Catalyst for removing olefin in aromatic hydrocarbon raw material as well as preparation method and application of catalyst

Abstract

The invention discloses a catalyst for removing olefin in an aromatic hydrocarbon raw material as well as a preparation method and application of the catalyst. The catalyst comprises an inorganic oxide and hydrogen type ion exchange resin compound, and the mass content of the inorganic oxide is 0.3%-30% based on the mass of the inorganic oxide and hydrogen type ion exchange resin compound. According to the present invention, with the catalyst, the macromolecular olefin in the aromatic hydrocarbon raw material can be efficiently removed, the problem of low olefin reduction efficiency in the current production is solved, and the problem that the treated material is not easily diffused and cannot run for a long time due to the easy swelling of the resin component during the treatment of the organic medium is solved.

Description

Technical Field

[0001] The present invention relates to the field of aromatic hydrocarbon production, and more specifically, to a catalyst for removing olefins from aromatic hydrocarbon raw materials, and a preparation method and application thereof. Background Art

[0002] The bromine index of aromatic raw materials from the hydrocracking unit is relatively high. In the production process of the aromatics complex unit, strict requirements are required for the bromine index of the target product C8 aromatics mixture generated by the reaction processes such as naphtha reforming, disproportionation and transalkylation, and isomerization, so that PX products can be obtained by adsorption separation. There are many impurities in each reaction product or intermediate, and its bromine index is relatively high. It can enter the downstream xylene tower after deolefination treatment. The C8 aromatics are separated at the top of the xylene tower, and the products at the bottom of the tower are converted into C8 aromatics target products by dedisproportionation and transalkylation units. Among them, the C8 aromatics at the top of the xylene tower require extremely low olefin content.

[0003] In industry, two technical routes, hydrogenation reaction and liquid-solid phase molecular sieve alkylation catalytic reaction, are used to saturate and remove most of the olefins in aromatics, thereby reducing their olefin content. Conventionally, clay and molecular sieve catalysts are used to reduce olefins. Because the olefin molecules in the raw materials are relatively large, including olefins in the C8 aromatics fraction and C9 and above aromatics fractions, and the catalyst is required to have stable olefin removal performance over a long period, resulting in high requirements for the catalyst.

[0004] CN102008976A, CN103041841B, CN102039160B and CN104907090A all use molecular sieves as the main active component of the deolefination catalyst. The deolefination catalyst disclosed in CN102008976A is based on ReUSY molecular sieve as the main active component, mordenite molecular sieve as the second active component, and alumina as a binder. CN103041841B discloses an aromatic non-hydrogenation deolefination catalyst prepared with Y molecular sieve. CN102039160B discloses a reformed oil deolefination catalyst, which uses 20-90 parts of molecular sieves and 10-80 parts of at least one selected from SiO2, Al2O3 or a mixture thereof, and a catalyst containing at least one metal selected from Mo, Zr, Nb or its oxide, at least one element selected from Cl, Br, S or its oxide, and at least one element selected from F, P or its oxide. CN104907090A discloses a catalyst for catalytic reforming oil refining and deolefination, comprising 30%-70% Al2O3 and 30%-70% molecular sieve.

[0005] Another way to remove olefins is the hydrogenation deolefination technology. The hydrogenation deolefination technology uses hydrogen to saturate the double bond reaction to selectively remove olefins in all fractions. At the same time, it will inevitably hydrogenate the unsaturated aromatic rings in some high-value aromatics to generate irreversible non-aromatics, thereby reducing the production capacity of the entire device. For example, CN1448474A uses precious metals as active metal components, alkali metals and alkaline earth metals as additives to suppress the performance of excessive hydrogenation, and there is a certain amount of aromatic loss. CN101260320A uses an eggshell-type method of optimizing metal distribution to reduce the performance of excessive hydrogenation. CN108636399A uses a non-precious metal hydrogenation method to remove olefins, which not only consumes hydrogen, but also requires reduction activation before the catalyst is used. The actual industrial application is difficult, and it is also inevitable that some aromatics will be lost during operation, and the activity is not easy to maintain stability.

[0006] In summary, the above methods use different catalysts to remove olefins from the entire fraction of aromatic feedstock, resulting in more aromatics involved in the reaction and high costs. Summary of the invention

[0007] The present invention provides a new catalyst for removing olefins from aromatic raw materials, and a preparation method and application thereof. The catalyst of the present invention can efficiently remove macromolecular olefins from aromatic raw materials, maximize the xylene aromatic content in the aromatic raw materials, and reduce the cost of removing olefins by alkylating carbon nine and above with olefins, thereby solving the problem of low olefin reduction efficiency in current production. At the same time, it also solves the problem that the resin component is easy to swell in the treatment of organic media, resulting in the difficulty of diffusion of the treated material and the inability to operate for a long time.

[0008] The first aspect of the present invention provides a catalyst for removing olefins from aromatic raw materials, wherein the catalyst comprises an inorganic oxide and a hydrogen-type ion exchange resin complex, wherein the mass content of the inorganic oxide is 0.3%-30%, preferably 1%-25%, based on the mass of the inorganic oxide and the hydrogen-type ion exchange resin complex.

[0009] According to the present invention, the catalyst contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups in the catalyst is 0.01-6.0 mmol / 100g.

[0010] According to the present invention, the inorganic oxide is at least one of silicon dioxide and aluminum oxide, preferably silicon dioxide. The inorganic oxide preferably contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups is 0.01-1.0 mmol / 100 g, preferably 0.01-0.7 mmol / 100 g.

[0011] According to the present invention, the hydrogen-type ion exchange resin is a hydrogen-type macroporous cation exchange resin containing a polystyrene group, and the hydrogen-type ion exchange resin is preferably at least one of NKC-9, D-001, and Amberlyst. The average particle size of the particles of the hydrogen-type ion exchange resin is above 100 μm, preferably 100-500 μm, and the average pore size is above 3 nm, preferably 4-12 nm.

[0012] According to the present invention, the hydrogen-type ion exchange resin preferably contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups is 0.05-5.0 mmol / 100 g.

[0013] According to the present invention, the swelling ratio of the catalyst to aromatic hydrocarbons is not more than 20%.

[0014] According to the present invention, in the catalyst, the inorganic oxide exists in the pores of the hydrogen-type ion exchange resin.

[0015] The second aspect of the present invention provides a method for preparing a catalyst for removing olefins from an aromatic hydrocarbon feedstock, comprising the following steps:

[0016] (1) mixing a sodium-type ion exchange resin with an organic solution of an inorganic oxide precursor, drying, and activating to obtain an inorganic oxide-resin composite precursor;

[0017] (2) The precursor obtained in step (1) is treated with an acidic solution, washed, and dried to obtain the catalyst.

[0018] According to the present invention, preferably, in step (1), the sodium type ion exchange resin is immersed in a low-carbon alcohol, filtered to obtain a resin mixture, and then mixed with an organic solution of an inorganic oxide precursor, dried, and activated to obtain an inorganic oxide-resin composite precursor. Further, the low-carbon alcohol is an alcohol with a carbon content of less than six, preferably selected from at least one of ethanol, propanol, methanol, and butanol. Further, the mass ratio of the sodium type ion exchange resin to the low-carbon alcohol is 0.2-2.0. Further, the impregnation conditions are: immersion at 25-35°C for 8-72 hours. The filtration is a conventional operation in the art, and its purpose is to remove excess low-carbon alcohol.

[0019] According to the present invention, in step (1), the sodium type ion exchange resin is a sodium type macroporous cation exchange resin containing polystyrene groups; preferably, the sodium type ion exchange resin contains sulfonic acid functional groups. Preferably, the sodium ion exchange resin is preferably selected from at least one of NKC-9, D-001, and Amberlyst. Preferably, the content of sulfonic acid functional groups in the sodium type ion exchange resin is 0.05-5.0mmol / 100g. The average particle size of the particles of the sodium type ion exchange resin is above 100μm, preferably 100-500μm, and the average pore size is above 3nm, preferably 4-12nm.

[0020] According to the present invention, in step (1), the organic solvent used in the organic solution of the inorganic oxide precursor is an organic substance stable at room temperature, such as at least one of halogenated hydrocarbons, hydrocarbons, nitrile compounds, and alcohols, preferably alcohols or one or more of alkanes and aromatic hydrocarbons with a boiling point greater than 59° C., and further preferably at least one of ethanol, methanol, n-heptane, or dichloromethane. The mass ratio of the organic solvent to the inorganic oxide precursor in terms of oxide is 1-100:1, preferably 1-50:1.

[0021] According to the present invention, in step (1), the inorganic oxide precursor is preferably at least one of a silicon oxide precursor or an aluminum oxide precursor, preferably a silicon oxide precursor. The silicon oxide precursor is selected from at least one of methyl silicate, ethyl silicate, butyl silicate, methyl silane, ethyl silane, monohalosilane, dihalosilane (such as dichlorodimethylsilane), trihalosilane or a mercapto-containing alkyl siloxane, preferably at least one of a mercapto-containing alkyl siloxane, wherein the alkyl group is preferably methyl, ethyl or propyl. The mercapto-containing alkyl siloxane is preferably at least one of (3-mercaptopropyl)-dimethoxysilane, γ-mercaptopropyldimethoxysilane, and methylmercaptotrimethoxysilane. The aluminum oxide precursor is selected from at least one of aluminum nitrate, aluminum chloride, and aluminum sulfate.

[0022] According to the present invention, in step (1), the mass ratio of the inorganic oxide precursor to the resin is 0.025-1.2 as oxide.

[0023] According to the present invention, in step (1), the mixing conditions are as follows: temperature is 0-90°C, time is 0.5-48h. The drying conditions are as follows: vacuum degree is not less than 0.01MPa, preferably 0.01-0.06MPa, temperature is 10-200°C, time is 0.5-48h.

[0024] According to the present invention, in step (1), the activation is to convert the inorganic oxide precursor into an inorganic oxide. When the inorganic oxide precursor is a silicon oxide precursor, it is preferably carried out by oxidation. Further, the activation is carried out in the presence of an oxidant, and the oxidant is selected from one or more of hydrogen peroxide, KMnO4, K2Cr2O7, (NH4)2Ce(NO3)6. The activation conditions are: the activation atmosphere is nitrogen or argon, the activation temperature is 20-110°C, and the activation time is 0.2-12h. When the inorganic oxide precursor is an aluminum oxide precursor, it is preferably carried out by hydrolysis.

[0025] According to the present invention, in step (1), after activation, the composite precursor is obtained by conventional filtration and washing, for example, washing with deionized water.

[0026] According to the present invention, in step (2), the inorganic oxide-resin composite precursor is treated with an acidic solution to convert the sodium type resin into the hydrogen type resin.

[0027] According to the present invention, in step (2), the inorganic oxide-resin composite precursor is treated with an acidic solution, wherein the acidic solution is a solution of at least one of hydrochloric acid, sulfuric acid, etc., and the concentration of the acidic solution is 0.01-2 mol / L. The amount of the acidic solution and the inorganic oxide-resin composite precursor is in the following relationship: relative to 1 g of the inorganic oxide-resin composite precursor, the amount of the acid is 0.01-20 mmol. The treatment conditions include: a temperature of 0-150° C. and a treatment time of 0.5-48 hours.

[0028] According to the present invention, in step (2), conventional filtration is first performed before washing. Washing is performed with deionized water until the pH value of the water at the outlet is above 5.0, preferably above 6.0, more preferably above 6.5, and not more than 7.0.

[0029] According to the present invention, in step (2), the drying conditions are as follows: vacuum degree is 0.01MPa-0.1MPa, drying temperature is 10-290°C, and drying time is 0.5-48 hours.

[0030] According to the present invention, in step (2), the obtained catalyst comprises a complex of an inorganic oxide and a hydrogen-type ion exchange resin, wherein the mass content of the inorganic oxide is 0.3%-30%, preferably 1%-25%, based on the mass of the complex of the inorganic oxide and the hydrogen-type ion exchange resin.

[0031] According to the present invention, the catalyst contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups in the catalyst is 0.01-6.0 mmol / 100g.

[0032] According to the present invention, the inorganic oxide is at least one of silicon dioxide and aluminum oxide, preferably silicon dioxide. The inorganic oxide preferably contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups is 0.01-1.0 mmol / 100 g, preferably 0.01-0.7 mmol / 100 g.

[0033] According to the present invention, the hydrogen-type ion exchange resin is a hydrogen-type macroporous cation exchange resin containing a polystyrene group, and the hydrogen-type ion exchange resin is preferably at least one of NKC-9, D-001, and Amberlyst. The average particle size of the particles of the hydrogen-type ion exchange resin is above 100 μm, preferably 100-500 μm, and the average pore size is above 3 nm, preferably 4-12 nm.

[0034] According to the present invention, the hydrogen-type ion exchange resin preferably contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups is 0.05-5.0 mmol / 100 g.

[0035] According to the present invention, the swelling ratio of the catalyst to aromatic hydrocarbons is not more than 20%.

[0036] According to the present invention, in the catalyst, the inorganic oxide exists in the pores of the hydrogen-type ion exchange resin.

[0037] The third aspect of the present invention provides a use of the above catalyst in removing olefins from aromatic feedstock.

[0038] According to the present invention, the application comprises: the aromatic hydrocarbon raw material is contacted with the above catalyst to react and obtain a product after olefin removal.

[0039] According to the present invention, the reaction conditions include: a mass space velocity of 0.1-20h -1 , temperature is 90-260°C, pressure is 0.2-5.0MPa; preferably, mass space velocity is 0.2-20h -1 , temperature is 90-260℃, reaction pressure is 0.3-5.0MPa.

[0040] According to the present invention, the aromatic hydrocarbon raw material can be derived from at least one of naphtha reforming, catalytic cracking and other processes. The aromatic hydrocarbons mentioned herein refer to at least one of benzene, toluene and other alkyl-containing monocyclic or bicyclic aromatic hydrocarbons, such as xylene, trimethylbenzene, ethylbenzene, propylbenzene, methylethylbenzene, diethylbenzene, tetramethylbenzene, butylbenzene, ethylxylene, naphthalene, methylnaphthalene, etc. In the aromatic hydrocarbon raw material, the mass content of aromatic hydrocarbons is above 50%, preferably above 80%.

[0041] According to the present invention, the bromine index of the aromatic hydrocarbon raw material is not less than 200 mgBr / 100g, preferably 200-5000 mgBr / 100g, and more preferably 700-2500 mgBr / 100g.

[0042] According to the present invention, the bromine index of the product after olefin removal is at least 80 mgBr / 100 g lower than the bromine index of the aromatic feedstock, preferably at least 100 mgBr / 100 g lower; preferably, the bromine index of the product after olefin removal is at least 30% of the bromine index in the aromatic feedstock; further preferably, the bromine index of the product after olefin removal is less than 5% of the bromine index in the aromatic feedstock.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] The catalyst for removing olefins from aromatic raw materials provided by the present invention overcomes the problem of diffusion obstruction of macromolecular olefins through macroporous active centers, removes olefins efficiently, maximizes the reaction between olefins and aromatics in aromatic raw materials, and solves the problem of low olefin reduction efficiency in current production. The catalyst prepared by the present invention has a low initial reaction temperature, not only efficiently removes olefin impurities, but also solves the problem of expansion of ion exchange resins, and can be used for large-scale production. DETAILED DESCRIPTION

[0045] The technical solution of the present invention is described in detail below in conjunction with embodiments.

[0046] In the present invention, the content of sulfonic acid functional groups in the catalyst is determined by a sodium hydroxide titration method. 50 g of the catalyst is added with 200 g of water, and titrated with 0.1 mol / L sodium hydroxide under stirring. The titration amount when the pH value reaches 7 is measured with a pH meter, and then the molar number of the sulfonic acid group is calculated.

[0047] In the present invention, the swelling rate of the catalyst obtained in each example to aromatic hydrocarbons is tested by taking 30g of the catalyst and placing it in a 500mL measuring cylinder at 30°C, adding 400mL of toluene, and treating it under closed conditions for 48 hours, and then calculating based on the volume change of the catalyst.

[0048] In the present invention, the swelling ratio of the catalyst to aromatic hydrocarbons is (V 催化剂48h -V 催化剂初始 ) / V 催化剂初始 ×100%;

[0049] Among them, V 催化剂48h It represents the volume of the catalyst after swelling treatment for 48 hours, in mL, V 催化剂初始 It represents the initial volume of the catalyst before swelling treatment, in mL.

[0050] [Example 1]

[0051] (1) 100 g of sodium-type ion exchange resin NKC-9 (sulfonic acid group content of 3.0 mmol / 100 g, average pore size of 5.00 nm, average particle size of 200 μm) was immersed in 200 g of ethanol for 48 hours, and then the excess ethanol was removed by filtration to obtain a resin NKC-9 mixture;

[0052] 30 g of ethyl orthosilicate ethanol solution (containing 70 wt% of ethyl orthosilicate) was mixed with the above-obtained resin NKC-9 mixture, and the mixture was soaked at 25° C. for 48 hours, and dried at 60° C. for 6 hours under a vacuum degree of 0.05 MPa to remove the ethanol, and then 100 g of water was added under a nitrogen atmosphere at a temperature of 50° C., and 300 g of a 3% hydrogen peroxide solution was added dropwise, and the mixture was stirred for 6 hours, filtered and washed to obtain a SiO2-NKC-9 composite precursor;

[0053] (2) The above-mentioned complex precursor was dissolved in 2 mol / L sulfuric acid solution (10 mmol 酸 / 1g 复合物前体 ) at 40°C for 6 hours, filtered, washed with deionized water until the pH of the filtrate is 6.5, then repeated twice, and finally vacuum dried at 50°C for 24 hours to obtain catalyst A.

[0054] The content of sulfonic acid functional groups in the catalyst A is 2.1 mmol / 100 g. The mass content of silicon dioxide in the catalyst A is 25%, and the average pore size of hydrogen-type ion exchange resin NKC-9 is 4.2 nm. The swelling rate of the catalyst A to aromatic hydrocarbons is 8.2%.

[0055] Catalyst Evaluation:

[0056] Take 5g of catalyst A, use aromatic hydrocarbon feedstock containing styrene (styrene mass content is 2010mgBr / 100g according to bromine index, xylene mass content is 50.1%, and carbon nine aromatic hydrocarbon mass content is 49.6%), and heat at a raw material mass space velocity of 6h -1 , 1.9MPa, the reaction was evaluated at a temperature of 80°C. After 10 hours from the start, the mass content of styrene at the outlet was 0.3mgBr / 100g (including 49.9% xylene content, 50.1% carbon nine aromatics and above, including olefins). After 300h, the mass content of styrene at the outlet was 1.0mgBr / 100g (including 49.9% xylene content, 50.1% carbon nine aromatics and above, including olefins).

[0057] [Example 2]

[0058] (1) 100 g of sodium-type ion exchange resin D-001 (sulfonic acid content 1.5 mmol / 100 g, average pore size 5.6 nm, average particle size 200 μm) was immersed in 150 g of ethanol for 24 hours, and then the excess ethanol was removed by filtration to obtain a resin D-001 mixture;

[0059] 50 g of an ethanol solution of aluminum chloride (containing 20 wt% aluminum chloride) was mixed with the resin D-001 mixture, and the mixture was soaked at 30° C. for 24 hours, and dried at 70° C. for 4 hours under a vacuum degree of 0.06 MPa to remove the ethanol, and then 500 g of a 3% sodium carbonate solution was added dropwise at 50° C., and the mixture was stirred for 3 hours, filtered and washed to obtain an Al2O3-D-001 composite precursor;

[0060] (2) The above complex precursor was dissolved in 2 mol / L hydrochloric acid solution (0.2 mmol 酸 / 1g 复合物前体 ) at 20°C for 3 hours, filtered, washed according to Example 1 until the pH of the filtrate is 6.2, then repeated once, and finally dried in vacuo at 50°C for 24 hours to obtain Catalyst B.

[0061] The content of sulfonic acid functional groups in the catalyst B is 1.1 mmol / 100 g. The mass content of aluminum oxide in the catalyst B is 18%, and the average pore size of hydrogen-type ion exchange resin D-001 is 4.9 nm. The swelling rate of the catalyst B to aromatic hydrocarbons is 12.2%.

[0062] Catalyst Evaluation:

[0063] Take 5g of catalyst B, use aromatic hydrocarbon material containing styrene (styrene mass content styrene mass content calculated by bromine index 800mgBr / 100g, xylene content 50.1%, carbon nine aromatic hydrocarbon content 49.7%), at a raw material mass space velocity of 4h -1 , under 1.9 MPa, the reaction was evaluated at a temperature of 120°C. Ten hours after the start, the outlet styrene content was 0.3 mgBr / 100 g (including 49.8% xylene content and 50.2% C9 aromatics and above, including olefins).

[0064] [Example 3]

[0065] (1) 100 g of sodium-type ion exchange resin D-001 (sulfonic acid content 1.5 mmol / 100 g, average particle size 500 μm, average pore size 6.0 nm) was immersed in 110 g of methanol for 24 hours, and then the excess methanol was removed by filtration to obtain a resin D-001 mixture;

[0066] The resin D-001 mixture was mixed with 30 g of aluminum nitrate methanol solution (containing 8.5% aluminum nitrate), soaked at 35° C. for 8 hours, dried at 40° C. for 4 hours under a vacuum degree of 0.07 MPa to remove methanol, and then 500 g of 3% sodium carbonate solution was added dropwise at 50° C., stirred for 3 hours, filtered and washed to obtain an Al2O3-D-001 composite precursor;

[0067] (2) The above-mentioned complex precursor was dissolved in 2 mol / L sulfuric acid solution (15 mmol 酸 / 1g 复合物前体 ) at 30°C for 8 hours, filtered, and washed according to the washing method of Example 1 until the pH of the filtrate is 6.0, then repeated once, and finally vacuum dried at 50°C for 24 hours to obtain Catalyst C.

[0068] The content of sulfonic acid functional groups in the catalyst C is 1.0 mmol / 100 g. The mass content of aluminum oxide in the catalyst C is 12%, and the average pore size of hydrogen-type ion exchange resin D-001 is 5.5 nm. The swelling rate of the catalyst C to aromatic hydrocarbons is 7.2%.

[0069] Catalyst Evaluation:

[0070] Take 5g of catalyst C, use aromatic materials containing hexene-1 and p-methylstyrene (hexene-1 mass content contains 708mgBr / 100g according to bromine index, p-methylstyrene mass content contains 630mgBr / 100g according to bromine index, wherein the benzene content is 12.3%, the toluene content is 28.1%, the non-aromatic material is 10.8%, the xylene content is 23.1%, the ethylbenzene content is 2.0%, and the carbon nine aromatics and above content is 24.7%), and heat the mixture at a mass space velocity of 3.0h -1 , 1.9 MPa, and the reaction was evaluated at a temperature of 130°C. Ten hours after the start, the mass content of hexene-1 at the outlet was 3.0 mgBr / 100 g in terms of bromine index, and the mass content of p-methylstyrene was 5.0 mgBr / 100 g in terms of bromine index.

[0071] [Example 4]

[0072] (1) 30 g of sodium-type Amberlyst (sulfonic acid content 0.5 mmol / 100 g, average particle size 200 μm, average pore size 5.2 nm) was immersed in 50 g of ethanol for 2 hours, and then the excess ethanol was removed by filtration to obtain an Amberlyst mixture;

[0073] The above mixture was mixed with 20g of dichlorodimethylsilane n-heptane solution (containing 30.2% silane), soaked at 30°C for 8 hours, filtered, added with 100g of water, slowly added with stirring at 28°C under nitrogen atmosphere, such as 1.5% potassium permanganate aqueous solution, until the solution was then subjected to vacuum degree of 0.08MPa at 80°C to remove butanol and methanol for 7 hours. Then, in an argon atmosphere and temperature of 20°C, 600g of 1% potassium permanganate solution was added dropwise, stirred for 8 hours, filtered and washed, to obtain a SiO2-Amberlyst composite precursor;

[0074] (2) The above-mentioned complex precursor was dissolved in 2 mol / L sulfuric acid solution (15 mmol 酸 / 1g 复合物前体 ) at 40°C for 2 hours, filtered, and washed in the manner of Example 1 until the pH of the filtrate is 5.6, then repeated twice, and finally vacuum dried at 30°C for 24 hours to obtain catalyst D.

[0075] The content of sulfonic acid functional groups in the catalyst D is 0.3 mmol / 100 g. The mass content of silicon dioxide in the catalyst D is 12%, and the pore size of hydrogen-type Amberlyst resin is 5.1 nm. The swelling rate of the catalyst D to aromatic hydrocarbons is 15.1%.

[0076] Catalyst Evaluation:

[0077] Take 5g of catalyst D, use aromatic hydrocarbon materials containing hexene-1 and styrene (hexene-1 mass content contains 200mgBr / 100g based on bromine index, styrene mass content contains 300mgBr / 100g based on bromine index, wherein the benzene content is 10.3%, the toluene content is 23.1%, the non-aromatic hydrocarbon material is 12.8%, the xylene content is 25.3%, the ethylbenzene content is 2.3%, and the carbon nine aromatic hydrocarbon content and above is 26.2%), at a raw material mass space velocity of 2.00h -1 , 1.9 MPa, and the reaction was evaluated at a temperature of 150°C. Ten hours after the start, the mass content of hexene-1 at the outlet contained 6.0 mgBr / 100g as calculated by the bromine index, and the mass content of styrene contained 1.5 mgBr / 100g as calculated by the bromine index.

[0078] [Example 5]

[0079] (1) 100 g of sodium-type ion exchange resin NKC-9 (sulfonic acid content 3.0 mmol / 100 g, average particle size 500 μm, average pore size 3.5 nm) was immersed in 200 g of ethanol for 48 hours, and then the excess ethanol was removed by filtration to obtain a resin NKC-9 mixture;

[0080] The resin NKC-9 mixture was mixed with 28g of a dichloromethane solution of methyl orthosilicate (containing 70% methyl silicate), soaked at 30°C for 48 hours, dried at 60°C for 8 hours under a vacuum degree of 0.05MPa to remove ethanol, 100g of water was added, and 30g of 20% hydrogen peroxide was slowly added dropwise at 28°C in a nitrogen atmosphere while stirring, stirred for 4 hours, filtered and washed to obtain a SiO2-NKC-9 composite precursor;

[0081] (2) The above-mentioned complex precursor was dissolved in 1 mol / L sulfuric acid solution (19 mmol 酸 / 1g 复合物前体 ) at 20°C for 3 hours, filtered, washed according to Example 1 until the pH of the filtrate is 6.0, then repeated twice, and finally vacuum dried at 50°C for 24 hours to obtain Catalyst E.

[0082] The content of sulfonic acid functional groups in the catalyst E is 2.3 mmol / 100 g. The mass content of silicon dioxide in the catalyst E is 10%, and the average pore size of hydrogen-type ion exchange resin NKC-9 is 3.4 nm. The swelling rate of the catalyst E to aromatic hydrocarbons is 6.2%.

[0083] Catalyst Evaluation:

[0084] Take 5g of catalyst E, use aromatic hydrocarbon material containing styrene (styrene mass content is calculated by bromine index 2010mgBr / 100g, xylene content 50.1%, carbon nine aromatic hydrocarbon content 49.6%), at a raw material mass space velocity of 6h -1 , under 1.9 MPa, the reaction was evaluated at a temperature of 80°C. Ten hours after the start, the mass content of styrene at the outlet was 0.2 mgBr / 100 g (including 49.9% xylene content and 50.1% C9 aromatics and above, including olefins) based on the bromine index.

[0085] [Example 6]

[0086] (1) 100 g of sodium-type ion exchange resin NKC-9 (sulfonic acid content 3.0 mmol / 100 g, average particle size 500 μm, average pore size 3.5 nm) was immersed in 200 g of ethanol for 20 hours, and then the excess ethanol was removed by filtration to obtain a resin NKC-9 mixture;

[0087] 32g of ethanol solution of (3-mercaptopropyl)-trimethoxysilane (containing 70% silane) and the above obtained resin NKC-9 mixture were mixed, soaked at 27°C for 48 hours, dried at 20°C under vacuum of 0.01MPa for 5 hours to remove ethanol, 100g of water was added, and 200g of 2% potassium permanganate was slowly added dropwise at 28°C under nitrogen atmosphere while stirring, and after stirring for 8 hours, filtered and washed to obtain a SiO2-NKC-9 composite precursor;

[0088] (2) The above complex precursor was dissolved in 1 mol / L sulfuric acid solution (0.02 mmol 酸 / 1g 复合物前体 ) at 20°C for 3 hours, filtered, and washed in the manner of Example 1 until the pH of the filtrate is 6.0, then repeated twice, and finally vacuum dried at 50°C for 24 hours to obtain Catalyst F.

[0089] The content of sulfonic acid functional groups in the catalyst F is 3.6 mmol / 100 g. The mass content of silicon dioxide in the catalyst F is 8%, and the average pore size of the hydrogen-type ion exchange resin NKC-9 is 3.2 nm. The swelling rate of the catalyst F to aromatic hydrocarbons is 7.0%.

[0090] Catalyst Evaluation:

[0091] Take 5g of catalyst F, use aromatic hydrocarbon material containing styrene (styrene mass content is calculated by bromine index 2010mgBr / 100g, xylene content 50.1%, carbon nine aromatic hydrocarbon content 49.6%), and heat for 6h. -1 , under 1.9 MPa, the reaction was evaluated at a temperature of 80°C. Ten hours after the start, the mass content of styrene at the outlet was 0.1 mgBr / 100 g (including 49.9% xylene content and 50.1% C9 aromatics and above, including olefins) based on the bromine index.

[0092] [Example 7]

[0093] (1) 100 g of sodium-type ion exchange resin NKC-9 (sulfonic acid group content of 3.0 mmol / 100 g, average pore size of 5.0 nm, average particle size of 200 μm) was mixed with 200 g of ethyl orthosilicate ethanol solution (containing 21 g of ethyl orthosilicate), soaked at 31° C. for 48 hours, dried at 60° C. for 6 hours under a vacuum degree of 0.05 MPa to remove ethanol, and then 450 g of 1.5% hydrogen peroxide solution was added dropwise under a nitrogen atmosphere at a temperature of 50° C., stirred for 6 hours, filtered and washed to obtain a SiO2-NKC-9 composite precursor;

[0094] (2) The above-mentioned complex precursor was dissolved in 2 mol / L sulfuric acid solution (7 mmol 酸 / 1g 复合物前体 ) at 40°C for 6 hours, filtered, and washed in the manner of Example 1 until the pH of the filtrate is 6.3, then repeated twice, and finally vacuum dried at 50°C for 24 hours to obtain Catalyst G.

[0095] The content of sulfonic acid functional groups in the catalyst G is 1.2 mmol / 100 g. The mass content of silicon dioxide in the catalyst G is 25%, and the average pore size of the hydrogen-type ion exchange resin NKC-9 is 4.8 nm. The swelling rate of the catalyst G to aromatic hydrocarbons is 15%.

[0096] Catalyst Evaluation:

[0097] Take 5g of catalyst G, use aromatic hydrocarbon materials containing styrene (the mass content of styrene is calculated by bromine index of 2010mgBr / 100g, the mass content of xylene is 50.1%, and the mass content of carbon nine aromatic hydrocarbons is 49.6%), and heat the raw material at a mass space velocity of 6h -1 , under 1.9 MPa, the reaction was evaluated at a temperature of 80°C. Ten hours after the start, the mass content of styrene at the outlet was 5.0 mgBr / 100 g (including 49.9% xylene content and 50.1% C9 aromatics and above, including olefins) based on the bromine index.

[0098] [Example 8]

[0099] (1) 100 g of sodium-type ion exchange resin NKC-9 (sulfonic acid content 3.0 mmol / 100 g, average particle size 500 μm, average pore size 3.5 nm) was immersed in 200 g of ethanol for 20 hours, and then the excess ethanol was removed by filtration to obtain a resin NKC-9 mixture;

[0100] 100 g of a n-heptane solution of γ-mercaptopropyldimethoxysilane (containing 20% ​​silane) was mixed with the above-obtained resin NKC-9 mixture, and the mixture was soaked at 27° C. for 48 hours, and dried at 20° C. for 5 hours under a vacuum of 0.01 MPa to remove ethanol, and 100 g of water was added, and 200 g of 2% potassium permanganate was slowly added dropwise at 28° C. under a nitrogen atmosphere, and the mixture was stirred for 8 hours, and then filtered and washed to obtain a SiO2-NKC-9 complex precursor;

[0101] (2) The above complex precursor was dissolved in 1 mol / L sulfuric acid solution (0.02 mmol 酸 / 1g 复合物前体 )500g at 20°C for 3 hours, filtered, washed according to Example 1 until the pH of the filtrate is 6.0, then repeated twice, and finally vacuum dried at 50°C for 24 hours to obtain Catalyst H.

[0102] The content of sulfonic acid functional groups in the catalyst H is 3.6 mmol / 100 g. The mass content of silicon dioxide in the catalyst H is 8%, and the average pore size of hydrogen-type ion exchange resin NKC-9 is 3.1 nm. The swelling rate of the catalyst H to aromatic hydrocarbons is 5.7%.

[0103] Catalyst Evaluation:

[0104] Take 5g of catalyst H, use aromatic hydrocarbon material containing styrene (styrene mass content is calculated by bromine index 2010mgBr / 100g, xylene content 50.1%, carbon nine aromatic hydrocarbon content 49.6%), and heat for 6h. -1 , 1.9MPa, the reaction was evaluated at a temperature of 80°C. After 10 hours from the start, the mass content of styrene at the outlet was 0.5mgBr / 100g (including 49.8% xylene, 50.2% carbon nine aromatics and above, including olefins). After 300h, the mass content of styrene at the outlet was 0.5mgBr / 100g (including 49.8% xylene, 50.2% carbon nine aromatics and above, including olefins).

[0105] [Example 8]

[0106] (1) 100 g of sodium-type ion exchange resin NKC-9 (sulfonic acid content 3.0 mmol / 100 g, average particle size 500 μm, average pore size 3.5 nm) was immersed in 200 g of ethanol for 20 hours, and then the excess ethanol was removed by filtration to obtain a resin NKC-9 mixture;

[0107] 120 g of a hexane solution of methylmercaptotrimethoxysilane (containing 30% silane) was mixed with the above-obtained resin NKC-9 mixture, and the mixture was soaked at 27° C. for 48 hours, and dried at 20° C. for 5 hours under a vacuum of 0.01 MPa to remove ethanol, and 100 g of water was added. Under a nitrogen atmosphere at 28° C., 200 g of 2% potassium permanganate was slowly added dropwise while stirring. After stirring for 8 hours, the mixture was filtered and washed to obtain a SiO2-NKC-9 complex precursor.

[0108] (2) The above complex precursor was dissolved in 1 mol / L sulfuric acid solution (0.02 mmol 酸 / 1g 复合物前体 )500g at 20°C for 3 hours, filtered, washed according to Example 1 until the pH of the filtrate is 6.0, then repeated twice, and finally vacuum dried at 50°C for 24 hours to obtain Catalyst F.

[0109] The content of sulfonic acid functional groups in the catalyst F is 3.3 mmol / 100 g. The mass content of silicon dioxide in the catalyst F is 8%, and the average pore size of the hydrogen-type ion exchange resin NKC-9 is 3.3 nm. The swelling rate of the catalyst F to aromatic hydrocarbons is 6.5%.

[0110] Catalyst Evaluation:

[0111] Take 5g of catalyst F, use aromatic hydrocarbon material containing styrene (styrene mass content is calculated by bromine index 2010mgBr / 100g, xylene content 50.1%, carbon nine aromatic hydrocarbon content 49.6%), and heat for 6h. -1 , 1.9MPa, the reaction was evaluated at a temperature of 80°C. After 10 hours from the start, the mass content of styrene at the outlet was 0.3mgBr / 100g (including 49.9% xylene content, 50.1% carbon nine aromatics and above, including olefins). After 300h, the mass content of styrene at the outlet was 0.4mgBr / 100g (including 49.9% xylene content, 50.1% carbon nine aromatics and above, including olefins).

[0112] [Comparative Example 1]

[0113] (1) 75 g of sodium-type ion exchange resin NKC-9 (sulfonic acid group content of 3.0 mmol / 100 g, average pore size of 5.0 nm, average particle size of 200 μm) was mixed with silica particles (average particle size of 200 μm), stirred for 7 hours, and then filtered and washed to obtain a SiO2-NKC-9 mixture precursor;

[0114] (2) The above mixture precursor was dissolved in 2 mol / L sulfuric acid solution (10 mmol 酸 / 1g 前体 ) at 40°C for 6 hours, filtered, and washed in the manner of Example 1 until the pH of the filtrate is 6.5, then repeated twice, and finally vacuum dried at 50°C for 24 hours to obtain catalyst DA1.

[0115] The content of sulfonic acid functional groups in the catalyst DA1 is 2.1 mmol / 100 g. The mass content of silicon dioxide in the catalyst DA1 is 25%. The swelling rate of the catalyst DA1 to aromatic hydrocarbons is 55%.

[0116] Catalyst Evaluation:

[0117] Take 5g of catalyst DA1, use aromatic hydrocarbon materials containing styrene (styrene mass content is 2010mgBr / 100g according to bromine index, of which xylene mass content is 50.1%, and carbon nine aromatic hydrocarbon mass content is 49.6%), and heat the raw material mass space velocity at 6h -1, 1.9MPa, the reaction was evaluated at a temperature of 80°C. After 10 hours from the start, the mass content of styrene at the outlet was 520mgBr / 100g (including 50.0% xylene, 50.0% carbon nine aromatics and above, including olefins) in terms of bromine index. After 100 hours from the start, the mass content of styrene at the outlet was 1501mgBr / 100g (including 50.0% xylene, 50.0% carbon nine aromatics and above, including olefins) in terms of bromine index.

[0118] [Comparative Example 2]

[0119] (1) 100 g of hydrogen-type ion exchange resin NKC-9 (sulfonic acid group content of 3.0 mmol / 100 g, average pore size of 5.0 nm, average particle size of 200 μm) was immersed in 200 g of ethanol for 48 hours, and then the ethanol was filtered to obtain a resin NKC-9 mixture;

[0120] 30 g of ethyl orthosilicate ethanol solution (containing ethyl silicate 70 wt%) was mixed with the above obtained resin NKC-9 mixture, soaked at 25° C. for 48 hours, dried at 60° C. for 6 hours under a vacuum degree of 0.05 MPa to remove ethanol, and then 300 g of 3% hydrogen peroxide solution was added dropwise under a nitrogen atmosphere at a temperature of 50° C., stirred for 6 hours, filtered and washed to obtain a SiO2-NKC-9 composite precursor;

[0121] (2) The composite precursor was dried under vacuum at 50° C. for 24 hours to obtain catalyst DA2.

[0122] The content of sulfonic acid functional groups in the catalyst DA2 is 1.2 mmol / 100 g. The mass content of silicon dioxide in the catalyst DA2 is 27%, and the average pore size of hydrogen-type ion exchange resin NKC-9 is 3.3 nm. The swelling rate of the catalyst DA2 to aromatic hydrocarbons is 21%.

[0123] Catalyst Evaluation:

[0124] Take 5g of catalyst DA2, use aromatic hydrocarbon materials containing styrene (styrene mass content is calculated by bromine index of 2010mgBr / 100g, of which xylene mass content is 50.1%, and carbon nine aromatic hydrocarbon mass content is 49.6%), and heat the raw material mass space velocity at 6h -1, 1.9MPa, the reaction was evaluated at a temperature of 80°C. After 10 hours from the start, the mass content of styrene at the outlet was 880mgBr / 100g (including 50.1% xylene, 49.9% carbon nine aromatics and above, including olefins) according to the bromine index. After 100 hours from the start, the mass content of styrene at the outlet was 1220mgBr / 100g (including 50.0% xylene, 50.0% carbon nine aromatics and above, including olefins) according to the bromine index.

[0125] The above describes the specific implementation of the present invention in detail, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A catalyst for removing olefins from aromatic raw materials, wherein: The catalyst comprises a composite of an inorganic oxide and a hydrogen-type ion exchange resin, wherein the mass content of the inorganic oxide is 0.3%-30%, preferably 1%-25%, based on the mass of the composite of the inorganic oxide and the hydrogen-type ion exchange resin.

2. The catalyst according to claim 1, characterized in that: The catalyst contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups in the catalyst is 0.01-6.0 mmol / 100g.

3. The catalyst according to claim 1, characterized in that: The inorganic oxide is at least one of silicon dioxide and aluminum oxide, preferably silicon dioxide; the inorganic oxide preferably contains a sulfonic acid functional group, wherein the content of the sulfonic acid functional group is 0.01-1.0 mmol / 100g; And / or, the hydrogen-type ion exchange resin is a hydrogen-type macroporous cation exchange resin containing polystyrene groups, selected from at least one of NKC-9, D-001, and Amberlyst; preferably, the hydrogen-type ion exchange resin contains sulfonic acid functional groups, wherein the content of the sulfonic acid functional groups is 0.05-5.0 mmol / 100g.

4. The catalyst according to claim 1, characterized in that: The swelling rate of the catalyst to aromatic hydrocarbons is not more than 20%.

5. A method for preparing a catalyst for removing olefins from aromatic raw materials, comprising the following steps: (1) mixing a sodium-type ion exchange resin with an organic solution of an inorganic oxide precursor, drying, and activating to obtain an inorganic oxide-resin composite precursor; (2) The precursor obtained in step (1) is treated with an acidic solution, washed, and dried to obtain the catalyst.

6. The preparation method according to claim 5, characterized in that: In step (1), the sodium type ion exchange resin is immersed in low carbon alcohol, filtered to obtain a resin mixture, and then mixed with an organic solution of an inorganic oxide precursor, dried, and activated to obtain an inorganic oxide-resin composite precursor.

7. The preparation method according to claim 6, characterized in that: The low-carbon alcohol is an alcohol with a carbon content of less than 6, preferably at least one selected from ethanol, propanol, methanol, and butanol; And / or, the mass ratio of the sodium type ion exchange resin to the low-carbon alcohol is 0.2-2.0; And / or, the immersion conditions are: immersion at 25-35° C. for 8-72 hours.

8. The preparation method according to claim 5, characterized in that: In step (1), the sodium type ion exchange resin is a sodium type macroporous cation exchange resin containing a polystyrene group; preferably, the sodium type ion exchange resin contains a sulfonic acid functional group; preferably, the sodium ion exchange resin is preferably selected from at least one of NKC-9, D-001, and Amberlyst; preferably, the content of the sulfonic acid functional group in the sodium type ion exchange resin is 0.05-5.0mmol / 100g.

9. The preparation method according to claim 5, characterized in that: In step (1), the organic solvent used in the organic solution of the inorganic oxide precursor is an organic substance that is stable at room temperature, and is selected from at least one of halogenated hydrocarbons, hydrocarbons, nitrile compounds, and alcohols, preferably alcohols or one or more of alkanes and aromatic hydrocarbons with a boiling point greater than 59° C., and further preferably at least one of ethanol, methanol, n-heptane, or dichloromethane; And / or, the mass ratio of the organic solvent to the inorganic oxide precursor is 1-100:1 in terms of oxide.

10. The preparation method according to claim 5, characterized in that: In step (1), the inorganic oxide precursor is at least one of a silicon oxide precursor or an aluminum oxide precursor, preferably a silicon oxide precursor; Preferably, the silicon oxide precursor is selected from at least one of methyl silicate, ethyl silicate, butyl silicate, methyl silane, ethyl silane, monohalosilane, dihalosilane, trihalosilane or alkyl siloxane containing a mercapto group, preferably at least one of alkyl siloxane containing a mercapto group, wherein the alkyl group is preferably methyl, ethyl or propyl; Preferably, the aluminum oxide precursor is selected from at least one of aluminum nitrate, aluminum chloride, and aluminum sulfate; And / or, the mass ratio of the inorganic oxide precursor to the resin is 0.025-1.2 in terms of oxide.

11. The preparation method according to claim 5, characterized in that: In step (1), the mixing conditions are as follows: temperature is 0-90° C., and time is 0.5-48 h; And / or, in step (1), the drying conditions are as follows: vacuum degree not less than 0.01 MPa, preferably 0.01-0.06 MPa, temperature 10-200°C, time 0.5-48h; And / or, in step (1), the activation is to convert the inorganic oxide precursor into an inorganic oxide.

12. The preparation method according to claim 5, characterized in that: In step (2), the acid solution treatment is to convert the sodium type resin into the hydrogen type resin; Preferably, the acidic solution is a solution of at least one of hydrochloric acid and sulfuric acid; Preferably, the concentration of the acidic solution is 0.01-2 mol / L; Preferably, the amount of the acidic solution and the inorganic oxide-resin composite precursor is in the following relationship: relative to 1 g of the inorganic oxide-resin composite precursor, the amount of the acid is 0.01-20 mmol; Preferably, the treatment conditions include: a temperature of 0-150°C and a treatment time of 0.5-48 hours; And / or, in step (2), the drying conditions are as follows: vacuum degree is 0.01MPa-0.1MPa, temperature is 10-290°C, and time is 0.5-48 hours.

13. The preparation method according to claim 5, characterized in that: In step (2), the washing is performed with deionized water until the pH value of the water at the outlet is above 5, preferably above 6, and more preferably above 6.5, and not more than 7.

0.

14. Use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the preparation method according to any one of claims 5 to 13 in removing olefins from aromatic raw materials; wherein, The application includes: the aromatic hydrocarbon raw material is contacted with the catalyst to react and obtain a product after olefin removal.

15. The use according to claim 14, characterized in that: The reaction conditions include: mass space velocity of 0.1-20h -1 , temperature is 90-260°C, pressure is 0.2-5.0MPa; preferably, mass space velocity is 0.2-20h -1 , temperature is 90-260℃, reaction pressure is 0.3-5.0MPa.