A method for the preparation of a supported continuous reforming catalyst and catalytic reforming applications

Abstract

The present application relates to the field of reforming catalyst preparation, in particular to a preparation method of a supported continuous reforming catalyst and catalytic reforming application. (1) A first aluminum source is subjected to a hydrothermal crystallization reaction to obtain a flaky stacked aluminum oxide material; (2) a second aluminum source is dissolved in acid, and a solution containing a tin compound, a rare earth element compound and a viscosity additive is added, and finally the flaky stacked aluminum oxide material is stirred to prepare a catalyst carrier precursor glue solution; (3) a pore-forming agent solution is added to the above glue solution, and a composite glue solution is prepared after mixing to obtain a spherical carrier; (4) a platinum source is dissolved in water and an amino acid is added to prepare an impregnation solution, and the spherical carrier is added; (5) a catalytic reforming catalyst is obtained by reduction. The present application uses a flaky stacked aluminum oxide material, and the platinum active component in the Pt / gamma-alumina catalyst provided can be more efficiently dispersed on the surface of the carrier and sintering thereof is inhibited, and the catalyst has high dispersity, high activity, sintering resistance and long service life.

Description

Technical Field

[0001] This invention relates to the field of reforming catalyst preparation, and particularly to a method for preparing a supported continuous reforming catalyst and its application in catalytic reforming. Background Technology

[0002] Catalytic reforming is an important petroleum processing technology, mainly aimed at producing high-octane gasoline, BTX aromatics, and by-product hydrogen. Its main reaction involves the isomerization and dehydrogenation of cycloalkanes and alkanes to produce aromatics. High-performance catalysts play a decisive role in improving the aromatic content of the product, increasing liquid yield, and reducing energy consumption in the catalytic reforming process.

[0003] Reforming catalysts possess dual functions, functioning as both metal centers and acid centers. The most commonly used industrial reforming catalyst is the Pt-Sn / Al₂O₃ catalyst for moving bed processes. In this catalyst, dehydrogenation occurs at the platinum metal centers, while isomerization occurs at the acid centers formed by halogens and alumina. The combination of these two centers catalyzes the reforming reaction. Given the same platinum metal loading, higher platinum dispersion leads to more complete dehydrogenation and cyclization reactions; therefore, increasing platinum metal dispersion is crucial. Furthermore, because reforming catalysts require circulation during operation to burn off generated carbon deposits, platinum metal aggregation can occur. Therefore, catalysts less prone to metal aggregation perform better.

[0004] For reforming units, at the same reaction temperature, a higher yield of aromatics can be achieved. The higher the octane number of the stabilized gasoline in the reformed product, the better the catalyst performance.

[0005] Chinese Patent Publication No. CN120827887A, entitled "Supported Reforming Catalyst and Its Preparation, Application, and Method for Catalytic Reforming," discloses a supported reforming catalyst. The catalyst comprises an alumina support containing rare earth metals and Group IVA metals, and an active component supported on the alumina support. The active component includes platinum group metals. In the alumina support, pores with a diameter of 6-10 nm account for 10-22% of the total pore volume, pores with a diameter of 10-20 nm account for 50-75%, and pores with a diameter of 20-50 nm account for 10-25%. This supported reforming catalyst exhibits excellent catalytic performance and demonstrates high reactivity and product selectivity when applied to hydrocarbon catalytic reforming. However, a problem exists: while the method of adjusting the pore structure of the catalyst support significantly affects the pore size distribution, whether this negatively impacts metal dispersion was not demonstrated in subsequent experiments.

[0006] Chinese Patent Publication No. CN117548102A, entitled "Supported Platinum and Tin Reforming Catalyst, Preparation Method and Application Thereof, and Naphtha Catalytic Reforming Method," describes a supported platinum and tin reforming catalyst comprising an inorganic oxide support and components in the following proportions calculated based on the support: 0.1-1.0 wt% platinum, 0.1-1.0 wt% Group IVA metals, and 0.1-2.0 wt% halogens. The total platinum content in the surface layer of the catalyst accounts for 0.1-30% of the total platinum content, and the total Group IVA metal content in the surface layer accounts for 25-70% of the total Group IVA metal content. The surface layer of the support refers to a layer whose thickness from the surface to the interior of the support is 0.1-30% of the total thickness of the support. When used in catalytic reforming reactions, the catalyst of this invention can significantly increase the C5 ratio. + The liquid product yield is high, the catalyst aromatics yield is high, and the coking rate is low. However, there are some problems: this invention is a surface-based catalyst metal enrichment technology, and it remains questionable whether the surface metal enrichment also has a positive impact on the metal dispersion, and whether its performance can be maintained after repeated regeneration. Summary of the Invention

[0007] The purpose of this invention is to address the aforementioned deficiencies in the existing technology by providing a method for preparing a supported continuous reforming catalyst and its application in catalytic reforming. The method uses sheet-like stacked alumina material as raw material, and the platinum active component in the provided Pt / γ-alumina catalyst can be more efficiently dispersed on the support surface and its sintering is inhibited. It has high dispersibility, high activity, resistance to sintering, and long service life.

[0008] The present invention discloses a method for preparing a supported continuous reforming catalyst, the technical solution of which includes the following preparation process, in parts by mass:

[0009] (1) A sheet-like stacked alumina material is obtained by hydrothermal crystallization reaction of a first aluminum source with a precipitant and a modifier; wherein the mass ratio of the first aluminum source: precipitant: modifier is 100: (75-140): (60-90).

[0010] (2) Dissolve the second aluminum source in acid, and add a solution of tin-containing compound, rare earth element compound and viscosity additive. Finally, stir and mix it with the sheet-like stacked alumina material in step (1) to prepare a catalyst support precursor solution. The mass ratio of the second aluminum source: tin-containing compound: rare earth element compound: viscosity additive is 100: (0.5-2): (0.5-2): (0.5-2). Then, add the sheet-like stacked alumina material in step (1), whose mass ratio with the second aluminum source is (5-10): 100.

[0011] (3) Add pore-forming agent solution to the above catalyst support precursor solution, mix evenly to form a composite solution, then drop the composite solution into an oil phase liquid column to form a spherical support after aging, drying and calcination; wherein, the mass ratio of catalyst support precursor solution to pore-forming agent solution is (98-99.5):(0.5-2);

[0012] (4) Dissolve the platinum source in water and add amino acids, adjust the pH value with hydrochloric acid to prepare an impregnation solution, add the spherical support prepared in step (3), load the platinum source onto the support by the solution excess impregnation method, and obtain the chlorinated spherical catalyst by vacuum impregnation, drying and air calcination; wherein, the mass ratio of spherical support: platinum source: amino acids: hydrochloric acid: water is 100: (0.3-1): (0.3-1): (0.5-2): (100-150);

[0013] (5) The chlorinated spherical catalyst obtained above is placed in a reduction device and reduced to obtain a reduced catalytic reforming catalyst.

[0014] Preferably, the detailed steps of step (1) are as follows:

[0015] The first aluminum source is dissolved in water to prepare solution A, and the precipitant and modifier are dissolved in water to prepare solution B. Solution B is added dropwise to solution A under electromagnetic stirring at 50-80℃ to form a solution or suspension. After standing for 2-6 hours, it is transferred to a stainless steel crystallization kettle and placed in a temperature-controlled electric heating oven at 120-200℃ for 12-60 hours. The solid is then filtered, washed with water, and dried to obtain sheet-like stacked alumina material.

[0016] Preferably, the detailed steps of step (2) are as follows:

[0017] First, dissolve the second aluminum source in acid, stir and heat it, and control the temperature rise to within 10℃ / h to form a uniform sol. Keep the original temperature and stir, and add tin-containing compound, rare earth element compound and viscosity additive in sequence to ensure complete dissolution. Then add the sheet-like stacked alumina material prepared in step (1), adjust the pH value to 7-9 with hydrochloric acid solution, and heat the well-stirred sol to 50-100℃ to obtain the catalyst support precursor sol.

[0018] Preferably, the detailed steps of step (3) are as follows:

[0019] The catalyst carrier precursor solution was kept at its original temperature, and a pore-forming agent solution was added to form a composite solution. The solution was stirred for 10 minutes. Using a circular needle with a diameter of 2-4 mm, the composite solution was dropped into the oil phase liquid column under constant pressure to form gel microspheres. The oil phase temperature was 90-100℃. The formed gel microspheres were then transferred to an aging solution for spherical solidification. The aging solution was dilute ammonia water at a temperature of 90-100℃, and the aging time was 6-12 hours. The temperature was 90-110℃ and the pressure was 0.1-1 bar.

[0020] The aged spheres are washed in water to remove residual ammonia; the washing is repeated 3-6 times, each time the spheres are placed in a strainer and immersed in water at 40-60℃ for 3-5 minutes. The washed spheres are then dried and shaped; dried in a circulating air atmosphere at 100-120℃ for 6-12 hours; the dried spheres are then calcined at a programmed temperature of 500-700℃ at a rate of 120-180℃ / h, and held for 2-8 hours while continuously purging with dry air to remove the generated water; after natural cooling in air, the oxidized spherical carrier is obtained.

[0021] Preferably, the detailed steps of step (4) are as follows:

[0022] Weigh 100 parts of spherical carrier, dissolve 0.5 parts of platinum source in 100 parts of water at 30-50℃, stir and add 0.5 parts of amino acid, add 1 part of hydrochloric acid and water to adjust the pH to 0.5-3, vacuum impregnate at 50-80℃, control the vacuum degree at an absolute pressure of 0.1-0.5 bar, control the vacuum pump power and heating power, and make the solution completely evaporate to dryness within 3-8 hours;

[0023] Dry at 120-180℃ for 6-12 hours, continuously purging with dry air to control the moisture content of the spherical support between 5-20%, and continue calcining in air atmosphere at 400-500℃ for 1-4 hours to obtain a chlorinated spherical catalyst.

[0024] Preferably, the detailed steps of step (5) are as follows:

[0025] The chlorinated spherical catalyst is loaded into a tube furnace, and a reducing gas is introduced, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, with the proportion of hydrogen being 10%-50%. The temperature is programmed to rise to 450-550℃ at a rate of 120-180℃ / h and held for 2-8 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. Afterward, the catalyst is cooled with nitrogen at a rate of 120-180℃ / h, which yields the reduced catalytic reforming catalyst.

[0026] Preferably, the first aluminum source mentioned above is aluminum chloride, aluminum nitrate, or aluminum ethoxide, the precipitant is concentrated ammonia, urea, or / and ammonium carbonate, and the modifier is triethanolamine (TEA) or diethanolamine.

[0027] The second aluminum source is boehmite, the tin-containing compound is tin chloride or stannous chloride, the rare earth element compound is one or more of cerium chloride, lanthanum chloride, cerium nitrate, and lanthanum nitrate, and the viscosity additive is ethylene glycol or glycerol.

[0028] Preferably, the above-mentioned pore-forming agent solution is composed of 1% by mass of hexamethylenetetramine (HMT) and 2% by mass of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), wherein the mass ratio of the composite adhesive to the pore-forming agent solution is 100:(0.5-2).

[0029] Preferably, the platinum source is chloroplatinic acid, platinum nitrate or platinum chloride, and the amino acid is glycine, serine or threonine.

[0030] The application of the supported continuous reforming catalyst mentioned in this invention in the catalytic reforming of C6-C12 hydrocarbons includes: contacting C6-C12 hydrocarbons with the catalytic reforming catalyst to obtain the target product;

[0031] The reaction conditions for the contact reaction include: a temperature of 350-700℃, a pressure of 0.1-2 MPa, and a liquid hourly space velocity of 0.5-4 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 500-2000:1.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] This invention uses sheet-like stacked alumina material as raw material to form a structure that improves platinum dispersion. It employs a method of co-gelling tin and rare earth elements in a slurry to ensure the prepared microspheres maintain a suitable microstructure for platinum dispersion. Furthermore, it uses amino acids to assist in adding the impregnation solution during the impregnation process, promoting uniform distribution and dispersion of platinum. The activation process in this invention does not require additional chlorine injection to achieve high platinum metal dispersion, resulting in high aromatic yield in gasoline, increased octane number, less metal aggregation, higher yield in application, and reduced energy consumption. Attached Figure Description

[0034] Figure 1 This is a SEM image of the sheet-like stacked alumina material of Embodiment 1 of the present invention;

[0035] Figure 2 This is a further magnified SEM image of the sheet-like stacked alumina material of Embodiment 1 of the present invention;

[0036] Figure 3 This is a SEM image of the sheet-like stacked alumina material of Embodiment 4 of the present invention;

[0037] Figure 4 This is a SEM image of the fibrous alumina material used in Comparative Example 2 of this invention;

[0038] Figure 5 This is a bright-field transmission electron microscope (TEM) image of the Pt distribution in Embodiment 1 of the present invention;

[0039] Figure 6 This is a bright-field transmission electron microscope (TEM) image of the Pt distribution in Example 4 of the present invention;

[0040] Figure 7 This is a dark-field transmission electron microscope (TEM) image of the Pt distribution in Embodiment 1 of the present invention;

[0041] Figure 8 This is a further magnified dark-field image of the Pt distribution in Embodiment 1 of the present invention using a transmission electron microscope (TEM).

[0042] Figure 9 This is a scanning electron microscope-electron spectroscopy (SEM-EDS) image of the distribution of metallic Pt on Al2O3 according to Example 1 of the present invention;

[0043] Figure 10 It is a chromatogram of the crude oil;

[0044] Figure 11 The chromatogram of the product oil obtained by reforming the catalyst prepared according to Example 1 is shown below.

[0045] Figure 12 The chromatogram of the product oil obtained by reforming the catalyst prepared according to Example 2 is shown below.

[0046] Figure 13 The chromatogram of the product oil obtained by reforming the catalyst prepared according to Example 3 is shown below.

[0047] Figure 14 The chromatogram of the product oil obtained by reforming the catalyst prepared according to Example 4 is shown below.

[0048] Figure 15 The image shows the chromatogram of the product oil obtained by reforming the catalyst prepared according to Comparative Example 1.

[0049] Figure 16 The image shows the chromatogram of the product oil obtained by reforming the catalyst prepared according to Comparative Example 2.

[0050] Figure 17 This is the BET adsorption-desorption curve of the catalyst. Detailed Implementation

[0051] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0052] Example 1: A method for preparing a supported continuous reforming catalyst mentioned in this invention includes the following preparation process:

[0053] The first step involves dissolving 100g of aluminum nitrate in 800ml of water to obtain solution A, and dissolving 115.6g of urea and 78g of triethanolamine (TEA) in 500ml of water to obtain solution B. Under electromagnetic stirring at 300rpm and a temperature of 60℃, solution B is slowly added dropwise to solution A. After standing for 6 hours, the solution is transferred to a stainless steel crystallization vessel and placed in a temperature-controlled electric heating oven at 120℃ for 24 hours for hydrothermal crystallization. The solid is then filtered, washed with water, and dried at 120℃ to obtain sheet-like stacked alumina material.

[0054] The second step is to dissolve 100g of boehmite in 100g of dilute hydrochloric acid with a mass percentage concentration of 5%, stir slowly and heat up, controlling the temperature rise to within 10℃ / h, until it reaches 60℃ to form a uniform sol; keep the original temperature and stir, add 0.53g of stannous chloride, 0.87g of cerium chloride and 0.5g of ethylene glycol in sequence to ensure complete dissolution, then add 10g of the sheet-like stacked alumina material prepared in step (1), adjust the pH value to 8.5 with hydrochloric acid solution, and heat the well-stirred sol to 85℃ to obtain the catalyst support precursor sol;

[0055] The third step involves maintaining the catalyst carrier precursor solution at its original temperature and adding a pore-forming agent solution. This solution is composed of 1% (w / w) hexamethylenetetramine (HMT) and 2% (w / w) polyethylene oxide-propylene oxide-ethylene oxide triblock copolymer (P123), forming a composite solution. The solution is stirred for 10 minutes. Using a 3mm diameter circular needle, the composite solution is dripped into an oil phase column under constant pressure to form gel spheres. The oil phase temperature is 95℃. The formed gel spheres are then transferred to an aging solution for spherical solidification. The aging solution is 5% (w / w) dilute ammonia solution at 90℃, with an aging time of 6-12 hours under natural pressure.

[0056] The aged spheres are washed in water to remove residual ammonia; the washing is repeated 3-6 times, each time the spheres are placed in a strainer, immersed in 50℃ water and washed for 3-5 minutes, the washed spheres are dried and shaped, dried in a circulating air atmosphere at 110℃ for 12 hours, the dried spheres are calcined to obtain a suitable pore structure and improve their strength, the calcination temperature is programmed to 650℃ at a heating rate of 120℃ / h, held for 4 hours, dry air is continuously introduced to remove the generated water, and then the spheres are naturally cooled by air to obtain the oxidized spherical carrier.

[0057] Fourth step: Weigh 100g of spherical carrier, dissolve 0.58g of chloroplatinic acid as platinum source in 120g of water at 40℃, stir and add 0.386g of glycine, add 0.5g of hydrochloric acid with a mass percentage concentration of 36% and water to adjust the pH value to 1.0, and use vacuum impregnation at a temperature of 60℃, control the vacuum degree at an absolute pressure of 0.2 bar, control the vacuum pump power and heating power, and make the solution completely evaporate to dryness within 8 hours;

[0058] The spherical support was dried at 150°C for 12 hours with continuous air circulation to control the moisture content at 5%. It was then calcined in air at 450°C for 2 hours to obtain a chlorinated spherical catalyst.

[0059] The fifth step involves loading 100g of chlorinated spherical catalyst into a tube furnace and introducing reducing gas, which is a mixture of hydrogen and nitrogen, with hydrogen accounting for 10% by volume. The temperature is programmed to rise to 500℃ at a rate of 120℃ / h and held for 2 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. The catalyst is then cooled with nitrogen at a rate of 180℃ / h, resulting in the reduced-state catalytic reforming catalyst.

[0060] Example 2, a method for preparing a supported continuous reforming catalyst mentioned in this invention, includes the following preparation process:

[0061] The first step involves dissolving 100g of aluminum chloride in 800ml of water to obtain solution A, and dissolving 94g of urea and 62.5g of diethanolamine in 500ml of water to obtain solution B. Under electromagnetic stirring at 300rpm and a temperature of 60℃, solution B is slowly added dropwise to solution A. After standing for 6 hours, the solution is transferred to a stainless steel crystallization vessel and placed in a temperature-controlled electric heating oven. The temperature is controlled at 150℃ for 30 hours for hydrothermal crystallization. The solid is then filtered, washed with water, and dried at 120℃ to obtain sheet-like stacked alumina material.

[0062] The second step is to dissolve 100g of boehmite in 100g of dilute hydrochloric acid with a mass percentage concentration of 5%, stir slowly and heat up, controlling the temperature rise to within 10℃ / h, until it reaches 60℃ to form a uniform sol; keep the original temperature and stir, add 1.63g of tin chloride, 1.27g of cerium chloride and 1.5g of ethylene glycol in sequence to ensure complete dissolution, then add 10g of the sheet-like stacked alumina material prepared in step (1), adjust the pH value to 8.5 with hydrochloric acid solution, and heat the well-stirred sol to 90℃ to obtain the catalyst support precursor sol;

[0063] The third step involves maintaining the catalyst carrier precursor solution at its original temperature and adding a pore-forming agent solution. The pore-forming agent solution is composed of 1% (w / w) hexamethylenetetramine (HMT) and 2% (w / w) polyethylene oxide-propylene oxide-ethylene oxide triblock copolymer (P123), with a catalyst carrier precursor solution to pore-forming agent solution ratio of 99:1, forming a composite solution. The solution is stirred for 10 minutes, and then, using a 3mm diameter circular needle, the composite solution is dripped into an oil phase column under constant pressure to form gel spheres. The oil phase temperature is 95℃. The formed gel spheres are then transferred to an aging solution for spherical solidification. The aging solution is 5% (w / w) dilute ammonia solution at 90℃, with an aging time of 6-12 hours at 90℃ and a pressure of 0.9 bar.

[0064] The aged spheres are washed in water to remove residual ammonia; the washing is repeated 3-6 times, each time the spheres are placed in a strainer, immersed in 50℃ water and washed for 3-5 minutes, the washed spheres are dried and shaped, dried in a circulating air atmosphere at 110℃ for 12 hours, the dried spheres are calcined to obtain a suitable pore structure and improve their strength, the calcination temperature is programmed to 650℃ at a heating rate of 120℃ / h, held for 4 hours, dry air is continuously introduced to remove the generated water, and then the spheres are naturally cooled by air to obtain the oxidized spherical carrier.

[0065] Fourth step: Weigh 100g of spherical carrier, dissolve 0.68g of chloroplatinic acid as platinum source in 120g of water at 40℃, stir and add 0.486g of glycine, add 2g of hydrochloric acid with a mass percentage concentration of 36% and water to adjust the pH value to 2.0, and use vacuum impregnation at a temperature of 70℃, control the vacuum degree at an absolute pressure of 0.3 bar, control the power of vacuum pump and heating power, and make the solution completely evaporate to dryness within 7 hours;

[0066] The spherical support was dried at 150°C for 10 hours with continuous air circulation to control the moisture content at 10%. It was then calcined in air at 460°C for 3 hours to obtain a chlorinated spherical catalyst.

[0067] The fifth step involves loading 100g of chlorinated spherical catalyst into a tube furnace and introducing reducing gas, which is a mixture of hydrogen and nitrogen, with hydrogen accounting for 20% by volume. The temperature is programmed to rise to 500℃ at a rate of 130℃ / h and held for 3 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. The catalyst is then cooled with nitrogen at a rate of 180℃ / h, resulting in the reduced-state catalytic reforming catalyst.

[0068] Example 3, a method for preparing a supported continuous reforming catalyst mentioned in this invention, includes the following preparation process:

[0069] The first step involves dissolving 100g of aluminum nitrate in 800ml of water to obtain solution A, and dissolving 45g of concentrated ammonia, 30g of urea, and 60g of TEA in 500ml of water to obtain solution B. The concentrated ammonia used has a mass percentage concentration of 35%. Under electromagnetic stirring at 300rpm and a temperature of 50℃, solution B is slowly added dropwise to solution A. After standing for 2 hours, the solution is transferred to a stainless steel crystallization vessel and placed in a temperature-controlled electric heating oven. The temperature is controlled at 200℃, and the hydrothermal crystallization reaction is carried out for 12 hours. The solid is then filtered, washed with water, and dried at 120℃ to obtain sheet-like stacked alumina material.

[0070] The second step is to dissolve 100g of boehmite in 100g of dilute hydrochloric acid with a mass percentage concentration of 5%, stir slowly and heat up, controlling the temperature rise to within 10℃ / h, until it reaches 60℃ to form a uniform sol; keep the original temperature and stir, add 0.5g of stannous chloride, 0.5g of cerium chloride and 0.5g of ethylene glycol in sequence to ensure complete dissolution, then add 5g of the sheet-like stacked alumina material prepared in step (1), adjust the pH value to 7 with hydrochloric acid solution, and heat the well-stirred sol to 85℃ to obtain the catalyst support precursor sol;

[0071] The third step involves maintaining the catalyst carrier precursor solution at its original temperature and adding a pore-forming agent solution. The pore-forming agent solution is composed of 1% (w / w) hexamethylenetetramine (HMT) and 2% (w / w) polyethylene oxide-propylene oxide-ethylene oxide triblock copolymer (P123). The ratio of the catalyst carrier precursor solution to the pore-forming agent solution is 98:2, forming a composite solution. The solution is stirred for 10 minutes. Using a circular needle with a diameter of 2 mm, the composite solution is dripped into the oil phase liquid column under constant pressure to form gel spheres. The temperature of the white oil is 90℃. The formed gel spheres are then transferred to an aging solution for spherical solidification. The aging solution is dilute ammonia water at 90℃ with a mass percentage concentration of 5%. The aging time is 6-8 hours, the temperature is 110℃, and the pressure is 0.1 bar.

[0072] The aged spheres are washed in water to remove residual ammonia; the washing is repeated 3-4 times, each time the spheres are placed in a strainer, immersed in 40℃ water and washed for 3-5 minutes, the washed spheres are dried and shaped, dried in a circulating air atmosphere at 100℃ for 12 hours, the dried spheres are calcined to obtain a suitable pore structure and improve their strength, the calcination temperature is programmed to 500℃ at a heating rate of 180℃ / h, held for 6-8 hours, dry air is continuously introduced to remove the generated water, and then the spheres are naturally cooled by air to obtain the oxidized spherical carrier.

[0073] Fourth step: Weigh 100g of spherical support, dissolve 0.3g of chloroplatinic acid as platinum source in 120g of water at 30℃, stir and add 0.3g of serine, 0.5g of 36% hydrochloric acid and water to adjust the pH to 0.5, vacuum impregnate at 50℃, control the vacuum degree at an absolute pressure of 0.1 bar, control the power of the vacuum pump and heating power, and allow the solution to evaporate completely within 7-8 hours; dry at 120℃ for 12 hours, continuously purging with dry air to control the moisture content of the spherical support between 5-10%, and continue calcining in air atmosphere at 500℃ for 1 hour to obtain the chlorinated spherical catalyst;

[0074] The fifth step involves loading 100g of chlorinated spherical catalyst into a tube furnace and introducing reducing gas, which is a mixture of hydrogen and nitrogen, with hydrogen accounting for 10% by volume. The temperature is programmed to rise to 550℃ at a rate of 120℃ / h and maintained for 2-3 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. The catalyst is then cooled with nitrogen at a rate of 120℃ / h, resulting in the reduced-state catalytic reforming catalyst.

[0075] Example 4, a method for preparing a supported continuous reforming catalyst mentioned in this invention, includes the following preparation process:

[0076] First, 100g of aluminum ethoxide was dissolved in 800ml of water to form solution A, and 140g of ammonium carbonate and 90g of TEA were dissolved in 500ml of water to form solution B. Under electromagnetic stirring at 300rpm and a temperature of 80℃, solution B was slowly added dropwise to solution A. After standing for 6 hours, the solution was transferred to a stainless steel crystallization vessel and placed in a temperature-controlled electric heating oven. The temperature was controlled at 120℃ for 60 hours for hydrothermal crystallization. The solid was then filtered, washed with water, and dried at 120℃ to obtain sheet-like stacked alumina material.

[0077] The second step is to dissolve 100g of boehmite in 100g of dilute hydrochloric acid with a mass percentage concentration of 5%, stir slowly and heat up, controlling the temperature rise to within 10℃ / h, until it reaches 100℃ to form a uniform sol; keep the original temperature and stir, add 2g of stannous chloride, 2g of lanthanum chloride and 2g of glycerol in sequence to ensure complete dissolution, and then add 10g of the sheet-like stacked alumina material prepared in step (1), adjust the pH value to 9 with hydrochloric acid solution, and heat the well-stirred sol to 85℃ to obtain the catalyst support precursor sol;

[0078] The third step involves maintaining the catalyst carrier precursor solution at its original temperature and adding a pore-forming agent solution. The pore-forming agent solution is composed of 1% (w / w) hexamethylenetetramine (HMT) and 2% (w / w) polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123). The ratio of the catalyst carrier precursor solution to the pore-forming agent solution is 98:2, forming a composite solution. The solution is stirred for 10 minutes. Using a circular needle with a diameter of 4 mm, the composite solution is dripped into the oil phase liquid column under constant pressure to form gel spheres. The temperature of the white oil is 100℃. The formed gel spheres are then transferred to an aging solution for spherical solidification. The aging solution is dilute ammonia water at 100℃ with a concentration of 8% (w / w), and the aging time is 10-12 hours at a temperature of 105-110℃ and a pressure of 1 bar.

[0079] The aged spheres are washed in water to remove residual ammonia; the washing is repeated 5-6 times, each time the spheres are placed in a strainer, immersed in 60℃ water and washed for 3-5 minutes, the washed spheres are dried and shaped, dried in a circulating air atmosphere at 120℃ for 6 hours, the dried spheres are calcined to obtain a suitable pore structure and improve their strength, the calcination temperature is programmed to rise to 700℃ at a rate of 120℃ / h, held for 2-4 hours, dry air is continuously introduced to remove the generated water, and then the spheres are naturally cooled by air to obtain the oxidized spherical carrier;

[0080] Fourth step: Weigh 100g of spherical support, dissolve 1g of platinum nitrate as platinum source in 150g of water at 50℃, stir and add 1g of glycine, 2g of hydrochloric acid with a mass percentage concentration of 36% and water to adjust the pH to 3.0, vacuum impregnate at 75-80℃, control the vacuum degree at an absolute pressure of 0.5 bar, control the power of the vacuum pump and heating power, and make the solution completely evaporate within 3-4 hours; dry at 180℃ for 6 hours, continuously purging with dry air to control the moisture content of the spherical support between 15-20%, and continue calcining in air atmosphere at 400℃ for 4 hours to obtain the chlorinated spherical catalyst;

[0081] The fifth step involves loading 100g of chlorinated spherical catalyst into a tube furnace and introducing reducing gas, which is a mixture of hydrogen and nitrogen, with hydrogen accounting for 50% by volume. The temperature is programmed to rise to 450℃ at a rate of 180℃ / h and maintained for 6-8 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. The catalyst is then cooled with nitrogen at a rate of 180℃ / h, resulting in the reduced-state catalytic reforming catalyst.

[0082] Comparative Example 1 includes the following preparation process:

[0083] First step: This comparative example does not involve the preparation of sheet-like stacked alumina materials;

[0084] The second step involves dissolving 100g of boehmite in 100g of dilute hydrochloric acid (5% by mass), stirring slowly and heating, controlling the temperature rise to within 10℃ / h, until reaching 60℃ to form a homogeneous sol. While maintaining the original temperature and stirring, 0.53g of tin chloride, 0.87g of lanthanum nitrate, and 1.5g of ethylene glycol are added sequentially, followed by 10g of boehmite. The pH is adjusted to 8 using hydrochloric acid solution, and the thoroughly stirred sol is heated to 85℃ to obtain the catalyst support precursor sol.

[0085] The third step involves maintaining the catalyst carrier precursor solution at its original temperature and adding a pore-forming agent solution. This solution is composed of 1% (by mass) hexamethylenetetramine (HMT) and 2% (by mass) polyethylene oxide-propylene oxide-ethylene oxide triblock copolymer (P123), with a pore-forming agent solution to catalyst carrier precursor solution ratio of 1:99, forming a composite solution. The solution is stirred for 10 minutes. Using a 3mm diameter circular needle, the composite solution is dripped into an oil phase column under constant pressure to form gel spheres. The white oil temperature is 95℃. The formed gel spheres are then transferred to an aging solution for spherical solidification. The aging solution temperature is 100℃, and the aging solution is 8% dilute ammonia. The aging time is 6-8 hours at 100℃ under natural pressure.

[0086] The aged spheres are washed in water to remove residual ammonia; the washing is repeated 3-4 times, each time the spheres are placed in a strainer, immersed in 50℃ water and washed for 3-5 minutes, the washed spheres are dried and shaped, dried in a circulating air atmosphere at 110℃ for 12 hours, the dried spheres are calcined to obtain a suitable pore structure and improve their strength, the calcination temperature is programmed to 650℃ at a heating rate of 120℃ / h, held for 4 hours, dry air is continuously introduced to remove the generated water, and then the spheres are naturally cooled by air to obtain the oxidized spherical carrier.

[0087] Fourth step: Weigh 100g of spherical support, dissolve 0.49g of platinum nitrate as platinum source in 100g of water at 30-50℃, stir and add 0.386g of glycine, 0.5g of 36% hydrochloric acid and water to adjust the pH to 1.0, vacuum impregnate at 60℃, control the vacuum degree at an absolute pressure of 0.2 bar, control the vacuum pump power and heating power, and allow the solution to evaporate completely within 8 hours; dry at 150℃ for 12 hours, continuously purging with dry air to control the moisture content of the spherical support to 10%, and continue calcining in air atmosphere at 450℃ for 2 hours to obtain the chlorinated spherical catalyst;

[0088] The fifth step involves loading 100g of chlorinated spherical catalyst into a tube furnace and introducing reducing gas, which is a mixture of hydrogen and nitrogen, with hydrogen accounting for 10% by volume. The temperature is programmed to rise to 530℃ at a rate of 120℃ / h and held for 2 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. The catalyst is then cooled with nitrogen at a rate of 180℃ / h, resulting in the reduced catalytic reforming catalyst.

[0089] Comparative Example 2 includes the following preparation process:

[0090] The first step in this comparative example does not involve the preparation of sheet-like stacked alumina materials; instead, commercially available fibrous alumina is used.

[0091] The second step involves dissolving 100g of boehmite in 100g of dilute hydrochloric acid (5% by mass), stirring slowly and heating, controlling the temperature rise to within 10℃ / h, until reaching 60℃ to form a uniform sol. While maintaining the original temperature and stirring, 0.53g of stannous chloride, 0.87g of cerium nitrate, and 0.8g of glycerol are added sequentially. Then, 10g of the fibrous alumina material purchased in the first step is added. The pH value is adjusted to 8.5 using hydrochloric acid solution, and the thoroughly stirred sol is heated to 85℃ to obtain the catalyst support precursor sol.

[0092] The third step involves maintaining the catalyst carrier precursor solution at its original temperature and adding a pore-forming agent solution. This solution is composed of 1% (w / w) hexamethylenetetramine (HMT) and 2% (w / w) polyethylene oxide-propylene oxide-ethylene oxide triblock copolymer (P123), with a pore-forming agent solution to catalyst carrier precursor solution ratio of 1:99, forming a composite solution. The solution is stirred for 10 minutes. Using a 3mm diameter circular needle, the composite solution is dripped into an oil phase column under constant pressure to form gel spheres. The white oil temperature is 95℃. The formed gel spheres are then transferred to an aging solution for spherical solidification. The aging solution is 5% (w / w) dilute ammonia at 90℃, with an aging time of 10-12 hours at 100℃ and natural pressure.

[0093] The aged spheres are washed in water to remove residual ammonia; the washing is repeated 5-6 times, each time the spheres are placed in a strainer, immersed in 50℃ water and washed for 3-5 minutes, the washed spheres are dried and shaped, dried in a circulating air atmosphere at 110℃ for 12 hours, the dried spheres are calcined to obtain a suitable pore structure and improve their strength, the calcination temperature is programmed to 550℃ at a heating rate of 180℃ / h, held for 4 hours, dry air is continuously introduced to remove the generated water, and then the spheres are naturally cooled by air to obtain the oxidized spherical carrier.

[0094] Fourth step: Weigh 100g of spherical support, dissolve 0.38g of platinum chloride as the platinum source in 100g of water at 30-50℃, stir and add 0.92g of threonine, 2g of 36% hydrochloric acid and water to adjust the pH to 1.0, vacuum impregnate at 30℃, control the vacuum degree at an absolute pressure of 0.2 bar, control the vacuum pump power and heating power, and allow the solution to evaporate completely within 8 hours; dry at 150℃ for 12 hours, continuously purging with dry air to control the moisture content of the spherical support to 10%, and continue calcining in air atmosphere at 450℃ for 2 hours to obtain the chloride-state spherical catalyst;

[0095] The fifth step involves loading 100g of chlorinated spherical catalyst into a tube furnace and introducing reducing gas, which is a mixture of hydrogen and nitrogen, with hydrogen accounting for 20% by volume. The temperature is programmed to rise to 500℃ at a rate of 120℃ / h and held for 2 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. The catalyst is then cooled with nitrogen at a rate of 180℃ / h, resulting in the reduced-state catalytic reforming catalyst.

[0096] Furthermore, the performance testing process and method of the embodiments and comparative examples of the present invention are as follows:

[0097] The reduced catalytic reforming catalyst was in the form of small spheres, and the diameter of 20 spheres was measured with vernier calipers and the average value was taken. The bulk density was calculated by filling a 200ml graduated cylinder with the small spheres of reduced catalytic reforming catalyst to 100ml and measuring its weight. The crushing strength was determined using a DL-3 intelligent particle strength testing machine produced by Dalian Penghui Company, with a loading speed of 5N / s and a range of 150N. The specific surface area and pore volume were determined using the low-temperature nitrogen adsorption method on a Micromeritics ASAP2400 instrument. The specific surface area was calculated using the BET method of adsorption curves, and the adsorption amount was calculated when the relative pressure P / P0 was 0-0.99, where P is the measurement pressure and P0 is the saturated vapor pressure of N2 at the adsorption temperature. The five-point method was used for calculation, and the pore volume of the sample was calculated using the BJH method in the desorption curve.

[0098] The reduced-state catalytic reforming catalyst was fully dissolved in acid to form a solution for elemental analysis. The distribution of Sn and Pt elements was determined using an ICP-OES elemental analyzer, employing a Thermo Fisher iCAP analyzer. The elemental content was calculated by comparing the concentrations of the sample solution and the standard solution. Cl elemental content was determined using a TLS-2000 thiol analyzer, following the Q / SH-3360-320-2020 method, by measuring and calculating the potential change during titration.

[0099] Metal dispersion was determined using a Micromeritics Autochem 2930 detector (USA), with a temperature range of -80℃ to 1200℃, atmospheric pressure, TCD detector, and a heating rate of 0.1 to 50℃ / min. The result was calculated by measuring the amount of hydrogen consumed during the reduction process.

[0100] The morphology of the material was tested using a FEI Quanta 200 field emission scanning electron microscope, and the elemental distribution of the catalyst was characterized using an EDS energy dispersive spectroscopy instrument, and photographs were taken. The fine structure of the reduced catalytic reforming catalyst sample was tested using a FEI Talos F200X transmission electron microscope at 200 kV, and photographs were taken.

[0101] The physicochemical properties of the four examples and two comparative examples are shown in the table below:

[0102] Table 1: Physicochemical properties of samples

[0103]

[0104] Table 2: Platinum metal dispersion

[0105]

[0106] As shown in Table 1, the physicochemical properties of the reduced catalytic reforming catalyst samples from Examples 1-4 and Comparative Examples 1-2 are quite similar, conforming to the performance indicators of general catalytic reforming catalysts, but with some minor differences. The spherical reduced catalytic reforming catalyst with a particle size between 1.5-1.9 mm, prepared using sheet-like stacked alumina as raw material, has a bulk density between 0.56-0.57 g / ml, while the spheres in the comparative examples generally have a diameter of around 1.7 mm and a slightly higher bulk density of 0.58 g / ml. The crushing strength of the particles is between 30-60 N, meeting the general requirements for catalyst applications. The highest value is 59.4 N in Example 4, and the lowest is 39.6 N in Example 3, mainly related to their particle size. The specific surface area is between 170-210 cm². 2 / g, pore volume greater than 0.65cm³3 The / g indicates that the apparent pore structure is good, with abundant micropores suitable for loading metals. The Pt / Sn / Cl elemental contents of each example and comparative example are similar, with the Pt content difference being less than ±0.01%. In addition, the Sn content in Example 3 is twice that of the others, consistent with the amount of tin-containing compound added, while the Cl content is controlled by the amount of hydrochloric acid used to adjust the pH, and there are certain differences among the samples.

[0107] As shown in Table 2, the platinum metal dispersion of Example 1 is the highest at 92%, which is closest to the theoretical maximum of 100%. The platinum metal dispersion of Examples 2-4 is slightly lower than that of Example 1, but is still between 88% and 90.5%. This indicates that the addition of sheet-like stacked alumina material has a significant promoting effect on improving the dispersion of platinum metal in the catalyst. The specific difference depends on the synthesis process parameters of the sheet-like stacked alumina material. The platinum metal dispersion of Comparative Examples 1-2 is all below 85.5%, indicating that the catalyst without the addition of sheet-like stacked alumina material has a lower promoting effect on dispersion.

[0108] In the reforming reaction test, the best example 1 is used as an example:

[0109] The catalyst was evaluated on a fixed-bed reactor evaluation device, which consisted of a reactor with an inner diameter of 18 mm, with the upper and lower sections filled with quartz sand and the middle section containing 50 mL of small spherical reduced catalytic reforming catalyst prepared according to Example 1 (the catalyst could be from Examples 1 / 2 / 3 / 4, or Comparative Example 1 / 2). The catalyst was evaluated using hydrotreated refined naphtha as raw material, and the composition of the refined naphtha was shown in Table 3.

[0110] Table 3: Properties of Feed Oil

[0111]

[0112] The evaluation conditions were: reaction temperature 480℃, reaction pressure 0.35MPa, hydrogen / hydrocarbon volume ratio 600, and liquid hourly space velocity (LISH) 1.2 h⁻¹. -1 The condenser temperature was 10℃, and the liquid product was collected every 8 hours. The average reaction results after a total of 72 hours of reaction are shown in Table 4.

[0113] Both raw materials and products were analyzed and sampled using Agilent gas chromatography with an autosampler and an FID detector, using N2 as the carrier gas and a standard time-dependent analysis method. The mass fractions of various detailed hydrocarbon components, such as benzene and toluene, in the raw materials and products were measured. The PONA software from the China Petroleum Research Institute (CPRI) was used to identify detailed hydrocarbons in the samples, and the octane number was calculated based on the content of each component. Simultaneously, bed temperature was measured to investigate the change in catalyst selectivity with reaction time. The amount of catalyst coke after the reaction was determined using a LECO CS844 high-frequency combustion infrared sulfur-carbon analyzer (USA), and the results are listed in Table 4.

[0114] Table 4: Test Results

[0115]

[0116] From the perspective of catalyst performance analysis, C5 + A higher liquid yield indicates a higher content of aromatic hydrocarbons in the product and a higher octane number of the liquid product, signifying better catalytic performance and suitability for catalytic reforming reactions. Conversely, higher catalyst coking indicates lower catalyst selectivity and poorer performance. As can be seen from the results in Table 4, the C5 value of Example 1... + The liquid product showed the highest aromatic content and octane number, indicating optimal catalytic performance. Simultaneously, it exhibited the lowest catalyst carbon deposition compared to Examples 2-4 and Comparative Examples 1-2 (C5). + The liquid yield was about 2% lower, the aromatic content of the product was about 1% lower, and the octane number was about 1% lower, indicating that the examples were all higher than the comparative example. This is directly related to the addition of sheet-like stacked alumina material.

[0117] Figures 1-4 These are SEM images of the sheet-like stacked alumina materials involved in step one of the preparation process in multiple embodiments and comparative examples;

[0118] Figures 1-2 The image shows a SEM image of the sheet-like stacked alumina material from Example 1, which exhibits a distinct sheet-like structure at the 0.1µm-1µm scale. The individual particles have a large area, a thin thickness, a uniform structure, and good dispersion.

[0119] Figure 3 The image shows a SEM image of the sheet-like stacked alumina material in Example 4. Its sheet structure is a large, monolithic structure with a size exceeding 10 μm, and its sheet structure is too dense.

[0120] Figure 4 The image shown is a SEM image of the fibrous alumina material in Comparative Example 2. It shows a fibrous structure with excessively fine diameter, low strength, and insufficient lamellar structure, which is not conducive to catalytic applications.

[0121] Figures 5-8 Provided are TEM images of several embodiments and comparative examples;

[0122] Figure 5 and Figure 6 This is a bright-field photograph of platinum distribution taken with a transmission electron microscope (TEM), where the black areas represent platinum. Figure 5 Example 1, Figure 6 Example 4, wherein Figure 5 The presence of less black aggregate indicates better platinum dispersion in the catalyst.

[0123] Figure 7 and Figure 8 Both are dark field images; the white areas represent platinum particles. Figure 8 To further magnify the photo and achieve higher resolution, it can be seen that the white Pt particles are relatively small, ranging from 1 to 3 nm, indicating that the Pt is well dispersed.

[0124] Figure 9 This is a scanning electron microscope (SEM-EDS) image of Pt metal dispersion from Example 1, showing that Pt metal is uniformly distributed on the Al2O3 support.

[0125] Figure 10 It is a chromatogram of the crude oil; Figures 11-16 The chromatograms of Examples 1-4 and Comparative Example 1 show that after the catalytic reaction, the peak heights of the chromatographic peaks corresponding to retention times of 23 min, 35.5 min, 48.5 min, 48.6 min, and 50.1 min increased, indicating that the aromatic hydrocarbon content in the product was significantly increased. The research octane number can be calculated by analytical software. Products with high aromatic hydrocarbon content also have higher octane numbers.

[0126] Figure 17 This is a BET adsorption-desorption curve of the catalyst and the support. Since BET adsorption-desorption is a material characterization method based on the principle of gas adsorption, it is mainly used to determine the specific surface area, pore volume and pore size distribution of porous materials. The core application is to calculate the specific surface area through nitrogen adsorption data. From this, we can see the changes in Quantity Adsorbed in the four examples and two comparative examples, that is, the changes in the amount of adsorption.

[0127] The above description is merely a partial preferred embodiment of the present invention. Any person skilled in the art can modify the above-described technical solutions or modify them into equivalent technical solutions. Therefore, any simple modifications or equivalent transformations made based on the technical solutions of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a supported continuous reforming catalyst, characterized in that: The preparation process includes the following steps, in parts by weight: (1) A sheet-like stacked alumina material is obtained by hydrothermal crystallization reaction of a first aluminum source with a precipitant and a modifier; wherein the mass ratio of the first aluminum source: precipitant: modifier is 100: (75-140): (60-90). The detailed steps are as follows: The first aluminum source is dissolved in water to prepare solution A, and the precipitant and modifier are dissolved in water to prepare solution B. Solution B is added dropwise to solution A under electromagnetic stirring at 50-80℃ to form a solution or suspension. After standing for 2-6 hours, it is transferred to a stainless steel crystallization kettle and placed in a temperature-controlled electric heating oven at 120-200℃ for 12-60 hours. The solid is then filtered, washed with water, and dried to obtain sheet-like stacked alumina material. The first aluminum source is aluminum chloride, aluminum nitrate, or aluminum ethoxide; the precipitant is concentrated ammonia, urea, or / and ammonium carbonate; and the modifier is triethanolamine (TEA) or diethanolamine. (2) Dissolve the second aluminum source in acid, and add a solution of tin-containing compound, rare earth element compound and viscosity additive. Finally, stir and mix it with the sheet-like stacked alumina material in step (1) to prepare a catalyst support precursor solution. The mass ratio of the second aluminum source: tin-containing compound: rare earth element compound: viscosity additive is 100: (0.5-2): (0.5-2): (0.5-2). Then, add the sheet-like stacked alumina material in step (1), whose mass ratio with the second aluminum source is (5-10):

100. (3) Add pore-forming agent solution to the above catalyst support precursor solution, mix evenly to form a composite solution, then drop the composite solution into an oil phase liquid column to form a spherical support after aging, drying and calcination; wherein, the mass ratio of catalyst support precursor solution to pore-forming agent solution is (98-99.5):(0.5-2); (4) Dissolve the platinum source in water and add amino acids, adjust the pH value with hydrochloric acid to prepare an impregnation solution, add the spherical support prepared in step (3), load the platinum source onto the support by the solution excess impregnation method, and obtain the chlorinated spherical catalyst by vacuum impregnation, drying and air calcination; wherein, the mass ratio of spherical support: platinum source: amino acids: hydrochloric acid: water is 100: (0.3-1): (0.3-1): (0.5-2): (100-150); (5) The chlorinated spherical catalyst obtained above is placed in a reduction device and reduced to obtain a reduced catalytic reforming catalyst.

2. The method for preparing the supported continuous reforming catalyst according to claim 1, characterized in that: The detailed steps of step (2) are as follows: First, dissolve the second aluminum source in acid, stir and heat it, and control the temperature rise to within 10℃ / h to form a uniform sol. Keep the original temperature and stir, and add tin-containing compound, rare earth element compound and viscosity additive in sequence to ensure complete dissolution. Then add the sheet-like stacked alumina material prepared in step (1), adjust the pH value to 7-9 with hydrochloric acid solution, and heat the well-stirred sol to 50-100℃ to obtain the catalyst support precursor sol.

3. The method for preparing the supported continuous reforming catalyst according to claim 2, characterized in that: The detailed steps of step (3) are as follows: The catalyst carrier precursor solution is kept at its original temperature, and a pore-forming agent solution is added to form a composite solution. The solution is stirred for 10 minutes. A circular needle with a diameter of 2-4 mm is used to drop the composite solution into the oil phase liquid column under constant pressure to form gel spheres. The oil phase temperature is 90-100℃. The formed gel spheres are then transferred to an aging solution to solidify into a spherical shape. The aging solution uses dilute ammonia water at a temperature of 90-100℃, with an aging time of 6-12 hours, a temperature of 90-110℃, and a pressure of 0.1-1 bar. The aged beads are washed in water to remove residual ammonia; Washing is performed 3-6 times. Each time, the small balls are placed in a strainer, immersed in water at 40-60℃ and washed for 3-5 minutes. The washed small balls are dried and shaped. They are then dried in a circulating air atmosphere at 100-120℃ for 6-12 hours. The dried small balls are then calcined at a programmed temperature of 500-700℃ at a rate of 120-180℃ / h for 2-8 hours. Dry air is continuously introduced to remove the generated water. After natural cooling in the air, the oxidized spherical carrier is obtained.

4. The method for preparing the supported continuous reforming catalyst according to claim 3, characterized in that: The detailed steps of step (4) are as follows: Weigh 100 parts of spherical carrier, dissolve 0.5 parts of platinum source in 100 parts of water at 30-50℃, stir and add 0.5 parts of amino acid, add 1 part of hydrochloric acid and water to adjust the pH to 0.5-3, vacuum impregnate at 50-80℃, control the vacuum degree at an absolute pressure of 0.1-0.5 bar, control the vacuum pump power and heating power, and make the solution completely evaporate to dryness within 3-8 hours; Dry at 120-180℃ for 6-12 hours, continuously purging with dry air to control the moisture content of the spherical support between 5-20%, and continue calcining in air atmosphere at 400-500℃ for 1-4 hours to obtain a chlorinated spherical catalyst.

5. The method for preparing the supported continuous reforming catalyst according to claim 4, characterized in that: The detailed steps of step (5) are as follows: The chlorinated spherical catalyst is loaded into a tube furnace, and a reducing gas is introduced, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, with the proportion of hydrogen being 10%-50%. The temperature is programmed to rise to 450-550℃ at a rate of 120-180℃ / h and held for 2-8 hours. The hydrogen-nitrogen mixture is continuously introduced to remove the generated water and HCl. Afterward, the catalyst is cooled with nitrogen at a rate of 120-180℃ / h, which yields the reduced catalytic reforming catalyst.

6. The method for preparing the supported continuous reforming catalyst according to claim 5, characterized in that: The second aluminum source is boehmite, the tin-containing compound is tin chloride or stannous chloride, the rare earth element compound is one or more of cerium chloride, lanthanum chloride, cerium nitrate, and lanthanum nitrate, and the viscosity additive is ethylene glycol or glycerol.

7. The method for preparing the supported continuous reforming catalyst according to claim 6, characterized in that: The pore-forming agent solution is composed of 1% by mass of hexamethylenetetramine (HMT) and 2% by mass of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), wherein the mass ratio of the composite adhesive to the pore-forming agent solution is 100:(0.5-2).

8. The method for preparing the supported continuous reforming catalyst according to claim 7, characterized in that: The platinum source is chloroplatinic acid, platinum nitrate or platinum chloride, and the amino acid is glycine, serine or threonine.

9. A catalytic reforming application of the supported continuous reforming catalyst as described in claim 8, characterized in that: Application in the catalytic reforming of C6-C12 hydrocarbons, the method includes: reacting C6-C12 hydrocarbons with a catalytic reforming catalyst to obtain the target product; The reaction conditions for the contact reaction include: a temperature of 350-700℃, a pressure of 0.1-2 MPa, and a liquid hourly space velocity of 0.5-4 h⁻¹. -1 The hydrogen-to-hydrogen volume ratio is 500-2000:1.

Images