A catalyst for removing olefins from an aromatic hydrocarbon feedstock, its preparation method and use

Abstract

The application discloses a catalyst for removing olefins in an aromatic hydrocarbon raw material and a preparation method and application thereof. The catalyst comprises an inorganic oxide and a hydrogen type ion exchange resin composite, wherein the mass content of the inorganic oxide in the inorganic oxide and hydrogen type ion exchange resin composite is 0.3%-30%. The catalyst can efficiently remove macromolecular olefins in the aromatic hydrocarbon raw material, solves the problem of low olefin reduction efficiency in the current production, and solves the problem that the resin component is easy to swell in the treatment of organic media, so that the treated material is not easy to diffuse and cannot be operated for a long time.

Description

Technical Field

[0001] This invention relates to the field of aromatics production, and more specifically, to a catalyst for removing olefins from aromatic feedstocks, its preparation method, and its application. Background Technology

[0002] The aromatic feedstock from the hydrocracking unit has a high bromine index. In the aromatics complex production process, strict requirements are placed on the bromine index of the target C8 aromatic mixture generated from naphtha reforming, disproportionation and alkyl transfer, and isomerization reactions before adsorption separation can yield PX. The various reaction products or intermediates contain numerous impurities, resulting in a high bromine index. After de-olefin treatment, they can enter the downstream xylene tower. C8 aromatics are separated at the top of the xylene tower, while the bottom products are converted into the target C8 aromatics through disproportionation and alkyl transfer processes. The C8 aromatics at the top of the xylene tower require extremely low olefin content.

[0003] Industrially, two technical routes are used to saturate and largely remove olefins from aromatics, thereby reducing their olefin content: hydrogenation and liquid-solid phase molecular sieve alkylation catalysis. Conventionally, clay and molecular sieve catalysts are used to reduce olefins. Because the olefin molecules in the feedstock are relatively large, including those in C8 and C9+ aromatic fractions, and because the catalyst must maintain stable olefin removal performance over long periods, the requirements for the catalyst are high.

[0004] CN102008976A, CN103041841B, CN102039160B, and CN104907090A all employ molecular sieves as the main active component of deolefination catalysts. CN102008976A discloses a deolefination catalyst with ReUSY molecular sieves as the main active component, mordenite molecular sieves as the second active component, and alumina as a binder. CN103041841B discloses an aromatic non-hydrogenated deolefination catalyst prepared using Y molecular sieves. CN102039160B discloses a reforming oil deolefination catalyst, employing 20-90 parts of molecular sieves and 10-80 parts of at least one element selected from SiO2, Al2O3, or mixtures thereof, and a catalyst containing at least one metal or oxide selected from Mo, Zr, and Nb (based on elemental composition), at least one element selected from Cl, Br, and S (based on elemental composition), and at least one element or oxide selected from F and P (based on elemental composition). CN104907090A discloses a catalyst for the refining and deolefinization of reformed oil, comprising 30%-70% Al2O3 and 30%-70% molecular sieve.

[0005] Another method for removing olefins is hydrodeolefins technology. Hydrodeolefins technology uses hydrogen to react with double bonds to saturate and selectively remove olefins from all fractions. However, it inevitably hydrogenates some unsaturated aromatic rings in high-value aromatics, generating irreversible non-aromatics, thus reducing the overall capacity of the unit. For example, CN1448474A uses noble metals as the active metal component and alkali and alkaline earth metals as promoters to suppress excessive hydrogenation, resulting in a certain amount of aromatic loss. CN101260320A uses an eggshell-type optimized metal distribution method to reduce excessive hydrogenation. CN108636399A uses a non-noble metal hydrogenation method to remove olefins, which not only consumes hydrogen but also requires catalyst reduction and activation before application, making practical industrial application difficult. Furthermore, it inevitably loses some aromatics during operation, and its activity is not easily stabilized.

[0006] In summary, the above methods use different catalysts to remove olefins from the entire fraction of aromatic feedstock, resulting in a large number of aromatics participating in the reaction and high costs. Summary of the Invention

[0007] This invention provides a novel catalyst for removing olefins from aromatic feedstocks, its preparation method, and its applications. The catalyst of this invention can efficiently remove large-molecule olefins from aromatic feedstocks, maximizing the xylene aromatic content. Through alkylation reactions with olefins at C9 and above, the cost of olefin removal is reduced, solving the problem of low olefin removal efficiency in current production processes. It also addresses the issue of resin components easily swelling in the organic processing medium, leading to poor diffusion of the treated material and hindering long-term operation.

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

[0009] According to the present invention, the catalyst contains a sulfonic acid functional group, wherein the content of the sulfonic acid functional group 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 a sulfonic acid functional group, wherein the content of the sulfonic acid functional group is 0.01-1.0 mmol / 100g, preferably 0.01-0.7 mmol / 100g.

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

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

[0013] According to the present invention, the swelling rate of the catalyst for aromatics is not greater than 20%.

[0014] According to the present invention, the inorganic oxides in the catalyst are present in the pores of the hydrogen-form ion exchange resin.

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

[0016] (1) Mix sodium-type ion exchange resin with an organic solution of inorganic oxide precursor, dry and activate to obtain 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 impregnated in a low-carbon alcohol, filtered, and a resin mixture is obtained. This mixture is 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 C6 or fewer atoms, 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: impregnation at 25-35°C for 8-72 hours. The filtration is a conventional operation in the art, aimed at removing 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-type ion exchange resin is 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 0.05-5.0 mmol / 100g. The average particle size of the sodium-type ion exchange resin is 100 μm or more, preferably 100-500 μm, and the average pore size is 3 nm or more, preferably 4-12 nm.

[0020] According to the present invention, in step (1), the organic solvent used in the organic solution of the inorganic oxide precursor is a room-temperature stable organic compound, such as at least one of haloalkanes, hydrocarbons, nitrile compounds, and alcohols, preferably one or more of alcohols or alkanes and aromatics with a boiling point greater than 59°C, and more preferably at least one of ethanol, methanol, n-heptane, or dichloromethane. The mass ratio of the organic solvent to the inorganic oxide precursor, based on oxides, 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 alumina precursor, with a silicon oxide precursor being more preferred. The silicon oxide precursor is selected from at least one of methyl silicate, ethyl silicate, butyl silicate, methylsilane, ethylsilane, monohalosilane, dihalosilane (e.g., dichlorodimethylsilane), trihalosilane, or thiol-containing alkylsiloxanes, preferably at least one of thiol-containing alkylsiloxanes, wherein the alkyl group is preferably methyl, ethyl, or propyl. The thiol-containing alkylsiloxane is preferably at least one of (3-mercaptopropyl)-dimethoxysilane, γ-mercaptopropyldimethoxysilane, or methimoxytrimethoxysilane. The alumina precursor is selected from at least one of aluminum nitrate, aluminum chloride, or aluminum sulfate.

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

[0023] According to the present invention, in step (1), the mixing conditions are as follows: temperature is 0-90℃, and 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℃, and time is 0.5-48h.

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

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

[0026] According to the present invention, in step (2), treating the inorganic oxide-resin composite precursor with an acidic solution is to convert the sodium-form resin into the hydrogen-form 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 acidic solution relative to the inorganic oxide-resin composite precursor 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), the water is first filtered conventionally before washing. The water is washed with deionized water until the pH of the outlet water is above 5.0, preferably above 6.0, more preferably above 6.5, and not exceeding 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℃, and drying time is 0.5-48 hours.

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

[0031] According to the present invention, the catalyst contains a sulfonic acid functional group, wherein the content of the sulfonic acid functional group 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 a sulfonic acid functional group, wherein the content of the sulfonic acid functional group is 0.01-1.0 mmol / 100g, preferably 0.01-0.7 mmol / 100g.

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

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

[0035] According to the present invention, the swelling rate of the catalyst for aromatics is not greater than 20%.

[0036] According to the present invention, the inorganic oxides in the catalyst are present in the pores of the hydrogen-form ion exchange resin.

[0037] A third aspect of the present invention provides the application of the above-described catalyst in the removal of olefins from aromatic feedstocks.

[0038] According to the present invention, the application includes: reacting an aromatic feedstock with the above-mentioned catalyst to obtain a product excluding olefins.

[0039] According to the present invention, the reaction conditions include a mass hourly space velocity (HHSV) of 0.1-20 h⁻¹. -1 The temperature is 90-260℃, and the pressure is 0.2-5.0MPa; preferably, the mass hourly space velocity is 0.2-20h. -1 The temperature ranges from 90 to 260℃, and the reaction pressure ranges from 0.3 to 5.0 MPa.

[0040] According to the present invention, the aromatic feedstock may be derived from at least one process in naphtha reforming, catalytic cracking, etc. The aromatics refer to benzene, toluene, and other alkyl-containing monocyclic or bicyclic aromatic hydrocarbons, such as at least one of xylene, trimethylbenzene, ethylbenzene, propylbenzene, methyl ethylbenzene, diethylbenzene, tetramethylbenzene, butadiene, ethylxylene, naphthalene, methylnaphthalene, etc. The aromatic feedstock contains at least 50% aromatics by mass, preferably at least 80%.

[0041] According to the present invention, the bromine index of the aromatic 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 / 100g lower than that of the aromatic feedstock, preferably at least 100 mgBr / 100g lower; preferably, the bromine index of the product after olefin removal is at least 30% or less of the bromine index of the aromatic feedstock; more preferably, the bromine index of the product after olefin removal is at least 5% or less of the bromine index of 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 feedstocks provided by this invention overcomes the problem of hindered diffusion of large olefin molecules through its large-pore active centers, efficiently removing olefins and maximizing the reaction between olefins and aromatics in the feedstock. This solves the problem of low olefin removal efficiency in current production processes. The catalyst prepared by this invention has a low initial reaction temperature, not only efficiently removing olefin impurities but also solving the swelling problem of ion exchange resins, making it suitable for large-scale production. Detailed Implementation

[0045] The technical solution of the present invention will be described in detail below with reference to the embodiments.

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

[0047] In this invention, the method for testing the swelling rate of the catalysts for aromatics obtained in each example is as follows: at 30°C, 30g of catalyst is placed in a 500mL graduated cylinder, 400mL of toluene is added, and after treatment under sealed conditions for 48 hours, the volume change of the catalyst is calculated.

[0048] In this invention, the swelling rate of the catalyst for aromatics % = (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 V represents the volume of catalyst swollen for 48 hours, in mL. 催化剂初始 This indicates the initial volume of the catalyst before swelling treatment, in mL.

[0050]

Example 1

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

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

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

[0054] The catalyst A contains 2.1 mmol / 100g of sulfonic acid functional groups. The catalyst A contains 25% silica by mass, and the hydrogen-form ion exchange resin NKC-9 has an average pore size of 4.2 nm. The catalyst A has a swelling rate of 8.2% for aromatic hydrocarbons.

[0055] Catalyst evaluation:

[0056] Take 5g of catalyst A, using a styrene-containing aromatic feedstock (styrene content is 2010 mgBr / 100g based on the bromine index, of which xylene content is 50.1% and C9 aromatic content is 49.6%), and set the feedstock mass hourly space velocity (MHSV) at 6h⁻¹. -1 The reaction was evaluated at 1.9 MPa and 80 °C. After 10 hours, the styrene content at the outlet, calculated by the bromine index, was 0.3 mgBr / 100g (49.9% xylene and 50.1% C9 aromatics and above, including olefins). After 300 hours, the styrene content at the outlet, calculated by the bromine index, was 1.0 mgBr / 100g (49.9% xylene and 50.1% C9 aromatics and above, including olefins).

[0057]

Example 2

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

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

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

[0061] The catalyst B contains 1.1 mmol / 100g of sulfonic acid functional groups. The catalyst B contains 18% alumina by mass, and the hydrogen-form ion exchange resin D-001 has an average pore size of 4.9 nm. The catalyst B has a swelling rate of 12.2% for aromatic hydrocarbons.

[0062] Catalyst evaluation:

[0063] Take 5g of catalyst B, using styrene-containing aromatic feedstock (styrene content, calculated as bromine index, is 800mgBr / 100g, with xylene content of 50.1% and C9 aromatic content of 49.7%), and set the feedstock mass hourly space velocity (MHSV) at 4h⁻¹. -1 The reaction was evaluated at 1.9 MPa and 120 °C. After 10 hours, the styrene content at the outlet was 0.3 mgBr / 100g (based on the bromine index, of which xylene content was 49.8% and C9 aromatic hydrocarbons and above content was 50.2%, of which C9 aromatic hydrocarbons and above included olefins).

[0064] [Example 3]

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

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

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

[0068] The catalyst C contains 1.0 mmol / 100g of sulfonic acid functional groups. The catalyst C contains 12% alumina by mass, and the hydrogen-form ion exchange resin D-001 has an average pore size of 5.5 nm. The catalyst C has a swelling rate of 7.2% for aromatic hydrocarbons.

[0069] Catalyst evaluation:

[0070] Take 5g of catalyst C and use an aromatic feedstock containing hexene-1 and p-methylstyrene (hexene-1 content, calculated by bromine index, is 708mgBr / 100g; p-methylstyrene content, calculated by bromine index, is 630mgBr / 100g; the content of benzene is 12.3%, toluene is 28.1%, non-aromatic feedstock is 10.8%, xylene is 23.1%, ethylbenzene is 2.0%, and C9 and above aromatics content is 24.7%), with a feedstock mass hourly space velocity (HHSV) of 3.0h. -1 The reaction was evaluated at 1.9 MPa and 130 °C. After 10 hours, the mass content of hexene-1 at the outlet was 3.0 mgBr / 100g based on the bromine index, and the mass content of p-methylstyrene was 5.0 mgBr / 100g based on the bromine index.

[0071]

Example 4

[0072] (1) 30g of sodium Amberlyst (sulfonic acid content 0.5mmol / 100g, average particle size 200μm, average pore size 5.2nm) was impregnated with 50g 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 a heptane solution of dichlorodimethylsilane (containing 30.2% silane), soaked at 30°C for 8 hours, filtered, and then 100g of water was added. Under a nitrogen atmosphere at 28°C, a 1.5% potassium permanganate aqueous solution was slowly added dropwise with stirring until the solution was complete. Then, the solution was subjected to a vacuum of 0.08MPa at 80°C to remove butanol and methanol for 7 hours. Then, under an argon atmosphere at 20°C, 600g of a 1% potassium permanganate solution was added dropwise, stirred for 8 hours, filtered, and washed to obtain the SiO2-Amberlyst complex precursor.

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

[0075] The catalyst D contains 0.3 mmol / 100g of sulfonic acid functional groups. The catalyst D contains 12% silica by mass, and the hydrogen-form Amberlyst resin has a pore size of 5.1 nm. The catalyst D has a swelling rate of 15.1% for aromatic hydrocarbons.

[0076] Catalyst evaluation:

[0077] Take 5g of catalyst D, using an aromatic feedstock containing hexene-1 and styrene (hexene-1 mass content, calculated by bromine index, is 200mgBr / 100g; styrene mass content, calculated by bromine index, is 300mgBr / 100g; benzene content is 10.3%, toluene content is 23.1%, non-aromatic feedstock is 12.8%, xylene is 25.3%, ethylbenzene is 2.3%, and C9 and above aromatic hydrocarbons content is 26.2%), at a feedstock mass hourly space velocity (HHSV) of 2.00 h⁻¹. -1 The reaction was evaluated at 1.9 MPa and 150 °C. After 10 hours, the mass content of hexene-1 at the outlet was 6.0 mgBr / 100g based on the bromine index, and the mass content of styrene was 1.5 mgBr / 100g based on the bromine index.

[0078]

Example 5

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

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

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

[0082] The catalyst E contains 2.3 mmol / 100g of sulfonic acid functional groups. The catalyst E contains 10% silica by mass, and the hydrogen-form ion exchange resin NKC-9 has an average pore size of 3.4 nm. The catalyst E has a swelling rate of 6.2% for aromatic hydrocarbons.

[0083] Catalyst evaluation:

[0084] Take 5g of catalyst E, using styrene-containing aromatic feedstock (styrene content is 2010 mgBr / 100g based on bromine index, with xylene content of 50.1% and C9 aromatic content of 49.6%), and set the feedstock mass hourly space velocity (MHSV) at 6h⁻¹. -1 The reaction was evaluated at 1.9 MPa and 80 °C. After 10 hours, the styrene content at the outlet was 0.2 mgBr / 100g (based on the bromine index, of which xylene content was 49.9% and C9 aromatic hydrocarbons and above content was 50.1%, of which C9 aromatic hydrocarbons and above included olefins).

[0085]

Example 6

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

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

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

[0089] The catalyst F contains 3.6 mmol / 100g of sulfonic acid functional groups. The catalyst F contains 8% silica by mass, and the hydrogen-form ion exchange resin NKC-9 has an average pore size of 3.2 nm. The catalyst F has a swelling rate of 7.0% for aromatic hydrocarbons.

[0090] Catalyst evaluation:

[0091] Take 5g of catalyst F, and use styrene-containing aromatic materials (styrene content is 2010mgBr / 100g based on bromine index, of which xylene content is 50.1% and C9 aromatic content is 49.6%), and in 6h -1 The reaction was evaluated at 1.9 MPa and 80 °C. After 10 hours, the styrene content at the outlet was 0.1 mgBr / 100g (based on the bromine index, of which xylene content was 49.9% and C9 aromatic hydrocarbons and above content was 50.1%, of which C9 aromatic hydrocarbons and above included olefins).

[0092]

Example 7

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

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

[0095] The catalyst G contains 1.2 mmol / 100g of sulfonic acid functional groups. The catalyst G contains 25% silica by mass, and the hydrogen-form ion exchange resin NKC-9 has an average pore size of 4.8 nm. The catalyst G has a swelling rate of 15% for aromatic hydrocarbons.

[0096] Catalyst evaluation:

[0097] Take 5g of catalyst G and use a styrene-containing aromatic feedstock (styrene content is 2010 mgBr / 100g based on bromine index, of which xylene content is 50.1% and C9 aromatic content is 49.6%), with a feedstock mass hourly space velocity of 6h⁻¹. -1 The reaction was evaluated at 1.9 MPa and 80 °C. After 10 hours, the styrene content at the outlet was 5.0 mgBr / 100g (based on the bromine index, of which xylene content was 49.9% and C9 aromatic hydrocarbons and above content was 50.1%, of which C9 aromatic hydrocarbons and above included olefins).

[0098]

Example 8

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

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

[0101] (2) The above-mentioned complex precursor was placed in a 1 mol / L sulfuric acid solution (0.02 mmol / L). 酸 / 1g 复合物前体 The catalyst was treated at 20°C for 3 hours in 500g of water, filtered, and washed until the pH of the filtrate was 6.0, as described in Example 1. This process was repeated twice, and finally the catalyst was dried under vacuum at 50°C for 24 hours to obtain catalyst H.

[0102] The catalyst H contains 3.6 mmol / 100g of sulfonic acid functional groups. The catalyst H contains 8% silica by mass, and the hydrogen-form ion exchange resin NKC-9 has an average pore size of 3.1 nm. The catalyst H has a swelling rate of 5.7% for aromatic hydrocarbons.

[0103] Catalyst evaluation:

[0104] Take 5g of catalyst H, and use styrene-containing aromatic materials (styrene content is 2010mgBr / 100g based on bromine index, with xylene content of 50.1% and C9 aromatic content of 49.6%), and in 6h... -1 The reaction was evaluated at 1.9 MPa and 80 °C. After 10 hours, the styrene content at the outlet, calculated by the bromine index, was 0.5 mgBr / 100g (of which xylene content was 49.8% and C9 or higher aromatic hydrocarbon content was 50.2%, including olefins). After 300 hours, the styrene content at the outlet, calculated by the bromine index, was 0.5 mgBr / 100g (of which xylene content was 49.8% and C9 or higher aromatic hydrocarbon content was 50.2%, including olefins).

[0105]

Example 8

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

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

[0108] (2) Dissolve the above-mentioned complex precursor in 1 mol / L sulfuric acid solution (0.02 mmol / L). 酸 / 1g 复合物前体 The catalyst was treated at 20°C for 3 hours in 500g of water, filtered, and washed until the pH of the filtrate was 6.0, as described in Example 1. This process was repeated twice, and finally the catalyst was dried under vacuum at 50°C for 24 hours to obtain catalyst F.

[0109] The catalyst F contains 3.3 mmol / 100g of sulfonic acid functional groups. The catalyst F contains 8% silica by mass, and the hydrogen-form ion exchange resin NKC-9 has an average pore size of 3.3 nm. The catalyst F has a swelling rate of 6.5% for aromatic hydrocarbons.

[0110] Catalyst evaluation:

[0111] Take 5g of catalyst F, and use styrene-containing aromatic materials (styrene content is 2010mgBr / 100g based on bromine index, of which xylene content is 50.1% and C9 aromatic content is 49.6%), and in 6h -1 The reaction was evaluated at 1.9 MPa and 80 °C. After 10 hours, the styrene content at the outlet, calculated by the bromine index, was 0.3 mgBr / 100g (of which xylene content was 49.9% and C9 aromatic hydrocarbons and above content were 50.1%, including olefins). After 300 hours, the styrene content at the outlet, calculated by the bromine index, was 0.4 mgBr / 100g (of which xylene content was 49.9% and C9 aromatic hydrocarbons and above content were 50.1%, including olefins).

[0112] Comparative Example 1

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

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

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

[0116] Catalyst evaluation:

[0117] Take 5g of catalyst DA1 and use styrene-containing aromatic feedstock (styrene content is 2010mgBr / 100g based on bromine index, of which xylene content is 50.1% and C9 aromatic content is 49.6%), with a feedstock mass hourly space velocity of 6h. -1At 1.9 MPa and 80 °C, the reaction was evaluated. After 10 hours, the styrene content at the outlet, calculated by the bromine index, was 520 mgBr / 100g (including 50.0% xylene and 50.0% C9 aromatics and above, which include olefins). After 100 hours, the styrene content at the outlet, calculated by the bromine index, was 1501 mgBr / 100g (including 50.0% xylene and 50.0% C9 aromatics and above, which include olefins).

[0118] Comparative Example 2

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

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

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

[0122] The catalyst DA2 contains 1.2 mmol / 100g of sulfonic acid functional groups. The catalyst DA2 contains 27% silica by mass, and the hydrogen-form ion exchange resin NKC-9 has an average pore size of 3.3 nm. The catalyst DA2 exhibits a 21% swelling rate for aromatic hydrocarbons.

[0123] Catalyst evaluation:

[0124] Take 5g of catalyst DA2, using styrene-containing aromatic feedstock (styrene content is 2010mgBr / 100g based on bromine index, of which xylene content is 50.1% and C9 aromatic content is 49.6%), and set the feedstock mass hourly space velocity (MHSV) at 6h⁻¹. -1At 1.9 MPa and 80 °C, the reaction was evaluated. After 10 hours, the styrene content at the outlet, calculated by the bromine index, was 880 mgBr / 100g (of which xylene content was 50.1%, and C9 and above aromatic hydrocarbons content was 49.9%, including olefins). After 100 hours, the styrene content at the outlet, calculated by the bromine index, was 1220 mgBr / 100g (of which xylene content was 50.0%, and C9 and above aromatic hydrocarbons content was 50.0%, including olefins).

[0125] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalyst for removing olefins from aromatic feedstocks, wherein, The catalyst comprises an inorganic oxide and a hydrogen-form ion exchange resin complex, wherein, based on the mass of the inorganic oxide and the hydrogen-form ion exchange resin complex, the mass content of the inorganic oxide is 0.3%-30%, the hydrogen-form ion exchange resin is a polystyrene-containing hydrogen-form macroporous cation exchange resin, and the swelling rate of the catalyst for aromatics is no greater than 20%, wherein the swelling rate of the catalyst for aromatics % = (V 催化剂48h -V 催化剂初始 ) / V 催化剂初始 ×100%, where V 催化剂48h V represents the volume of catalyst swollen for 48 hours, in mL. 催化剂初始 The initial volume of the catalyst before swelling treatment is expressed in mL; the inorganic oxide in the catalyst is present in the pores of the hydrogen-form ion exchange resin; the inorganic oxide is at least one of silicon dioxide and aluminum oxide.

2. The catalyst according to claim 1, characterized in that: In the catalyst, the mass content of the inorganic oxide is 1%-25%, based on the mass of the inorganic oxide and hydrogen-form ion exchange resin complex.

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

4. The catalyst according to claim 1, characterized in that: The inorganic oxide contains a sulfonic acid functional group, wherein the content of the sulfonic acid functional group is 0.01-1.0 mmol / 100g; the hydrogen-form ion exchange resin contains a sulfonic acid functional group, wherein the content of the sulfonic acid functional group is 0.05-5.0 mmol / 100g.

5. The catalyst according to claim 4, characterized in that: The inorganic oxide is silicon dioxide.

6. A method for preparing the catalyst for removing olefins from aromatic feedstock according to any one of claims 1-5, comprising the following steps: (1) The sodium-type ion exchange resin was mixed with an organic solution of an inorganic oxide precursor, dried, and activated 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; In step (1), the sodium-type ion exchange resin is a sodium-type macroporous cation exchange resin containing polystyrene groups; In step (1), the inorganic oxide precursor is at least one of silicon oxide precursor or aluminum oxide precursor; In step (1), the activation is to convert the inorganic oxide precursor into an inorganic oxide.

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

8. The preparation method according to claim 7, characterized in that: The lower alcohol is an alcohol with fewer than six carbons, selected from at least one of 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 impregnation conditions are: impregnation at 25-35°C for 8-72 hours.

9. The preparation method according to claim 6, characterized in that: The sodium-type ion exchange resin contains sulfonic acid functional groups.

10. The preparation method according to claim 6, characterized in that: The sodium-type ion exchange resin is selected from at least one of NKC-9, D-001, and Amberlyst.

11. The preparation method according to claim 10, characterized in that: The sodium-type ion exchange resin contains 0.05-5.0 mmol / 100g of sulfonic acid functional groups.

12. The preparation method according to claim 6, characterized in that: In step (1), the organic solvent used in the organic solution of the inorganic oxide precursor is a room-temperature stable organic compound selected from at least one of halogenated hydrocarbons, hydrocarbons, nitrile compounds, and alcohols, and the mass ratio of the organic solvent to the inorganic oxide precursor, based on oxides, is 1-100:

1.

13. The preparation method according to claim 12, characterized in that: The organic solvent is one or more of alcohols, alkanes with a boiling point greater than 59°C, and aromatics.

14. The preparation method according to claim 12, characterized in that: The organic solvent is at least one of ethanol, methanol, n-heptane, or dichloromethane.

15. The preparation method according to claim 6, characterized in that: The inorganic oxide precursor is a silicon oxide precursor.

16. The preparation method according to claim 15, characterized in that: The silicon oxide precursor is selected from at least one of methyl silicate, ethyl silicate, butyl silicate, methylsilane, ethylsilane, monohalosilane, dihalosilane, trihalosilane, or alkylsiloxane containing a mercapto group.

17. The preparation method according to claim 16, characterized in that: The silicon oxide precursor is at least one of alkylsiloxanes containing mercapto groups, wherein the alkyl group is methyl, ethyl, or propyl.

18. The preparation method according to claim 6, characterized in that: The alumina precursor is selected from at least one of aluminum nitrate, aluminum chloride, and aluminum sulfate.

19. The preparation method according to claim 6, characterized in that: In step (1), the mixing conditions are as follows: temperature is 0-90℃, and time is 0.5-48h; And / or, in step (1), the drying conditions are as follows: vacuum degree not less than 0.01MPa, temperature 10-200℃, and time 0.5-48h.

20. The preparation method according to claim 19, characterized in that: The vacuum level is 0.01-0.06 MPa.

21. The preparation method according to claim 6, characterized in that: In step (2), the acidic solution treatment converts the sodium-form resin into the hydrogen-form resin; And / or, in step (2), the drying conditions are as follows: vacuum degree of 0.01MPa-0.1MPa, temperature of 10-290℃, and time of 0.5-48 hours.

22. The preparation method according to claim 21, characterized in that: The acidic solution is a solution of at least one of hydrochloric acid and sulfuric acid.

23. The preparation method according to claim 22, characterized in that: The concentration of the acidic solution is 0.01-2 mol / L.

24. The preparation method according to claim 21, characterized in that: The relationship between the amount of acidic solution and the inorganic oxide-resin complex precursor is as follows: the amount of acid used is 0.01-20 mmol relative to 1 g of inorganic oxide-resin complex precursor.

25. The preparation method according to claim 21, characterized in that: The processing conditions include: a temperature of 0-150℃ and a processing time of 0.5-48 hours.

26. The preparation method according to claim 6, characterized in that: In step (2), the washing is performed using deionized water until the pH value of the outlet water is above 5.

27. The preparation method according to claim 26, characterized in that: Until the pH of the effluent is above 6.

28. The preparation method according to claim 27, characterized in that: Until the pH of the effluent is above 6.5 and does not exceed 7.

0.

29. The use of the catalyst according to any one of claims 1-5 in the removal of olefins from aromatic feedstocks; wherein, The application includes: reacting aromatic feedstock with the catalyst to obtain a product after removing olefins.

30. The application according to claim 29, characterized in that: The reaction conditions include a mass hourly space velocity (HHSV) of 0.1–20 h⁻¹. -1 The temperature ranges from 90 to 260 ℃, and the pressure ranges from 0.2 to 5.0 MPa.

31. The application according to claim 30, characterized in that: The reaction conditions include a mass hourly space velocity (HHSV) of 0.2–20 h⁻¹. -1 The temperature ranges from 90 to 260 ℃, and the reaction pressure ranges from 0.3 to 5.0 MPa.