A Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction and its preparation method

Abstract

The application discloses a catalytic cracking gasoline hydro-upgrading olefin-reducing Ni2P catalyst and a preparation method thereof. 2+ The solution of the complex is impregnated on a carrier to obtain a supported Ni 2+ complex, and the supported Ni 2+ complex is phosphorized by using a phosphorus-containing substance to obtain the catalytic cracking gasoline hydro-upgrading olefin-reducing Ni2P catalyst. The Ni2P catalyst prepared by the preparation method has the advantages of high desulfurization rate, high liquid yield, high olefin reduction amount and small octane loss in catalyzing FCC gasoline.

Description

Technical Field

[0001] This invention belongs to the technical field of clean production of catalytic cracking gasoline and preparation of Ni2P catalysts, specifically involving the technical field of hydrotreating and reducing olefins in catalytic cracking gasoline and the preparation of supported, highly dispersed, highly active, and pure-phase Ni2P. Background Technology

[0002] Currently, researchers both domestically and internationally have conducted extensive research on technologies and catalysts related to reducing olefins and maintaining octane number in low-quality gasoline and FCC gasoline.

[0003] CN03133990.5 discloses a method for hydrotreating inferior gasoline. The hydrotreating process in this method includes two catalyst beds. First, the inferior gasoline fraction is separated into light and heavy components. The heavy gasoline component, along with hydrogen, undergoes a hydrodesulfurization reaction in the first catalyst bed with a hydrorefining catalyst. The effluent is not separated and is then mixed with the light gasoline component before directly entering the second catalyst bed, where it undergoes a hydrotreating reaction with a hydrotreating catalyst. The effluent enters a high-pressure separator for gas-liquid separation. The liquid phase is used as gasoline, while the hydrogen-rich gas is purified and returned to the reaction system. The active metal of the hydrotreating catalyst (octane number recovery catalyst) used in the second bed is one or more of Co, Mo, Ni, W, Pt, Re, and Ir. Among them, Pt, Re and Ir are precious metals, which are expensive and have poor sulfur resistance. Although Co, Mo, Ni and W are non-precious metals, their hydrogenation active phase is Co(Ni) promoted Mo(W)S2. The control technology of this active phase is becoming increasingly mature, and the room for improvement of its hydrogenation modification activity is limited.

[0004] US8603324B2 discloses a method for hydrotreating inferior gasoline through ultra-deep desulfurization and octane number recovery. The method includes the following steps: first, FCC gasoline is split into light and heavy gasoline fractions; then, the light gasoline fraction undergoes selective hydrogenation, desulfurization, and multi-branched isomerization of dienes; the resulting heavy gasoline is desulfurized in a selective hydrodesulfurization unit, and then undergoes octane number recovery and supplementary desulfurization in an octane number recovery unit; finally, the hydrotreated light and heavy gasoline are blended into a gasoline blending component. The active metals of the octane number recovery and supplementary desulfurization catalyst used in this invention are Co-Mo, similar to the Co and Mo used in CN03133990.5, which also suffers from limited potential for improving hydrotreating activity.

[0005] Song et al. (Catalysis Today, 2003, 86:211-263) reported a method for hydrotreating FCC gasoline jointly developed by INTEPE, SA, and UOP. First, FCC gasoline undergoes deep hydrodesulfurization and olefin saturation reaction on the upper bed of a catalyst (Co-Mo-P / Al2O3) (high hydrogen consumption). Then, under high temperature conditions, it undergoes cracking, isomerization, and alkylation reactions on the lower bed of a catalyst (Ga-Cr / H-ZSM-5) (low liquid yield of hydrotreated gasoline). The technical shortcomings of this method are: (1) a combination of two catalysts is required to achieve the goals of deep desulfurization, olefin reduction, and octane number retention for FCC gasoline; (2) olefin saturation reaction occurs on the Co-Mo-P / Al2O3 catalyst, resulting in high hydrogen consumption; (3) excessive cracking occurs on the Ga-Cr / H-ZSM-5 catalyst under high temperature conditions, resulting in low liquid yield and high energy consumption of the hydrotreated gasoline.

[0006] In summary, it can be seen that the active metals used in current low-quality gasoline octane number restoration catalysts are generally non-precious metals (Co, Mo, Ni, W, Ga-Cr, etc.) or precious metals (Pt, Re, Ir, etc.). Among them, non-precious metals show no significant difference in performance in deep desulfurization, olefin reduction, and octane number maintenance of FCC gasoline, or even result in lower product yield; while precious metals have good performance in olefin reduction and octane number maintenance, their sulfur resistance is extremely poor.

[0007] Numerous studies have shown that supported, highly dispersed nickel phosphide (Ni2P) catalysts not only possess hydrogenation / dehydrogenation performance similar to the noble metal platinum, but also exhibit low cost, good sulfur resistance, and good thermal stability. Currently, the most promising method for preparing supported, highly dispersed Ni2P catalysts for industrial applications is the preparation of hypophosphite (H2PO2) catalysts. - The reduction reaction between nickel phosphide and divalent nickel ions. CN200810234685.0 discloses a method for preparing nickel phosphide. First, a mixed solution of nickel hypophosphite and ammonium hypophosphite is impregnated onto a support, and then H2PO2 is used to... - and Ni 2+ A solid-state reaction at a relatively low temperature yielded a supported Ni2P catalyst with high dispersion of active components and good catalytic activity. However, H2PO2... - The disproportionation reaction is very fast, and some of the generated PH3 does not have enough time to react with Ni. 2+ The reaction may produce some nickel phosphates (such as NiP4O). 11 ); residual PO3 2- PO4 3- Some species will occupy part of the pores of the catalyst.

[0008] Dillen et al. (Journal of Catalysis, 2003, 216: 257-264) pointed out that complex metal precursors have the following beneficial effects in the catalyst preparation process: (1) Complex metal precursor solutions have relatively high stability, which is conducive to the preparation of impregnation solutions with high concentrations of metal ions, and can be used to increase the loading of supported active metal components; (2) During the drying process, as the solvent evaporates, the viscosity of the complex solution increases sharply, which inhibits the redistribution of the complex solution, thus facilitating the uniform distribution of active metal components on the support surface; (3) Complex metal precursors do not exist as crystalline compounds, but in a gel-like state. After further drying, this gel still interacts with the support through hydrogen bonds, and this gel-like state usually keeps the active metal components in a highly dispersed state.

[0009] Given the beneficial role of complex metal precursors in catalyst preparation, it is expected that a supported Ni catalyst can be prepared first. 2+ A complex was obtained, followed by in-situ phosphating to yield a supported, highly dispersed, and highly active pure-phase Ni2P catalyst, thus providing an FCC gasoline hydrotreating method that combines deep desulfurization, deep olefin reduction, and octane number preservation. However, no relevant research reports have been found to date. Summary of the Invention

[0010] The technical problem this invention aims to solve lies in the significant technical challenge of deep desulfurization and deep olefin reduction in catalytic cracking gasoline while maintaining octane number. Addressing the shortcomings of existing technologies, the purpose of this invention is to provide a Ni2P catalyst for hydrotreating and reducing olefins in catalytic cracking gasoline, and its preparation method. The Ni2P catalyst obtained by this method exhibits advantages such as high desulfurization rate, high liquid yield, high olefin reduction, and low octane number loss for FCC gasoline.

[0011] To achieve the above objectives, the present invention provides a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, the method comprising the following steps:

[0012] Will contain Ni 2+ The solution of the complex was impregnated onto the support to obtain supported Ni. 2+ Complexes, using phosphorus-containing materials to support Ni 2+ The complex is phosphated to obtain the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction.

[0013] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention includes, for example but not limited to, the preparation method of the support as follows: mixing acidic mesoporous molecular sieve with alumina raw powder, adding extrusion aid and aqueous solution containing adhesive solvent respectively, and obtaining the catalyst by kneading, molding, drying and calcining.

[0014] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction according to the present invention, wherein the acidic mesoporous molecular sieve is, for example but not limited to, at least one of H-ZSM-5, SAPO-11, Hβ, and HMOR, preferably at least one of H-ZSM-5 and SAPO-11; the average pore size and BET specific surface area of ​​the acidic mesoporous molecular sieve are 2-20 nm and 250-500 nm, respectively. 2 / g, preferably 3-10nm and 300-400nm respectively. 2 / g;

[0015] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention, wherein the alumina raw powder is, for example but not limited to, at least one of boehmite powder, aluminum hydroxide powder, and SB powder, preferably boehmite powder and SB powder.

[0016] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction according to the present invention, wherein the dry basis mass ratio of the acidic mesoporous molecular sieve to the alumina raw powder is, for example but not limited to, (3.0-3.7):1, preferably (3.2-3.5):1.

[0017] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention includes, but is not limited to, at least one of guar gum powder, polyacrylamide, graphite, and lubricating oil, preferably guar gum powder.

[0018] The Ni2P catalyst for catalytic cracking of gasoline hydrotreating and olefin reduction of the present invention, wherein the gum-containing solvent is, for example but not limited to, at least one of nitric acid, hydrochloric acid, acetic acid, and citric acid, preferably nitric acid.

[0019] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention, wherein the mass percentages of the extrusion aid and the adhesive solvent, based on the dry weight of the support, are, for example, but not limited to, 6-8 wt% and 3-4 wt%, respectively, preferably 6.5-7.5 wt% and 3.2-3.8 wt%, respectively.

[0020] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction according to the present invention includes the following steps during the preparation of the support: the drying temperature is, for example, but not limited to, 100-140°C, and the time is, for example, but not limited to, 3-6 hours, preferably the drying temperature is, for example, but not limited to, 110-130°C, and the time is 4-5 hours; the calcination temperature is, for example, but not limited to, about 500-600°C, and the time is, for example, but not limited to, 3-6 hours, preferably the calcination temperature is 540-560°C, and the time is 4-5 hours.

[0021] The present invention relates to a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, wherein the catalyst contains Ni. 2+The preparation method of the complex solution is not particularly limited, for example, but not limited to, preparation by the following method: first, adjusting the pH of the aqueous solution with ammonia to a value greater than 8.1, preferably greater than 8.2; then adding the complexing agent; and finally adding Ni. 2+ Salt, yielding a product containing Ni 2+ A solution of a complex. However, the present invention contains Ni. 2+ The preparation methods for the solution of the complex are not limited to this.

[0022] The present invention relates to a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, wherein the catalyst contains Ni. 2+ In the method for preparing the solution of the complex, the complexing agent is, for example but not limited to, at least one of ethylenediaminetetraacetic acid (EDTA), nitric acid triacetic acid (NTA), ethylenediamine (EDA), cyclohexanediaminetetraacetic acid (CyDTA), citric acid (CA), and ethylene glycol (EG), preferably at least one of EDTA, NTA, and EDA.

[0023] The present invention relates to a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, wherein the catalyst contains Ni. 2+ In the method for preparing the solution of the complex, the Ni 2+ The salt is, for example, but not limited to, at least one of nickel nitrate, nickel carbonate, nickel acetate, basic nickel carbonate, nickel oxalate, and nickel formate, preferably at least one of nickel nitrate, nickel carbonate, basic nickel carbonate, and nickel oxalate.

[0024] The present invention relates to a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, wherein the catalyst contains Ni. 2+ In the method for preparing the solution of the complex, the complexing agent / Ni 2+ The molar ratio is, for example, but not limited to, 1.0-2.2, preferably 1.2-1.7.

[0025] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention, wherein the loading is, for example but not limited to, equal volume impregnation or supersaturated impregnation, preferably equal volume impregnation.

[0026] The present invention relates to a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, wherein the catalyst contains Ni. 2+ The solution of the complex can be impregnated on the carrier and then aged and dried.

[0027] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention includes an aging time of, but not limited to, 4-10 hours, preferably 6-8 hours; a drying temperature of, but not limited to, 100-130°C, preferably 110-120°C; and a drying time of, but not limited to, 4-6 hours, preferably 3-7 hours.

[0028] The present invention discloses a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, wherein the phosphorus-containing substance is hydrotreated naphtha containing an organophosphorus agent; the phosphorus atom content in the hydrotreated naphtha is, for example, but not limited to, 3000-15000 ppm, preferably 5000-10000 ppm; the organophosphorus agent includes, for example, but not limited to, at least one of triethylphosphine, tripropylphosphine, tributylphosphine, triisopropylphosphine, di-tert-butylphosphine, triphenylphosphine, trioctylphosphine, tri-p-tolylphosphine, and diphenylmethylphosphine, preferably at least one of triethylphosphine, tripropylphosphine, and tributylphosphine.

[0029] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention, wherein the concentration of phosphine generated after the decomposition of the organophosphorus agent in hydrogen gas is, for example, but not limited to, 2000-15000 ppm, preferably 5000-10000 ppm.

[0030] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction of the present invention includes a phosphating temperature of, for example but not limited to, 150-400°C, preferably 200-300°C; a phosphating time of, for example but not limited to, 12-60h, preferably 24-48h; and a phosphating pressure of, for example but not limited to, 0.1-1.0MPa, preferably 0.3-0.7MPa.

[0031] The method for preparing the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction according to the present invention, wherein the Ni content in the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction is, for example, but not limited to, 0.3-30.0 wt%, preferably 1.0-20.0 wt%, based on the mass of the catalyst.

[0032] The present invention relates to a method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction. The number of active sites of the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction is expressed as the amount of CO chemical adsorption, for example, but not limited to, 1000-4000 μmol / g, preferably 1500-4000 μmol / g.

[0033] The present invention also provides a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction obtained by the above preparation method.

[0034] This invention uses Ni 2+The complex is a metal precursor, and the active metal component used is the transition metal phosphide Ni₂P. During the preparation of the supported Ni₂P catalyst, no acid anion species remain and no nickel phosphate is generated; Ni 2+ It can be completely phosphated in situ into highly dispersed, highly active, pure-phase Ni2P. The dispersion of Ni2P is positively correlated with the number of its active sites (the higher the dispersion, the more active sites it has). The number of active sites is usually expressed as the amount of CO chemically adsorbed on the surface of Ni2P. The amount of CO chemically adsorbed on the surface of the catalyst Ni2P obtained in this invention can be 1000-4000 μmol / g.

[0035] Compared with existing technologies, the Ni2P catalyst of this invention has advantages such as high desulfurization rate, high liquid yield and olefin reduction, and low octane number loss. Detailed Implementation

[0036] The following provides a detailed description of the embodiments of the present invention. These embodiments are implemented based on the technical solution of the present invention and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0037] Source of raw materials or equipment:

[0038] The feedstock for hydrotreating is catalytic cracked gasoline with a sulfur content of 220 ppm, an olefin content of 38.6 v%, and a RON of 90.5.

[0039] Evaluation and analysis methods:

[0040] (1) SH / T 0689-2000 is used to determine the total sulfur content of catalytic cracking gasoline and its hydrotreated products;

[0041] (2) GB / T 5487-1995 is used to determine the research octane number (RON) of catalytic cracking gasoline and its hydrotreated products;

[0042] (3) GB / T 11132 is used to determine the olefin content of catalytic cracking gasoline and its hydrotreated products.

[0043] Example 1

[0044] In this embodiment, a Ni2P catalyst (CAT-1) was prepared, which, by mass, contained 4.0 wt% Ni, 75.2 wt% mesoporous H-ZSM-5 molecular sieve, and 20.8 wt% alumina.

[0045] 375g of mesoporous H-ZSM-5 molecular sieve (self-made, specific surface area 334m²) was used. 2The following ingredients were mixed evenly: 150g of pseudoboehmite powder HC-07 (produced by Shandong Xingdu Chemical Co., Ltd., which loses about 30wt% water when made into alumina), 32.5g of guar gum powder, 16.9g of concentrated nitric acid (65wt%) and 180g of deionized water were added, and the mixture was thoroughly kneaded and then extruded into 1.7mm clover strips in an extruder. After drying at 110℃ for 6 hours, calcining at 540℃ for 4 hours, cooling, cutting into strips, and sieving, a composite carrier with a length of 3-10mm was obtained.

[0046] Then, based on the water absorption rate of the support, the active metal loading of the target catalyst, and the amount of support used, a mixture containing 41g of nickel nitrate hexahydrate and 49.4g of EDTA (EDTA / Ni) was prepared. 2+ A concentrated ammonia solution (molar ratio 1.2) was prepared and impregnated onto 200g of the above-mentioned support. After aging at room temperature for about 8 hours and drying at 120℃ for about 4 hours, supported Ni was obtained. 2+ Complex.

[0047] The above-mentioned loaded Ni 2+ The complex was placed in a fixed-bed reactor and reacted with triphenylphosphine hydrogenated naphtha containing 6000 ppm phosphorus at a reaction temperature of 245 °C, a reaction pressure of 0.5 MPa, and a volume hourly space velocity of 2.0 h⁻¹. -1 Under the condition of a hydrogen / triphenylphosphine hydrogenated naphtha volume ratio of 400:1, and maintaining the concentration of phosphine in the hydrogen gas at approximately 5000 ppm, CAT-1 was obtained after phosphating for 36 hours. The CO chemisorption capacity of CAT-1 was 3000 μmol / g.

[0048] Example 2

[0049] This embodiment prepares a Ni2P catalyst (CAT-2), and the preparation steps are the same as in Example 1, except that the Ni2P content in the catalyst is: Ni 0.8 wt%, mesoporous H-ZSM-5 molecular sieve 76.2 wt%, and alumina 22.0 wt% by catalyst mass; triethylphosphine hydrogenated naphtha containing 10000 ppm phosphorus is used, and the reaction is carried out at a reaction temperature of 250°C, a reaction pressure of 0.4 MPa, and a volume hourly space velocity of 1.5 h⁻¹. -1 Under the condition of a hydrogen / triethylphosphine hydrogenated naphtha volume ratio of 500:1, and maintaining the concentration of phosphine in the hydrogen in the system at approximately 6200 ppm, CAT-2 was obtained after phosphating for 26 hours. The CO chemisorption capacity of CAT-2 was 1100 μmol / g.

[0050] Example 3

[0051] In this embodiment, the Ni2P catalyst (CAT-3) was prepared using the same steps as in Example 1, except that NTA was used as the complexing agent; tributylphosphine hydrogenated naphtha containing 9000 ppm phosphorus was used, and the reaction was carried out at a reaction temperature of 300°C, a reaction pressure of 0.6 MPa, and a volume hourly space velocity of 1.8 h⁻¹. -1 Under the condition that the volume ratio of hydrogen to tributylphosphine hydrogenated naphtha is 600:1, and the concentration of phosphine in the hydrogen is maintained at about 6700 ppm, CAT-3 is obtained after phosphating for 24 hours. The CO chemisorption capacity of CAT-3 is 2500 μmol / g.

[0052] Example 4

[0053] This embodiment prepares a Ni2P catalyst (CAT-4) using the same steps as in Example 1, except that EDA is used as the complexing agent; trioctylphosphine hydrogenated naphtha containing 9500 ppm phosphorus is used, and the reaction is carried out at a temperature of 350°C, a pressure of 0.8 MPa, and a volume hourly space velocity of 1.7 h⁻¹. -1 Under the condition that the volume ratio of hydrogen to trioctylphosphine hydrogenated naphtha is 550:1, and the concentration of phosphine in the hydrogen is maintained at about 5300 ppm, CAT-4 is obtained after phosphating for 25 hours. The CO chemisorption capacity of CAT-4 is 2490 μmol / g.

[0054] Example 5

[0055] This embodiment prepares a Ni2P catalyst (CAT-5) using the same steps as in Example 1, except that CyDTA is used as the complexing agent; diphenylmethylphosphine hydrogenated naphtha containing 9800 ppm phosphorus is used, and the reaction is carried out at a temperature of 210°C, a pressure of 0.7 MPa, and a volume hourly space velocity of 1.8 h⁻¹. -1 Under the condition of a hydrogen / diphenylmethylphosphine hydrogenated naphtha volume ratio of 540:1, and maintaining the concentration of phosphine in the hydrogen gas at approximately 5900 ppm, CAT-5 was obtained after phosphating for 48 hours. The CO chemisorption capacity of CAT-5 was 2520 μmol / g.

[0056] Example 6

[0057] In this embodiment, the Ni2P catalyst (CAT-6) was prepared using the same steps as in Example 1, except that CA and EG were used as complexing agents and tri-tolylphosphine was used as a phosphating agent. The resulting CAT-6 had a CO chemisorption capacity of 2420 μmol / g.

[0058] Example 7

[0059] In this embodiment, the Ni2P catalyst (CAT-7) was prepared using the same steps as in Example 1, except that the EDTA / Ni 2+The molar ratio is 1.0; supported Ni 2+ The complex was obtained by phosphating tri-p-tolylphosphine hydrogenated naphtha containing 3000 ppm phosphorus for 60 h. The CO chemisorption capacity of CAT-7 was 2500 μmol / g.

[0060] Example 8

[0061] In this embodiment, the Ni2P catalyst (CAT-8) was prepared using the same steps as in Example 1, except that the EDTA / Ni 2+ The molar ratio is 2.2; supported Ni 2+ The complex was obtained by phosphating triisopropylphosphine hydrogenated naphtha containing 15,000 ppm phosphorus for 12 hours to obtain catalyst CAT-8. The CO chemisorption capacity of CAT-8 can reach 4000 μmol / g.

[0062] Example 9

[0063] In this embodiment, the Ni2P catalyst (CAT-9) was prepared using the same steps as in Example 1, except that after aging at room temperature for about 4 hours and drying at 100°C for about 6 hours, a supported Ni was obtained. 2+ The complex was obtained; the CO chemisorption capacity of the obtained CAT-9 was 3100 μmol / g.

[0064] Example 10

[0065] In this embodiment, a Ni2P catalyst (CAT-10) was prepared using the same steps as in Example 1, except that the Ni content of the obtained CAT-10 was 0.3 wt% and the CO chemisorption capacity was 1100 μmol / g.

[0066] Example 11

[0067] In this embodiment, the Ni2P catalyst (CAT-11) was prepared using the same steps as in Example 1, except that the Ni content of the obtained CAT-11 was 30 wt% and the CO chemisorption capacity was 4000 μmol / g.

[0068] Example 12

[0069] In this embodiment, the preparation steps for the Ni2P catalyst (CAT-12) differ from those in Example 1 in that 315g of mesoporous SAPO-11 molecular sieve (self-made, specific surface area 400m²) was used. 2The following ingredients were mixed evenly: 150g aluminum hydroxide powder (produced by Shandong Xingdu Chemical Co., Ltd., with an alumina loss of approximately 30wt%), 37.2g polyacrylamide, 14.0g acetic acid, and 200g deionized water. After thorough mixing, the mixture was extruded into 1.7mm clover-shaped strips using an extruder. The strips were then dried at 140℃ for 3 hours, calcined at 600℃ for 3 hours, cooled, cut into strips, and sieved to obtain a 3-10mm long composite carrier. The CO chemisorption capacity of CAT-12 was 3000μmol / g.

[0070] Comparative Example 1

[0071] This comparative example prepared a Ni2P catalyst (CAT-13) using the same support as in Example 1. The Ni2P preparation steps were identical to those described in patent CN200810234685.0 for the supported Ni2P catalyst. The catalyst composition (by mass) was 0.8 wt% Ni, 76.2 wt% mesoporous ZSM-5 molecular sieve, and 22.0 wt% alumina, ignoring residual species and any potential nickel phosphate formation. CAT-13 exhibited a CO chemisorption capacity of 800 μmol / g.

[0072] Comparative Example 2

[0073] This embodiment describes the preparation of a CoMo industrial octane number recovery catalyst (CAT-14) compatible with GARDES-II technology.

[0074] Example 13

[0075] Catalytic cracked gasoline with a sulfur content of 220 ppm, an olefin content of 38.6 v%, and a RON of 90.5 was used to conduct a comparative evaluation of CAT-1, CAT-2, CAT-3, CAT-13, and CAT-14 in a 250 mL gasoline hydrotreating evaluation unit. The evaluation conditions were: inlet temperature 360℃, inlet pressure 1.6 MPa, hydrogen-to-oil volume ratio 400, and volume hourly space velocity 1.5 h⁻¹. -1 The comparative evaluation results are shown in Table 1.

[0076] Table 1 Catalyst analysis data for CAT-1, CAT-2, CAT-3, CAT-13 and CAT-14

[0077] catalyst Total sulfur, mg / kg Olefin content, v% RON Liquid yield, % CAT-1 33.9 26.0 1.9 99.2 CAT-2 33.2 26.2 1.9 99.2 CAT-3 34.1 26.6 1.9 99.1 CAT-13 77.9 28.7 2.0 89.9 CAT-14 121.9 29.5 2.0 89.9

[0078] As shown in Table 1, compared with the comparative catalysts (CAT-13 and CAT-14), the Ni2P catalysts prepared in this invention (CAT-1, CAT-2, and CAT-3) exhibit the following advantages for catalytic cracking gasoline with a sulfur content of 220 ppm and an olefin content of 38.6 v%, resulting in a desulfurization rate of approximately 40% higher and an olefin content reduction of approximately 3 v%, while also showing a lower research octane number (RON) loss of 0.1 units and a higher liquid yield of 0.2-0.3%.

[0079] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, characterized in that, Includes the following steps: Will contain Ni 2+ The solution of the complex was impregnated onto the support to obtain supported Ni. 2+ Complexes, using phosphorus-containing materials to support Ni 2+ Phosphating of the complex yields the Ni2P catalyst for hydrotreating and reducing olefins in catalytic cracking gasoline. The phosphorus-containing substance contains an organophosphorus agent, which includes at least one of triethylphosphine, tripropylphosphine, tributylphosphine, triisopropylphosphine, di-tert-butylphosphine, triphenylphosphine, trioctylphosphine, tri-p-tolylphosphine, and diphenylmethylphosphine.

2. The preparation method according to claim 1, characterized in that, The carrier is a mixture of acidic mesoporous molecular sieve and alumina powder, with extrusion aid and an aqueous solution containing a binder added separately, followed by kneading, molding, drying, and calcination. The acidic mesoporous molecular sieve is at least one of H-ZSM-5, SAPO-11, Hβ, and HMOR. The average pore size and BET specific surface area of ​​the acidic mesoporous molecular sieve are 2-20 nm and 250-500 m², respectively. 2 / g; the alumina raw powder is at least one of boehmite powder, aluminum hydroxide powder, and SB powder; the dry basis mass ratio of the acidic mesoporous molecular sieve to the alumina raw powder is (3.0-3.7):

1.

3. The preparation method according to claim 1, characterized in that, The Ni-containing 2+ The solution of the complex was prepared by the following method: first, the pH of the aqueous solution was adjusted to be greater than 8.1 using ammonia; then, the complexing agent was added; and finally, Ni was added. 2+ Salt, yielding a product containing Ni 2+ Solution of complex.

4. The preparation method according to claim 3, characterized in that, The pH value is greater than 8.

2.

5. The preparation method according to claim 3, characterized in that, The complexing agent is at least one selected from ethylenediaminetetraacetic acid, aziridine triacetic acid, ethylenediamine, cyclohexanediaminetetraacetic acid, citric acid, and ethylene glycol; the complexing agent / Ni 2+ The molar ratio is 1.0-2.

2.

6. The preparation method according to claim 3, characterized in that, The Ni 2+ The salt is at least one of nickel nitrate, nickel carbonate, nickel acetate, basic nickel carbonate, nickel oxalate, and nickel formate.

7. The preparation method according to claim 1, characterized in that, The phosphorus-containing substance is hydrogenated naphtha containing an organophosphorus agent; the phosphorus content in the hydrogenated naphtha is 3000-15000 ppm.

8. The preparation method according to claim 1 or 7, characterized in that, The concentration of phosphine generated after the decomposition of the organophosphorus agent in hydrogen gas is 2000-15000 ppm.

9. The preparation method according to claim 1, characterized in that, The phosphating temperature is 150-400 ℃, the phosphating time is 12-60 h, and the phosphating pressure is 0.1-1.0 MPa.

10. A Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction obtained by the preparation method according to any one of claims 1-9, characterized in that, The Ni content in the catalytic cracking gasoline hydrotreating and olefin reduction Ni2P catalyst is 0.3-30.0 wt% based on the catalyst mass.

11. The catalyst according to claim 10, characterized in that, The number of active sites in the Ni2P catalyst for catalytic cracking gasoline hydrotreating and olefin reduction, expressed as the amount of CO chemically adsorbed, is 1000-4000 μmol / g.