Aromatic hydrocarbon olefin removal catalyst as well as preparation method and application thereof

Abstract

The preparation method comprises the following steps: treating a molecular sieve at a high temperature by adopting an aluminum-containing alkaline solution to obtain an active molecular sieve, uniformly mixing and pulping the active molecular sieve and a binder, adding an auxiliary agent, and carrying out flash drying to obtain active powder; and finally, uniformly mixing the active powder, an acid peptizing solvent and a pore-forming agent, extruding, forming and roasting to obtain the aromatic hydrocarbon olefin removal catalyst. The prepared catalyst is reasonable in pore size distribution, proper in B acid property, high in reaction activity, long in service life, high in hydrothermal stability and low in aromatic loss.

Description

Technical Field

[0001] The present invention belongs to the field of olefin removal catalysts, and particularly relates to an aromatics deolefination catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] At present, aromatics are one of the most important basic raw materials for organic chemical industry. The main means for industrial production of aromatics relies on catalytic reforming technology. Reformed aromatics generally contain trace amounts of olefins. Since olefins are chemically active, they will have a serious impact on the subsequent processing of aromatics. Therefore, it is very necessary to remove these trace olefins. Firstly, the product has requirements for the purity of olefin impurities. If these olefins are not removed, there is a great possibility that they will react with aromatics to form non-ideal components, thus having a greater impact on the quality of aromatic products. Secondly, removing trace olefin impurities will also protect subsequent process steps that are sensitive to the presence of olefins, such as the molecular sieve adsorption separation process. Trace olefin impurities will occupy the pores of the molecular sieve, thereby affecting its separation performance.

[0003] At present, the main methods for removing olefin impurities in aromatics are hydrorefining and clay refining. Hydrorefining uses noble metal platinum or palladium catalysts to carry out a "post-hydrogenation process" on aromatic raw materials after the petroleum reforming process to saturate olefins and remove olefin impurities. However, hydrorefining technology has disadvantages such as large construction investment, high operating costs, and large losses of aromatics. Clay refining uses activated clay to remove trace olefins in reformed aromatics. This is because clay has active acid centers and has certain catalytic polymerization ability and pore adsorption ability under high-pressure liquid phase and at 150 - 200 °C, which can cause hydrocarbonation, polymerization, etc. reactions of trace olefins contained in reformed oil to generate high-boiling compounds, which are then adsorbed by the clay or removed in subsequent separation processes. However, the activity of clay is low and its lifespan is short, and it needs to be replaced frequently, resulting in a very large amount of clay usage and high labor intensity, which severely restricts the "long-term, stable, and excellent" operation of the device. In recent years, with the popularization of low-pressure reforming technology, the olefin content in reformed oil has further increased, and the above problems will be further exacerbated.

[0004] Since molecular sieves have a regular pore structure and suitable acidic properties, they are widely used in acid-catalyzed reactions. The process of using molecular sieve catalysts to remove olefins from reformed product oil is the same as that of the clay refining process in terms of process and process conditions. Therefore, molecular sieve catalysts can well make up for the deficiencies of the above two traditional processes.

[0005] CN200410046820.0 proposes a reformed aromatic oil deolefination catalyst with molecular sieve as the active component and alumina as the binder. Using this catalyst to treat reformed aromatic oil can effectively remove trace olefins in aromatics, and the aromatics do not lose but increase instead, especially the C8 aromatics increase significantly. However, there are still deficiencies such as low activity and short lifespan of the catalyst used.

[0006] A preparation method of a deolefinization catalyst invented in CN102008976A, the catalyst consists of a high silica-alumina ratio ReUSY molecular sieve as the main active component, mordenite molecular sieve as the second active component, and alumina as the binder. The mixed molecular sieve active components significantly improve the deolefinization performance of the catalyst.

[0007] CN102029180A proposes a catalyst for removing trace olefins in reformed naphtha with HY, USY, ZSM-5, MCM-22, β molecular sieves as active components, alumina as the binder, and loaded with rare earths, phosphorus, magnesium and other substances. Compared with industrial clay, the olefin removal ability is improved. Under the same comparison conditions, the olefin removal time reaches 5 to 7 times that of clay.

[0008] Wang Yinan et al. studied the removal of trace olefins in aromatics by zeolite molecular sieves in "Study on the Removal of Trace Olefins in Aromatics by Zeolite Molecular Sieves". A zeolite molecular sieve catalyst modified with rare earth element La was used to deeply remove olefin impurities in aromatics. The experimental results show that the mechanical mixing method is the best for the catalyst; for ZSM-5 molecular sieve, the optimal addition mass fraction of rare earth element La is 10%, and both the initial activity and the service life are greatly improved.

[0009] The above catalysts use molecular sieves as the main active components. However, when the gum and olefin contents in aromatics are relatively high, the service life of the molecular sieve catalyst is rapidly shortened, and the olefin removal accuracy of the catalyst is reduced, unable to achieve the best use effect, resulting in waste of the catalyst and an increase in the regeneration frequency. This not only causes a significant increase in cost, but also causes environmental pollution due to the treatment and disposal of a large amount of catalyst. At the same time, the hydrothermal stability of the molecular sieve catalyst is poor, and the overall performance of the catalyst drops significantly after multiple regenerations, and it can no longer be used in industrial production and can only be treated as hazardous waste.

[0010] Therefore, based on these problems, it is of great practical significance to provide a method and catalyst that can not only improve the activity of the deolefinization catalyst for aromatic oils, but also increase the hydrothermal stability of the catalyst, thereby increasing the number of catalyst regenerations and extending the service life of the catalyst. Summary of the Invention

[0011] The present invention is proposed to solve the problems existing in the prior art, and its purpose is to provide an aromatic deolefinization catalyst, its preparation method and application.

[0012] The present invention is achieved through the following technical solutions: A preparation method of an aromatic deolefinization catalyst, characterized in that it includes the following steps: (i) High-temperature aluminization of molecular sieve The molecular sieve is treated with an aluminum-containing alkaline solution at high temperature, and after treatment, it is filtered, washed and ammonium-exchanged to obtain an active molecular sieve; (ⅱ)Preparation of active powder by modifying molecular sieve The active molecular sieve prepared in step (ⅰ) and the binder are mixed and slurried evenly, additives are added, and then flash drying is carried out to obtain an active powder; (ⅲ)Catalyst forming After the active powder, acid colloid solvent and pore-forming agent are mixed evenly, extrusion forming and calcination are carried out to obtain an aromatics deolefination catalyst.

[0013] In the above technical solution, the molecular sieve is any one or a mixture of several of MCM-22, MCM-56, MCM-49, ultrastable Y or Beta molecular sieve; The aluminum source in the aluminum-containing alkaline solution is any one or a mixture of several of sodium aluminate, aluminum sulfate, aluminum isopropoxide or pseudo-boehmite; The alkali source in the aluminum-containing alkaline solution is sodium hydroxide and / or potassium hydroxide; The concentration of alumina in the aluminum-containing alkaline solution is 0.1 mol / L to 0.3 mol / L, and the alkali concentration is 0.05 mol / L to 0.3 mol / L. In the aluminization process, under high-temperature alkaline conditions, alumina in the solution enters the molecular sieve framework to form framework alumina, so it is still calculated in terms of alumina; because the alkali is in excess, an alkaline sodium aluminate clear solution will be formed finally.

[0014] In the above technical solution, the solid-liquid mass ratio of the molecular sieve to the aluminum-containing alkaline solution is 1:10.

[0015] In the above technical solution, the conditions for high-temperature treatment of the molecular sieve in step (ⅰ) are: the treatment temperature is 100 °C to 180 °C, and the treatment duration is 0.5 h to 48 h.

[0016] In the above technical solution, the specific method of ammonium exchange is: using a 0.2 mol / L to 0.35 mol / L ammonium sulfate solution according to a solid-liquid mass ratio of 1:10, and carrying out ammonium exchange 3 times at 80 °C, 2 h each time.

[0017] In the above technical solution, the binder is any one or a mixture of several of macroporous silica, mesoporous silica, macroporous alumina, mesoporous alumina or mesoporous amorphous silica-alumina; the additives are any one or a mixture of several of zinc nitrate, iron nitrate, cerium nitrate, lanthanum chloride or phosphoric acid.

[0018] In the above technical solution, the mass ratio of the active molecular sieve to the binder is (40 to 90):(10 to 50); the mass of the additives is 0.5% to 5% of the dry basis of the active molecular sieve.

[0019] In the above technical solution, the acid-gum solvent is any one or a mixture of several of nitric acid, formic acid, or acetic acid; the pore-forming agent is any one or a mixture of several of polyethylene glycol, polyethylene oxide, methyl cellulose, or sesbania powder; the mass ratio of the active powder, the acid-gum solvent, and the pore-forming agent is (1.2~1.6):1:(0.012~0.048).

[0020] In the above technical solution, the temperature of the calcination is 540°C to 570°C, and the duration is 3h to 7h.

[0021] An aromatics deolefination catalyst prepared by the foregoing method, the ratio of the pore volume of the larger pores to the pore volume of the smaller pores in the pore volume of the aromatics deolefination catalyst is (0.2~10):1; the pore diameter of the larger pores is 10 nm to 30 nm, and the pore diameter of the smaller pores is 2 nm to 10 nm; calculated by the pyridine infrared desorption result at 200°C, the ratio of the amount of B acid to the amount of L acid in the aromatics deolefination catalyst is (0.2~2.8):1.

[0022] An application of an aromatics deolefination catalyst prepared by the foregoing method in removing trace olefins from aromatic oil, the deolefination reaction conditions are: the temperature is 130°C to 240°C, the pressure is 1MPa to 5MPa, and the volume space velocity is 1h -1 -50h -1 .

[0023] The beneficial effects of the present invention are as follows: The present invention provides an aromatics deolefination catalyst, a preparation method thereof, and an application thereof. The catalyst prepared by the present invention can effectively remove trace olefins in aromatic oil under non-hydrogenation conditions, reduce the bromine index of the raw material by at least 70%, greatly improve the activity and stability of the catalyst, and extend the service life of the deolefination catalyst to the greatest extent; the present invention greatly simplifies the catalyst preparation process, prepares an active powder with suitable B acid properties in one step by flash drying, inhibits the generation of overly strong B acid, avoids the occurrence of side reactions during the reaction process, improves the stability of the catalyst to the greatest extent, and extends the total service life of the catalyst; during the catalyst forming process, the binder is a mesoporous or macroporous material, which improves the diffusion performance of reactants and products to the greatest extent and extends the service life of the catalyst; the coupling of the active component and the metal promoter improves the inhibition of dealumination during the regeneration process, greatly improves the regeneration activity of the catalyst, and extends the total service life of the catalyst. Specific embodiments

[0024] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be further described below through specific embodiments.

[0025] Example 1 A preparation method of an aromatic hydrocarbon de-olefination catalyst, comprising the following steps: (i) Dissolve 18.89 g of sodium meta-aluminate (w(Al2O3)% = 54, w(Na2O)% = 40) and 2.28 g of sodium hydroxide (w(NaOH)% = 98.5) in 1 L of water. After stirring evenly, add 100 g of MCM-56 molecular sieve, heat up to 150 °C, react for 2 h, then filter, wash, and perform 0.3 mol / L ammonium sulfate exchange to prepare MCM-56 active molecular sieve.

[0026] (ii) Mechanically mix 100 g of MCM-56 active molecular sieve (87 wt%) and 43.8 g of macroporous silica (85 wt%) evenly, add 704 g of deionized water and mechanically beat into a homogeneous slurry. Then add 0.81 g of concentrated phosphoric acid with a mass fraction of 85%, mix evenly, and perform flash drying using a flash dryer to obtain active powder M-1. (iii) Mix 100 g of the active powder M-1 molecular sieve obtained in step (i) and 1 g of sesbania powder evenly, then add 100 g of dilute nitric acid with a mass fraction of 5%, mix well to make it a paste-like plastic substance, extrude cylindrical bars with a diameter of 1.5 mm on an extruder, dry the cylindrical bars at 120 °C for 16 h, and then calcine in an air atmosphere at 550 °C for 4 h to obtain catalyst T-1.

[0027] A method for removing olefins from aromatic hydrocarbon oil, specifically: contacting the catalyst T-1 with reformate containing olefins for de-olefination reaction. The bromine index of the raw material is 1000 mgBr / 100 g of oil, and the reaction conditions include: temperature of 180 °C, gauge pressure of 2.0 MPa, and mass space velocity of 15 h -1 , taking the outlet bromine index of 300 mgBr / 100 g of oil as the standard, the catalyst is deactivated after reacting for 280 h. After the reaction, the catalyst is carbonized and regenerated, that is, calcined in an air atmosphere at 550 °C for 4 h, and then the regenerated catalyst is evaluated under the same reaction conditions and requirements as above, with a service life of 210 h.

[0028] Example 2 A preparation method of an aromatic hydrocarbon de-olefination catalyst, comprising the following steps: (i) Dissolve 134 g of aluminum sulfate (w(Al2O3)% = 15.16) and 8.12 g of sodium hydroxide (w(NaOH)% = 98.5) in 1 L of water. After stirring evenly, add 100 g of MCM-22 molecular sieve, heat up to 180 °C, react for 4 h, then filter, wash, and perform 0.3 mol / L ammonium sulfate exchange to prepare MCM-22 active molecular sieve.

[0029] (ii) 100 g of MCM-22 active molecular sieve (87 wt%) and 102 g of mesoporous silica (85 wt%) were mechanically mixed and uniformly mixed, 800 g of deionized water was added for mechanical slurrying, and then 5.04 g of 99% by mass cerium nitrate nonahydrate was added. After mixing uniformly, the mixture was flash dried with a flash desiccant to obtain active powder M-2.

[0030] (iii) 100 g of the active powder M-2 molecular sieve obtained in step (i) and 1 g of polyethylene glycol were mixed evenly, and then 90 g of 5% by mass acetic acid was added and kneaded thoroughly to make it into a paste-like plastic material, which was extruded into cylindrical strips with a diameter of 1.5 mm on an extruder. The cylindrical strips were dried at 120°C for 16 h and then calcined at 540°C in an air atmosphere for 7 h to obtain catalyst T-2.

[0031] A method for removing olefins from aromatic oil, specifically: contacting the catalyst T-2 with reformed oil containing olefins to carry out a deolefination reaction, the raw material bromine index is 1000 mgBr / 100 g oil, and the reaction conditions include: temperature of 180°C, pressure of 2.0 MPa on a pressure gauge, and mass space velocity of 15 h -1 The catalyst was deactivated after 240 hours of reaction, with the export bromine index of 300 mg Br / 100 g oil as the standard. After the reaction, the catalyst was regenerated by charring, that is, calcined at 550°C in air atmosphere for 4 hours, and then the regenerated catalyst was evaluated under the same reaction conditions and requirements as above, with a life of 190 hours.

[0032] Example 3 A method for preparing an aromatic deolefination catalyst comprises the following steps: (i) Dissolve 306 g of aluminum isopropoxide (w(Al2O3)%=10) and 4.06 g of sodium hydroxide (w(NaOH)%=98.5) in 1 L of water, stir evenly, add 100 g of MCM-49 molecular sieve, heat to 120°C, react for 2 h, filter, wash and exchange with 0.3 mol / L ammonium sulfate to prepare MCM-49 active molecular sieve.

[0033] (ii) 100 g of MCM-49 active molecular sieve (87 wt%) and 190 g of mesoporous alumina (69 wt%) were mechanically mixed and uniformly mixed, 570 g of deionized water was added for mechanical slurrying, and then 18.3 g of 99% by mass zinc nitrate hexahydrate was added. After mixing uniformly, the mixture was flash dried with a flash desiccant to obtain active powder M-3.

[0034] (ⅲ) Mix 100 g of the activated powder M-3 molecular sieve obtained in step (ⅰ) and 1 g of methyl cellulose evenly, then add 110 g of formic acid with a mass fraction of 5%, and knead thoroughly to make a paste-like plastic. Extrude cylindrical bars with a diameter of 1.5 mm on an extruder. The cylindrical bars are dried at 120 °C for 16 h, and then calcined in an air atmosphere at 560 °C for 4 h to obtain catalyst T-3.

[0035] A method for removing olefins from aromatic hydrocarbon oil production. Specifically: Contact the catalyst T-3 with the reforming product oil containing olefins for olefin removal reaction. The bromine index of the raw material is 1000 mgBr / 100 g oil. The reaction conditions include: the temperature is 180 °C, the pressure measured by the pressure gauge is 2.0 MPa, and the mass space velocity is 15 h -1 Based on the standard of an outlet bromine index of 300 mgBr / 100 g oil, the catalyst is deactivated after reacting for 310 h. After the reaction, the catalyst is carbon-burned and regenerated, that is, calcined in an air atmosphere at 550 °C for 4 h, and then the regenerated catalyst is evaluated under the same reaction conditions and requirements as above, with a service life of 217 h.

[0036] Example 4 A preparation method of an aromatic hydrocarbon de-olefin catalyst, comprising the following steps: (ⅰ)Dissolve 47.2 g of sodium aluminate (w(Al2O3)% = 54, w(Na2O)% = 40) and 12.18 g of sodium hydroxide (w(NaOH)% = 98.5) in 1 L of water. After stirring evenly, add 100 g of MCM-56 molecular sieve, heat up to 100 °C, react for 48 h, then filter, wash, and exchange with 0.3 mol / L ammonium sulfate to prepare MCM-56 activated molecular sieve.

[0037] (ⅱ)Mechanically mix 100 g of MCM-56 activated molecular sieve (87 wt%) and 54 g of macroporous alumina (69 wt%) evenly, add 424 g of deionized water and mechanically beat into a slurry evenly, then add 7.56 g of lanthanum nitrate nonahydrate with a mass fraction of 99%, mix evenly, and perform flash drying using a flash dryer to obtain activated powder M-4.

[0038] (ⅲ)Mix 100 g of the activated powder M-4 molecular sieve obtained in step (ⅰ) and 1 g of polyethylene oxide evenly, then add 110 g of dilute nitric acid with a mass fraction of 5%, knead thoroughly to make a paste-like plastic, extrude cylindrical bars with a diameter of 1.5 mm on an extruder. The cylindrical bars are dried at 120 °C for 16 h, and then calcined in an air atmosphere at 560 °C for 6 h to obtain catalyst T-4.

[0039] A method for removing olefins from aromatic oil, specifically: contacting the catalyst T-4 with reformed oil containing olefins to carry out a deolefination reaction, the raw material bromine index is 1000 mgBr / 100 g oil, and the reaction conditions include: temperature of 180°C, pressure of 2.0 MPa on a pressure gauge, and mass space velocity of 15 h -1 The catalyst was deactivated after 360 hours of reaction, with the export bromine index of 300 mg Br / 100 g oil as the standard. After the reaction, the catalyst was regenerated by charring, that is, calcined at 550°C in air atmosphere for 4 hours, and then the regenerated catalyst was evaluated under the same reaction conditions and requirements as above, with a life of 256 hours.

[0040] Example 5 A method for preparing an aromatic deolefination catalyst comprises the following steps: (i) Dissolve 67.2 g aluminum sulfate (w(Al2O3)%=15.16) and 12.18 g sodium hydroxide (w(NaOH)%=98.5) in 1 L of water, stir evenly, add 100 g ultra-stable Y molecular sieve, heat to 170°C, react for 1 h, filter, wash and exchange with 0.3 mol / L ammonium sulfate to prepare ultra-stable Y active molecular sieve.

[0041] (ii) 100 g of ultrastable Y active molecular sieve (87 wt%) and 12 g of mesoporous amorphous silica-alumina (80 wt%) were mechanically mixed and uniformly mixed, 208 g of deionized water was added for mechanical slurrying, and then 5.05 g of 99% by mass ferric nitrate hexahydrate was added. After mixing uniformly, flash drying was performed using a flash desiccant to obtain active powder M-5.

[0042] (iii) 100 g of the active powder M-5 molecular sieve obtained in step (i) and 1 g of sesbania powder were mixed evenly, and then 85 g of 5% by mass dilute nitric acid were added and kneaded thoroughly to make a paste-like plastic material, which was extruded into cylindrical strips with a diameter of 1.5 mm on an extruder. The cylindrical strips were dried at 120°C for 16 h and then calcined at 540°C in an air atmosphere for 6 h to obtain catalyst T-5.

[0043] A method for removing olefins from aromatic oil, specifically: contacting the catalyst T-5 with reforming oil containing olefins to carry out a deolefination reaction, the raw material bromine index is 1000mgBr / 100g oil, and the reaction conditions include: temperature of 180°C, pressure of 2.0MPa on a pressure gauge, and mass space velocity of 15h -1 The catalyst was deactivated after 180 hours of reaction, with the export bromine index of 300 mg Br / 100 g oil as the standard. After the reaction, the catalyst was regenerated by charring, that is, calcined at 550°C in air atmosphere for 4 hours, and then the regenerated catalyst was evaluated under the same reaction conditions and requirements as above, with a life of 162 hours.

[0044] Example 6 A preparation method of an aromatics de-olefination catalyst comprises the following steps: (i) Dissolve 29.58 g of pseudo-boehmite (w(Al2O3)% = 69) and 35.4 g of potassium hydroxide (w(KOH)% = 85) in 1 L of water. After stirring evenly, add 100 g of Beta zeolite, heat up to 150 °C, react for 24 h, then through filtration, washing, and ammonium sulfate exchange with a concentration of 0.3 mol / L, prepare Beta active zeolite.

[0045] (ii) Mechanically mix 100 g of Beta active zeolite (87 wt%) and 31.5 g of mesoporous alumina (69 wt%) evenly, add 300 g of deionized water and mechanically beat into a slurry evenly. Then add 3.99 g of cerium nitrate nonahydrate with a mass fraction of 99%. After mixing evenly, perform flash drying with a flash dryer to obtain active powder M-6.

[0046] (iii) Mix 100 g of the active powder M-6 zeolite obtained in step (i) and 1 g of sesbania powder evenly, then add 91 g of dilute nitric acid with a mass fraction of 5%, and fully knead to make it into a paste-like plastic. Extrude cylindrical bars with a diameter of 1.5 mm on an extruder. The cylindrical bars are dried at 120 °C for 16 h, and then calcined in an air atmosphere at 570 °C for 3 h to obtain catalyst T-6.

[0047] A method for removing olefins from aromatic oil, specifically: contacting the catalyst T-1 with reformate containing olefins for de-olefination reaction. The bromine index of the raw material is 1000 mgBr / 100 g of oil, and the reaction conditions include: the temperature is 180 °C, the pressure measured by the pressure gauge is 2.0 MPa, and the mass space velocity is 15 h -1 , taking the outlet bromine index of 300 mgBr / 100 g of oil as the standard, the catalyst is deactivated after reacting for 140 h. After the reaction, the catalyst is carbon-burned and regenerated, that is, calcined in an air atmosphere at 550 °C for 4 h, and then the regenerated catalyst is evaluated under the same reaction conditions and requirements as above, and the service life is 120 h.

[0048] Comparative Example 1 Prepare catalyst C-1 according to the scale-up of Comparative Example CN112337505A, that is, evenly mix cerium-exchanged CeY zeolite, MCM-41 zeolite, alumina, sesbania powder, citric acid, and dilute nitric acid, knead, extrude into a cylindrical bar with a diameter of 1.5 mm, and calcine at 620 °C for 2 h to obtain catalyst C-1.

[0049] The method for removing olefins from aromatic oil in this comparative example is specifically as follows: contacting the catalyst C-1 with the reformate containing olefins for olefin removal reaction. The bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: temperature of 180 °C, gauge pressure of 2.0 MPa, and mass space velocity of 15 h -1 , taking the outlet bromine index of 300 mg Br / 100 g oil as the standard, the catalyst is deactivated after reacting for 60 h. After the reaction, the catalyst is calcined and regenerated, that is, calcined in an air atmosphere at 550 °C for 4 h, and then the regenerated catalyst is evaluated under the same reaction conditions and requirements as above, with a service life of 54 h.

[0050] The applicant declares that the above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A preparation method of an aromatic hydrocarbon de-olefin catalyst, characterized in that: It includes the following steps: (i) High-temperature aluminization of molecular sieve The molecular sieve is treated with an aluminous alkaline solution at high temperature, and after treatment, it is filtered, washed, and ammonium-exchanged to obtain an active molecular sieve; The solid-liquid mass ratio of the molecular sieve to the aluminous alkaline solution is 1:10; The conditions for high-temperature treatment of the molecular sieve are: the treatment temperature is 100°C to 180°C, and the treatment duration is 0.5 h to 48 h; (ii) Modification of molecular sieve to prepare active powder The active molecular sieve prepared in step (i) and the binder are mixed and slurried evenly, additives are added, and then flash drying is carried out to obtain active powder; The mass ratio of the active molecular sieve to the binder is (40 - 90):(10 - 50); The mass of the additives is 0.5% to 5% of the dry basis of the active molecular sieve; (iii) Catalyst shaping After the active powder, acid binder solvent, and pore-forming agent are mixed evenly, they are extruded into shape and calcined to obtain an aromatics deolefination catalyst; The mass ratio of the active powder, acid binder solvent, and pore-forming agent is (1.2 - 1.6):1:(0.012 - 0.048).

2. The preparation method of the aromatic hydrocarbon de-olefination catalyst according to claim 1, characterized in that: The molecular sieve is any one or a mixture of several of MCM-22, MCM-56, MCM-49, ultrastable Y, or Beta molecular sieve; The aluminum source in the aluminous alkaline solution is any one or a mixture of several of sodium aluminate, aluminum sulfate, aluminum isopropoxide, or pseudo-boehmite; The alkali source in the aluminous alkaline solution is sodium hydroxide and / or potassium hydroxide; The concentration of alumina in the aluminous alkaline solution is 0.1 mol / L to 0.3 mol / L, and the alkali concentration is 0.05 mol / L to 0.3 mol / L.

3. The preparation method of the aromatic hydrocarbon de-olefination catalyst according to claim 1, wherein: The specific method of ammonium exchange is: ammonium exchange is carried out 3 times at 80°C for 2 h each time using a 0.2 mol / L to 0.35 mol / L ammonium sulfate solution according to a solid-liquid mass ratio of 1:

10.

4. The preparation method of the aromatic hydrocarbon de-olefination catalyst according to claim 1, wherein: The binder is any one or a mixture of several of macroporous silica, mesoporous silica, macroporous alumina, mesoporous alumina, or mesoporous amorphous silica-alumina; the additives are any one or a mixture of several of zinc nitrate, iron nitrate, cerium nitrate, lanthanum chloride, or phosphoric acid.

5. The preparation method of the aromatic hydrocarbon de-olefin catalyst according to claim 1, characterized in that: The acid binder solvent is any one or a mixture of several of nitric acid, formic acid, or acetic acid; the pore-forming agent is any one or a mixture of several of polyethylene glycol, polyethylene oxide, methyl cellulose, or sesbania powder; the specific calcination conditions in step (iii) are: the calcination temperature is 540°C to 570°C, and the calcination time is 3 h to 7 h.

6. An aromatics deolefination catalyst prepared by the method according to any one of claims 1 to 5, characterized in that: The ratio of the pore volume of larger pores to that of smaller pores in the pore volume of the aromatics deolefination catalyst is (0.2 - 10):1; the pore diameter of the larger pores is 10 nm to 30 nm, and the pore diameter of the smaller pores is 2 nm to 10 nm; calculated from the pyridine infrared desorption results at 200°C, the ratio of the amount of B acid to the amount of L acid in the aromatics deolefination catalyst is (0.2 - 2.8):

1.

7. Use of an aromatic hydrocarbon de-olefination catalyst prepared by the method according to any one of claims 1 to 5 in removing trace olefins from aromatic hydrocarbon oil, characterized in that, The de-olefination reaction conditions are as follows: the temperature is 130°C to 240°C, the pressure is 1 MPa to 5 MPa, and the volume space velocity is 1 h -1 -50 h -1 .