Reformed oil deolefination catalyst and preparation method thereof

Abstract

The invention discloses a reformate deolefination catalyst and a preparation method thereof. The olefin removal catalyst comprises 10-80 parts by weight of an active component and 20-90 parts by weight of a binder, the active component is obtained by carrying out hydrothermal synthesis on an active silicon source, an aluminum source, an alkali source and a template agent as raw materials, and the active silicon source is prepared by loading a metal or non-metal additive on the silicon source by adopting an impregnation method. The preparation method of the catalyst comprises the following steps: loading a metal or non-metal auxiliary agent into a silicon source by adopting an impregnation method to prepare an active silicon source, carrying out hydrothermal synthesis on the active silicon source, an aluminum source, an alkali source and a template agent as raw materials to prepare an active component, uniformly mixing the active component and a binder, acidifying and peptizing, kneading, extruding, forming and roasting, thereby obtaining the catalyst. The reformed oil olefin removal catalyst is obtained. The catalyst provided by the invention has optimal pore structure distribution and appropriate acid properties, and the addition of the coupling aid greatly improves the regeneration activity of the catalyst and prolongs the total service life of the catalyst.

Description

Technical Field

[0001] The invention relates to the field of deolefination catalysts, and in particular to a reforming oil deolefination catalyst and a preparation method thereof. Background Art

[0002] There are often trace amounts of olefins in reforming oil, and it is very necessary to remove these olefins. First, the product requires a certain degree of purity of olefin impurities. If these olefins are not removed, they will most likely react with aromatics to generate non-ideal components, thus having a significant impact on the quality of the aromatic products. Second, removing trace olefin impurities will also protect subsequent processes that are sensitive to olefins, such as the molecular sieve adsorption separation process. Trace olefin impurities will occupy the gaps in the molecular sieve and affect its separation performance.

[0003] At present, the main methods for removing olefin impurities from reformed oil are hydrorefining and clay refining. Hydrorefining is the use of precious metal platinum or palladium catalysts to perform a "post-hydrogenation process" on aromatic raw materials after the petroleum reforming process to saturate olefins and remove olefin impurities, but the hydrorefining technology has the disadvantages of large construction investment, high operating costs, and high aromatic losses. Clay refining is the use of activated clay to remove trace olefins from reformed aromatics. This is because clay has active acid centers and has certain catalytic superposition capabilities and pore adsorption capabilities under high-pressure liquid phase and 150-200°C conditions. It can cause trace olefins contained in the reformed oil to undergo hydrocarbonization, polymerization and other reactions to generate high-boiling point compounds, which are then adsorbed by clay or removed in subsequent separation processes. However, clay has low activity and short life, and needs to be replaced frequently, resulting in a very large amount of clay used and high labor intensity, which seriously restricts the "long-term, stable and excellent" operation of the device. In recent years, with the promotion of low-pressure reforming technology, the olefin content in reformed oil has further increased, and the above problems will be further aggravated.

[0004] Since molecular sieves have regular pore structures and suitable acid properties, they are widely used in acid-catalyzed reactions. The process of removing olefins from reformed oil using molecular sieve catalysts is the same as that of clay refining process and process conditions, so molecular sieve catalysts can well make up for the shortcomings of the above two traditional processes. For example, CN1269938C proposes a catalyst for removing olefins from reformed aromatic oil using molecular sieve as an active component and alumina as a binder. The use of this catalyst to treat reformed aromatic oil can effectively remove trace olefins in aromatics, and aromatics are not lost but increased, especially C8 aromatics. However, there are still shortcomings such as low activity and short life of the catalyst used; CN101433856A proposes using Y-type and β-type molecular sieves loaded with rare earth, P, Mo, etc. as catalysts for removing trace olefins from aromatics, which improves the ability to remove olefins compared to industrial clay. Under the same comparison conditions, the time for removing olefins is extended by nearly 3 times. Wang Yinan and others studied the removal of trace olefins from aromatics by zeolite molecular sieves, and used zeolite molecular sieve catalysts modified with rare earth element La to deeply remove olefin impurities from aromatics. The experimental results showed that the best catalyst was mechanical mixing; for Z-type molecular sieves, the best addition mass fraction of rare earth element La was 10%, and the initial activity and life were greatly improved.

[0005] The above catalysts use molecular sieve as the main active component, but when the content of colloid and olefin in the reforming oil is high, the life of the molecular sieve catalyst is rapidly shortened, and the accuracy of the catalyst in removing olefins is reduced, and the optimal effect of use cannot be achieved, resulting in waste of catalysts and increased regeneration frequency, which not only greatly increases costs, but also causes environmental pollution due to the treatment and disposal of a large number of catalysts. At the same time, the hydrothermal stability of molecular sieve catalysts is poor. After multiple regenerations, the overall performance of the catalyst is greatly reduced, and it cannot continue to be used in industrial production and can only be treated as hazardous waste.

[0006] Therefore, based on the above problems, it is of great practical significance to provide a method and a catalyst that can not only improve the activity of the reforming oil deolefination catalyst, but also increase the hydrothermal stability of the catalyst, thereby increasing the number of catalyst regeneration times and extending the service life of the catalyst. Summary of the invention

[0007] In order to solve the above technical problems, the present invention provides a reforming oil deolefination catalyst and a preparation method. The catalyst of the present invention can be used to remove trace olefins in the reforming oil under non-hydrogenation conditions, and the bromine index of the raw material can be reduced by at least 70%, the activity and stability of the catalyst are greatly improved, and the service life of the deolefination catalyst is extended to the greatest extent.

[0008] In a first aspect, the present invention provides a reforming oil deolefination catalyst, which is realized by adopting the following technical scheme.

[0009] A reforming oil deolefination catalyst comprises 10-80 parts by weight of an active component and 20-90 parts by weight of a binder; the active component is obtained by hydrothermal synthesis using an active silicon source, an aluminum source, an alkali source and a template as raw materials, and the active silicon source is prepared by loading a metal or non-metal auxiliary agent on the silicon source by an impregnation method.

[0010] By adopting the above technical scheme, the external specific surface area of ​​the active component of the present invention is 20% to 50% of the total specific surface area; according to the pyridine infrared desorption result at 200°C, the ratio of the amount of B acid to the amount of L acid in the catalyst is (0.2 to 3): 1. The catalyst of the present invention can effectively remove trace olefins in the reforming oil, and the catalyst has the advantages of high activity, long service life, high hydrothermal stability and low aromatic loss.

[0011] Preferably, the active component is 50-80 parts by weight and the binder is 20-50 parts by weight.

[0012] Furthermore, the preparation method of the active silicon source is as follows: based on the dry weight of the molecular sieve, 1% to 10% of the metal salt or non-metallic additive is dissolved in water, the silicon source is added, mixed evenly, and then dried at 80-200°C for 10 to 24 hours to prepare the active silicon source.

[0013] Preferably, the content of the metal salt or non-metal additive is 1% to 7% of the dry weight of the molecular sieve.

[0014] Furthermore, the metal salt is selected from one or a mixture of ferric chloride, zinc chloride, ferric nitrate, zinc nitrate, cerium nitrate, and lanthanum chloride; and the non-metallic additive is selected from boric acid and / or phosphoric acid.

[0015] Furthermore, the silicon source is selected from one or a mixture of white carbon black, column chromatography silica gel, and silica sol.

[0016] Furthermore, the aluminum source is selected from one or a mixture of pseudo-boehmite, aluminum sulfate, sodium aluminate, and aluminum isopropoxide.

[0017] Furthermore, the template agent is selected from one or a mixture of hexamethyleneimine, piperidine, tetrapropylammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH), and cyclohexylamine.

[0018] Furthermore, the alkali source is selected from sodium hydroxide, potassium hydroxide or a mixture of the two.

[0019] Further, the preparation method of the active component is: mixing an active silicon source, an alkali source, a template, an aluminum source and water to obtain an initial gel having the following molar ratio: SiO2 in the active silicon source: alkali source: template: Al2O3 in the aluminum source: H2O = 1: (0.03-0.28): (0.06-0.35): (0.025-0.05): (6-25), then hydrothermally crystallizing at 120-180°C for 20-72h, filtering, washing, drying, and calcining to obtain a heteroatom molecular sieve, and then using an ammonium sulfate solution to perform ammonium exchange at a solid-liquid mass ratio of 1:8-10, and drying and calcining to obtain an active component. The active component includes a mixture of one or more of MCM-22, MCM-56, MCM-49, Beta, and ZSM-5 molecular sieves.

[0020] Preferably, the hydrothermal synthesis crystallization conditions are a temperature of 140-170° C. and a time of 36-60 h.

[0021] Furthermore, the ammonium exchange conditions are: the concentration of ammonium sulfate solution is 0.2 mol / L, and the exchange is performed at 80°C for 3 times, each time for 2 h.

[0022] Furthermore, the binder is selected from one or a mixture of silicon oxide, aluminum oxide, amorphous silicon aluminum, and kaolin.

[0023] In a second aspect, the present invention provides a method for preparing a reforming oil deolefination catalyst, which is achieved by adopting the following technical scheme.

[0024] A method for preparing the above-mentioned reforming oil deolefination catalyst comprises the following steps: uniformly mixing a specified amount of active components and a binder, adding dilute nitric acid for kneading and extrusion, drying at 100-200°C for 1-10 hours, and calcining at 550°C for 4-10 hours to prepare a reforming oil deolefination catalyst.

[0025] Specifically, the mass concentration of dilute nitric acid is 5%.

[0026] The reaction conditions for removing trace olefins in reforming oil by using the catalyst of the present invention include: temperature of 100-250°C, preferably 130-240°C; pressure of 1-5MPa in gauge pressure, volume space velocity of 1-50h -1 .

[0027] This application has the following beneficial effects.

[0028] (1) When the catalyst of the present invention is used for the deolefination reaction of reforming oil, it has good activity and catalyst stability. The deactivated catalyst can be regenerated and used multiple times, and the performance after regeneration is good; (2) The present invention controls the acid distribution in the hydrothermal synthesis process by adding an auxiliary agent, thereby obtaining a maximum proportion of medium-strong B acid and appropriate L acid, thereby inhibiting the occurrence of initial side reactions and extending the service life of the catalyst to the greatest extent; (3) The present invention greatly simplifies the catalyst preparation process. An active powder with optimal pore structure distribution and suitable acid properties is prepared in one step by a hydrothermal synthesis method, thereby avoiding the damage to the molecular sieve structure by post-treatment. Combined with the addition of auxiliary agents, the inhibition of dealumination during the regeneration process is improved, thereby greatly improving the regeneration activity of the catalyst and extending the total service life of the catalyst. DETAILED DESCRIPTION

[0029] The present patent application is further described below in conjunction with embodiments.

[0030] The materials used in the preparation process of the following examples were not further processed unless otherwise specified and were purchased from commercial sources.

[0031] Example 1 A method for preparing a reforming oil deolefination catalyst comprises the following steps: 3.01 g of cerium nitrate nonahydrate was dissolved in 10 g of water, added to 200 g of silica sol under stirring to make it completely dissolved, stirred in a 60°C water bath for 30 min, and dried in an oven at 80°C for 24 hours to obtain a modified silica sol with a cerium oxide content of 2%.

[0032] 7.5 g of sodium aluminate (Wt (Al2O3)% = 54%, Wt (Na2O)% = 40%) and 0.944 g of sodium hydroxide were weighed and dissolved in 360 g of deionized water. After stirring and dissolving, 14.87 g of hexamethyleneimine (99 wt%) and 70 g (85.7 wt%) of modified silica sol were added in sequence. After stirring for 30 min, a mixed gel was obtained. The gel was transferred to a polytetrafluoroethylene-lined reactor for dynamic crystallization at 150 ° C for 60 h. After the crystallization was completed, the temperature was lowered. The product was filtered, washed, dried and calcined to obtain a heteroatom Ce-Al-MCM-22 molecular sieve. Then, the heteroatom MCM-22 molecular sieve was exchanged with 0.2 mol / L ammonium sulfate solution for 2 h at a solid-liquid ratio of 1:10. After 3 exchanges, the product was filtered, washed, dried and calcined to obtain a heteroatom Ce-Al-MCM-22 molecular sieve.

[0033] 100 g of heteroatom Ce-Al-MCM-22 molecular sieve, 54 g of alumina and 0.87 g of sesbania powder were mixed evenly, and then 120 g of dilute nitric acid (mass concentration of 5%) was added and kneaded thoroughly to make it into a paste-like plastic. Cylindrical strips with a diameter of 1.5 mm were extruded on an extruder. The cylindrical strips were dried at 120°C for 16 hours and then calcined at 550°C in an air atmosphere for 4 hours to obtain the catalyst T-1 of the present invention.

[0034] BET and pyridine infrared characterization analysis showed that the external specific surface area of ​​Ce-Al-MCM-22 molecular sieve was 38% of the total specific surface area. Based on the pyridine infrared desorption results at 200°C, the ratio of B acid to L acid in T-1 catalyst was 1.6.

[0035] The method for removing olefins from reforming oil comprises the following steps: contacting the catalyst T-1 with the reforming oil containing olefins to carry out a deolefination reaction, wherein the bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: a temperature of 180°C, a pressure gauge pressure of 2.0 MPa, and a 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, i.e., 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 270 hours.

[0036] Embodiment 2: A method for preparing a reforming oil deolefination catalyst comprises the following steps: 5.61 g of lanthanum nitrate nonahydrate was dissolved in 120 g of water, added to 65.2 g of column chromatography silica gel under stirring to completely dissolve it, stirred in a 60°C water bath for 30 min, and dried in a 120°C oven for 10 hours to obtain modified silica gel with a lanthanum oxide content of 3.5%.

[0037] Weigh 33.3g of aluminum sulfate and 11.4g of sodium hydroxide and dissolve them in 396g of deionized water. After stirring and dissolving, add 17.02g of piperidine (99wt%) and 68.90g (87wt%) modified silica gel in turn. After stirring for 30min, a mixed gel is obtained. The gel is transferred to a polytetrafluoroethylene-lined reactor for dynamic crystallization at 140°C for 36h. After the crystallization is completed, the temperature is lowered. The product is filtered, washed, dried, and calcined to obtain a heteroatom La-Al-MCM-56 molecular sieve. Then, the heteroatom MCM-56 molecular sieve is exchanged with a 0.2mol / L ammonium sulfate solution for 2h at a solid-liquid ratio of 1:10. After 3 exchanges, the product is filtered, washed, dried, and calcined to obtain a heteroatom La-Al-MCM-56 molecular sieve.

[0038] 100 g of heteroatom La-Al-MCM-56 molecular sieve, 108.75 g of silicon oxide and 0.87 g of sesbania powder were mixed evenly, and then 200 g of dilute nitric acid (mass concentration of 5%) was added and kneaded thoroughly to make it into a paste-like plastic. Cylindrical strips with a diameter of 1.5 mm were extruded on an extruder. The cylindrical strips were dried at 120° C. for 16 hours and then calcined at 550° C. in an air atmosphere for 4 hours to obtain the catalyst T-2 of the present invention.

[0039] BET and pyridine infrared characterization analysis showed that the external specific surface area of ​​La-Al-MCM-56 molecular sieve was 48% of the total specific surface area. Based on the pyridine infrared desorption results at 200°C, the ratio of B acid to L acid in the T-2 catalyst was 2.2.

[0040] The method for removing olefins from reforming oil comprises the following steps: contacting the catalyst T-2 with the reforming oil containing olefins to carry out a deolefination reaction, wherein the bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: a temperature of 180°C, a pressure gauge pressure of 2.0 MPa, and a mass space velocity of 15 h -1 The catalyst was deactivated after 248 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 195 hours.

[0041] Embodiment 3: A method for preparing a reforming oil deolefination catalyst comprises the following steps: 3.23 g of boric acid was dissolved in 100 g of water, added to 65.2 g of white carbon black under stirring to make it completely dissolved, stirred in a 60°C water bath for 30 min, and dried in an oven at 180°C for 6 hours to obtain modified white carbon black with a boron oxide content of 3%.

[0042] Weigh 3.15g of sodium aluminate (Wt(Al2O3)%=54%, Wt(Na2O)%=40%) and 0.87g of sodium hydroxide and dissolve them in 360g of deionized water. After stirring and dissolving, add 25.2g of piperidine (99wt%) and 68.90g (87wt%) of modified white carbon black in turn. After stirring for 30min, a mixed gel is obtained. The gel is transferred to a polytetrafluoroethylene-lined reactor for dynamic crystallization at 150°C for 72h. After the crystallization is completed, the temperature is lowered. The product is filtered, washed, dried and calcined to obtain a heteroatom B-Al-MCM-22 molecular sieve. Then, the heteroatom MCM-22 molecular sieve is exchanged with 0.2mol / L ammonium sulfate solution for 2h at a solid-liquid ratio of 1:10. After 3 exchanges, the product is filtered, washed, dried and calcined to obtain a heteroatom B-Al-MCM-22 molecular sieve.

[0043] 100 g of heteroatom B-Al-MCM-22 molecular sieve, 63 g of amorphous silica-alumina and 0.87 g of sesbania powder were mixed evenly, and then 156 g of dilute nitric acid (mass concentration of 5%) was added and kneaded thoroughly to make it into a paste-like plastic. Cylindrical strips with a diameter of 1.5 mm were extruded on an extruder. The cylindrical strips were dried at 120° C. for 16 hours and then calcined at 550° C. in an air atmosphere for 4 hours to obtain the catalyst T-3 of the present invention.

[0044] BET and pyridine infrared characterization analysis showed that the external specific surface area of ​​B-Al-MCM-22 molecular sieve was 42% of the total specific surface area. Based on the pyridine infrared desorption results at 200°C, the ratio of B acid to L acid in the T-3 catalyst was 2.8.

[0045] The method for removing olefins from reforming oil comprises the following steps: contacting the catalyst T-3 with the reforming oil containing olefins to carry out a deolefination reaction, wherein the bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: a temperature of 180°C, a pressure gauge pressure of 2.0 MPa, and a mass space velocity of 15 h -1 The catalyst was deactivated after 320 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 270 hours.

[0046] Embodiment 4: A method for preparing a reforming oil deolefination catalyst comprises the following steps: 15.4 g of zinc nitrate hexahydrate was dissolved in 10 g of water, and added to 65.2 g of column chromatography silica gel under stirring to completely dissolve it. After stirring in a 60°C water bath for 30 min, it was placed in a 100°C oven and dried for 24 hours to obtain modified silica gel with a zinc oxide content of 7%.

[0047] Weigh 19g aluminum sulfate (99%) and 9.75g sodium hydroxide and dissolve them in 450g deionized water. After stirring and dissolving, add 34.7g cyclohexylamine (99wt%) and 68.90g (87wt%) modified silica gel in turn. After stirring for 30min, a mixed gel is obtained. The gel is transferred to a polytetrafluoroethylene-lined reactor for dynamic crystallization at 160°C for 68h. After the crystallization is completed, the temperature is lowered. The product is filtered, washed, dried, and calcined to obtain a heteroatom Zn-Al-MCM-49 molecular sieve. Then, the heteroatom MCM-49 molecular sieve is exchanged with a 0.2mol / L ammonium sulfate solution for 2h at a solid-liquid ratio of 1:10. After 3 exchanges, the product is filtered, washed, dried, and calcined to obtain a heteroatom Zn-Al-MCM-49 molecular sieve.

[0048] 100 g of heteroatom Zn-Al-MCM-49 molecular sieve, 54 g of alumina and 0.87 g of sesbania powder were mixed evenly, and then 120 g of dilute nitric acid (mass concentration of 5%) was added and kneaded thoroughly to make it into a paste-like plastic. Cylindrical strips with a diameter of 1.5 mm were extruded on an extruder. The cylindrical strips were dried at 120° C. for 16 hours and then calcined at 550° C. in an air atmosphere for 4 hours to obtain the catalyst T-4 of the present invention.

[0049] BET and pyridine infrared characterization analysis showed that the external specific surface area of ​​Zn-Al-MCM-49 molecular sieve was 34% of the total specific surface area. The ratio of B acid to L acid in T-4 catalyst was 2.6 according to the pyridine infrared desorption results at 200°C.

[0050] The method for removing olefins from reforming oil comprises the following steps: contacting the catalyst T-4 with the reforming oil containing olefins to carry out a deolefination reaction, wherein the bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: a temperature of 180°C, a pressure gauge pressure of 2.0 MPa, and a 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 186 hours.

[0051] Embodiment 5: A method for preparing a reforming oil deolefination catalyst comprises the following steps: 6.06 g of ferric nitrate nonahydrate was dissolved in 100 g of water, added to 65.2 g of white carbon black under stirring to make it completely dissolved, stirred in a 60°C water bath for 30 minutes, and dried in a 150°C oven for 10 hours to obtain modified white carbon black with an iron oxide content of 2%.

[0052] Weigh 3.639g pseudo-boehmite (Wt(Al2O3)%=69%) and 6.12g sodium hydroxide and dissolve them in 41.7g deionized water. After stirring and dissolving, add 88.4g tetraethylammonium hydroxide (25wt%) and 68.90g (87wt%) modified white carbon black in turn. After stirring for 30min, a mixed gel is obtained. The gel is transferred to a polytetrafluoroethylene-lined reactor for dynamic crystallization at 150°C for 60h. After the crystallization is completed, the temperature is lowered. The product is filtered, washed, dried and calcined to obtain a heteroatom Fe-Al-Beta molecular sieve. Then, the heteroatom Beta molecular sieve is exchanged with 0.2mol / L ammonium sulfate solution for 2h at a solid-liquid ratio of 1:10. After 3 exchanges, the product is filtered, washed, dried and calcined to obtain a heteroatom Fe-Al-Beta molecular sieve.

[0053] 100 g of heteroatom Fe-Al-Beta molecular sieve, 108 g of kaolin and 0.87 g of sesbania powder were mixed evenly, and then 190 g of dilute nitric acid (mass concentration of 5%) was added and kneaded thoroughly to make it into a paste-like plastic. Cylindrical strips with a diameter of 1.5 mm were extruded on an extruder. The cylindrical strips were dried at 120° C. for 16 hours and then calcined at 550° C. in an air atmosphere for 4 hours to obtain the catalyst T-5 of the present invention.

[0054] BET and pyridine infrared characterization analysis showed that the external specific surface area of ​​Fe-Al-Beta molecular sieve was 24% of the total specific surface area. Based on the pyridine infrared desorption results at 200°C, the ratio of B acid to L acid in T-5 catalyst was 0.6.

[0055] The method for removing olefins from reforming oil comprises the following steps: contacting the catalyst T-5 with the reforming oil containing olefins to carry out a deolefination reaction, wherein the bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: a temperature of 180°C, a pressure gauge pressure of 2.0 MPa, and a mass space velocity of 15 h -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 140 hours.

[0056] Embodiment 6: A method for preparing a reforming oil deolefination catalyst comprises the following steps: 0.87 g of phosphoric acid (85%) was dissolved in 70 g of water, and added to 65.2 g of column chromatography silica gel under stirring to completely dissolve it. After stirring in a 60°C water bath for 30 minutes, it was placed in a 160°C oven and dried for 12 hours to obtain modified silica gel with a phosphorus oxide content of 0.5%.

[0057] Weigh 13.6g of aluminum isopropoxide (99%) and 8.12g of sodium hydroxide and dissolve them in 287g of deionized water. After stirring and dissolving, add 48.8g of tetrapropylammonium hydroxide (25wt%) and 68.90g (87wt%) modified silica gel in turn. Stir for 30min to obtain a mixed gel. Transfer the gel to a polytetrafluoroethylene-lined reactor for dynamic crystallization at 170°C for 36h. After crystallization, cool the product to obtain a heteroatom P-Al-ZSM-5 molecular sieve by filtering, washing, drying and calcining. Then, the heteroatom ZSM-5 molecular sieve is exchanged with 0.2mol / L ammonium sulfate solution for 2h at a solid-liquid ratio of 1:10. After 3 exchanges, the product is filtered, washed, dried and calcined to obtain a heteroatom P-Al-ZSM-5 molecular sieve.

[0058] 100 g of heteroatom P-Al-ZSM-5 molecular sieve, 31.52 g of alumina and 0.87 g of sesbania powder were mixed evenly, and then 120 g of dilute nitric acid (mass concentration of 5%) was added and kneaded thoroughly to make it into a paste-like plastic. Cylindrical strips with a diameter of 1.5 mm were extruded on an extruder. The cylindrical strips were dried at 120° C. for 16 hours and then calcined at 550° C. in an air atmosphere for 4 hours to obtain the catalyst T-6 of the present invention.

[0059] BET and pyridine infrared characterization analysis showed that the external specific surface area of ​​P-Al-ZSM-5 molecular sieve was 24% of the total specific surface area. Based on the pyridine infrared desorption results at 200°C, the ratio of B acid to L acid in T-6 catalyst was 0.8.

[0060] The method for removing olefins from reforming oil comprises the following steps: contacting the catalyst T-6 with the reforming oil containing olefins to carry out a deolefination reaction, wherein the bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: a temperature of 180°C, a pressure gauge pressure of 2.0 MPa, and a mass space velocity of 15 h -1 The catalyst was deactivated after 120 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 110 hours.

[0061] Comparative Example 1: Catalyst C-1 was prepared according to the technical scheme with publication number CN112337505A, namely, CeY molecular sieve exchanged with metal cerium was uniformly mixed with MCM-41 molecular sieve, alumina, sesbania powder, citric acid and dilute nitric acid, kneaded, extruded into strip cylinders with a diameter of 1.5 mm, and calcined at 620°C for 2 hours to obtain catalyst C-1.

[0062] The method for removing olefins from reforming oil comprises the following steps: contacting the catalyst C-1 with the reforming oil containing olefins to carry out a deolefination reaction, wherein the bromine index of the raw material is 1000 mgBr / 100 g oil, and the reaction conditions include: a temperature of 180°C, a pressure of 2.0 MPa as measured by a pressure gauge, and a mass space velocity of 15 h -1 The catalyst was deactivated after 60 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 54 hours.

[0063] The embodiments of this specific implementation method are all preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A reforming oil deolefination catalyst, characterized in that: The deolefination catalyst comprises 10-80 parts by weight of an active component and 20-90 parts by weight of a binder; the active component is obtained by hydrothermal synthesis using an active silicon source, an aluminum source, an alkali source and a template as raw materials, and the active silicon source is prepared by loading a metal or non-metal auxiliary agent on the silicon source by an impregnation method.

2. The catalyst for deolefination of reformed oil according to claim 1, characterized in that: The preparation method of the active silicon source is as follows: based on the dry weight of the molecular sieve, 1% to 10% of the metal salt or non-metallic additive is dissolved in water, the silicon source is added, mixed evenly, and then dried at 80-200° C. for 10 to 24 hours to prepare the active silicon source.

3. A reforming oil deolefination catalyst according to claim 2, characterized in that: The metal salt is selected from one or a mixture of ferric chloride, zinc chloride, cerium nitrate, and lanthanum chloride; the non-metallic additive is selected from boric acid and / or phosphoric acid.

4. The catalyst for deolefination of reformed oil according to claim 2, characterized in that: The silicon source is selected from white carbon black, column chromatography silica gel, silica sol or a mixture of the two or more thereof.

5. The catalyst for deolefination of reformed oil according to claim 1, characterized in that: The aluminum source is selected from one or a mixture of pseudo-boehmite, aluminum sulfate, sodium aluminate, and aluminum isopropoxide.

6. The catalyst for deolefination of reformed oil according to claim 1, characterized in that: The template agent is selected from one or a mixture of hexamethyleneimine, piperidine, tetrapropylammonium hydroxide, tetraethylammonium hydroxide and cyclohexylamine.

7. The catalyst for deolefination of reformed oil according to claim 1, characterized in that: The alkali source is selected from sodium hydroxide and potassium hydroxide or a mixture of the two.

8. The catalyst for deolefination of reformed oil according to claim 1, characterized in that: The preparation method of the active component is as follows: an active silicon source, an alkali source, a template, an aluminum source and water are mixed to obtain an initial gel having the following molar ratio: SiO2 in the active silicon source: alkali source: template: Al2O3 in the aluminum source: H2O = 1: (0.03-0.28): (0.06-0.35): (0.025-0.05): (6-25), then hydrothermally crystallized at 120-180° C. for 20-72 hours, filtered, washed, dried and calcined to obtain a heteroatom molecular sieve, and then ammonium exchange is performed using an ammonium sulfate solution at a solid-liquid mass ratio of 1:8-10, and the active component is obtained after drying and calcining.

9. The catalyst for deolefination of reformed oil according to claim 1, characterized in that: The binder is selected from one or a mixture of silicon oxide, aluminum oxide, amorphous silicon aluminum, and kaolin.

10. A method for preparing the reformed oil deolefination catalyst according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: uniformly mixing a specified amount of active components and a binder, adding dilute nitric acid for kneading and extrusion, drying at 100-200°C for 1-10 hours, and calcining at 550°C for 4-10 hours to prepare a reforming oil deolefination catalyst.