Olefin conversion catalyst, its preparation method and its use

Abstract

An olefin conversion catalyst, its preparation method and its use are disclosed. The olefin conversion catalyst comprises the following components in parts by weight: a) 50-90 parts of a molecular sieve having a 12-membered or more ring structure; b) 0.1-10 parts of an additive component selected from a group IA metal element, a group IIA metal element, or a combination thereof, calculated as oxide; c) 0.1-10 parts of a modifier component selected from silicon, germanium, bismuth, tin, boron, gallium, or a combination thereof, calculated as oxide; and d) 10-49 parts of a carrier component. When the catalyst is used to convert a small amount of olefins in an aromatic rich distillate, the catalyst has the characteristics of high activity, stability, long life, and effective utilization of olefins.

Description

Detailed Description of the Invention

[0001] [Technical field] The present application relates to the field of catalysis, in particular to olefin conversion catalysts, their preparation methods and applications.

[0002] [Background technology] Benzene products, which have the largest production capacity among petroleum aromatics, are mainly produced from aromatics complex units, ethylene units, and refining units. Among the aromatic hydrocarbon mixtures, a certain amount of olefin compounds will inevitably be generated from the intermediate production process. The chemical properties of these olefin compounds are relatively active and prone to generate new components, which can have a significant impact on the quality of the product and also interfere with the steady operation of downstream facilities. In order to obtain high-quality aromatic products such as para-xylene and ensure that there are no problems in the downstream processes, it is necessary to remove trace amounts of olefin compounds after the reforming process, aromatics extraction process, isomerization process, and toluene disproportionation process. In current technology, the above olefins are removed as waste resources, but are not effectively utilized.

[0003] As a traditional aromatic hydrocarbon dealkenization refining agent, white clay has low activity, short life, high usage, cannot be regenerated, and needs to be replaced frequently. White clay not only has a negative impact on safe production, but waste white clay also pollutes the environment and requires high disposal costs. For this reason, molecular sieve olefin removal purification technology has been developed. This technology uses a molecular sieve catalyst with increased active centers instead of industrial white clay, and utilizes its relatively large specific surface area and acid content to achieve a long single-cycle service life and total service life, and removes olefins as impurities. However, it is necessary to regenerate the catalyst on the spot every time it is deactivated. During the molecular sieve regeneration process, the activity of the molecular sieve catalyst is easily reduced due to high-temperature carbon combustion. During the regeneration process, a large amount of olefin products will generate carbon dioxide and water, which will be discharged into the atmosphere, wasting a lot of resources.

[0004] CN102008976A, CN103041841B, CN102039160B and CN104907090A all use molecular sieves as the main active component of the olefin removal catalyst, which have been improved in various ways to suit the olefin removal reaction process, preventing the catalyst from coking and deactivating too quickly. The catalyst life is relatively long, but the organic matter in the olefin product is more adsorbed, and the life is not long. At the same time, there is a lot of association and decomposition, which affects the stable operation of the device. Among them, the olefin removal catalyst disclosed in CN102008976A uses ReUSY molecular sieve with a high silicon to aluminum ratio as the main active component, mordenite as the second active component, and alumina as the binder. High molecular olefin impurities are difficult to diffuse in the catalyst, which causes coking and deactivation of the catalytic active center. CN103041841B discloses an aromatic hydrocarbon non-hydrogenated olefin removal catalyst and its preparation method, which uses a waste catalytic cracking catalyst containing Y molecular sieve as raw material to produce an aromatic hydrocarbon non-hydrogenated olefin removal catalyst. The waste catalytic cracking catalyst with a metal content of less than 5000μg / g is mixed with alumina dried rubber powder, extruded into a long shape, and calcined at 540℃ for 4 hours to obtain an aromatic hydrocarbon non-hydrogenated olefin removal catalyst. This method is only intended to reactivate the inactivated catalyst, and reduces catalyst costs by reducing catalyst preparation costs, but does not improve the actual production cycle. The reformate olefin removal catalyst introduced in CN102039160B is made of 20-90 parts of molecular sieve and 10-80 parts of SiO 2、A catalyst containing at least one selected from Al2O3 or a mixture thereof and at least one metal selected from Mo, Zr, Nb or their oxides, at least one element selected from Cl, Br, S or their oxides, and at least one element selected from F, P or their oxides is used, which effectively extends the regeneration cycle of the catalyst, but it cannot be regenerated because it contains Cl, Br, S, and F. In addition, the activity is easily covered, i.e., blocked, by coke, and the life is short, and the olefins after removal cannot be used. CN104907090A introduces a catalytic reforming oil refining olefin removal catalyst and its preparation method, which contains 30%-70% Al2O3 and 30%-70% molecular sieve with Al oxide as the active center, and is prepared by impregnation method. The active center in the molecular sieve is easily blocked by coking, and the catalyst cannot be used after removing the olefins.

[0005] Another method for olefin removal is hydrogenation technology. Hydrogenation technology reacts olefins with hydrogen to saturate double bonds and selectively remove olefins. However, the above technology inevitably hydrogenates unsaturated aromatic rings in some expensive aromatic hydrocarbons, which irreversibly generates non-aromatic hydrocarbons and reduces the production capacity of the entire unit. For example, in CN1448474A, precious metals are used as active metal components. Due to excessive hydrogenation performance, alkali metals and alkaline earth metals are used as additives to suppress the excessive hydrogenation performance. However, the loss of aromatic hydrocarbons is high, reaching nearly 0.5 wt%, which directly leads to the increase in the cost of aromatic processing. In CN101260320A, the eggshell mode is used to optimize the metal distribution and reduce the excessive hydrogenation performance, but the loss of aromatics is still inevitable. In CN108636399A, a non-precious metal hydrogenation method is used to remove olefins. This method not only consumes hydrogen, but also requires reduction and activation before using the catalyst. This method is difficult to apply to practical industries, and at the same time, it is inevitable that some aromatic hydrocarbons will be lost during operation, and it is difficult to maintain the activity stably.

[0006] The above catalysts use different reforming methods to achieve deolefination. The molecular sieve olefin removal method has a short life span, and the hydrogenation technology is expensive and difficult to operate. In both methods, the olefins are not fully utilized, which increases the production cost of aromatics.

[0007] Summary of the Invention In order to solve the problems of the prior art, such as the tendency of olefin removal catalysts to coke, to be deactivated, to have poor stability, and to have a short life, the object of the present invention is to provide an olefin conversion catalyst, a preparation method thereof, and its use. When this catalyst is used for the conversion of olefins in aromatic-rich reformate, it has the advantages of high activity stability, long life, and effective utilization of olefins.

[0008] In order to achieve the above object, on the one hand, the present application provides an olefin conversion catalyst comprising the following components in parts by weight: a) molecular sieves having 50 to 90 parts of a 12- or more-membered ring structure; b) 0.1 to 10 parts, calculated on oxide, of an additive component selected from Group IA metal elements, Group IIA metal elements, or combinations thereof; c) 0.1 to 10 parts, calculated on oxide, of a modifying component selected from silicon, germanium, bismuth, tin, boron, gallium, or combinations thereof; and d) 10 to 49 parts of a carrier component.

[0009] In another aspect, the present application provides a method for preparing the catalyst of the present application, comprising: (1) forming a mixture of the molecular sieve, the carrier, and the precursor of the additive component, and drying and calcining the mixture to obtain a formed body; and (2) The modifying component is supported on the molded body, which is then dried and calcined to obtain a catalyst.

[0010] In yet another aspect, the present application provides a method for converting olefins contained in an aromatic-rich distillate, the method comprising the step of catalytically reacting the aromatic-rich distillate containing olefins with a catalyst of the present application.

[0011] When the catalyst of the present application is used in the conversion process of small amounts of olefins in aromatic-rich distillate, the olefins and aromatic hydrocarbons in the aromatic-rich feedstock can be effectively converted into required aromatic components (such as C-8 aromatic hydrocarbons) through alkylation reaction, disproportionation reaction, transalkylation reaction, or lightening reaction of heavy aromatic hydrocarbons, etc. It not only reduces the content of olefins in aromatic-rich distillate, but also increases the content of useful aromatic hydrocarbon components in aromatic-rich distillate. It can also limit the generation of high boiling point products. In addition, it can greatly improve the activity stability and service life of the catalyst, thereby increasing the single cycle life of the olefin conversion catalyst by more than 2 to 8 times that of the current olefin removal catalyst.

[0012] Description of the drawings The drawings are used to provide a further understanding of the present application and constitute a part of this specification. They are used to explain the present application together with the following specific embodiments, but are not intended to limit the present application.

[0013] In the drawings: FIG. 1 shows the mesopore distribution of the catalyst obtained in Example 1, as measured by BET and calculated by the t-plot method.

[0014] Detailed Description of the Invention Hereinafter, specific embodiments of the present application will be described in detail with reference to the drawings. It should be understood that the specific embodiments described herein are for the purpose of illustrating and explaining the present application, and are not intended to limit the present application.

[0015] Any specific numerical value disclosed herein (including the endpoints of a numerical range) is not intended to be limited to the exact value of the numerical value, but is also intended to encompass values ​​that approximate the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, for any of the disclosed numerical ranges, any combination between the endpoints of the ranges, between the endpoints and any particular point within the range, and between each particular point within the range, can result in one or more new numerical ranges, which new numerical ranges are also to be considered specifically disclosed herein.

[0016] Unless otherwise specified, terms used herein have the same meaning as commonly understood by those of ordinary skill in the art. Where a term is defined herein and the definition differs from the commonly understood meaning of those of ordinary skill in the art, the definition herein shall prevail.

[0017] In this application, a liquid nitrogen adsorption / desorption apparatus is used to measure the pore volume and pore size distribution of molecular sieves and catalysts. The measurement method is as follows: the test is carried out at the liquid nitrogen saturation temperature (77K), N2 isothermal adsorption / desorption curves are obtained through different relative pressures, and the pore volume and pore distribution are obtained by the t-plot method; the relative pressure during the experiment is 0.001-0.995.

[0018] In this application, the composition of the catalyst is determined by X-ray fluorescence (XRF) spectroscopy.

[0019] In the present application, the pore volume of micropores, the pore volume of mesopores and the total pore volume are measured by the liquid nitrogen adsorption / desorption BET method and calculated by the t-plot method, and the total pore volume is calculated by the single-point method at a relative pressure of 0.995.

[0020] In this application, unless expressly described, any undescribed matter or item shall be directly applied to what is known in the art without modification. In addition, any embodiment described in this specification can be freely combined with one or more other embodiments described in this specification, and the technical solution or technical idea formed thereby shall be considered as part of the original disclosure or original record of the present invention, and shall not be considered as new content not disclosed or anticipated in this disclosure, unless a person skilled in the art considers that the combination is obviously unreasonable.

[0021] All patent and non-patent literature referred to herein, including but not limited to textbooks and journal articles, is hereby incorporated by reference in its entirety.

[0022] In a first aspect, the present application provides an olefin conversion catalyst comprising the following components, in parts by weight: a) 50 to 90 parts of a molecular sieve having a 12 or more membered ring structure; b) 0.1 to 10 parts, calculated on oxide, of an additive component selected from Group IA metal elements, Group IIA metal elements, or combinations thereof; c) 0.1 to 10 parts, calculated on oxide, of a modifying component selected from silicon, germanium, bismuth, tin, boron, gallium, or combinations thereof; and d) 10 to 49 parts of a carrier component.

[0023] In the catalyst of the present application, the "additive component" is introduced into the catalyst before the molecular sieve and carrier components are formed, and is mainly distributed on the outer surface of the molecular sieve grains, as can be detected by scanning electron microscopy-energy spectroscopy (SEM-EDS). For example, the ratio of the content of the additive component on the outer surface of the molecular sieve grains measured by SEM-EDS to the total content of the additive component in the catalyst measured by X-ray fluorescence analysis is 50% or more, for example, 50-98%, 60-98%, or 70-95%.

[0024] In the catalyst of the present application, after the molecular sieve and carrier components are formed, a "modifying component" is introduced into the catalyst. For non-silica modifying components, it can be detected through characterization by SEM-EDS that the portion distributed on the outer surface of the molecular sieve grain is relatively small compared to the total amount, indicating that it should be distributed mainly inside the molecular sieve grain. For example, the ratio of the content of the additive component on the outer surface of the molecular sieve grain measured by SEM-EDS to the total content of the additive component in the catalyst measured by X-ray fluorescence analysis is less than 50%, for example, 10-45%, 10-40%, or 10-35%.

[0025] Without being limited to a particular theory, it is believed that in the catalyst of the present application, the added component prevents the colloid from being adsorbed onto the support and inhibits further reaction of the reaction product, and the modifying component has a function of adjusting the pore flow path diameter and has a function of increasing the probability of producing C8 aromatic hydrocarbons from C9 aromatic hydrocarbons when the alkylation reaction product is produced.

[0026] In a preferred embodiment, the molecular sieve is selected from those having a 12-membered ring structure or an 18-membered ring structure, preferably selected from Y zeolite (such as USY), β zeolite, MCM-22, MCM-56, SAPO-5, SAPO-37, SAPO-40, RZM-3, or a combination thereof. More preferably, the zeolite is selected from Y, β, MCM-56, MCM-22, or a combination thereof. Particularly preferably, the molecular sieve has a SiO2 / Al2O3 molar ratio of 2-60, preferably 5-30, for example 8, 10, 12, 15, 18, 20, 22, 25, or 28.

[0027] In a particular preferred embodiment, the molecular sieve is an ammonium type molecular sieve.According to the present application, the term "ammonium type molecular sieve" has the meaning generally understood in the art, specifically refers to the zeolite obtained by combining the acid sites on framework Al or other non-silicon elements with ammonia-derived molecular sieve, which can generally be obtained by using a synthesis solution containing ammonium ions during the synthesis process, or by ion-exchanging the solution containing ammonium ions with the molecular sieve after synthesis, or by combining ammonia gas with the hydrogen type molecular sieve.

[0028] In a preferred embodiment, the support component is selected from or derived from alumina, alumina-containing clay, silica, or a combination thereof, preferably selected from or derived from alumina, kaolin, attapulgite, bentonite, diatomaceous earth, silica, or a combination thereof, more preferably alumina.

[0029] In a preferred embodiment, the added component is selected from potassium, sodium, calcium, magnesium, or a combination thereof, preferably magnesium.

[0030] In a preferred embodiment, the catalyst has the following pore distribution, characterized by BET nitrogen adsorption / desorption: the pore volume of micropores having a diameter of more than 0.5 nm and less than 2.0 nm accounts for 4-28%, preferably 5-22%, for example 8%, 10%, 12%, 15%, 18% or 20% of the total pore volume, and the pore volume of mesopores having a diameter of 2-50 nm accounts for 6-50%, preferably 10-40%, for example 15%, 20%, 25%, 30% or 35% of the total pore volume.

[0031] In a further preferred embodiment, the ratio of the pore volume of mesopores to the pore volume of micropores in the catalyst is from 0.5 to 8.0, preferably from 0.8 to 4.5, for example 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0.

[0032] In the catalyst of the present application, the content of the additive component in the catalyst is mainly bound to the molecular sieve, and the active center is distributed on the surface of the flow path of the molecular sieve, so that it correlates with the content of the molecular sieve, and further correlates with the ratio of the mesopore volume to the total pore volume of the molecular sieve. Preferably, the ratio of the mass of the additive component calculated as an oxide to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst is 0.50 or less, preferably 0.08 to 0.35, for example, 0.1, 0.12, 0.15, 0.18, 0.20, 0.22, 0.25, 0.28, 0.30 or 0.32.

[0033] In a preferred embodiment, the modifying component is a combination of silicon and at least one selected from tin, bismuth, germanium, gallium and boron, preferably a combination of silicon and tin.Preferably, the mass ratio of silicon to non-silicon modifying components (i.e., tin, bismuth, germanium, gallium, boron, or a combination thereof) in terms of oxide is 0.1 to 10.0:1, preferably 1.5 to 5.0:1, for example, 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, or 4.5:1.

[0034] In a preferred embodiment of the catalyst, the molecular sieve is present in an amount, by weight, of 55 to 80 parts, such as 58, 60, 65, 68, 70, 72, or 75 parts.

[0035] In a preferred embodiment of the catalyst, the support component is in parts by weight from 15 to 40 parts, for example, 18, 20, 22, 25, 28, 30, 32, 35, or 38 parts.

[0036] In a preferred embodiment of the catalyst, the added component is, by weight, 1.0 parts to 8.0 parts, for example, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, 5.5 parts, 6.0 parts, 6.5 parts, 7.0 parts, or 7.5 parts.

[0037] In a preferred embodiment of the catalyst, the modifying component is, by weight, 1.0 parts to 8.0 parts, for example, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, 5.5 parts, 6.0 parts, 6.5 parts, 7.0 parts, or 7.5 parts.

[0038] In certain preferred embodiments, the total amount of catalyst, by weight, is 100 parts.

[0039] In a second aspect, the present application provides a method for preparing an olefin conversion catalyst, the method comprising the steps of: (1) forming a mixture containing a molecular sieve having a 12-membered or greater ring structure, a carrier, and a precursor of an additive component, followed by drying and calcining to obtain a formed body; and (2) A precursor of the modifying component is supported on a molded body, dried, and optionally calcined to obtain a catalyst.

[0040] In the method of the present application, the molecular sieve, carrier and additive component in step (1), and the modifying component in step (2) are as described in the first embodiment of the present application, and therefore will not be described again here.

[0041] In a preferred embodiment, the catalyst obtained in step (2) has the following pore distribution characteristics as characterized by BET nitrogen adsorption / desorption method: The pore volume of micropores having a diameter of more than 0.5 nm and less than 2.0 nm accounts for 4 to 28%, preferably 5 to 22%, for example, 8%, 10%, 12%, 15%, 18%, or 20%, of the total pore volume, and the pore volume of mesopores having a diameter of 2 to 50 nm accounts for 6 to 50%, preferably 10 to 40%, for example, 15%, 20%, 25%, 30%, or 35% of the total pore volume.

[0042] In a more preferred embodiment, the molecular sieve has a ratio of mesopore volume to micropore volume of 0.4 to 4.5, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4.0.

[0043] In a more preferred embodiment, the ratio of the mass of the added component calculated as an oxide to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume is 0.50 or less, preferably 0.08 to 0.35, for example, 0.1, 0.12, 0.15, 0.18, 0.20, 0.22, 0.25, 0.28, 0.30 or 0.32.

[0044] In a preferred embodiment, the support used in step (1) is selected from alumina, alumina-containing clay, silica, or a combination thereof, preferably selected from alumina, kaolin, attapulgite, bentonite, diatomaceous earth, silica, or a combination thereof, more preferably alumina.

[0045] In a preferred embodiment, the precursor of the additive component may be a soluble salt of the additive component, preferably a nitrate, halide, haloate, or combinations thereof of the additive component.

[0046] In the method of the present application, the molding in step (1) can be performed by a conventional molding method such as extrusion molding, tablet molding, etc. Depending on the need for molding, a molding aid such as nitric acid, an extrusion aid (such as sesbania powder), water, or a combination thereof can be added.

[0047] In a preferred embodiment, the drying conditions described in step (1) include the following: drying temperature is 30-300°C, preferably 60-260°C, drying time is 0.5-72 hours, preferably 1-48 hours; and the calcination conditions are as follows: calcination temperature is 450-700°C, preferably 450-600°C, calcination time is 0.2-30 hours, preferably 1-24 hours. Drying and calcination are performed in an oxygen-containing atmosphere (air, oxygen, etc.).

[0048] In a preferred embodiment, among the precursors of the modifying component used in step (2), the precursor of silicon is an organosilicon, such as ethyl orthosilicate, silicone oil (preferably selected from phenylmethylsilicone oil, aminosilicone oil, hydroxylsilicone oil, or a combination thereof), methyl silicate, siloxane monomers having an alkyl group with 1 to 4 carbon atoms, and halosiloxane (such as chlorosilane) monomers having an alkyl group with 1 to 4 carbon atoms, or a combination thereof; the precursors of germanium, bismuth, gallium, and tin are soluble salts thereof, such as nitrates, halides, halogen acid salts, sulfates, etc., and the precursor of boron may be boric acid, etc.

[0049] In a preferred embodiment, the loading in step (2) is carried out in the following manner: first, the molded body is impregnated with a precursor of silicon and loaded with it, and then, other modifying components selected from germanium, bismuth, tin, gallium and boron, or a combination thereof, are impregnated with it and loaded with it. In a further preferred embodiment, the specific steps of step (2) include impregnating the molded body with an impregnation solution containing silicone, drying it to obtain a silicon-containing molded body, then impregnating the silicon-containing molded body with an impregnation solution containing a precursor of another modifying component selected from germanium, bismuth, tin, gallium and boron, or a combination thereof, and drying and calcining it to obtain a catalyst. More preferably, the solvent used in the silicone-containing impregnation solution is toluene, an alkane (preferably one having 5 to 16 carbon atoms), or a combination thereof, and the drying conditions in preparing the silicon-containing molded body include a drying temperature of 30 to 200° C. and a drying time of 0.1 to 72 hours, and the drying is carried out under an inert atmosphere (such as nitrogen). Preferably, the impregnation is performed by an equal volume impregnation method.

[0050] In a preferred embodiment, the drying conditions described in step (2) include: drying temperature is 30-200°C, preferably 60-150°C, drying time is 0.1-72 hours, preferably 1-48 hours; calcination conditions include: calcination temperature is 400-650°C, preferably 450-600°C, calcination time is 0.5-8 hours, preferably 1-5 hours. Preferably, drying and calcination are carried out under an inert atmosphere (such as nitrogen).

[0051] In a third aspect, the present application provides an olefin conversion catalyst prepared by the method of the present application.

[0052] In specific embodiments, various properties of the olefin conversion catalyst obtained by the process of the present application are as described in the first aspect of the present application and will not be described again here.

[0053] In a fourth aspect, the present application provides the use of the present olefin conversion catalyst in the conversion of olefins contained in aromatic rich distillates.

[0054] In a fifth aspect, the present application provides a method for converting olefins contained in an aromatic-rich distillate, the method comprising a step of catalytically reacting an aromatic-rich distillate containing olefins with an olefin conversion catalyst of the present application.

[0055] In a preferred embodiment, the aromatic-rich distillate is selected from reformate, isomerization reaction product, extracted aromatic hydrocarbon mixture, or a combination thereof. More preferably, the aromatic-rich distillate has a distillation range of 75-220°C, and the aromatic hydrocarbons contained therein may be benzene, toluene, C8 aromatic hydrocarbons, C9 aromatic hydrocarbons, or a combination thereof. For example, the isomerization reaction product may be a para-xylene-containing product produced by the isomerization reaction of mixed C8 aromatic hydrocarbons after removing para-xylene by adsorption separation of the aromatic hydrocarbon composite unit. The mixed C8 aromatic hydrocarbons mainly contain ethylbenzene, xylene and a small amount of olefins, and need to be purified before adsorption separation to remove olefins; the extracted aromatic hydrocarbon mixture may be the liquid extracted from the extraction unit, mainly contains benzene and toluene, as well as a small amount of olefins, and needs to be purified to obtain eligible benzene and toluene products and remove olefins.

[0056] In a preferred embodiment, in the aromatic rich distillate, the olefin content is expressed by the Bromine Index, and the Bromine Index is 100 to 2800 mgBr / 100g, preferably 300 to 2000 mgBr / 100g.

[0057] In a preferred embodiment, the reaction is carried out under non-hydrogen conditions, and the reaction conditions include the following: reaction temperature is 130-350° C., reaction pressure is 0.5-4.0 MPa, and liquid hourly space velocity is 0.5-35 h -1Preferably, the reaction conditions include the following: the reaction temperature is 130 to 260° C., the reaction pressure is 0.5 to 3.0 MPa, and the liquid hourly space velocity is 0.5 to 8 h -1 It is.

[0058] [Example] Hereinafter, the present application will be described in detail with reference to examples, but the scope of protection of the present application is not limited to the examples.

[0059] In the following examples and comparative examples, the pore volume and pore distribution were measured using a liquid nitrogen adsorption / desorption apparatus according to the BET method. The measurement method is as follows: the test was performed at the liquid nitrogen saturation temperature (77K), and the N2 isothermal adsorption / desorption curve was obtained by changing the relative pressure, and the pore distribution was obtained by the t-plot method. The relative pressure during the experiment was 0.001-0.995. The total pore volume was calculated by the single-point method at a relative pressure of 0.995.

[0060] In the following Examples and Comparative Examples, the composition of the catalyst was measured by X-ray fluorescence analysis using a Philips Co Magix 601 instrument.

[0061] In the following examples and comparative examples, SEM-EDS characterization was completed using a Philips XL30 scanning electron microscope. Measurements were taken by drawing a parallel line on the particle, dividing it into 20 equal parts in the vertical direction, and averaging the results.

[0062] [Example 1] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 15, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 19% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 45% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% nitric acid, and magnesium nitrate aqueous solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing phenylmethyl silicone oil (solvent is toluene), and then treated under nitrogen at 70°C for 3 hours to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of a sample was taken and immersed in an equal volume of an aqueous tin sulfate solution so that the mass ratio of silica to tin oxide was 2.0. The sample was then dried at 120°C for 5 hours in a nitrogen atmosphere and calcined at 550°C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 64.5%, the support content (since the relative ratio of the molecular sieve to the support used during molding is determined, the aluminum content in the molecular sieve can be calculated from the total aluminum content of the obtained catalyst, and the molecular sieve content and support content of the obtained catalyst are determined, and the same applies below) was 27.5%, the silica mass content was 3.6%, the tin oxide mass content was 1.8% (according to SEM-EDS analysis, the tin oxide content dispersed on the outer surface of the molecular sieve particles was 0.6%), the magnesium oxide mass content was 2.1% (according to SEM-EDS analysis, the magnesium oxide content dispersed on the outer surface of the molecular sieve particles was 2.0%), and the ratio of the pore volume of 2-50 nm mesopores (accounting for 32% of the total pore volume) to the pore volume of 0.5-2 nm micropores (accounting for 11% of the total pore volume) was 2.9. The ratio of the mass of the added components (in terms of oxides) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.10. The BET measurement of the mesopore distribution of the obtained catalyst and the calculation results by the t-plot method are shown in Figure 1.

[0063] 5 g of catalyst was collected, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52.0%) was heated for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 260 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 54.3% by mass.

[0064] [Example 2] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 15, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 15% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 35% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and an aqueous solution of sodium nitrate were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of an impregnation solution containing phenylmethyl silicone oil (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume aqueous solution of bismuth nitrate so that the mass ratio of silica to bismuth oxide was 4.9, then dried at 120 ° C for 5 hours under a nitrogen atmosphere and calcined at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 62.4%, the support content was 26.7%, the silica mass content was 7.8%, the bismuth oxide mass content was 1.6%, and the sodium oxide mass content was 1.1%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 23.0% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 8.5% of the total pore volume) was 2.7. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.077.

[0065] 5 g of catalyst was collected, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52%) was added to the reformate for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 240 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 3.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 55.5% by mass.

[0066] [Example 3] 100g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 12, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 20% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 20% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, to which 12g of sesbania powder, 6g of 65% by weight nitric acid, and magnesium nitrate aqueous solution were added, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing ethyl orthosilicate (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of ethanol solution of germanium chloride so that the mass ratio of silica to germanium oxide was 5.0, then dried at 120 ° C for 5 hours under a nitrogen atmosphere, and calcined at 550 ° C for 3 hours under a nitrogen atmosphere to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 64.3%, the support content was 27.5%, the silica mass content was 4.0%, the germanium oxide mass content was 0.8%, and the magnesium oxide mass content was 3.0%, and the ratio of the pore volume of the mesopores of 2 to 50 nm (accounting for 13.5% of the total pore volume) to the pore volume of the micropores of 0.5 to 2 nm (accounting for 11.8% of the total pore volume) was 1.1. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.346.

[0067] 5 g of catalyst was taken, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52%) was added for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 120 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 52.5% by mass.

[0068] [Example 4] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 15, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 25% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 35% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and magnesium nitrate aqueous solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing phenylmethyl silicone oil (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of boric acid aqueous solution so that the mass ratio of silica to boron oxide was 2.0, and then dried at 120 ° C for 10 hours under a nitrogen atmosphere and calcined at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 65.5%, the support content was 28.2%, the silica mass content was 2.0%, the boron oxide mass content was 1.0%, and the magnesium oxide mass content was 3%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 23.1% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 16% of the total pore volume) was 1.4. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.20.

[0069] 5 g of catalyst was collected, and a reformate with a bromine index of 910 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added for 30 h. -1 The reaction was carried out at 1.9 MPa and 200°C, and 0.059% of styrene and xylene alkylation products (dimethylphenyl, phenyl-1,2-ethane) were added to the product for evaluation. After 300 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g, and after 300 hours, the amount of dimethylphenyl and phenyl-1,2-ethane in the product increased: 0.058%. The above reformate was added for 3.0 hours. -1The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 57.5% by mass.

[0070] [Example 5] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 15, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 12% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 50% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and magnesium nitrate aqueous solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation liquid containing phenylmethyl silicone oil (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal amount of tin sulfate aqueous solution so that the mass ratio of silica to tin oxide was 1.0, then dried at 120 ° C for 10 hours under a nitrogen atmosphere, and calcined at 650 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 57.2%, the support content was 24.6%, the silica mass content was 5.0%, the tin oxide mass content was 5.0%, and the magnesium oxide mass content was 7.9%, and the ratio of the pore volume of mesopores of 2 to 50 nm (48% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (9.9% of the total pore volume) was 4.8. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.288.

[0071] 5 g of catalyst was collected, and a reformate with a bromine index of 910 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 500 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 3.0 hours.-1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 58.2% by mass.

[0072] [Example 6] 100g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 6, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 22% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 33% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, an aqueous solution of sodium nitrate, and an aqueous solution of magnesium nitrate were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation liquid containing amino silicone oil (solvent is heptane), and then treated under nitrogen at 26°C for 3 hours to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of an aqueous solution of bismuth nitrate so that the mass ratio of silica to bismuth oxide was 10.0, and then dried at 120°C for 8 hours in a nitrogen atmosphere and calcined at 650°C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 60.7%, the support content was 26.0%, the mass content of silica was 7.0%, the mass content of bismuth oxide was 0.7%, the mass content of magnesium oxide was 5.0%, and the mass content of sodium oxide was 0.2%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 21.3% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 12.8% of the total pore volume) was 1.7. The ratio of the mass of the added component (in terms of oxide) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.402.

[0073] 5 g of catalyst was collected, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added for 10 h. -1The reaction was evaluated at 1.9 MPa and 180°C. After 160 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 180°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 57.5% by mass.

[0074] [Example 7] 100g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 6, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 20% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 33% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, to which 12g of sesbania powder, an aqueous solution of sodium nitrate, and an aqueous solution of magnesium nitrate were added, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of the sample was collected and immersed in 50g of an impregnation solution containing amino silicone oil (solvent is heptane), and then treated under nitrogen at 26°C for 3 hours to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of tin sulfate aqueous solution so that the mass ratio of silica to tin oxide was 10.0, then dried at 120°C for 8 hours in a nitrogen atmosphere and calcined at 500°C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 66.0%, the support content was 28.1%, the silica mass content was 3.5%, the tin oxide mass content was 0.35%, the magnesium oxide mass content was 0.8%, and the sodium oxide mass content was 0.6%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 22.6% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 13.0% of the total pore volume) was 1.7. The ratio of the mass of the added component (in terms of oxide) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.094.

[0075] 5 g of catalyst was collected, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52.0%) was added for 8 h. -1 The reaction was evaluated at 1.9 MPa and 170°C. After 90 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and a temperature of 170°C, and the content of C8 aromatic hydrocarbons was evaluated, and the mass content of C8 aromatic hydrocarbons was found to be 53.1%.

[0076] [Example 8] 100g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 6, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 21% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 30% of the total pore volume), 30g of silica sol (containing 40% by weight of silicon oxide) and 20g of kaolin were collected, and 12g of sesbania powder and an aqueous solution of sodium nitrate and calcium nitrate were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing methyl silicone oil (solvent is heptane), and then treated under nitrogen at 26°C for 3 hours to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume aqueous solution of bismuth nitrate so that the mass ratio of silica to bismuth oxide was 10.0, then dried at 120°C for 8 hours under a nitrogen atmosphere and calcined at 550°C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 64.3%, the support content was 27.7%, the mass content of the silica additive component was 6.0%, the mass content of bismuth oxide was 0.6%, the mass content of calcium oxide was 0.3%, and the mass content of sodium oxide was 1.2%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 23.1% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 13.1% of the total pore volume) was 1.8. The ratio of the mass of the added component (in terms of oxide) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.093.

[0077] 5 g of catalyst was collected, and a reformate with a bromine index of 1106 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 48.1%) was heated for 30 h. -1 The reaction was evaluated at 1.9 MPa and 280°C. After 260 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 50.1% by mass.

[0078] [Example 9] 90g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 6, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 11% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 29% of the total pore volume), 30g of diatomaceous earth, and 30g of attapulgite were collected, to which 12g of sesbania powder and magnesium nitrate aqueous solution were added, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and calcined at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing chlorosilane (solvent is heptane), and then treated under nitrogen at 26°C for 3 hours to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of bismuth nitrate aqueous solution so that the mass ratio of silica to bismuth oxide was 5.0, then dried at 120 ° C for 8 hours under a nitrogen atmosphere and calcined at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 55.2%, the support content was 36.6%, the silica mass content was 5.0%, the bismuth oxide mass content was 1.0%, and the magnesium oxide mass content was 2.0%, and the ratio of the pore volume of mesopores of 2 to 50 nm (occupying 17.0% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (occupying 5.6% of the total pore volume) was 3.0. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.213.

[0079] 5 g of the catalyst was collected, and a reformate with a bromine index of 1106 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 48.1%) was added for 6 h. -1 The reaction was evaluated at 1.9 MPa and 160°C. After 150 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 48.6% by mass.

[0080] [Example 10] 100g of ammoniacal β zeolite (SiO2 / Al2O3 molar ratio is 19, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 35% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 30% of the total pore volume), 40g of silica sol (containing 40% by weight of silicon oxide) were collected, 12g of sesbania powder and magnesium nitrate aqueous solution were added thereto, the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 550°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing ethyl orthosilicate (solvent is ethanol), and then treated under nitrogen at 26°C for 3 hours to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of tin sulfate aqueous solution so that the mass ratio of silica to tin oxide was 1.0, then dried at 120 ° C for 8 hours under a nitrogen atmosphere and calcined at 500 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 81.8%, the support content was 13.0%, the silica mass content was 2.0%, the tin oxide mass content was 2.0%, and the magnesium oxide mass content was 1.0%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 25.6% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 27.1% of the total pore volume) was 0.94. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.048.

[0081] 5 g of catalyst was collected, and the reformate with a bromine index of 1106 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 48.1%) was heated for 15 h. -1 The reaction was evaluated at 1.9 MPa and 195°C. After 210 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 49.8% by mass.

[0082] [Example 11] 100 g of ammoniacal MCM-56 molecular sieve (SiO2 / Al2O3 molar ratio is 20, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0 nm accounts for 20% of the total pore volume, and pore volume with pore diameter of 2-50 nm accounts for 48% of the total pore volume), 40 g of silica sol (containing 40% by weight of silicon oxide) were collected, and 12 g of sesbania powder and an aqueous magnesium nitrate solution were added thereto, and the mixture was kneaded and molded, and then dried at 120 ° C for 12 hours in an air atmosphere and fired at 550 ° C for 2 hours to obtain a molded body. Next, 100 g of this molded body was collected and immersed in 50 g of impregnation solution containing ethyl orthosilicate (solvent is ethanol), and then treated under nitrogen at 26 ° C for 3 hours to remove the solvent, and dried at 120 ° C for 10 hours. Next, 100 g of the sample was taken, immersed in an equal volume of tin sulfate aqueous solution, dried at 120 ° C for 8 hours under a nitrogen atmosphere, and calcined at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 73.5%, the carrier content was 11.7%, the mass content of silica was 5.2%, the mass content of tin oxide was 1.8%, and the mass content of magnesium oxide was 7.5%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 38.1% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 13.5% of the total pore volume) was 2.82. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.268.

[0083] 5 g of catalyst was collected, and a reformate with a bromine index of 1106 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 48.1%) was heated for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 700 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 3.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 50.1% by mass.

[0084] 5 g of the catalyst was sampled and subjected to 30 h purification using an isomerization product with a bromine index of 208 mgBr / 100 g (olefin content is expressed as a bromine index, the mass content of C8 aromatic hydrocarbons is 98.5%, the mass content of non-aromatic hydrocarbons is 1.41%, and the mass content of C9 aromatic hydrocarbons is 0.09%). -1 The reaction was evaluated at 1.9 MPa and 175°C. After 650 hours, the bromine index at the outlet exceeded 20 mgBr / 100 g. The above reformate was reacted for 5.0 hours. -1 The reaction was carried out at 1.9 MPa and 170°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 98.49% by mass.

[0085] 5 g of the catalyst was collected and subjected to 36 h purification using an isomerization product with a bromine index of 180 mgBr / 100 g (olefin content is expressed as a bromine index, the mass content of benzene is 32.02%, the mass content of non-aromatic hydrocarbons is 0.05%, and the mass content of toluene aromatic hydrocarbons is 67.93%). -1 The reaction was evaluated under the conditions of 1.9 MPa and 180°C. After 750 hours, the bromine index at the outlet exceeded 20 mgBr / 100 g. -1 The reaction was carried out at 1.9 MPa and a temperature of 170°C, and the aromatic hydrocarbon content was evaluated, and the mass content of benzene and toluene was found to be 99.95%.

[0086] [Example 12] 100g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 12, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 20% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 20.5% of the total pore volume), 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and magnesium nitrate aqueous solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and calcined at 580°C for 2 hours to obtain a molded body. Next, 100g of the sample was collected, immersed in an equal volume of ethanol solution of germanium chloride, dried at 120°C for 5 hours under nitrogen, and calcined at 550°C for 3 hours under nitrogen to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 67.1%, the support content was 28.9%, the mass content of germanium oxide was 0.8%, the mass content of magnesium oxide was 3.0%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 13.0% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 12.9% of the total pore volume) was 1.01. The ratio of the mass of the added components (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.344.

[0087] 5 g of the catalyst was collected, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by the bromine index, and the mass content of C8 aromatic hydrocarbons is 52.0%) was added for 10 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 180 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 1.5 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 52.6% by mass.

[0088] [Example 13] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 15, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 25% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 35% of the total pore volume) and 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and an aqueous calcium nitrate solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of an impregnation solution containing phenylmethyl silicone oil (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of boric acid aqueous solution so that the mass ratio of silica to boron oxide was 2.0, and then dried at 120 ° C for 10 hours under a nitrogen atmosphere and calcined at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 64.5%, the support content was 27.8%, the silica mass content was 2.2%, the calcium oxide mass content was 1.2%, and the boron oxide mass content was 4.1%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 23.6% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 15.2% of the total pore volume) was 1.57. The ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.267.

[0089] 5 g of catalyst was collected, and a reformate with a bromine index of 910 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 358 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g, and after 300 hours, dimethylphenyl and phenyl-1,2-ethane increased in the product: 0.058%. The above reformate was reacted for 3.0 hours. -1 The reaction was carried out at 1.9 MPa and a temperature of 200°C, and the mass content of C8 aromatic hydrocarbons was evaluated, which was found to be 57.4%.

[0090] [Example 14] 100 g of ammoniated SAPO-5 molecular sieve (SiO2 / Al2O3 molar ratio 0.4, SiO2 / P2O5 molar ratio 1, pore distribution as follows: pore volume with pore diameter of 0.5-2.0 nm accounts for 31.0% of the total pore volume, and pore volume with pore diameter of 2-50 nm accounts for 15.1% of the total pore volume) and 98.2 g of pseudoboehmite (containing 67% by weight of alumina) were taken, to which was added a solution of 12 g of sesbania powder, 6 g of 65% by weight nitric acid, and 2.7 g of sodium nitrate dissolved in 10 g of water, and the mixture was kneaded and molded, and then dried in an air atmosphere at 120°C for 12 hours and calcined at 580°C for 2 hours to obtain a molded body. Next, 100 g of this molded body was collected and immersed in 50 g of an impregnation solution containing methylsilicone oil (the solvent was toluene, and the viscosity of the silicone oil was 100 cps), and then treated under nitrogen at 70° C. for 3 hours to remove the solvent, and dried at 150° C. for 10 hours. Next, 100 g of a sample was collected and immersed in an equal volume of tin sulfate aqueous solution so that the mass ratio of silica to tin oxide was 1.0, and then dried at 120° C. for 10 hours under a nitrogen atmosphere and calcined at 550° C. for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 59.0%, the support content was 38.8%, the mass content of silica was 2.2%, the mass content of sodium oxide was 0.6%, the mass content of tin oxide was 0.5%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 9.1% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 17.7% of the total pore volume) was 0.51. The ratio of the mass of the added components (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.11.

[0091] 5 g of catalyst was taken, and a reformate with a bromine index of 630 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52.8%) was added for 10 h. -1 The reaction was evaluated at 1.9 MPa and 220°C. After 170 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 53.5% by mass.

[0092] [Example 15] 20 g of ammoniated SAPO-37 molecular sieve (SiO2 / Al2O3 molar ratio: 0.43, SiO2 / P2O5 molar ratio: 1, pore distribution as follows: pore volume with pore diameters of 0.5-2.0 nm accounts for 31.1% of the total pore volume, and pore volume with pore diameters of 2-50 nm accounts for 14.9% of the total pore volume) and 27.0 g of pseudoboehmite (containing 67% by weight of alumina) were taken, to which 4 g of sesbania powder, 1.5 g of 65% by weight of nitric acid, and a solution of 0.7 g of potassium nitrate in 4 g of water were added, and the mixture was kneaded and molded, and then dried in an air atmosphere at 120°C for 12 hours and calcined at 580°C for 2 hours to obtain a molded body. Next, 20 g of this molded body was collected and immersed in 10 g of an impregnation solution containing methyl silicone oil (solvent: toluene, silicone oil 10%, silicone oil viscosity 100 cps), then treated under nitrogen at 70 ° C for 3 hours to remove the solvent, and dried at 150 ° C for 10 hours. Next, 15 g of the sample was collected and immersed in an equal volume of tin sulfate aqueous solution so that the mass ratio of silica to tin oxide was 1.0, then dried at 120 ° C for 10 hours under a nitrogen atmosphere, and calcined at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 53.8%, the support content was 43.8%, the mass content of silica was 0.8%, the mass content of potassium oxide was 0.6%, the mass content of tin oxide was 0.5%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 8.1% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 16.2% of the total pore volume) was 0.50. The ratio of the mass of the added components (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.16.

[0093] 5 g of catalyst was collected, and a reformate with a bromine index of 630 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52.8%) was added for 8 h. -1The reaction was evaluated at 2.9 MPa and 300°C. After 190 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 53.0% by mass.

[0094] [Comparative Example 1] 100 g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 12, pore distribution is as follows: pore volume with pore diameters of 0.5 to 2.0 nm accounts for 20% of the total pore volume, and pore volume with pore diameters of 2 to 50 nm accounts for 20.5% of the total pore volume) and 65 g of pseudoboehmite (containing 67% by weight of alumina) were collected, to which 12 g of sesbania powder, 6 g of 65% by weight nitric acid, and an appropriate amount of water were added, and the mixture was kneaded and molded. The mixture was then dried in an air atmosphere at 120°C for 10 hours and calcined at 550°C for 3 hours to obtain a catalyst. The obtained catalyst did not contain any additive or modifying components, had a molecular sieve content of 69.7%, a support content of 30.2%, and a ratio of the pore volume of mesopores with a size of 2 to 50 nm (accounting for 14.0% of the total pore volume) to the pore volume of micropores with a size of 0.5 to 2 nm (accounting for 13.8% of the total pore volume) of 1.01.

[0095] 5 g of catalyst was collected, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52.5%) was heated for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 30 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 51.2% by mass.

[0096] [Comparative Example 2] 100g of ammoniacal USY molecular sieve (SiO2 / Al2O3 molar ratio is 12, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 20% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 20.5% of the total pore volume), 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, 12g of sesbania powder and 6g of 65% by weight nitric acid were added thereto, the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing ethyl orthosilicate (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an ethanol solution of an equal amount of germanium chloride so that the mass ratio of silica to germanium oxide was 5.0, then dried at 120°C for 5 hours under a nitrogen atmosphere, and calcined at 550°C for 3 hours under a nitrogen atmosphere to obtain a catalyst. The obtained catalyst did not contain any added components, had a molecular sieve content of 66.4%, a carrier content of 28.5%, a silica mass content of 4.0%, and a germanium oxide mass content of 0.8%, and the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 13.4% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 13% of the total pore volume) was 1.03.

[0097] 5 g of catalyst was collected, and a reformate with a bromine index of 1520 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 52.0%) was heated for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 82 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 2.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 51.5% by mass.

[0098] [Comparative Example 3] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 15, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 12% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 20% of the total pore volume), 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and magnesium nitrate aqueous solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing phenylmethyl silicone oil (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken and immersed in an equal volume of tin sulfate aqueous solution so that the mass ratio of silica to tin oxide was 1.0, then dried at 120 ° C for 10 hours under a nitrogen atmosphere, and calcined at 650 ° C for 3 hours under a nitrogen atmosphere to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 47.3%, the carrier content was 20.3%, the silica mass content was 5.0%, the tin oxide mass content was 15.1%, and the magnesium oxide mass content was 12.1%; the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 12.3% of the total pore volume) to the pore volume of micropores (accounting for 6.7% of the total pore volume) was 1.84; and the ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 2.1.

[0099] 5 g of catalyst was collected, and a reformate with a bromine index of 910 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added to the catalyst for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 228 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 3.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 56.8% by mass.

[0100] [Comparative Example 4] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 18, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 5% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 36% of the total pore volume), 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and bismuth nitrate aqueous solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing phenylmethyl silicone oil (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken, immersed in an equal volume of boric acid aqueous solution so that the mass ratio of silica to boron oxide was 2.0, dried in nitrogen at 120 ° C for 10 hours, and then calcined in a nitrogen atmosphere at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 64.5%, the support content was 27.8%, the silica mass content was 2.2%, the bismuth oxide mass content was 1.2%, and the boron oxide mass content was 4.1%; the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 22.2% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 3.0% of the total pore volume) was 7.40; and the ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.286.

[0101] 5 g of the catalyst was collected, and a reformate with a bromine index of 9100 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added to the reformate for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 358 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g, and after 300 hours, dimethylphenyl and phenyl-1,2-ethane increased in the product: 0.058%. The above reformate was reacted for 3.0 hours. -1The reaction was carried out at 1.9 MPa and a temperature of 200°C, and the mass content of C8 aromatic hydrocarbons was evaluated, which was found to be 57.0%.

[0102] [Comparative Example 5] 100g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 20, pore distribution is as follows: pore volume with pore diameter of 0.5-2.0nm accounts for 25% of the total pore volume, and pore volume with pore diameter of 2-50nm accounts for 8% of the total pore volume), 65g of pseudoboehmite (containing 67% by weight of alumina) were collected, and 12g of sesbania powder, 6g of 65% by weight nitric acid, and bismuth nitrate aqueous solution were added thereto, and the mixture was kneaded and molded, and then dried at 120°C for 12 hours in an air atmosphere and fired at 580°C for 2 hours to obtain a molded body. Next, 100g of this molded body was collected and immersed in 50g of impregnation solution containing phenylmethyl silicone oil (solvent is toluene), and then treated at 70°C for 3 hours under nitrogen to remove the solvent, and dried at 120°C for 10 hours. Next, 100 g of the sample was taken, immersed in an equal volume of boric acid aqueous solution so that the mass ratio of silica to boron oxide was 2.0, dried in nitrogen at 120 ° C for 10 hours, and then calcined in a nitrogen atmosphere at 550 ° C for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 64.5%, the support content was 27.8%, the silica mass content was 2.2%, the bismuth oxide mass content was 1.2%, and the boron oxide mass content was 4.1%; the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 6.5% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 15.9% of the total pore volume) was 0.41; and the ratio of the mass of the added component (oxide equivalent) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.954.

[0103] 5 g of catalyst was collected, and a reformate with a bromine index of 910 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added for 30 h. -1The reaction was evaluated at 1.9 MPa and 200°C. After 358 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g, and after 300 hours, dimethylphenyl and phenyl-1,2-ethane increased in the product: 0.058%. The above reformate was reacted for 3.0 hours. -1 The reaction was carried out at 1.9 MPa and a temperature of 200°C, and the mass content of C8 aromatic hydrocarbons was evaluated, which was found to be 56.9%.

[0104] [Comparative Example 6] 100 g of ammoniacal MCM-22 molecular sieve (SiO2 / Al2O3 molar ratio is 20, and the pore distribution is as follows: the pore volume with a pore diameter of 0.5 to 2.0 nm accounts for 25% of the total pore volume, and the pore volume with a pore diameter of 2 to 50 nm accounts for 8% of the total pore volume) and 65 g of pseudoboehmite (containing 67% by weight of alumina) were collected, to which 12 g of sesbania powder and 6 g of 65% by weight of nitric acid were added. The mixture was kneaded and molded, and then dried in an air atmosphere at 120°C for 12 hours and calcined at 580°C for 2 hours to obtain a molded body. Next, 100 g of this molded catalyst was collected, immersed in an equal volume of 40 g of magnesium nitrate-containing solution, kept at room temperature for 7 hours, then dried at 180 ° C. for 6 hours, then immersed in 50 g of impregnation solution containing phenylmethyl silicone oil (solvent is toluene), treated under nitrogen at 70 ° C. for 3 hours to remove the solvent, and dried at 120 ° C. for 10 hours. Next, 100 g of sample was collected, immersed in an equal volume of boric acid aqueous solution so that the mass ratio of silica to boron oxide was 2.0, then dried at 120 ° C. for 10 hours under nitrogen atmosphere, and calcined at 550 ° C. for 3 hours to obtain a catalyst. In the obtained catalyst, the molecular sieve content was 64.0%, the support content was 27.9%, the magnesium oxide mass content was 1.5%, the silica mass content was 2.2%, and the boron oxide mass content was 4.1%; the ratio of the pore volume of mesopores of 2 to 50 nm (accounting for 7.2% of the total pore volume) to the pore volume of micropores of 0.5 to 2 nm (accounting for 15.4% of the total pore volume) was 0.47; and the ratio of the mass of the added components (in terms of oxides) to the product of the mass of the molecular sieve and the ratio of the mesopore volume to the total pore volume of the catalyst was 0.416.

[0105] 5 g of catalyst was collected, and a reformate with a bromine index of 910 mgBr / 100 g (olefin content is expressed by bromine index, and the mass content of C8 aromatic hydrocarbons is 57.1%) was added to the catalyst for 30 h. -1 The reaction was evaluated at 1.9 MPa and 200°C. After 158 hours, the bromine index at the outlet exceeded 200 mgBr / 100 g. The above reformate was reacted for 3.0 hours. -1 The reaction was carried out at 1.9 MPa and 200°C to evaluate the content of C8 aromatic hydrocarbons, which was found to be 56.4% by mass.

[0106] The above is a detailed description of the preferred embodiments of the present invention. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical idea of ​​the present invention, various simple modifications can be made to the technical solutions of the present invention, and all of these simple modifications belong to the protection scope of the present invention.

[0107] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any suitable manner unless there is a contradiction. In order to avoid unnecessary repetition, this application will not further describe various possible combinations.

[0108] Furthermore, unless contrary to the concept of the present application, it is possible to implement various embodiments of the present application in any combination, and these should also be considered as contents disclosed in the present application. [Brief description of the drawings]

[0109] [Figure 1] 1 shows the results of BET measurement and calculation by t-plot method for the mesopore distribution of the catalyst obtained in Example 1.

Claims

1. An olefin conversion catalyst comprising the following components in a mass part: a) 50 to 90 parts, preferably 55 to 80 parts, of a molecular sieve having a structure of 12-membered ring or more; b) An additive component selected from Group IA metal elements, Group IIA metal elements, or a combination thereof, in an amount of 0.1 to 10 parts, preferably 1.0 to 8.0 parts, in terms of oxide; c) A modifying component selected from silicon, germanium, bismuth, tin, boron, gallium, or a combination thereof, in an amount of 0.1 to 10 parts, preferably 1.0 to 8.0 parts, in terms of oxide; and d) 10 to 49 parts, preferably 15 to 40 parts, of a carrier component.

2. The molecular sieve is selected from Y, β, MCM-22, MCM-56, SAPO-5, SAPO-37, SAPO-40, RZM-3, or a combination thereof; Preferably, the molecular sieve is selected from Y, β, MCM-56, MCM-22, SAPO-5, SAPO-37, or a combination thereof; More preferably, the SiO in the molecular sieve ２ / Al ２ O ３ molar ratio is 2 to 60, preferably 5 to 30, and the catalyst according to claim 1.

3. The catalyst according to claim 1, having the following pore distribution characterized by the BET nitrogen adsorption and desorption method: the pore volume of micropores with a diameter exceeding 0.5 nm and less than 2.0 nm occupies 4 to 28%, preferably 5 to 22%, of the total pore volume, and the pore volume of mesopores with a diameter of 2 to 50 nm occupies 6 to 50%, preferably 10 to 40%, of the total pore volume.

4. The catalyst according to claim 3, wherein the ratio of the pore volume of mesopores to the pore volume of micropores in the catalyst is 0.5 to 8.0, preferably 0.8 to 4.

5.

5. The catalyst according to claim 3, wherein the ratio of the mass of the additive component in terms of oxide to the product of the mass of the molecular sieve and the ratio of the mesopore volume of the catalyst to the total pore volume of the catalyst is 0.50 or less, preferably 0.08 to 0.

35.

6. The carrier component is selected from or derived from alumina, alumina-containing clay, silica, or a combination thereof, preferably selected from or derived from alumina, kaolin, attapulgite, bentonite, diatomaceous earth, silica, or a combination thereof, and more preferably alumina, for the catalyst according to claim 1.

7. The catalyst according to claim 1, wherein the additive component is selected from calcium, magnesium, potassium, sodium or a combination thereof, preferably magnesium.

8. The modifying component is a combination of silicon and at least one selected from tin, bismuth, germanium, gallium and boron, preferably a combination of silicon and tin; Preferably, the mass ratio of silicon to the non-silicon modifying component is 0.1 to 10.0:1, preferably 1.5 to 5.0:1 in terms of oxide conversion, for the catalyst according to claim 1.

9. A method for preparing the olefin conversion catalyst according to any one of claims 1 to 8, the method comprising the following steps: (1) molding a mixture of the molecular sieve, the carrier, and the precursor of the additive component, and drying and calcining to obtain a molded body; and (2) supporting a modifying component on the molded body, and drying and calcining to obtain a catalyst.

10. The precursor of the additive component in step (1) is a soluble salt of the additive component, preferably a nitrate, a halide, a haloate or a combination thereof; Among the precursors of the modifying component in step (2), the precursor of silicon is an organosilicon; the precursors of germanium, bismuth, gallium, and tin are their soluble salts; the precursor of boron is boric acid; Preferably, the precursor of silicon is selected from ethyl orthosilicate, silicone oil, methyl silicate, a siloxane monomer having an alkyl group with 1 to 4 carbon atoms, and a halosiloxane monomer having an alkyl group with 1 to 4 carbon atoms, or a combination thereof, and the silicone oil is preferably selected from phenylmethyl silicone oil, aminosilicone oil, hydroxyl silicone oil, or a combination thereof, for the method according to claim 9.

11. The supporting step in step (2) includes first impregnating and supporting the precursor of silicon on the molded body, and then impregnating and supporting the precursor of another modifying component selected from germanium, bismuth, tin, gallium and boron, or a combination thereof, on the molded body, for the method according to claim 9.

12. In step (2), the drying conditions include: the drying temperature is 30 to 200 ° C, preferably 60 ° C to 150 ° C, the drying time is 0.1 to 72 hours, preferably 1 to 48 hours; the firing conditions include: the firing temperature is 400 to 650 ° C, preferably 450 to 600 ° C, the firing time is 0.5 to 8 hours, preferably 1 to 5 hours; the drying and firing are carried out in an inert atmosphere, the method according to claim 9.

13. A method for converting olefins contained in an aromatic-rich distillate oil, the method comprising a step of subjecting an aromatic-rich distillate oil containing olefins to a catalytic reaction in contact with the olefin conversion catalyst according to any one of claims 1 to 8.

14. The aromatic-rich distillate oil is selected from reformed oil, isomerization reaction products, extracted aromatic hydrocarbon mixtures, or combinations thereof; the aromatic hydrocarbons contained in the aromatic-rich distillate oil are benzene, toluene, C8 aromatic hydrocarbons, C9 aromatic hydrocarbons, or combinations thereof; in the aromatic-rich distillate oil, the olefin content is represented by the bromine index, and the bromine index is 100 to 2800 mgBr / 100 g, preferably 300 to 2000 mgBr / 100 g, the method according to claim 13.

15. The reaction is carried out under non-hydrogen conditions, and the reaction conditions include: the reaction temperature is 130 to 350 °C, preferably 130 to 260 °C, the reaction pressure is 0.5 to 4.0 MPa, preferably 0.5 to 3.0 MPa, and the liquid hourly space velocity is 0.5 to 35 h －１ , preferably 0.5 to 8 h －１ The method according to claim 13, wherein the method is as described above.

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