Silicon-aluminum molecular sieve catalyst, and its preparation and use

Abstract

A silicon-aluminum molecular sieve catalyst, and its preparation and use, are disclosed. The desorption curve of the NH3-TPD spectrum of the catalyst shows three peaks P1, P2, and P3, and the peak positions of the three peaks P1, P2, and P3 correspond to desorption temperatures in the ranges of 180-220°C, 250-290°C, and 370-410°C, respectively. The catalyst has high activity, selectivity, and stability when used in the vapor-phase alkylation reaction of aromatic hydrocarbons with olefins to prepare alkyl aromatic hydrocarbons.

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Chinese Patent Application No. 202011158111.7, filed on October 26, 2020, entitled "Catalyst for alkylation of benzene with ethylene, its preparation, and their use," the contents of which are incorporated herein by reference in their entirety.

[0002] [Technical Field] This application relates to the field of aromatic alkylation catalysts, and more particularly to aluminosilicate molecular sieve catalysts useful in the alkylation of aromatics with olefins, their preparation, and their use.

[0003] [Background technology] Ethylbenzene is an important basic organic raw material and is primarily used to produce styrene, which has a wide range of applications, including polystyrene, styrene-butadiene rubber, ABS, and SBS, as well as in the pharmaceutical, coating, and textile industries.

[0004] Ethylbenzene is primarily produced by the alkylation reaction of benzene with ethylene. In practical catalytic processes, the gas-phase alkylation of benzene with ethylene is a complex reaction system with coexisting series and parallel side reactions. In addition to ethylbenzene, other by-products may be produced, such as diethylbenzene, triethylbenzene, toluene, xylene, propylbenzene, methylethylbenzene, and butylbenzene. Among these by-products, xylene has a boiling point close to that of ethylbenzene and is difficult to effectively remove by fractional distillation. Therefore, controlling the xylene content in the alkylation product is particularly important. Furthermore, to improve the yield of ethylbenzene in industrial production, polyethylbenzenes (e.g., diethylbenzene and triethylbenzene) are separated from the alkylation product and then converted to ethylbenzene via a transalkylation reaction. Therefore, reducing the polyethylbenzene content in the alkylation product can reduce the load for the subsequent transalkylation reaction, which is of great significance for energy conservation and efficiency improvement in enterprises.

[0005] Industrially used benzene and ethylene alkylation catalysts have certain requirements regarding shape and mechanical strength, so a large amount of binder needs to be added in the process of molding the molecular sieve catalyst. Adding a large amount of binder increases the mechanical strength of the catalyst, but it also has several adverse effects, such as diluting the active center of the catalyst, blocking the pore channels of the molecular sieve, and causing more side reactions, thereby resulting in a decrease in product purity. To address the adverse effects of binders, methods for producing binderless catalysts have been disclosed in the prior art.

[0006] CN107512729B discloses a method for producing a binderless ZSM-5 molecular sieve, the method comprising the steps of: a) providing a synthesized ZSM-5 molecular sieve; b) mixing the synthesized ZSM-5 molecular sieve with a binder, a pore-forming agent, and an aqueous acid solution, shaping, and drying to obtain a ZSM-5 molecular sieve precursor; wherein the binder is at least one selected from silica sol and alumina; the silica sol provides a first silicon source, and the alumina provides a first aluminum source; and c) crystallizing a mixture of the ZSM-5 molecular sieve precursor, a second silicon source, a second aluminum source, an alkali source, an organic template, and water, and separating and drying the resulting solid product to obtain a binderless ZSM-5 molecular sieve.

[0007] In the currently reported methods for preparing binderless molecular sieve catalysts in the prior art, a certain amount of molecular sieve powder is typically added in the molding process, which means that such molecular sieve powder needs to be prepared in advance, which undoubtedly increases the operation steps and production costs.

[0008] DISCLOSURE OF THE INVENTION The present invention provides an aluminosilicate molecular sieve catalyst useful for the alkylation of aromatics with olefins, its preparation, and its use. When used to produce alkylaromatics by vapor-phase alkylation of aromatics with olefins, the catalyst has high activity, selectivity, and stability, and can significantly reduce the content of by-products.

[0009] To achieve the above object, in one aspect, the present application provides an aluminosilicate molecular sieve catalyst, the catalyst having an NH3-TPD pattern showing a desorption curve with three peaks P1, P2, and P3, and the desorption temperatures corresponding to the apexes of the three peaks P1, P2, and P3 are in the ranges of 180 to 220°C, 250 to 290°C, and 370 to 410°C, respectively.

[0010] Preferably, the peak heights H1, H2, and H3 of the three peaks P1, P2, and P3 satisfy the relationship H1>H2>H3.

[0011] More preferably, the peak heights H1, H2, and H3 of the three peaks P1, P2, and P3 satisfy the following relationship: H2 / H1=(0.5~0.8):1; H3 / H2=(0.8~0.9):1; and H3 / H1=(0.4~0.7):1.

[0012] In another aspect, the present application provides a method for producing an aluminosilicate molecular sieve catalyst, comprising the steps of: 1) mixing a template, a silicon source, a first aluminum source, and water under heating to obtain a first mixture; 2) mixing the first mixture, silicon powder, and a second aluminum source to obtain a second mixture; 3) shaping the second mixture to obtain a third mixture; 4) contacting the third mixture with an alkalinity source and a regulator to obtain a fourth mixture, wherein the regulator is a polyhydroxy polymeric compound; and 5) treating the fourth mixture to obtain the aluminosilicate molecular sieve catalyst, wherein the treating includes calcining.

[0013] Preferably, the silicon powder used in step 2) comprises two types of silica particles having different sizes, the sizes of the two types of silica particles being in the ranges of 0.1-2 μm and 4-12 μm, respectively, and the mass ratio of the two types of silica particles is (0.5-2.0):1.

[0014] In yet another aspect, the present application provides a process for the vapor phase alkylation of an aromatic hydrocarbon with an olefin, the process comprising subjecting the aromatic hydrocarbon and the olefin to an alkylation reaction in the presence of a catalyst of the present application or a catalyst obtained by a process of the present application to obtain an alkylaromatic hydrocarbon.

[0015] The present aluminosilicate molecular sieve catalyst offers the following advantages: 1. The present inventors have found through research that the acidity distribution of aluminosilicate molecular sieve catalysts, particularly binderless ZSM-5 molecular sieve catalysts, significantly affects the catalyst's catalytic performance for catalyzing the gas-phase alkylation of aromatics with olefins, particularly the yield of by-products. The present inventors have also found through research that when the NH3-TPD desorption curve of an aluminosilicate molecular sieve catalyst shows three peaks, and particularly when the heights of the three peaks show a specific proportional relationship from low to high temperatures, this is beneficial for improving the catalytic performance for the gas-phase alkylation of aromatics with olefins, and in particular for reducing the content of by-products such as xylenes and polyethylbenzenes in the product. Furthermore, when the catalyst particle size has a bimodal distribution, there are synergistic and relay effects in the diffusion and reaction of reactant molecules, which align the catalyst's diffusion performance with its reaction performance, thereby improving catalyst activity and selectivity while significantly reducing the content of by-products in the product.

[0016] 2. The catalyst preparation method of the present application does not require the addition of pre-prepared molecular sieve powder during the preparation process, but instead uses a polyhydroxy polymer compound regulator and preferably silicon powders with two different particle sizes, so the resulting catalyst has a specific acidity distribution and crystal size distribution. The catalyst obtained by this method is particularly suitable for producing alkylaromatic hydrocarbons by the vapor-phase alkylation of aromatics with olefins, and has high activity, selectivity, and stability.

[0017] 3. When the catalyst is used in the gas phase alkylation of benzene with ethylene, the content of xylene in the alkylation product can be reduced to below 500 ppm, and the mass content of diethylbenzene and triethylbenzene can be reduced to below 8%.

[0018] Other features and advantages of the present application are explained in detail in the detailed description that follows.

[0019] BRIEF DESCRIPTION OF THE DRAWINGS The drawings that form part of this specification are provided to aid in the understanding of the application and should not be considered limiting. The application can be read with reference to the drawings in combination with the following detailed description. In the drawings: FIG. 1 shows the XRD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 1 of the present application; FIG. 2 shows an SEM image of the aluminosilicate molecular sieve catalyst obtained in Example 1 of the present application; FIG. 3 shows the NH3-TPD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 1 of the present application; FIG. 4 shows the XRD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 2 of the present application; FIG. 5 shows the XRD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 3 of the present application; FIG. 6 shows an SEM image of the aluminosilicate molecular sieve catalyst obtained in Comparative Example 1; FIG. 7 shows the NH3-TPD pattern of the aluminosilicate molecular sieve catalyst obtained in Comparative Example 1.

[0020] Detailed Description of the Invention The present application is described in further detail below with reference to the drawings and specific embodiments thereof. It should be noted that the specific embodiments of the present application are provided for illustrative purposes only and are not intended to be limiting in any way.

[0021] Any specific numerical value, including the endpoint of a numerical range, described in the context of this application should be interpreted as not being limited to that exact value, but also encompassing all values ​​close to that exact value, for example, all values ​​within ±5% of that exact value. Furthermore, with respect to any numerical range described herein, any combination between the endpoints of the range, between each endpoint and any specific value within the range, or between any two specific values ​​within the range, can be made to provide one or more new numerical ranges, which new numerical ranges should also be considered to be specifically described in this application.

[0022] Unless otherwise specified, terms used herein have the same meaning as commonly understood by one of ordinary skill in the art; where terms are defined herein and their definitions differ from the common understanding in the art, the definitions provided herein shall prevail.

[0023] As used herein, the term "polyhydroxy polymer" refers to a polymer having multiple hydroxyl groups in its molecule, including, but not limited to, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, casein, or gum arabic.

[0024] As used herein, the term "acidic molecular sieve" has the meaning commonly understood in the art and refers to a molecular sieve having B acid and / or L acid sites.

[0025] In this application, pressures given are gauge pressures unless otherwise specified.

[0026] In the context of this application, in addition to the explicitly stated content, any content or unmentioned content shall be deemed to be the same as that known in the art without any modifications.In addition, any of the embodiments described herein can be freely combined with one or more of the embodiments described herein, and the technical solutions or concepts thus obtained shall be deemed to be part of the original disclosure or original description of this application, and shall not be deemed to be new matters not disclosed or anticipated herein, unless it is obvious to those skilled in the art that such combination is obviously unreasonable.

[0027] All patent and non-patent literature cited herein, including but not limited to textbooks and journal articles, is hereby incorporated by reference in its entirety.

[0028] As described above, in a first aspect, the present application provides an aluminosilicate molecular sieve catalyst, the catalyst having an NH3-TPD pattern showing a desorption curve having three peaks P1, P2, and P3, and the desorption temperatures corresponding to the apexes of the three peaks P1, P2, and P3 are in the ranges of 180 to 220°C, 250 to 290°C, and 370 to 410°C, respectively, and preferably in the ranges of 190 to 210°C, 260 to 280°C, and 380 to 400°C.

[0029] In a preferred embodiment, the peak heights H1, H2, and H3 of the three peaks P1, P2, and P3 satisfy the relationship H1>H2>H3, and more preferably, the peak heights H1, H2, and H3 satisfy the following relationship: H2 / H1=(0.5~0.8):1; H3 / H2=(0.8~0.9):1; and H3 / H1=(0.4~0.7):1.

[0030] According to the present application, the desorption temperature in the NH3-TPD pattern is divided into three ranges, namely, 100-240°C, 240-300°C, and 300-500°C, and the integrated areas of the desorption curve within the three temperature ranges correspond to the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst, respectively. Preferably, the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst satisfy the following relationship: S2 / S1=(0.38~0.52):1, more preferably S2 / S1=(0.4~0.5):1; S2 / S3=(0.32-0.58):1, more preferably S2 / S3=(0.35-0.55):1; and S3 / S1=(0.8-1.2):1, more preferably S3 / S1=(0.9-1.1):1.

[0031] In a preferred embodiment of the catalyst, the ratio of the weak acid content S1 to the total acid content of the catalyst (i.e., the sum of the weak acid content, the medium-strong acid content, and the strong acid content) is 40 to 50%, the ratio of the medium-strong acid content S2 to the total acid content is 15 to 25%, and the ratio of the strong acid content S3 to the total acid content is 35 to 45%, and the ratios of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content are calculated from the ratios of the integrated area of ​​the NH3-TPD desorption curve of the catalyst in the temperature ranges of 100 to 240°C, 240 to 300°C, and 300 to 500°C to the total integrated area in the temperature range of 100 to 500°C, respectively.

[0032] In a preferred embodiment, the ratio of the content of the super strong acid to the total acid content of the catalyst is less than 5%, preferably less than 3%, where the ratio of the content of the super strong acid to the total acid content is calculated from the ratio of the integrated area of ​​the desorption curve in the temperature range above 500°C in the NH3-TPD pattern of the catalyst to the total integrated area of ​​the desorption curve in the temperature range of 100 to 500°C in the NH3-TPD pattern of the catalyst.

[0033] In a preferred embodiment, the aluminosilicate molecular sieve catalyst is a binderless aluminosilicate molecular sieve catalyst, more preferably the aluminosilicate molecular sieve is an acidic molecular sieve having a pore structure of 10 or 12 membered rings, and particularly preferably the aluminosilicate molecular sieve is a ZSM-5 molecular sieve.

[0034] In a preferred embodiment, no additional modifying metal or non-metallic components such as zinc, magnesium, calcium, iron, cobalt, nickel, phosphorus, lanthanum, copper, zirconium, chromium, manganese, silver, ruthenium, palladium, platinum, titanium, tin, strontium, barium, vanadium, lithium, etc. are supported on the aluminosilicate molecular sieve catalyst.

[0035] In a preferred embodiment, the aluminosilicate molecular sieve catalyst has two different sizes of crystal grains, 10 to 300 nm and 400 to 1600 nm, respectively. More preferably, the number of crystal grains in the 10 to 300 nm range accounts for 5 to 60%, preferably 30 to 60%, of the total number of crystal grains, and the number of crystal grains in the 400 to 1600 nm range accounts for 40 to 95%, preferably 40 to 70%, of the total number of crystal grains.

[0036] In a preferred embodiment, the content of isolated aluminum in the catalyst is 97.5-100%, preferably 99-100%. According to the present application, the content of isolated aluminum can be measured as follows: Isolated aluminum content = (1-2 × C コバルト / C アルミニウム )×100% In the formula, the Co-Na type catalyst is prepared by ion exchange, and C コバルト and C アルミニウム refer to the Co content and Al content in the catalyst measured by ICP test, respectively.

[0037] In a preferred embodiment, the mechanical strength of the aluminosilicate molecular sieve catalyst is 100 to 170 N / cm, more preferably 110 to 160 N / cm.

[0038] In a preferred embodiment, the aluminosilicate molecular sieve catalyst has a SiO2 / Al2O3 molar ratio of 30-400.

[0039] In a second aspect, the present application provides a method for preparing an aluminosilicate molecular sieve catalyst, comprising the steps of: (1) mixing a template, a silicon source, a first aluminum source, and water under heating to obtain a first mixture; (2) mixing the first mixture, silicon powder, and a second aluminum source to obtain a second mixture; (3) forming the second mixture to obtain a third mixture; (4) contacting the third mixture with an alkali source and a regulator to obtain a fourth mixture, wherein the regulator is a polyhydroxy polymeric compound; (5) treating the fourth mixture to obtain an aluminosilicate molecular sieve catalyst, wherein the treating includes calcining.

[0040] In a preferred embodiment, the template used in step 1) is one or more selected from the group consisting of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, and tetraethylammonium bromide; the silicon source is one or more selected from the group consisting of silica sol, white carbon black, tetraethyl silicate, and silicon powder; and the first aluminum source is one or more selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, isopropoxyaluminum, and pseudoboehmite.

[0041] In a preferred embodiment, the molar ratios among the template, silicon source, first aluminum source, and water in step 1) are as follows, respectively: template: silicon source=(0.05-1.0):1, silicon source: first aluminum source=(30-400):1, water: silicon source=(3-12):1, where the silicon source is calculated as SiO2, and the first aluminum source is calculated as Al2O3.

[0042] In a preferred embodiment, in step 1), the step of mixing a template, a silicon source, a first aluminum source, and water with heating to obtain a first mixture is performed by mixing the template, the silicon source, the first aluminum source, and water in a sealed container with stirring at a temperature of 90 to 150°C for 4 to 20 hours.

[0043] In a preferred embodiment, the silicon powder used in step 2) comprises two types of silica particles having different sizes, the sizes of the two types of silica particles being in the ranges of 0.1 to 2 μm and 4 to 12 μm, respectively, the mass ratio of the two types of silica particles being (0.5 to 2.0):1, and the second aluminum source being one or more selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum alkoxide, pseudoboehmite, and aluminum hydroxide.

[0044] In a preferred embodiment, the ratios of the first mixture, silicon powder, and second aluminum source used in step 2) are as follows: the weight ratio of the first mixture to the silicon powder is (0.2-0.8):1; the molar ratio of the silicon powder to the second aluminum source is (30-400):1, where the silicon powder is calculated as SiO and the second aluminum source is calculated as AlO.

[0045] In the present application, there is no particular limitation on the molding method in step 3), and the catalyst may be molded by a method commonly used in the art, such as extrusion molding.

[0046] According to the present application, in step 3), the third mixture can be formed into various shapes according to need, for example, the third mixture can be formed into a strip shape, and the pieces thereof can be circular, gear-shaped, trilobal, four-leaf clover-shaped, or honeycomb-shaped. In a preferred embodiment, the third mixture has a diameter of 1.0 to 6.0 mm and a length of 3 to 10 mm.

[0047] In a preferred embodiment, the alkali source used in step 4) is one or more selected from the group consisting of tetrapropylammonium hydroxide, tetraethylammonium hydroxide, aqueous ammonia, ethylamine, ethylenediamine, n-butylamine, hexamethylenediamine, cyclohexylamine, piperidine, hexamethyleneimine, homopiperazine, and dicyclohexylamine.

[0048] In a preferred embodiment, the regulator used in step 4) is one or more selected from the group consisting of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, casein, and gum arabic.

[0049] In a preferred embodiment, the mass ratio of the third mixture, the alkali source, and the regulator in step 4) is as follows: alkali source:third mixture=(0.1 to 0.4):1, regulator:third mixture=(0.01 to 0.05):1.

[0050] In a preferred embodiment, in step 4), the step of contacting the third mixture with the alkali source and the regulator to obtain a fourth mixture is carried out by mixing the alkali source and the regulator with stirring at 30 to 60°C for 3 to 10 hours, then adding the third mixture thereto, and allowing the mixture to stand in a sealed space at 30 to 60°C for 5 to 10 hours.

[0051] In a preferred embodiment, in step 5), the fourth mixture is treated to obtain an aluminosilicate molecular sieve catalyst by allowing the fourth mixture to stand or stir in a sealed space at 130-190°C for 12-72 hours, and then optionally washing, drying, calcining, and acid-washing. According to the present application, washing (e.g., washing with deionized water until the solution reaches a pH of 7-8), drying, and calcining can be performed by conventional methods. For example, the drying conditions can include a drying temperature of 80-150°C and a drying time of 5-12 hours; the calcination conditions can include a calcination temperature of 500-600°C and a calcination time of 4-10 hours; and the acid-washing conditions can include an acid-washing temperature of 30-90°C, an acid-washing time of 2-10 hours, at least one acid selected from hydrochloric acid, sulfuric acid, oxalic acid, and nitric acid, and a mass concentration of the acid solution of 0.5%-5%.

[0052] In a preferred embodiment, the properties of the aluminosilicate molecular sieve catalyst obtained by the process of the present application are as described above in the first aspect, and a detailed description thereof will be omitted herein for the sake of brevity.

[0053] In a third aspect, the present application provides a process for the vapor phase alkylation of an aromatic hydrocarbon with an olefin, the process comprising subjecting an aromatic hydrocarbon and an olefin to an alkylation reaction in the presence of a catalyst of the present application or a catalyst obtained by a process of the present application to obtain an alkylaromatic hydrocarbon.

[0054] In a preferred embodiment, the aromatic hydrocarbon is selected from benzene, alkylbenzene, or a combination thereof, preferably selected from benzene, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, tert-butylbenzene, or a combination thereof; and the olefin is selected from C2 to C6 olefin, preferably ethylene, propylene, n-butene, isobutylene, or a combination thereof.

[0055] In a preferred embodiment, the alkylation conditions are a reaction temperature of 260°C to 400°C, a reaction pressure of 0.1 to 3.0 MPa, and a reaction time of 0.1 to 10.0 hours. -1 The mass hourly space velocity of olefins is 0.01, and the molar ratio of aromatic hydrocarbons to olefins is 2 to 20.

[0056] In a fourth aspect, the present application provides the use of a catalyst according to the present application or a catalyst obtainable by a method according to the present application for catalyzing the vapor phase alkylation of aromatic hydrocarbons with olefins.

[0057] [Example] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0058] In the following examples and comparative examples, a Rigaku Ultima IV X-ray powder diffractometer was used, with a voltage of 35 kV, a current of 30 mA, and a diffraction grating of 1°·min. -1 The XRD patterns of the catalysts were measured at a scan rate of .

[0059] In the following examples and comparative examples, the acidity distribution of the catalysts was measured by NH3-TPD test, and NH3-TPD spectra were obtained using a 200906PX18 Temperature Programmed Desorption Apparatus manufactured by Tianjin Golden Eagle Technology Co., Ltd., as follows: 0.05-0.20 g of the sample (20-40 mesh) obtained after tableting and sieving was placed in a quartz sample tube, which was first activated by heating in a helium atmosphere for 1 hour, stabilized for 1 hour, then cooled to below 40°C, then heated to 100°C again, and subjected to ammonia absorption at 100°C until saturation was reached; finally, it was blown with helium for 1 hour, and then subjected to temperature-programmed desorption by heating to 600°C at a rate of 10°C / min, and the operating curve was recorded.

[0060] In the following examples and comparative examples, the mechanical strength of the catalyst was measured using a smart particle strength tester, and the mechanical strength of the calcined catalyst was measured using a DLIII Smart Particle Strength Tester manufactured by Dalian Penghui Technology Development Co., Ltd. The catalyst to be measured was placed horizontally on the tester, the maximum pressure that the catalyst received when it was crushed was measured, and the average value of the crushing strength of 20 measured catalyst particles was calculated.

[0061] In the following examples and comparative examples, SEM images were obtained using a Hitachi S-4800 cold field emission high-resolution scanning electron microscope manufactured by Hitachi, Ltd. Grain size distribution was obtained by calculating the ratio of the number of grains in a specific grain size range to the total number of grains based on statistical data for at least 300 grains in the corresponding SEM image.

[0062] In the following examples and comparative examples, the SiO2 / Al2O3 molar ratio of the catalysts was determined by ICP testing using a Kontron Model S-35 ICP-AES analyzer, where 50 mg of sample was completely dissolved in 50 g of hydrofluoric acid solution before ICP testing.

[0063] In the following examples and comparative examples, the isolated aluminum content of the catalyst was measured as follows: first, the synthesized catalyst was subjected to ion exchange to obtain a Na-type catalyst, and the catalyst was mixed with a 0.5 mol / L sodium chloride solution in a solid-liquid mass ratio of 1:100 and stirred at room temperature for 4 hours. Then, the solution was poured out and the obtained solid was washed with deionized water. The liquid obtained after washing was detected with a silver nitrate solution. When no white precipitate was found in the liquid obtained after washing, the washing was terminated, thereby obtaining a Na-type catalyst; then, the Na-type catalyst was exchanged with Co 2+The Na-type catalyst was subjected to ion exchange. The Na-type catalyst was mixed with a 0.05 mol / L cobalt nitrate solution at a solid-liquid mass ratio of 1:200 and stirred at room temperature for 10 hours. The solution was then poured off and the resulting solid was washed with deionized water. The resulting liquid was analyzed with an aqueous ammonia solution. The washing was stopped when no blue precipitate was observed in the resulting liquid. This gave a Co-type catalyst. After drying, the Co content and Al content of the Co-type catalyst were measured by ICP testing. The isolated aluminum content was calculated according to the following formula: Isolated aluminum content = (1-2 × C コバルト / C アルミニウム ) × 100%, In the formula, C コバルト and C アルミニウム refer to the Co content and Al content of the Co-type catalyst, respectively.

[0064] In the following examples and comparative examples, unless otherwise specified, the reagents and starting materials used are commercially available products of reagent purity grade.

[0065] [Example 1] 27.7 g of 40 wt% aqueous tetrapropylammonium hydroxide solution, 60 g of white carbon black, 13.32 g of aluminum sulfate hexahydrate, and 54 g of water were homogeneously mixed and stirred in a sealed container at 90°C for 20 hours to obtain Mixture A1. 12 g of Mixture A1 was mixed with 60 g of silicon powder containing two types of silica particles, each with a size range of 0.3-1.2 μm and 5-9 μm, in amounts of 20 g and 40 g, and 13.32 g of aluminum sulfate hexahydrate to obtain Mixture B1. Mixture B1 was extruded to obtain Mixture C1 (cylindrical shape, 1.8 mm diameter, 5 mm length). 5 g of ethylamine and 0.5 g of hydroxyethyl cellulose were mixed with stirring at 50°C for 5 hours, followed by the addition of 50 g of Mixture C1. The mixture was then allowed to stand in a sealed container at 30°C for 10 hours to obtain Mixture D1. The mixture D1 was allowed to stand in a sealed space at 130°C for 72 hours, then washed with deionized water until a pH value of 8 was obtained, dried at 80°C for 12 hours, calcined at 500°C for 10 hours, and subjected to acid washing with oxalic acid having a mass concentration of 3% at 60°C for 5 hours to obtain an aluminosilicate molecular sieve catalyst E1.

[0066] The XRD pattern of the aluminosilicate catalyst E1 is shown in Figure 1. It has typical diffraction peaks of an MFI topology structure, indicating that the catalyst is a ZSM-5 molecular sieve catalyst. The SEM image of the aluminosilicate molecular sieve catalyst E1 is shown in Figure 2. It can be seen that the catalyst contains two types of crystal grains with different sizes, with the sizes of the two types of crystal grains being 50-200 nm and 400-1000 nm, respectively, and the proportions of the two types of crystal grains by number being 35% and 65%, respectively. The NH3-TPD pattern of the aluminosilicate molecular sieve catalyst E1 is shown in Fig. 3, which shows three peaks designated as P1, P2, and P3 according to the desorption temperature from low to high, respectively. The desorption temperatures corresponding to the tops of the three peaks are 196 °C, 265 °C, and 385 °C, respectively. The heights of the three peaks, i.e., the ratios between H1, H2, and H3, are as follows: H2 / H1 = 0.66, H3 / H2 = 0.82; H3 / H1 = 0.54; and H3 / H1 = 0.54. The ratios of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst calculated based on the integrated areas of the desorption curves within the three temperature ranges of ~240°C, 240-300°C, and 300-500°C are as follows: S2 / S1 = 0.46, S2 / S3 = 0.49, S3 / S1 = 0.94. Correspondingly, the proportions of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content are 42%, 19%, and 39%, respectively.

[0067] According to the measurement, the aluminosilicate molecular sieve catalyst E1 has a mechanical strength of 155 N / cm, a SiO2 / Al2O3 molar ratio of 50.8, and an isolated aluminum content of 99.0%.

[0068] [Example 2] 253 g of 40 wt% aqueous tetrapropylammonium hydroxide solution, 133 g of tetrapropylammonium bromide, 208.3 g of tetraethyl silicate, 2.22 g of aluminum sulfate 18-hydrate, and 60 g of water were homogeneously mixed and stirred in a sealed container at 150 °C for 4 hours to obtain Mixture A2. 48 g of Mixture A2 was mixed with 60 g of silicon powder containing two types of silica particles, each with a size range of 1.2-2 μm and 9-12 μm, in amounts of 30 g and 30 g, and 1.665 g of aluminum sulfate 18-hydrate to obtain Mixture B2. Mixture B2 was extruded to obtain Mixture C2 (cylindrical shape, 2.2 mm diameter, 5 mm length). A mixture of 20 g of cyclohexylamine, 0.5 g of casein, and 2 g of hydroxypropylmethylcellulose was stirred at 50°C for 5 hours, and then 50 g of mixture C2 was added and allowed to stand in a sealed space at 60°C for 5 hours to obtain mixture D2. Mixture D2 was allowed to stand in a sealed space at 190°C for 12 hours, then washed with deionized water until a pH value of 7 was obtained, dried at 150°C for 5 hours, calcined at 600°C for 4 hours, and subjected to acid washing with 0.5% oxalic acid at 30°C for 10 hours to obtain aluminosilicate molecular sieve catalyst E2.

[0069] The XRD pattern of aluminosilicate catalyst E2 is shown in Figure 4. It has typical diffraction peaks of an MFI topology structure, indicating that the catalyst is a ZSM-5 molecular sieve catalyst. SEM images of aluminosilicate catalyst E2 show that the catalyst contains two types of crystal grains with different sizes. Statistical analysis revealed that the sizes of the two types of crystal grains were 250-300 nm and 1000-1600 nm, respectively, and the proportions of the two types of crystal grains were 40% and 60%, respectively. The NH3-TPD pattern of the aluminosilicate molecular sieve catalyst E2 exhibits three peaks, designated as P1, P2, and P3, according to desorption from low to high temperatures. The desorption temperatures corresponding to the peaks of the three peaks are 191°C, 260°C, and 381°C, respectively. The heights of the three peaks, i.e., the ratios between H1, H2, and H3, are as follows: H2 / H1 = 0.51, H3 / H2 = 0.80, and H3 / H1 = 0.41; from 100 to 240°C, 240 to 381°C, respectively. The ratios of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst calculated based on the integrated areas of the desorption curves within the three temperature ranges of 0 to 300°C and 300 to 500°C are as follows: S2 / S1 = 0.48, S2 / S3 = 0.52, and S3 / S1 = 0.92. Correspondingly, the proportions of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content are 42%, 20%, and 38%, respectively.

[0070] According to the measurement, the aluminosilicate molecular sieve catalyst E2 has a mechanical strength of 112 N / cm, a SiO2 / Al2O3 molar ratio of 398, and an isolated aluminum content of 99.6%.

[0071] [Example 3] 126 g of 40 wt% aqueous tetrapropylammonium hydroxide solution, 66 g of tetrapropylammonium bromide, 208.3 g of tetraethyl silicate, 6.66 g of aluminum sulfate 18-hydrate, and 50 g of water were homogeneously mixed and stirred in a sealed container at 120 °C for 12 hours to obtain Mixture A3. 24 g of Mixture A3 was mixed with 60 g of silicon powder containing two types of silica particles, each with a size range of 0.1-0.3 μm and 4-7 μm, in amounts of 40 g and 20 g, and 6.66 g of aluminum sulfate 18-hydrate to obtain Mixture B3. Mixture B3 was extruded to obtain Mixture C3 (cylindrical shape, 1.2 mm diameter, 5 mm length). 10 g of n-butylamine and 1.5 g of gum arabic were mixed at 50°C for 5 hours with stirring, and then 50 g of mixture C3 was added thereto and allowed to stand at 40°C for 7 hours in a sealed space to obtain mixture D3. Mixture D3 was allowed to stand at 170°C for 36 hours in a sealed space, then washed with deionized water until a pH value of 7.5 was obtained, dried at 100°C for 8 hours, calcined at 550°C for 6 hours, and subjected to acid washing with 3% by mass hydrochloric acid at 60°C for 6 hours to obtain aluminosilicate molecular sieve catalyst E3.

[0072] The XRD pattern of the aluminosilicate catalyst E3 is shown in Figure 5. It has typical diffraction peaks of an MFI topology structure, indicating that the catalyst is a ZSM-5 molecular sieve. The SEM image of the aluminosilicate molecular sieve catalyst E3 shows that the catalyst contains two types of crystal grains with different sizes. According to statistical analysis, the sizes of the two types of crystal grains are 10-100 nm and 400-700 nm, respectively, and the proportions of the two types of crystal grains are 56% and 44%, respectively. The NH3-TPD pattern of the aluminosilicate molecular sieve catalyst E3 shows three peaks, designated as P1, P2, and P3, according to the desorption from low to high temperatures. The desorption temperatures corresponding to the peaks of the three peaks are 208°C, 277°C, and 399°C, respectively. The heights of the three peaks, i.e., the ratios between H1, H2, and H3, are as follows: H2 / H1 = 0.79, H3 / H2 = 0.89, and H3 / H1 = 0.70; from 100 to 240°C, 2 The ratios of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst calculated based on the integrated areas of the desorption curves within the three temperature ranges of 40 to 300°C and 300 to 500°C are as follows: S2 / S1 = 0.41, S2 / S3 = 0.38, S3 / S1 = 1.07. Correspondingly, the proportions of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content are 40%, 17%, and 43%, respectively.

[0073] According to the measurement, the aluminosilicate molecular sieve catalyst E3 has a mechanical strength of 145 N / cm, a SiO2 / Al2O3 molar ratio of 125, and an isolated aluminum content of 99.2%.

[0074] [Comparative Example 1] A catalyst was prepared as described in Example 3, except that silicon powder containing only one type of silica particles with a size range of 0.1 to 0.3 μm was used and no regulator was added in step 4). The catalyst was prepared as follows: 126 g of 40 wt % aqueous tetrapropylammonium hydroxide solution, 66 g of tetrapropylammonium bromide, 208.3 g of tetraethyl silicate, 6.66 g of aluminum sulfate 18-hydrate, and 50 g of water were homogeneously mixed and stirred in a sealed container at 120°C for 12 hours to obtain Mixture A4. 24 g of Mixture A4 was mixed with 60 g of silicon powder containing only one type of silica particles with a size range of 0.1 to 0.3 μm and 6.66 g of aluminum sulfate 18-hydrate to obtain Mixture B4. Mixture B4 was extruded to obtain Mixture C4 (cylindrical shape with a diameter of 1.2 mm and a length of 5 mm). 10 g of n-butylamine was stirred at 50° C. for 5 hours, and then 50 g of mixture C4 was added thereto, and the mixture was allowed to stand in a sealed space at 40° C. for 7 hours to obtain mixture D4. Mixture D4 was allowed to stand in a sealed space at 170° C. for 36 hours, and then washed with deionized water until a pH value of 7.5 was obtained, dried at 100° C. for 8 hours, calcined at 550° C. for 6 hours, and subjected to acid washing with 3% by mass hydrochloric acid at 60° C. for 6 hours to obtain aluminosilicate molecular sieve catalyst F1.

[0075] The SEM image of the aluminosilicate molecular sieve catalyst F1 is shown in Figure 6, from which statistical analysis reveals that the catalyst contains only one type of crystal grain with a size ranging from 180 to 250 nm. The NH3-TPD pattern of the aluminosilicate molecular sieve catalyst F1 is shown in Figure 7, which shows two peaks, designated as P1 and P2, depending on the desorption temperature from low to high. The desorption temperatures corresponding to the apex of the two peaks are 194°C and 396°C, respectively. The height ratio of the two peaks, i.e., H1 and H2, is as follows: H2 / H1 = 0.96, 100-240°C, 240-300°C, and 396°C, respectively. The ratios of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst calculated based on the integrated areas of the desorption curves within the three temperature ranges of 300 to 500°C are as follows: S2 / S1 = 0.28, S2 / S3 = 0.17, S3 / S1 = 1.63. Correspondingly, the proportions of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content are 34%, 10%, and 56%, respectively.

[0076] According to the measurements, the aluminosilicate molecular sieve catalyst F1 has a mechanical strength of 155 N / cm, a SiO2 / Al2O3 molar ratio of 128, and an isolated aluminum content of 95.8%.

[0077] Comparative Example 2 A catalyst was prepared as described in Example 1, except for changing the order of addition of the regulator hydroxyethyl cellulose. The catalyst was prepared as follows: 27.7 g of 40 wt % tetrapropylammonium hydroxide aqueous solution, 60 g of white carbon black, 13.32 g of aluminum sulfate hexahydrate, 54 g of water, and 0.5 g of hydroxyethyl cellulose were homogeneously mixed and stirred in a sealed container at 90°C for 20 hours to obtain Mixture A5. 12 g of Mixture A5 was mixed with 60 g of silicon powder containing two types of silica particles, each with a size range of 0.3-1.2 μm and 5-9 μm, in amounts of 20 g and 40 g, and 13.32 g of aluminum sulfate hexahydrate to obtain Mixture B5. Mixture B5 was extruded to obtain Mixture C5 (cylindrical shape, 1.8 mm diameter, 5 mm length). 5 g of ethylamine was stirred at 50° C. for 5 hours, and then 50 g of mixture C5 was added thereto and allowed to stand in a sealed space at 30° C. for 10 hours to obtain mixture D5. Mixture D5 was allowed to stand in a sealed space at 130° C. for 72 hours, then washed with deionized water until a pH value of 8 was obtained, dried at 80° C. for 12 hours, calcined at 500° C. for 10 hours, and subjected to acid washing with 3% by mass oxalic acid at 60° C. for 5 hours to obtain aluminosilicate molecular sieve catalyst F2.

[0078] SEM images of aluminosilicate molecular sieve catalyst F2 show that the catalyst contains two types of crystal grains with different sizes, which, according to statistical analysis, are 200-420 nm and 1500-2000 nm, respectively. The NH3-TPD pattern of aluminosilicate molecular sieve catalyst F2 exhibits two peaks, designated P1 and P2, depending on the desorption temperature from low to high. The desorption temperatures corresponding to the peaks of the two peaks are 197°C and 399°C, respectively. The height ratios of the two peaks, i.e., H1 and H2, are as follows: H2 / H1 = 0.76; 100-240°C, 240-300°C, and 399°C, respectively. Based on the integrated areas of the desorption curves within the three temperature ranges of 00 to 500°C, the ratios of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst were calculated as follows: S2 / S1 = 0.26, S2 / S3 = 0.16, S3 / S1 = 1.60. The proportions of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content were 35%, 9%, and 56%, respectively.

[0079] According to the measurement, the aluminosilicate molecular sieve catalyst F2 has a mechanical strength of 135 N / cm, a SiO2 / Al2O3 molar ratio of 52.4, and an isolated aluminum content of 96.6%.

[0080] Comparative Example 3 A catalyst was prepared as described in Example 3, except that silicon powder containing only one type of silica particles with a size range of 0.1 to 0.3 μm was used. The catalyst was prepared as follows: 126 g of 40 wt % aqueous tetrapropylammonium hydroxide solution, 66 g of tetrapropylammonium bromide, 208.3 g of tetraethyl silicate, 6.66 g of aluminum sulfate 18-hydrate, and 50 g of water were uniformly mixed and stirred in a sealed container at 120°C for 12 hours to obtain Mixture A6. 24 g of Mixture A6 was mixed with 60 g of silicon powder containing only one type of silica particles with a size range of 0.1 to 0.3 μm and 6.66 g of aluminum sulfate 18-hydrate to obtain Mixture B6. Mixture B6 was extruded to obtain Mixture C6 (cylindrical shape with a diameter of 1.2 mm and a length of 5 mm). 10 g of n-butylamine and 1.5 g of gum arabic were stirred at 50° C. for 5 hours, and then 50 g of mixture C6 was added and allowed to stand in a sealed space at 40° C. for 7 hours to obtain mixture D6. Mixture D6 was allowed to stand in a sealed space at 170° C. for 36 hours, then washed with deionized water until a pH value of 7.5 was obtained, dried at 100° C. for 8 hours, calcined at 550° C. for 6 hours, and acid-washed with 3% by mass hydrochloric acid at 60° C. for 6 hours to obtain aluminosilicate molecular sieve catalyst F3.

[0081] The SEM image of the aluminosilicate catalyst F3 shows that the catalyst contains only one type of crystal grains, with a size ranging from 170 to 245 nm, according to statistical analysis. The NH3-TPD pattern of the aluminosilicate molecular sieve catalyst F3 exhibits two peaks, designated as P1 and P2, depending on the desorption temperature from low to high. The desorption temperatures corresponding to the apex of the two peaks are 189°C and 366°C, respectively. The height ratio of the two peaks, i.e., H1 and H2, is as follows: H2 / H1 = 0.76; 100-240°C, 240-300°C, and 300°C, respectively. The ratios of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst, calculated based on the integrated areas of the desorption curves within three temperature ranges from 500°C to 500°C, are as follows: S2 / S1 = 0.43, S2 / S3 = 0.35, S3 / S1 = 1.23. Correspondingly, the proportions of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content are 38%, 16%, and 46%, respectively.

[0082] According to the measurement, the aluminosilicate molecular sieve catalyst F3 has a mechanical strength of 142 N / cm, a SiO2 / Al2O3 molar ratio of 126, and an isolated aluminum content of 97.3%.

[0083] Comparative Example 4 The catalyst was prepared according to the method of CN107512729A as follows: Preparation of the synthesized ZSM-5 molecular sieve: Alkaline silica sol, aluminum sulfate octadecahydrate, tetrapropylammonium hydroxide (TPAOH), and water were used as raw materials. The raw materials were homogeneously mixed in the molar ratios of SiO2 / Al2O3 = 180, TPAOH / SiO2 = 0.22, and H2O / SiO2 = 18, and then charged into a stainless steel reaction kettle and crystallized at 150 °C for 3 days under stirring. After the crystallization was completed, the resulting material was filtered, washed, and dried to obtain the synthesized ZSM-5 molecular sieve.

[0084] Preparation of ZSM-5 molecular sieve precursor: 41.866 g of the synthesized ZSM-5 molecular sieve, 37.5 g of alkaline silica sol (SiO content: 40.0 wt%), 0.5616 g of methyl cellulose, and 5 wt% aqueous nitric acid solution were uniformly mixed and extruded into four-leaf clover-shaped pieces with a diameter of 1.2 mm and a length of 5 mm to obtain a molecular sieve precursor containing 70 wt% ZSM-5 molecular sieve.

[0085] Preparation of the target catalyst: 1.97 g of sodium aluminate (containing 43.0 wt% Al2O3 and 35.0 wt% Na2O), 247 g of water, and 8.865 g of n-butylamine (99.0 wt% n-butylamine) were homogeneously mixed and then mixed with the entire molecular sieve precursor obtained above. The resulting mixture was crystallized at 150°C for 28 hours. After completion of crystallization, the resulting material was filtered, washed, dried, calcined in air at 550°C for 5 hours, ammonia-exchanged three times with 10 wt% ammonium sulfate solution, and calcined in air at 550°C for 5 hours to obtain binderless ZSM-5 molecular sieve catalyst F4.

[0086] SEM images of catalyst F4 show that the catalyst contains only one type of crystal grain, with a size ranging from 300 to 450 nm, according to statistical analysis. The NH3-TPD pattern of catalyst F4 exhibits two peaks, designated P1 and P2, depending on the desorption temperature from low to high. The desorption temperatures corresponding to the peaks of the two peaks are 193°C and 390°C, respectively. The height ratio of the two peaks, i.e., H1 and H2, is as follows: H2 / H1 = 1.21; and the three peaks at 100-240°C, 240-300°C, and 300-500°C, respectively. The ratios between the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 of the catalyst calculated based on the integrated areas of the desorption curves within the temperature range of 0.15 to 0.37, 0.18, and 2.03, respectively. Correspondingly, the proportions of the weak acid content S1, the medium-strong acid content S2, and the strong acid content S3 to the total acid content are 29%, 11%, and 60%, respectively.

[0087] Measurements show that catalyst F4 has a mechanical strength of 78 N / cm, a SiO2 / Al2O3 molar ratio of 145, and an isolated aluminum content of 93.7%.

[0088] [Table 1]

[0089] As can be seen from Table 1, the particle size of the catalyst of the present invention is bimodal, and its NH3-TPD desorption curve shows three distinct peaks. Compared with the catalyst obtained in the comparative example, the catalyst of the present invention shows a significantly different acidity distribution, in particular, the content ratio of medium and strong acids is significantly improved, while the content ratio of strong acids is reduced, and the content ratio of weak acids is improved.

[0090] [Test Example 1] The aluminosilicate molecular sieve catalysts E1 to E3 obtained in Examples 1 to 3 and the catalysts F1 to F4 obtained in Comparative Examples 1 to 4 were each applied to a gas phase alkylation reaction of benzene with ethylene at a reaction temperature of 380°C, a reaction pressure of 1.5 MPa, and a reaction time of 2.2 hours. -1 The reaction was carried out for 10 hours under conditions including an ethylene mass space velocity of 1000 kJ / mole and a benzene to ethylene molar ratio of 5.5. The xylene content, diethylbenzene and triethylbenzene contents in the alkylation product were detected, and the ethylene conversion and ethyl selectivity were calculated. The reaction results are shown in Table 2 below: Ethylene conversion rate = (total amount of ethylene input - amount of ethylene in reactor effluent) / total amount of ethylene input × 100% Ethyl selectivity = (moles of ethylbenzene produced + moles of diethylbenzene x 2 + moles of triethylbenzene x 3) / moles of ethylene consumed x 100%

[0091] [Table 2]

[0092] [Test Example 2] The single-pass life of the aluminosilicate molecular sieve catalysts E1 to E3 obtained in Examples 1 to 3 and the catalysts F1 to F4 obtained in Comparative Examples 1 to 4 in the gas-phase alkylation reaction of benzene with ethylene was tested under reaction conditions including an ultra-high ethylene space velocity. The detailed conditions were a reaction temperature of 400°C, a pressure of 2.0 MPa, and a reaction time of 6 hours. -1 The conditions included an ethylene mass hourly space velocity of 0.05, an ethylene to benzene molar ratio of 2, and a benzene to ethylene molar ratio of 2. The single-pass lifetime refers to the period of time from the start of the reaction to the time when the ethylene conversion dropped to 60% of the initial conversion. The reaction results are shown in Table 3 below.

[0093] [Table 3]

[0094] As shown in the data in Table 2, compared with the catalyst obtained in the comparative example, the catalyst of the present application exhibits higher activity and selectivity in the alkylation reaction of aromatics with olefins, significantly reduces the content of by-products, and improves the olefin conversion and product selectivity. In particular, in the reaction to produce ethylbenzene by alkylation of benzene with ethylene, the mass content of key impurities, xylene, in the resulting alkylation product can be reduced to a level of less than 500 ppm, and the mass contents of diethylbenzene and triethylbenzene can be reduced to a level of less than 8%.

[0095] As shown by the data in Table 3, compared to the catalyst obtained in the comparative example, the catalyst of the present application exhibits higher stability and significantly increased single-pass life in the vapor-phase alkylation of benzene with ethylene under reaction conditions including ultra-high ethylene space velocity.

[0096] Although the present application has been described in detail above with reference to preferred embodiments, it is not intended to be limited to these embodiments. Various modifications may be made in accordance with the inventive concept of the present application, and these modifications should be within the scope of the present application.

[0097] It should be noted that the various technical features described in the above embodiments may be combined in any suitable manner without contradiction, and in order to avoid unnecessary repetition, the present application does not describe various possible combinations, but such combinations should also be included within the scope of the present application.

[0098] Furthermore, various embodiments of the present application may be combined in any manner unless such combination deviates from the spirit of the present application, and such combined embodiments should be considered as the disclosure of the present application. [Brief explanation of the drawings]

[0099] [Figure 1] FIG. 1 shows the XRD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 1 of the present application. [Figure 2] FIG. 2 shows an SEM image of the aluminosilicate molecular sieve catalyst obtained in Example 1 of the present application. [Figure 3] FIG. 3 shows the NH3-TPD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 1 of the present application. [Figure 4] FIG. 4 shows the XRD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 2 of the present application. [Figure 5] FIG. 5 shows the XRD pattern of the aluminosilicate molecular sieve catalyst obtained in Example 3 of the present application. [Figure 6] FIG. 6 shows an SEM image of the aluminosilicate molecular sieve catalyst obtained in Comparative Example 1. [Figure 7] FIG. 7 shows the NH3-TPD pattern of the aluminosilicate molecular sieve catalyst obtained in Comparative Example 1.

Claims

1. Aluminosilicate molecular sieve catalyst for vapor phase alkylation of aromatic hydrocarbons with olefins, comprising: ３ - The TPD pattern shows a desorption curve with three peaks P1, P2, and P3, and the desorption temperatures corresponding to the apexes of the three peaks P1, P2, and P3 are within the ranges of 180-220°C, 250-290°C, and 370-410°C, respectively; The content S1 of the weak acid, the content S2 of the medium-strong acid, and the content S3 of the strong acid satisfy the following relationship: S2 / S1=(0.38-0.52):1; S2 / S3=(0.32-0.58):1; and S3 / S1=(0.8~1.2):1, Here, the ratio between the content S1 of the weak acid, the content S2 of the medium-strong acid, and the content S3 of the strong acid is determined by the NH ３ - Calculated based on the ratio between the integrated areas of the desorption curves in the temperature ranges of 100-240°C, 240-300°C, and 300-500°C in the TPD pattern.

2. 2. The catalyst according to claim 1, wherein the desorption temperatures corresponding to the apexes of the three peaks P1, P2, and P3 are in the ranges of 190 to 210°C, 260 to 280°C, and 380 to 400°C, respectively.

3. The catalyst according to claim 1, wherein the content S1 of the weak acid, the content S2 of the medium-strong acid, and the content S3 of the strong acid satisfy the following relationship: S2 / S1=(0.4-0.5):1; S2 / S3=(0.35-0.55):1; and S3 / S1=(0.9-1.1):

1.

4. The catalyst according to claim 1 , wherein the peak heights H1, H2, and H3 of the three peaks P1, P2, and P3 satisfy the relationship H1>H2>H3.

5. 5. The catalyst of claim 4, wherein the peak heights H1, H2, and H3 satisfy the following relationship: H2 / H1=(0.5-0.8):1; H3 / H2=(0.8-0.9):1; and H3 / H1=(0.4-0.7):

1.

6. The ratio of the content S1 of the weak acid to the total content of the acid in the catalyst is 40 to 50%, the ratio of the content S2 of the medium-strong acid to the total content of the acid is 15 to 25%, and the ratio of the content S3 of the strong acid to the total content of the acid is 35 to 45%, and the ratios of the content S1 of the weak acid, the content S2 of the medium-strong acid, and the content S3 of the strong acid to the total content of the acid are determined by the NH ３ - NH of the catalyst compared with the total integrated area of ​​the desorption curve in the temperature range of 100 to 500 ° C. in the TPD pattern ３ - calculated from the percentage of the total integrated area of ​​the desorption curve in the temperature ranges of 100-240°C, 240-300°C, and 300-500°C in the TPD pattern; Here, the total acid content is the sum of the weak acid content, the medium-strong acid content, and the strong acid content. The catalyst according to any one of claims 1 to 5.

7. The catalyst according to any one of claims 1 to 6, wherein the catalyst is a binderless aluminosilicate molecular sieve catalyst.

8. 8. The catalyst according to claim 7, wherein the aluminosilicate molecular sieve is an acidic molecular sieve having a pore structure of 10-membered rings or 12-membered rings.

9. 9. The catalyst of claim 8, wherein the acidic molecular sieve is a ZSM-5 molecular sieve.

10. Catalyst according to any one of claims 1 to 9, wherein the catalyst has one or more of the following characteristics: The ratio of the content of super acid to the total content of acid of the catalyst is less than 5%, wherein the ratio of the content of super acid to the total content of acid is less than 5% by weight of the NH ３ - NH of the catalyst relative to the total integrated area of ​​the desorption curve in the temperature range of 100 to 500 ° C. in the TPD pattern ３ - calculated from the percentage of the integrated area of ​​the desorption curve in the temperature range above 500°C in the TPD pattern; wherein the total acid content is the sum of the weak acid content, the medium-strong acid content, and the strong acid content; No additional modifying metal or non-metallic components of zinc, magnesium, calcium, iron, cobalt, nickel, phosphorus, lanthanum, copper, zirconium, chromium, manganese, silver, ruthenium, palladium, platinum, titanium, tin, strontium, barium, vanadium, and lithium are supported on said catalyst; The catalyst comprises two types of crystal grains of different sizes, the sizes of the crystal grains being 10-300 nm and 400-1600 nm, respectively; The catalyst has an isolated aluminum content of 97.5 to 100%; The catalyst has a mechanical strength of 100 to 170 N / cm; and The catalyst is SiO ２ / Al ２ O ３ The molar ratio is 30 to 400.

11. 11. The catalyst of claim 10, wherein the number of types of crystal grains having a size of 10 to 300 nm accounts for 5 to 60% of the total number of crystal grains, and the number of types of crystal grains having a size of 400 to 1600 nm accounts for 40 to 95% of the total number of crystal grains.

12. The catalyst of claim 10, wherein the catalyst has an isolated aluminum content of 99-100%.

13. A method for producing the aluminosilicate molecular sieve catalyst according to any one of claims 1 to 12, comprising the steps of: 1) mixing a template, a silicon source, a first aluminum source, and water under heating to obtain a first mixture; 2) mixing the first mixture, silicon powder, and a second aluminum source to obtain a second mixture; 3) shaping the second mixture to obtain a third mixture; 4) contacting the third mixture with an alkalinity source and a regulator to obtain a fourth mixture, wherein the regulator is a polyhydroxy polymeric compound; and 5) treating the fourth mixture to obtain the aluminosilicate molecular sieve catalyst, wherein the treating includes a calcination step.

14. 14. The method of claim 13, wherein the regulator is selected from the group consisting of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, casein, gum arabic, or any combination thereof.

15. 14. The method of claim 13, wherein step 1) has one or more of the following features: the template is selected from tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium bromide, or a combination thereof; the silicon source is selected from silica sol, white carbon black, tetraethyl silicate, silicon powder, or a combination thereof; and the first aluminum source is selected from aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum isopropoxide, pseudoboehmite, or a combination thereof; The molar ratios among the template, the silicon source, the first aluminum source, and water satisfy the following: template: silicon source = (0.05 to 1.0): 1, silicon source: first aluminum source = (30 to 400): 1, water: silicon source = (3 to 12): 1, wherein the silicon source is SiO ２ and the first aluminum source is Al ２ O ３ is calculated as: The step of mixing under heating in step 1) includes a step of mixing the template, the silicon source, the first aluminum source, and water in a sealed container with stirring at a temperature of 90 to 150°C for 4 to 20 hours.

16. The method according to any one of claims 13 to 15, wherein step 2) has one or more of the following characteristics: The silicon powder includes two types of silica particles having different sizes, the sizes of the silica particles being 0.1-2 μm and 4-12 μm, respectively, and the mass ratio of the two types of silica particles is (0.5-2.0):1; The second aluminum source is selected from aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum alkoxide, pseudoboehmite, aluminum hydroxide, or a combination thereof; and The ratio between the first mixture, the silicon powder, and the second aluminum source satisfies the following: the weight ratio of the first mixture to the silicon powder is (0.2-0.8):1, and the molar ratio of the silicon powder to the second aluminum source is (30-400):1; wherein the silicon powder is SiO ２ and the second aluminum source is Al ２ O ３ It is calculated as:

17. The method according to any one of claims 13 to 16, wherein step 4) has one or more of the following characteristics: The alkaline source is selected from tetrapropylammonium hydroxide, tetraethylammonium hydroxide, aqueous ammonia, ethylamine, ethylenediamine, n-butylamine, hexamethylenediamine, cyclohexylamine, piperidine, hexamethyleneimine, homopiperazine, dicyclohexylamine, or a combination thereof; a mass ratio of the third mixture, the alkalinity source, and the regulator satisfies alkalinity source:third mixture=(0.1 to 0.4):1; regulator:third mixture=(0.01 to 0.05):1; and The contacting step of step 4) includes a step of mixing the alkalinity source and the regulator with stirring at 30 to 60°C for 3 to 10 hours, then adding the third mixture, and allowing the mixture to stand in a sealed space at 30 to 60°C for 5 to 10 hours.

18. The method according to any one of claims 13 to 17, wherein the treatment in step 5) comprises leaving the fourth mixture to stand or stirring it in a sealed space at 130 to 190°C for 12 to 72 hours, followed by a washing step, a drying step, a calcination step, and an acid washing step.

19. 13. A process for the vapor phase alkylation of an aromatic hydrocarbon with an olefin, comprising the step of contacting said aromatic hydrocarbon with said olefin in the presence of a catalyst according to any one of claims 1 to 12 for an alkylation reaction to obtain an alkylaromatic hydrocarbon.

20. 20. The method of claim 19, wherein the aromatic hydrocarbon is selected from benzene, alkylbenzene, or a combination thereof; and the olefin is selected from C2 to C6 olefins.

21. The alkylation conditions are a reaction temperature of 260 to 400° C., a reaction pressure of 0.1 to 3.0 MPa, and a reaction time of 0.1 to 10.0 hours. －１ and a molar ratio of said aromatic hydrocarbon to said olefin of from 2 to 20.

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