support ZA was replaced by catalyst support ZC. Catalyst ZCC was obtained.

[0232] [Example 13] This example was used to illustrate the preparation of the support and catalyst of the present disclosure. (1) Preparation of the carrier Example 11 was repeated, except that a strip was extruded using a trilobe orifice plate having a diameter of 1.6 mm and a core, and the orifice plate was provided with four shaped rods (one equilateral triangular prism with a circumscribing circle diameter of 0.1 mm and three cylinders with a diameter of 0.1 mm). Catalyst Support ZD was obtained. The support had the shape of a trilobe strip, the diameter of the circumscribing circle of its cross section was 1.6 mm, and the support contained four internal channels (one equilateral triangular prism with a circumscribing circle diameter of 0.1 mm and three cylinders with a diameter of 0.1 mm) penetrating the support. The triangular prism-shaped channel extended along the central axis of the circumscribing circle of the trilobe, and the three cylindrical channels each extended along the central axis of the circumscribing circle of each of the trilobes. The cross section of Catalyst Support ZD is shown in Figure 13, and the radial crushing strength of Catalyst Support ZD is listed in Table 3.

[0233] (2) Preparation of catalyst The catalyst preparation outlined in Example 10 was repeated using catalyst support ZD to obtain catalyst ZDC.

[0234] [Example 14] This example was used to illustrate the preparation of the support and catalyst of the present disclosure. (1) Preparation of the carrier Example 11 was repeated, except that a four-lobed orifice plate with a diameter of 1.6 mm and a core was used to extrude the strip, and four shaped rods (four cylinders with a diameter of 0.1 mm) were provided on the orifice plate. Catalyst support ZE was obtained. The support was in the form of a four-lobed strip, the diameter of the circumscribed circle of its cross section was 1.6 mm, and the support contained four internal channels (four cylinders with a diameter of 0.1 mm) penetrating the support, each of the four cylindrical channels extending along the central axis of the circumscribed circle of each of the four lobes. The cross section of catalyst support ZE is shown in Figure 14, and the radial crushing strength of catalyst support ZE is listed in Table 3.

[0235] (2) Preparation of catalyst The catalyst preparation outlined in Example 10 was repeated using catalyst support ZE, resulting in catalyst ZEC.

[0236] [Example 15] This example was used to illustrate the preparation of the support and catalyst of the present disclosure. (1) Preparation of the carrier Example 11 was repeated, except that a four-lobed orifice plate with a diameter of 1.6 mm and a core was used to extrude the strip, and five shaped rods (five cylinders with a diameter of 0.1 mm) were provided on the orifice plate. Catalyst support ZF was obtained. The support was in the form of a four-lobed strip, the diameter of the circumscribed circle of its cross section was 1.6 mm, and the support contained five internal channels (five cylinders with a diameter of 0.1 mm) penetrating the support, with one cylindrical channel extending along the central axis of the circumscribed circle of the four-lobed shape, and the other four cylindrical channels each extending along the central axis of the circumscribed circle of each of the four lobes. The cross section of catalyst support ZF is shown in Figure 15, and the radial crushing strength of catalyst support ZF is listed in Table 3.

[0237] (2) Preparation of catalyst The catalyst preparation outlined in Example 10 was repeated using catalyst support ZF, resulting in catalyst ZFC.

[0238] [Example 16] Example 10 was repeated, except that a trilobe orifice plate having a core and a diameter of 1.6 mm was used to extrude the strip, and the orifice plate was provided with one shaped rod (which was a cylinder with a diameter of 0.2 mm). Catalyst support ZG was obtained. The support was in the form of a trilobe strip, the diameter of the circumscribed circle of its cross section was 1.6 mm, and the support contained one internal channel (a cylindrical channel with a diameter of 0.2 mm) penetrating the support, which extended along the central axis of the circumscribed circle of the trilobe. The radial crushing strength of catalyst support ZG is listed in Table 3.

[0239] (2) Preparation of catalyst The catalyst preparation outlined in Example 10 was repeated using catalyst support ZG, resulting in catalyst ZGC.

[0240] [Example 17] (1) Step (1) of Example 10 was repeated to prepare carrier ZA.

[0241] (2) Preparation of catalyst A solution of ruthenium chloride and cobalt nitrate was prepared, corresponding to 0.3 wt.% of Ru and 35 wt.% of cobalt oxide in the catalyst. The support ZA was impregnated twice with the solution of ruthenium chloride and cobalt nitrate by the pore saturation method. After each impregnation, the impregnated support was dried at 120°C for 3 hours and then calcined at 400°C for 3 hours. The catalyst ZHC was obtained.

[0242] [Example 17] (1) Step (1) of Example 10 was repeated to prepare carrier ZA.

[0243] (2) Preparation of catalyst A solution of ruthenium chloride, cobalt nitrate, and magnesium chloride was prepared, corresponding to 0.2 wt.% of Ru, 25 wt.% of cobalt oxide, and 5 wt.% of magnesium oxide in the catalyst. The support ZA was impregnated twice with the solution of ruthenium chloride, cobalt nitrate, and magnesium chloride by the pore saturation method. After each impregnation, the impregnated support was dried at 120°C for 3 hours and then calcined at 400°C for 3 hours. The catalyst ZIC was obtained.

[0244] Comparative Example 2 This comparative example was used to illustrate the preparation of a comparative support and catalyst.

[0245] (1) Preparation of the carrier Example 10 was repeated, except that a conventional orifice plate was used for molding. A solid catalyst support DA-2 (without internal channels) was obtained. The catalyst support DA-2 was in the shape of a trilobe strip, and the diameter of the circumscribed circle of its cross section was 1.6 mm. The cross section of the catalyst support DA-2 is shown in Figure 16, and the radial crushing strength of the catalyst support DA-2 is listed in Table 3.

[0246] (2) Preparation of comparative catalysts The catalyst preparation outlined in Example 10 was repeated using catalyst support DA-2 to obtain comparative catalyst DAC-2.

[0247] [Test example] This test example was used to demonstrate the performance of the catalyst obtained above in the Fischer-Tropsch synthesis reaction.

[0248] (1) Catalyst activation 5 mL of each of the catalysts prepared above was inserted into a fixed-bed microreactor, and the remaining space was filled with quartz sand. -1 The catalyst was reduced at a space velocity of 1000kJ / cm2 and a temperature of 400°C, and activated with hydrogen for 5 hours.

[0249] (2) Evaluation of catalysts for activity in Fischer-Tropsch synthesis The Fischer-Tropsch synthesis reaction was carried out at a temperature of 210°C, a pressure of 2.5 MPa, and a space velocity of 2000 h -1 The reaction was carried out under the conditions of H2 / CO / N2 = 60 / 30 / 10 and the volume composition of the synthesis gas. After 8 hours of reaction, the gas was sampled online for calculation.

[0250] The activity of the catalyst was characterized by the conversion of CO, and the selectivity of the Fischer-Tropsch synthesis catalyst was characterized by the selectivity to methane and C5+ hydrocarbons. The results are shown in Table 4. [Table 3]

[0251] [Table 4] As can be seen from the results in Table 4, compared to Comparative Example 2, the catalyst of the present disclosure had significantly higher activity and selectivity to C5+ hydrocarbons in the Fischer-Tropsch synthesis, and lower selectivity to methane.

[0252] [Part III: On the influence of the diameter of channels incorporated into the support on the support's radial crushing strength] Example 10 was repeated, except that a circular orifice plate with a diameter of 1.6 mm and a core was used to extrude the strip, and one shaped rod was provided on the orifice plate. The shaped rods were configured as cylinders with diameters of 0, 0.1 mm, 0.2 mm, 0.3 mm, 0.5 mm, 0.7 mm, and 1 mm, respectively. A series of catalyst supports Z0 to Z6 were obtained. Supports Z0 to Z6 were all cylindrical, with a cross-sectional diameter of 1.6 mm. Each support contained one internal channel (0, 0.1 mm, 0.2 mm, 0.3 mm, 0.5 mm, 0.7 mm, and 1 mm diameter, respectively) extending through the support, and the channel extended along the central axis of the cylindrical shape. The radial crushing strength of catalyst supports Z0 to Z6 was tested, and the pressure applied to the tested catalyst support was recorded when a radial deformation of approximately 0.17 mm occurred. It was observed that the tested catalyst support fractured when the deformation exceeded approximately 0.17 mm. Therefore, the pressure applied to the catalyst support at that time was recorded as the crush pressure. When comparing the data for the support having internal channels penetrating the support with the data for the support without channels, i.e., comparing the measured crush pressure for each of Z1-Z6 with the measured crush pressure for Z0, the resulting ratio was the percent compressive strength retention. The test results are listed in Table 5.

[0253] [Table 5] The above data was plotted in the profile shown in Figure 17. As can be seen from the above results, when the ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the support was 3:100 or less, the strength reduction of the support was less than about 10%.

[0254] The results of the above examples suggest that by controlling the ratio of the cross-sectional area of ​​the channel to the cross-sectional area of ​​the support to 3:100 or less, the corresponding supported catalyst can have both high strength and high catalytic activity. The resulting catalyst may be suitable for use in fixed-bed reactors, especially microreactors, microchannel reactors, microchemical reactors, or mesoscopic reactors.

[0255] Although the preferred embodiments of the present disclosure have been described in detail above, the present disclosure is not limited thereto. Simple modifications, including combinations of various technical features in any other appropriate manner, may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure. These simple modifications and combinations should also be considered as the contents disclosed in the present disclosure. All of them fall within the protection scope of the present disclosure. [Brief explanation of the drawings]

[0256] [Figure 1] FIG. 2 is a schematic diagram illustrating a structure of a base of an orifice plate according to an embodiment of the present disclosure. [Figure 2] FIG. 2 is a schematic diagram illustrating a structure of a bracket of an orifice plate according to an embodiment of the present disclosure. [Figure 3] FIG. 2 is a schematic diagram illustrating a structure of a molding rod of an orifice plate according to an embodiment of the present disclosure. [Figure 4] 1 is a schematic diagram showing a cross section of a carrier SA in Example 1 according to the present disclosure. [Figure 5] FIG. 2 is a schematic diagram illustrating a structure of a bracket of an orifice plate according to an embodiment of the present disclosure. [Figure 6] FIG. 2 is a schematic diagram showing a cross section of a carrier DA of Comparative Example 1. [Figure 7] FIG. 10 is a schematic diagram showing a cross section of a carrier SB in Example 2 according to the present disclosure. [Figure 8] FIG. 10 is a schematic diagram showing a cross section of a carrier SC according to a third embodiment of the present invention. [Figure 9] FIG. 10 is a schematic diagram showing a cross section of a carrier SD according to Example 4 of the present invention. [Figure 10] FIG. 12 is a schematic diagram showing a cross section of a carrier ZA according to Example 10 of the present invention. [Figure 11] FIG. 11 is a schematic diagram showing a cross section of the carrier ZB of Example 11 according to the present invention. [Figure 12] FIG. 12 is a schematic diagram showing a cross section of a carrier ZC according to Example 12 of the present invention. [Figure 13]FIG. 13 is a schematic diagram showing a cross section of the carrier ZD of Example 13 according to the present invention. [Figure 14] FIG. 12 is a schematic diagram showing a cross section of a carrier ZE according to Example 14 of the present invention. [Figure 15] FIG. 2 is a schematic diagram showing a cross section of the carrier ZF of Example 15 according to the present invention. [Figure 16] FIG. 2 is a schematic diagram showing a cross section of the carrier DA-2 of Comparative Example 2. [Figure 17] 1 is a graph showing the relationship between the channel size of a carrier and the radial crushing strength.

Claims

1. A catalyst comprising a support and a metal active component supported on the support, The metal active component is at least one selected from the group consisting of Group VIB metal elements and Group VIII metal elements, the support contains at least one of a heat-resistant inorganic oxide and a molecular sieve; the carrier includes an internal channel extending therethrough, the ratio of a cross-sectional area of ​​the channel to a cross-sectional area of ​​the carrier being 0.05 to 3:100; A supported catalyst for hydrocracking, wherein the difference R between the water absorption rate and the BET pore volume of the support is 0.2 mL / g or more.

2. the Group VIB metal element is Mo and / or W, and the Group VIII metal element is Co and / or Ni; 10. The catalyst of claim 1, wherein the Group VIB metal element is present in an amount of 10 to 35 wt. %, the Group VIII metal element is present in an amount of 2 to 15 wt. %, and the support is present in an amount of 50 to 88 wt. %, all on an oxide basis, based on the total amount of the catalyst.

3. the heat-resistant inorganic oxide is at least one selected from the group consisting of alumina, silica, titania, magnesium oxide, zirconia, thorium oxide, and beryllium oxide; the molecular sieve comprises at least one selected from the group consisting of a 10-membered ring silica-alumina molecular sieve, a 12-membered ring silica-alumina molecular sieve, a 14-membered ring silica-alumina molecular sieve, and an 18-membered ring silica-alumina molecular sieve; 2. The catalyst of claim 1, wherein the thermotolerant inorganic oxide is present in an amount of 1 to 99% by weight and the molecular sieve is present in an amount of 1 to 99% by weight, based on the total amount of the support.

4. the heat-resistant inorganic oxide is at least one of alumina, silica, titania, and zirconia; the molecular sieve comprises at least one of a Y molecular sieve, a beta molecular sieve, a ZSM-5 molecular sieve, and a mordenite; 2. The catalyst of claim 1, wherein the thermotolerant inorganic oxide is present in an amount of 1 to 99% by weight and the molecular sieve is present in an amount of 1 to 99% by weight, based on the total amount of the support.

5. 10. The catalyst of claim 1, wherein the metal active component is at least one of Group VIII metal elements.

6. 2. The catalyst of claim 1, wherein the metal active component is at least one of Ni, Fe, and Co.

7. 6. The catalyst of claim 5, further comprising a first metal promoter supported on the support, wherein the first metal promoter is at least one selected from transition metals.

8. 6. The catalyst of claim 5, further comprising a first metal promoter supported on the support, wherein the first metal promoter is at least one selected from the group consisting of Cu, Ru, Rh, Re, Pd, and Pt.

9. the metal active component is Co; Co is present in an amount of 5 to 80 wt. % based on the total amount of the catalyst on an oxide basis; 8. The catalyst of claim 7, wherein, on an oxide basis, the first metal promoter is present in an amount of 0 to 40 wt. % based on the total weight of the catalyst.

10. the metal active component is Co; Co is present in an amount of 20 to 40 wt. % based on the total amount of the catalyst, on an oxide basis; 8. The catalyst of claim 7, wherein, on an oxide basis, the first metal promoter is present in an amount of 0.1 to 20 wt. % based on the total weight of the catalyst.

11. The catalyst further comprises a second metal promoter supported on the carrier, wherein the second metal promoter is at least one selected from the group consisting of alkali metals and alkaline earth metals; 6. The catalyst of claim 5, wherein, on an oxide basis, the second metal promoter is present in an amount of 0 to 20 wt. % based on the total weight of the catalyst.

12. The catalyst further comprises a second metal promoter supported on the support, the second metal promoter being at least one of Na, K, Mg, and Ca; 6. The catalyst of claim 5, wherein, on an oxide basis, the second metal promoter is present in an amount of 2 to 10 wt. % based on the total weight of the catalyst.

13. The carrier is in the form of a sphere and / or a strip, the carrier has an equivalent diameter of 5 mm or less; 10. The catalyst of claim 1, wherein the channels are passages of uniform cross section.

14. the carrier is in the form of a multi-lobed strip; the carrier has an equivalent diameter of 0.8 to 2 mm; 2. The catalyst of claim 1, wherein the channels are passages of uniform cross section, the channels are in the shape of a cylinder and / or a regular polygonal prism, and the diameter of the cylinder and the diameter of the circumscribed circle of the regular polygonal prism are independently 0.01 to 0.5 mm.

15. 2. The catalyst of claim 1, wherein the support has a radial crushing strength of 14 to 30 N / mm or the catalyst has a bulk density of 0.5 to 1 g / mL.

16. 2. The catalyst of claim 1, wherein the support has a radial crushing strength of 18 to 26 N / mm or the catalyst has a bulk density of 0.6 to 0.9 g / mL.

17. the number of channels is 1 to 10, 2. The catalyst of claim 1, wherein the support has a circular cross section and the channels extend in a cylindrical shape along a central axis of the support and / or are equally spaced circumferentially along the central axis.

18. the number of channels is 1 to 6, 2. The catalyst of claim 1, wherein the support has a multi-lobed cross section and the channels extend along the central axis of a circumscribing cylinder of the multi-lobed shape and / or along the central axis of a circumscribing cylinder of each lobe.

19. (I) mixing a precursor of the carrier and water to obtain a mixture; (II) molding the mixture to obtain a molded body, wherein an internal channel penetrates the molded body; (III) subjecting the molded body obtained in step (II) to a first firing to obtain a carrier; (IV) impregnating the support obtained in step (III) with a solution containing a precursor of a metal active component, followed by drying and a second calcination.

20. 20. The method of claim 19, wherein the mixing step (I) comprises mixing a precursor of the carrier, water, a foaming agent, an extrusion aid, and a binder to obtain a mixture.

21. the foaming agent is an animal protein-based foaming agent and / or a plant-based foaming agent; The extrusion aid is at least one selected from the group consisting of sesban powder, cellulose, starch, ethylene glycol, and diethylene glycol; the binder is at least one selected from the group consisting of hydroxymethyl cellulose, inorganic acid, starch, silica sol, and aluminum sol; the foaming agent is present in an amount of 0 to 50 mL per 100 g of the carrier precursor, on a dry basis; the extrusion aid is present in an amount of 0.1 to 6 g per 100 g of the carrier precursor, on a dry basis; 21. The method of claim 20, wherein the binder is present in an amount of 0.1 to 10 g per 100 g of the carrier precursor on a dry basis.

22. the foaming agent is at least one selected from the group consisting of an animal hoof-based foaming agent, an animal hair-based foaming agent, and an animal blood gel-based foaming agent; The extrusion aid is at least one selected from the group consisting of sesban powder, cellulose, starch, ethylene glycol, and diethylene glycol; the binder is at least one selected from the group consisting of hydroxymethyl cellulose, inorganic acid, starch, silica sol, and aluminum sol; the foaming agent is present in an amount of 0.5 to 20 mL per 100 g of the carrier precursor, on a dry basis; the extrusion aid is present in an amount of 0.1 to 6 g per 100 g of the carrier precursor, on a dry basis; 21. The method of claim 20, wherein the binder is present in an amount of 0.1 to 10 g per 100 g of the carrier precursor on a dry basis.

23. The first firing is carried out at a temperature of 350 to 700°C for 1 to 10 hours; The drying is carried out at a temperature of 80 to 300°C for a time of 0.5 to 24 hours; 20. The method of claim 19, wherein the second firing is carried out at a temperature of 350 to 750°C for 0.2 to 12 hours.

24. The first firing is carried out at a temperature of 450 to 650°C for 2 to 6 hours; The drying is carried out at a temperature of 100 to 200°C for 1 to 12 hours; 20. The method of claim 19, wherein the second firing is carried out at a temperature of 400 to 650°C for 1 to 10 hours.

25. The precursor of the metal active component is one or more selected from the group consisting of cobalt hydroxide, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt bicarbonate, cobalt formate, cobalt acetate, cobalt oxalate, and cobalt naphthenate, or The solution used in step (IV) further contains a precursor of the first metal promoter, or 20. The method of claim 19, wherein the solution used in step (IV) further contains a precursor of a second metal promoter.

26. Use of the supported catalyst according to any one of claims 1 to 18 in hydrocracking.

27. contacting a hydrocarbon oil with a hydrocracking catalyst under hydrocracking conditions; A hydrocracking method, wherein the hydrocracking catalyst is a supported catalyst according to any one of claims 1 to 18.

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