Method and system for processing gasoline components

Abstract

A method and system for treating gasoline components is disclosed, which includes the steps of: a) reacting the gasoline components in an aromatization unit and separating the reaction products to form C4 - component, C5 component, C6-C7 component, C8 component and C9 component + b) obtaining the C6-C7 components and the C9 + The components are reacted in a cracking and aromatization unit, and the reaction products are separated to produce C4 - component, C5 component, C6-C7 component, C8 component and C9 component + and c) obtaining the C6-C7 components obtained in step b) and the C9 + and recycling at least a portion of at least one of the components to the cracking and aromatization unit for continuous reaction. The method and system can effectively convert gasoline components into C aromatic compounds and produce both low-carbon olefins and high-quality light gasoline. As a result, efficient and comprehensive utilization is achieved.

Description

Detailed description of the invention

[0001] [Cross-reference of related applications] This application claims priority to Chinese Patent Application No. 202011138771.9, titled "System and Method for Processing Gasoline Fractions," filed on 22 October 2020. The entire contents of that application are incorporated herein by reference.

[0002] [Technical Field] This application relates to the treatment of hydrocarbons. In particular, this application relates to a method and system for treating gasoline fractions.

[0003] [Background technology] Aromatic hydrocarbons are fundamental raw materials for the petrochemical industry. Paraxylene is a major aromatic hydrocarbon product, and the supply gap for paraxylene in China has reached over 1 billion tons in recent years. Accelerating the development of the aromatic hydrocarbon industry is crucial for the development of the basic chemical industry in China. In industrial plants, aromatic hydrocarbons are mainly produced through catalytic reforming of naphtha, followed by toluene / benzene and C9 + A is converted to xylene via isomerization and transalkylation units. Furthermore, steam cracking plants in China that produce light olefins also primarily use naphtha as a raw material. As a result, there is competition between raw materials for producing aromatic compounds and raw materials for producing olefins, driving up the costs of raw materials for both aromatic compounds and olefins. Therefore, the search for lower-cost and more diverse raw materials for producing aromatic compounds and olefins is a key factor in solving the problems that will be faced in the future development of the aromatic compound and olefin industries.

[0004] With the application and spread of new energy technologies in China, as well as improvements in gasoline, the future demand for vehicle gasoline is expected to decline. This will likely result in a supply surplus in the gasoline market. Therefore, intentionally converting some of the low-quality gasoline into high-value C8 aromatic hydrocarbons is an effective way to expand gasoline utilization, thereby alleviating the shortage of raw materials for paraxylene production.

[0005] CN1923965 discloses a method for producing ethylene, propylene, and aromatic hydrocarbons from catalytic cracking gasoline. In this method, the raw materials are first brought into contact with a catalyst in order to convert them into a mixture of ethylene, propylene, and aromatic hydrocarbons.

[0006] The conversion of hydrocarbon raw materials containing non-aromatic hydrocarbons into aromatic hydrocarbons is primarily achieved through aromatization technology. Aromaticization technology uses light olefins and alkanes to produce aromatic hydrocarbons through complex aromatization processes, thereby enabling diversification of aromatic compound production raw materials. The distribution of products in this process is closely related to the structure of the raw materials, with the main products including benzene components, toluene components, C8 aromatic hydrocarbon components, heavy aromatic hydrocarbon components, and non-aromatic hydrocarbon components. Therefore, increasing the directivity to the production of high-purity C8 aromatic hydrocarbons is difficult to achieve with aromatization technology alone. Aromatic compound transalkylation technology allows for the maximum conversion of benzene, toluene, and heavy aromatic compounds into C8 aromatic hydrocarbons, while simultaneously generating some light hydrocarbons as byproducts. For example, CN1122571 discloses a molecular sieve catalyst containing a noble metal. The molecular sieve catalyst containing the noble metal comprises 10 to 80% by weight of mordenite or β molecular sieve, 0 to 70% by weight of ZSM-5 and 5 to 90% by weight of γ-Al2O3 as a support, and 0.001 to 0.5 parts by weight of platinum and 0.01 to 10.0 parts by weight of tin or 0.01 to 7.0 parts by weight of lead supported on the support.

[0007] US2008 / 0026931A1 discloses a catalyst comprising an acidic molecular sieve and metallic components of rhenium, tin, and germanium. This catalyst is used for the transalkylation of heavy aromatic compounds and exhibits relatively high activity and a relatively low ring loss rate.

[0008] In processes that produce aromatic hydrocarbons as the target product, obtaining a high-purity product is extremely important. Aromatic compound plants are mainly involved in the separation of aromatic hydrocarbons from non-aromatic hydrocarbons by extraction or rectification, and the decomposition of non-aromatic hydrocarbons into small molecule light hydrocarbons by chemical cracking, which can improve the purity of the aromatic product.

[0009] US3,729,409 proposes converting non-aromatic hydrocarbons mixed with aromatic hydrocarbons into lower alkanes by hydrocracking in the presence of a catalyst. In this case, aromatic hydrocarbons can be separated from non-aromatic hydrocarbons using a gas-liquid separator.

[0010] However, existing methods still suffer from the challenge of limited comprehensive utilization of gasoline fractions and low product value.

[0011] [Summary of the Invention] The object of this application is to provide a novel method and system for processing gasoline fractions that can effectively expand the raw materials for producing aromatic compounds and olefins and enable the efficient and comprehensive utilization of gasoline fractions.

[0012] To achieve the above objective, in one embodiment, this application relates to a method for processing gasoline fractions, Step I) The gasoline fraction is reacted in an aromatization unit, and the resulting reaction product is separated and C4 - Components, C5 component, C6-C7 component, C8 component and C9 + The process of obtaining the components, wherein the reaction occurring within the aromatization unit includes an aromatization reaction; Step II) Reacting the C6-C7 components and the C9 components from Step I) in a cracking and aromatic compound conversion unit, separating the resulting reaction product to obtain C4 + components, C5 components, C6-C7 components, C8 components, and C9 - components, wherein the reactions occurring in the cracking and aromatic compound conversion unit include non-aromatic compound cracking reactions and transalkylation reactions; + Step III) Optionally, purifying at least one of the C8 components from Step I) and the C8 components from Step II), separating the resulting product to obtain C4 components, C5 components, C6-C7 components, (one or more) C8 aromatic hydrocarbons, and C9 - components; + Step IV) Optionally, subjecting at least a part of at least one of the C4 components from Step I), the C4 components from Step II), and the C4 components from Step III) to steam cracking or dehydrogenation reaction; Step V) Optionally, using at least a part of at least one of the C5 components from Step I), the C5 components from Step II), and the C5 components from Step III) for gasoline blending; and - Step VI) Recycling at least a part of at least one of the C6-C7 components and the C9 components from Step II) and at least a part of at least one of the C6-C7 components and the C9 components from Step III) to the cracking and aromatic compound conversion unit of Step II) for further reaction - to provide a method comprising. - In another aspect, the present application is a method for treating a gasoline fraction, comprising -

[0013] + +

[0013] Step 1) The gasoline fraction is reacted in the presence of an aromatizing catalyst, and the resulting reaction product is separated to form C4 - Components, C5 component, C6-C7 component, C8 component and C9 + The process of obtaining the components; Step 2) The C6-C7 components and the C9 from Step 1) + The components are reacted in the presence of an aromatic compound conversion catalyst, and the resulting reaction product is separated to obtain C4 - Components, C5 component, C6-C7 component, C8 component and C9 + The process of obtaining the components; Step 3) Optionally, purify at least one of the C8 components from Step 1) and Step 2), and separate the resulting product to obtain C4 - Components, C5 components, C6-C7 components, (one or more) C8 aromatic hydrocarbons, and C9 + The process of obtaining the components; Step 4) Optionally, the C4 from Step 1) - Components, C4 from step 2) - Components and the C4 from step 3) - At least one of the components is C4 - A step of subjecting at least a portion of the components to a steam decomposition or dehydrogenation reaction; Step 5) optionally using at least a portion of at least one of the C5 components from Step 1), Step 2), and Step 3) for gasoline blending; and, Step 6) The C6-C7 components and the C9 from Step 2) + The components, and the C6-C7 components and the C9 from step 3) + A step of recycling at least a portion of at least one of the components for a further reaction in the presence of the aromatic compound conversion catalyst in step 2). This provides a method that includes this.

[0014] In yet another aspect, the present application is a system for carrying out the gasoline fraction processing method of the present application, The gasoline fraction is reacted internally, and the resulting reaction product is separated to form C4 - Components, C5 component, C6-C7 component, C8 component and C9 + A fragrance unit for obtaining components, The C6-C7 component and the C9 from the aromaticization unit + The components are reacted, and the resulting reaction product is separated, C4 - Components, C5 component, C6-C7 component, C8 component and C9 + A cracking and aromatic compound conversion unit for obtaining components, Optionally, the C8 component from the aromatization unit and at least one of the C8 components from the cracking and aromatic compound conversion unit are purified, and the resulting product is separated to obtain C4 - Components, C5 components, C6-C7 components, (one or more) C8 aromatic hydrocarbons, and C9 + A unit for purifying aromatic compounds to obtain components, Optionally, the C4 from the aromaticization unit - Components, the C4 from the cracking and aromatic compound conversion unit - Components, and optionally, the C4 from the aromatic compound purification unit. - At least one of the components is C4 - A light hydrocarbon conversion unit for carrying out steam decomposition or dehydrogenation reactions on at least a portion of the components, A light gasoline blending unit for gasoline blending that optionally uses at least a portion of at least one of the C5 components from the aromatization unit, the cracking and aromatic compound conversion unit, and optionally from the aromatic compound purification unit, We provide a system that includes the following features.

[0015] In the method and system described in this application, a gasoline fraction containing non-aromatic hydrocarbons is passed through an aromatization unit, thereby increasing the yield of the mixed aromatic hydrocarbon product, and simultaneously generating non-aromatic hydrocarbon components having a low olefin content and a high isoparaffin content as byproducts. C6-C7 components and C9 components containing a small amount of C8 aromatic hydrocarbons. + The components are passed through a cracking and aromatic compound conversion unit, and benzene, toluene, and C9 in these components are removed. + Aromatic hydrocarbons are selectively converted to (one or more) C8 aromatic hydrocarbons, while non-aromatic hydrocarbons are slightly decomposed into light hydrocarbons. Optionally, the C8 aromatic hydrocarbon products are further purified in an aromatic compound purification unit to obtain (one or more) high-purity C8 aromatic hydrocarbons. The resulting by-products C4 and lower hydrocarbons can be used as high-quality raw materials for steam decomposition or dehydrogenation reactions. The resulting by-product C5 component is characterized by low olefin and high isoparaffin content and can be used as a high-quality gasoline blending material. This process allows for the effective and selective conversion of gasoline fractions (such as catalytic gasoline fractions and LPG) to (one or more) C8 aromatic hydrocarbons, generating light olefins and high-quality light gasoline as by-products. As a result, efficient and comprehensive utilization can be achieved.

[0016] By using the method described in this application, the aromatic compound content in the reaction product of the aromatization unit increases by 15% or more, preferably by 25% or more, compared to the raw materials. The C8 aromatic compound content in the product of the cracking and aromatic compound conversion unit increases by 20% or more, preferably by 25% or more, compared to the raw materials. Optionally, the aromatic compound purification unit is an extraction and separation unit or a non-aromatic compound selective decomposition unit, and the purity of the C8 aromatic hydrocarbon product of the aromatic compound purification unit can reach 99% or more.

[0017] Other features and advantages of this application will be described in detail in the following detailed description.

[0018] [Brief explanation of the drawing] The drawings, which form part of this specification, are provided to aid in understanding this application and should not be considered limiting. This application can be interpreted by referring to the drawings in conjunction with the following detailed description. In the drawings: Figure 1 is a schematic flowchart of a preferred embodiment of the method described in this application; Figure 2 is a schematic flowchart of another preferred embodiment of the method relating to this application; Figure 3 shows the NH3-TPD pattern of the catalyst obtained in Preparation Example 1 of this application; Figure 4 shows a TEM image of the catalyst obtained in Preparation Example 1 of this application.

[0019] [Detailed description of the invention] This application is described further below in detail with reference to the drawings and specific embodiments thereof. It should be noted that the specific embodiments of this application are provided for illustrative purposes only and are not intended to limit in any way.

[0020] Any specific numerical value described in the context of this application (including the endpoints of a numerical range) should be interpreted not as being limited to its exact value, but as further encompassing all values ​​close to the exact value, for example, all values ​​within ±5% of the exact value. Furthermore, with respect to any numerical range described herein, any combination can be made 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, resulting in one or more new numerical ranges. In this case, the (one or more) new numerical ranges should also be deemed to be specifically described in this application.

[0021] Unless otherwise specified, terms used herein have the same meanings as those generally understood by those skilled in the art. If a term is defined herein and that definition differs from the general understanding in the art, the definition provided herein shall prevail.

[0022] In the context of this application, the term “gasoline fraction” refers to a fraction having a boiling point within the boiling point range of gasoline (typically 30–205°C). This includes, but is not limited to, catalytically cracked gasoline, hydrocracked gasoline, ethylenecracked gasoline, catalytically reformed gasoline, straight-run gasoline, LPG, any mixture thereof, or partial fractions thereof.

[0023] In the context of this application, C4 - The C5 component refers to hydrocarbon components with a boiling point below 30°C, the C6-C7 component refers to hydrocarbon components with a boiling point in the range of 30°C to less than 70°C, the C8 component refers to hydrocarbon components with a boiling point in the range of 70°C to less than 130°C, and the C8 component refers to hydrocarbon components with a boiling point in the range of 130°C to 145°C. o This refers to hydrocarbon components with boiling points in the range up to C, C9 + The ingredients are 145 o This refers to hydrocarbon components that have a higher boiling point than carbon (C).

[0024] In the context of this application, (one or more) high-purity C8 aromatic hydrocarbons refer to (one or more) C8 aromatic hydrocarbons that satisfy the purity requirements for adsorption separation or crystallization separation of paraxylene. This requirement is, for example, greater than 99%.

[0025] In the context of this application, the term “acidic molecular sieve” has the meaning commonly understood in the art and refers to a molecular sieve having B acid sites and / or L acid sites.

[0026] In this application, the moderate acid content of the catalyst is calculated according to the peak area of ​​its NH3-TPD pattern within the temperature range of 200-400°C. The ratio of moderate acid content to total acid content refers to the ratio of the peak area within the temperature range of 200-400°C to the total peak area within the temperature range of 100-600°C of the NH3-TPD pattern.

[0027] In the context of this application, unless otherwise specified, all given pressures are gauge pressures.

[0028] In the context of this application, matters not explicitly stated, in addition to those explicitly stated, shall be deemed to be the same as those known in the art without any modification. Furthermore, any embodiment described herein may be freely combined with one or more other embodiments described herein. Such technical solutions or ideas shall be deemed to be part of the original disclosure or description of this application and shall not be deemed to be novel matters not disclosed or foreseen herein unless such combination is clearly unreasonable to a person skilled in the art.

[0029] All patent and non-patent documents cited herein (including, but not limited to, textbooks and academic papers) are incorporated herein by reference in their entirety.

[0030] As described above, in the first aspect, the present application relates to a method for processing gasoline fractions, Step I) The gasoline fraction is reacted in an aromatization unit, and the resulting reaction product is separated and C4 - Components, C5 component, C6-C7 component, C8 component and C9 + The process of obtaining the components, wherein the reaction occurring within the aromatization unit includes an aromatization reaction; Step II) The C6-C7 components and the C9 from Step I) + The components are reacted in a cracking and aromatic compound conversion unit, and the resulting reaction product is separated to form C4- Components, C5 component, C6-C7 component, C8 component and C9 + The process of obtaining the components, wherein the reactions occurring within the cracking and aromatic compound conversion unit include a non-aromatic compound cracking reaction and a transalkylation reaction; Step III) Optionally, purify at least one of the C8 components from Step I) and Step II), and separate the resulting product to obtain C4 - Components, C5 components, C6-C7 components, (one or more) C8 aromatic hydrocarbons, and C9 + The process of obtaining the components; Step IV) Optionally, the C4 from Step I) - Components, from step II) the C4 - Components and the C4 from step III) - At least one of the components is C4 - A step of subjecting at least a portion of the components to a steam decomposition or dehydrogenation reaction; Step V) A step in which at least a portion of at least one of the C5 components from Step I), Step II), and Step III) is optionally used for gasoline blending; and, Process VI) The C6-C7 component and the C9 from Process II) + The components, and optionally the C6-C7 components and the C9 from step III). + A step of recycling at least a portion of at least one of the components to the cracking and aromatic compound conversion unit of step II) for further reaction. This provides a method that includes this.

[0031] In a second aspect, the present application relates to a method for processing gasoline fractions, Step 1) The gasoline fraction is reacted in the presence of an aromatizing catalyst, and the resulting reaction product is separated to form C4 - Components, C5 component, C6-C7 component, C8 component and C9 + The process of obtaining the components; Step 2) The C6-C7 components and the C9 from Step 1) + The components are reacted in the presence of an aromatic compound conversion catalyst, and the resulting reaction product is separated to obtain C4 - Components, C5 component, C6-C7 component, C8 component and C9 + The process of obtaining the components; Step 3) Optionally, purify at least one of the C8 components from Step 1) and Step 2), and separate the resulting product to obtain C4 - Components, C5 components, C6-C7 components, (one or more) C8 aromatic hydrocarbons, and C9 + The process of obtaining the components; Step 4) Optionally, the C4 from Step 1) - Components, C4 from step 2) - Components and the C4 from step 3) - At least one of the components is C4 - A step of subjecting at least a portion of the components to a steam decomposition or dehydrogenation reaction; Step 5) optionally using at least a portion of at least one of the C5 components from Step 1), Step 2), and Step 3) for gasoline blending; and, Step 6) The C6-C7 components and the C9 from Step 2) + The components, and optionally the C6-C7 components and the C9 from step 3). + A step of recycling at least a portion of at least one of the components for a further reaction in the presence of the aromatic compound conversion catalyst in step 2). This provides a method that includes this.

[0032] According to this application, the separation of components in steps I), II), and III) is carried out by separating a hydrocarbon-containing mixture into components having various boiling points or boiling point ranges through distillation, rectification, or fractionation according to their boiling points. The specific operations and conditions used can be easily determined by those skilled in the art, taking into account the target components to be separated. Therefore, for the sake of brevity, a detailed description thereof is omitted herein.

[0033] In one preferred embodiment, the gasoline fraction used in steps I) and 1) has one or more of the following characteristics: The boiling point range is 40 to 250°C, preferably 50 to 200°C; The aromatic compound content is 10 to 100% by weight, preferably 20 to 80% by weight, and more preferably 20 to 35% by weight; The sulfur content must be 2-4 ppm by weight; The nitrogen content should be 0.5 to 2 ppm by weight; The olefin content is 20-40% by weight; and, The alkane content should be 40-45% by weight.

[0034] In one preferred embodiment, the gasoline fraction used in steps I) and 1) is selected from the group consisting of catalytically cracked gasoline, hydrocracked gasoline, ethylenecracked gasoline, catalytically reformed gasoline, straight-run gasoline, LPG, or any mixture thereof, or partial fractions thereof.

[0035] The gasoline fraction according to the above preferred embodiment can be utilized more efficiently by processing it using the method described in this application.

[0036] In this application, the aromatizing catalyst used in the aromatizing unit of step I) and the aromatizing catalyst used in step 1) may be conventional, and may include 50 to 90% by weight of a molecular sieve selected from those having a 10-membered ring pore structure or a 12-membered ring pore structure, such as aluminosilicate, aluminogallosilicate, aluminosilicophosphate, and aluminoferrosilicate, and 0.5 to 10% by weight of a modifying metal (calculated as a metal). The modifying metal is selected from group IB metals, group IIB metals, group VIB metals, group VIIB metals, and group VIII metals, and is preferably selected from Zn, Mo, Ga, and Pt. The molecular sieve used in the aromatizing catalyst is preferably ZSM-5, and the modifying metal is preferably Zn and Ga.

[0037] In one preferred embodiment, the reaction conditions for steps I) and 1) are a reaction temperature of 400-600°C, a reaction pressure of 0.2-3 MPa, and 0.5-5 hours. -1 This includes the supply space velocity.

[0038] In this application, the aromatic compound conversion catalyst used in the cracking and aromatic compound conversion unit of step II), and the aromatic compound conversion catalyst used in step 1), may be conventional, for example, selected from aluminosilicates and silicoaluminophosphates having an 8-membered ring pore structure, a 10-membered ring pore structure, or a 12-membered ring pore structure, and preferably selected from ZSM-5 molecular sieves, ZSM-12 molecular sieves, MOR molecular sieves, and β molecular sieves, and may contain 50 to 90% by weight of a molecular sieve and 0.05 to 10% by weight of a modified metal. The modified metal component is selected from the group consisting of group VB metals, group VIB metals, group VIIB metals, group VIII metals, and their metal oxides.

[0039] In a preferred embodiment, the aromatic compound conversion catalyst comprises an acidic molecular sieve component, an oxide additive, a first metal component (which may be in the form of a metal and / or a metal oxide), and a second metal component (which may be in the form of a metal and / or a metal oxide), wherein the first metal of the first metal component is one or more metals selected from the group consisting of VB metals, VIB metals, and VIIB metals, the second metal of the second metal component is a different metal from the first metal, the first metal component is immobilized on the acidic molecular sieve component, and the catalyst has a moderate acid content of 0.05 to 2.0 mmol / g and a ratio of moderate acid content to a total acid content of 60 to 99%.

[0040] In one preferred embodiment, the catalyst has a moderate acid content of 0.1 to 1 mmol / g and a ratio of the moderate acid content to a total acid content of 68 to 92%.

[0041] In this application, VB group metals, VIB group metals, and VIIB group metals are used as the first metal component of the aromatic compound conversion catalyst. As a result, the catalyst has advantages such as high reaction activity and a low loss rate of aromatic hydrocarbons. In one preferred embodiment, the first metal is selected from Mo, Re, W, or a combination thereof. In one more preferred embodiment, the first metal is at least two of Mo, Re, and W, with a weight mixing ratio of 0.1 to 10:1 calculated as metal elements, or Mo, Re, and W are combined in a weight ratio of Mo:Re:W = 1:0.1 to 0.4:0.1 to 0.6.

[0042] According to this application, the type of the second metal may be selected from a wide range, and any metal different from the first metal may be used. Preferably, the second metal is selected from the group consisting of group IA metals, group IIA metals, group IIIA metals, group IVA metals, group VA metals, lanthanide metals, and combinations thereof. More preferably, it is selected from Sr, Bi, Ce, Zr, Ge, or combinations thereof.

[0043] In one preferred embodiment, the first metal component is immobilized on the acidic molecular sieve component by physical mixing and / or chemical bonding.

[0044] In one preferred embodiment, the second metal component is immobilized on the oxide additive, preferably by physical mixing and / or chemical bonding.

[0045] In one particularly preferred embodiment, the first metal component is immobilized on the acidic molecular sieve component by physical mixing and / or chemical bonding, and the second metal component is immobilized on the oxide additive by physical mixing and / or chemical bonding.

[0046] In this application, it has been discovered for the first time that the distribution of metals supported on the catalyst can be adjusted and controlled according to the influence of various metal components on the aromatic compound conversion process, that the efficiency of aromatic compound conversion can be enhanced by immobilizing VB, VIB, and VIIB group metals, which have relatively strong hydrogenation capabilities on the surface of the molecular sieve, and that by immobilizing other metals on the oxide additive, the hydrogenation saturation side reaction of aromatic compounds on the surface of the oxide additive can be inhibited, and as a result, the conversion efficiency and selectivity of the target product of the aromatic compound conversion catalyst when used in the aromatic compound conversion reaction can be greatly improved.

[0047] According to this application, the type of acidic molecular sieve component may be selected from a wide range, and all commonly used acidic molecular sieve components may be used herein. The acidic molecular sieve component is preferably selected from acidic molecular sieves having an 8-membered ring pore structure, acidic molecular sieves having a 10-membered ring pore structure, or acidic molecular sieves having a 12-membered ring pore structure, and more preferably selected from the group consisting of ZSM-5 molecular sieves, MCM-22 molecular sieves, MOR molecular sieves, β molecular sieves, ZSM-12 molecular sieves, and combinations thereof.

[0048] According to this application, the type of oxide additive can be selected from a wide range, and all commonly used oxide additives can be used herein. The oxide additive is preferably selected from alumina, magnesia, kaolin, or a combination thereof.

[0049] In this application, the content of each component of the aromatic compound conversion catalyst can be selected within a wide range. Preferably, with the total weight of the catalyst being 100% by weight, the acidic molecular sieve component is present in an amount of 40 to 90% by weight, the oxide additive is present in an amount of 5 to 40% by weight, the first metal component (calculated as a metallic element) is present in an amount of 0.01 to 20% by weight, and the second metal component (calculated as a metallic element) is present in an amount of 0.01 to 20% by weight.

[0050] In a preferred embodiment, with the total weight of the aromatic compound conversion catalyst being 100% by weight, the acidic molecular sieve component is present in an amount of 50-80% by weight, the oxide additive is present in an amount of 10-30% by weight, the first metal component is present in an amount of 0.05-15% by weight, and the second metal component is present in an amount of 0.05-15% by weight.

[0051] Aromatic compound conversion catalysts that satisfy the above-mentioned requirements of this application may be used, and the method of preparation thereof is not particularly limited. In one preferred embodiment, the aromatic compound conversion catalyst is prepared by a) immobilizing a first metal component on the acidic molecular sieve, b) immobilizing a second metal component on the oxide additive, and c) forming the product of step a) and the product of step b) by kneading.

[0052] In a more preferred embodiment, the aromatic compound conversion catalyst is prepared by a method comprising: a) impregnating an acidic molecular sieve component source with a first metal source solution and performing a first heat treatment to obtain a first solid; b) impregnating an oxide additive source with a second metal source solution and performing a second heat treatment to obtain a second solid; and c) forming the first solid and the second solid by kneading. In this application, the impregnation may be isovolumetric impregnation, supersaturated impregnation, etc., and is preferably supersaturated impregnation.

[0053] In one preferred embodiment, the first heat treatment and the second heat treatment each include roasting, or a combination of drying and roasting.

[0054] In a more preferred embodiment, each of the first and second heat treatments includes a combination of drying and roasting.

[0055] In this application, the drying conditions can be selected from a wide range, and general drying conditions can be used in this application. Preferred drying conditions include a temperature of 50 to 200°C and a time of 1 to 30 hours.

[0056] In this application, the roasting conditions can be selected from a wide range, and all conventional roasting conditions can be used in this application. Preferred roasting conditions include heat treatment at a temperature of 300 to 700°C for 1 to 30 hours in an oxygen-containing atmosphere.

[0057] In a preferred embodiment, the oxygen-containing atmosphere is a gas mixture of air and water vapor in a volume ratio of 5 to 100:1.

[0058] In this application, the first metal source may be a soluble compound containing a Group VB metal, a Group VIB metal, or a Group VIIB metal. All commonly used soluble compounds, such as nitrates, sulfates, chlorides (i.e., hydrochlorides), or ammonium salts, can be used in this application. For brevity, a detailed description thereof is omitted in this specification.

[0059] In this application, the second metal source may be a soluble compound containing the second metal. All commonly used soluble compounds, such as nitrates, sulfates, chlorides, or ammonium salts, can be used in this application. For brevity, a detailed description thereof is omitted in this specification.

[0060] In this application, the acidic molecular sieve component source may be an acidic molecular sieve selected from the group consisting of, for example, those having an 8-membered ring pore structure, a 10-membered ring pore structure, or a 12-membered ring pore structure, and preferably an acidic molecular sieve selected from the group consisting of ZSM-5 molecular sieve, MCM-22 molecular sieve, MOR molecular sieve, β molecular sieve, ZSM-12 molecular sieve, and combinations thereof.

[0061] In this application, the oxide additive source can be selected from, for example, alumina, magnesia, kaolin, their precursors, or a combination thereof.

[0062] According to this application, the aromatic compound conversion catalyst can be used for disproportionation and transalkylation of alkyl aromatic hydrocarbons and has advantages such as high reaction activity and a low loss rate of aromatic hydrocarbons.

[0063] The aromatic compound conversion catalyst of this application may be reduced before use as necessary. The reduction step does not have specific requirements and may be carried out, for example, by introducing hydrogen for reduction or by using other reducing agents. For the sake of brevity, a detailed description thereof is omitted herein.

[0064] In one preferred embodiment, the reaction conditions for steps II) and II) are a reaction temperature of 250-500°C, a reaction pressure of 1.5-6.5 MPa, a molar ratio of hydrogen to hydrocarbons of 1-10, and 0.5-5h -1 This includes the feeding weight hourly space velocity.

[0065] In one preferred embodiment, the purification in steps III) and 3) is by extraction and separation of aromatic compounds, selective decomposition of non-aromatic compounds, or a combination thereof.

[0066] In some further preferred embodiments, the purification is an extraction separation carried out by extraction distillation using a sulfolane solvent.

[0067] In this application, the catalyst used in the selective decomposition of the non-aromatic compound may be a conventional one. For example, the catalyst may include 60 to 100% by weight of at least one type of acidic molecular sieve (e.g., at least one type of acidic molecular sieve selected from ZSM-5 molecular sieve, MCM-22 molecular sieve, MOR molecular sieve, and β molecular sieve) selected from the group consisting of those having an 8-membered ring structure, a 10-membered ring structure, or a 12-membered ring structure, and optionally 0.5 to 10% by weight of a metal component selected from group VIB metals, group VIIB metals, and group VIII metals.

[0068] In one preferred embodiment, the operating conditions for the selective decomposition of the non-aromatic compound are a reaction temperature of 300-600°C, a reaction pressure of 0.5-3.0 MPa, a molar ratio of hydrogen to hydrocarbons of 1-10, and 1-15 hours. -1 The supply weight includes the space velocity per hour.

[0069] In some preferred embodiments, the operating conditions for steam decomposition in steps IV) and 4) include a decomposition temperature of 600 to 1000°C, a residence time of 0.01 to 0.8 seconds, and a reaction pressure of 0.1 to 0.3 MPa.

[0070] In some other preferred embodiments, the dehydrogenation reactions of steps IV) and 4) are carried out in the presence of a catalyst comprising 0.05 to 20% by weight of a metallic component selected from Pt, Pd, Cr, and Fe, and the remaining amount of a support selected from alumina, silica, aluminosilicate, magnesia, and calcia. More preferably, the operating conditions for the dehydrogenation reaction are a reaction temperature of 500 to 600°C and 0.5 to 3.0 h. -1 This includes the space velocity per unit weight and the reaction pressure of 0.3 to 1.5 MPa.

[0071] In a second aspect, the present application relates to a system for carrying out the gasoline fraction processing method of the present application, The gasoline fraction is reacted internally, and the resulting reaction product is separated to form C4 - Components, C5 component, C6-C7 component, C8 component and C9 + A fragrance unit for obtaining components, The C6-C7 component and the C9 from the aromaticization unit + The components are reacted, and the resulting reaction product is separated, C4 - Components, C5 component, C6-C7 component, C8 component and C9 + A cracking and aromatic compound conversion unit for obtaining components, Optionally, the C8 component from the aromatization unit and at least one of the C8 components from the cracking and aromatic compound conversion unit are purified, and the resulting product is separated to obtain C4 - Components, C5 components, C6-C7 components, (one or more) C8 aromatic hydrocarbons, and C9 + A unit for purifying aromatic compounds to obtain components, Optionally, the C4 from the aromaticization unit - Components, the C4 from the cracking and aromatic compound conversion unit - Components, and optionally, the C4 from the aromatic compound purification unit. - At least one of the components is C4 -A light hydrocarbon conversion unit for performing steam cracking or dehydrogenation reaction on at least a part of the components, Optionally, a light gasoline mixing unit for gasoline mixing that uses at least a part of at least one of the C5 components from the aromatization unit, the C5 components from the cracking and aromatic compound conversion unit, and optionally the C5 components from the aromatic compound purification unit, A system comprising the above is provided.

[0072] In some embodiments, the aromatization unit has a gasoline fraction inlet, C4 - component outlet, C5 component outlet, C6-C7 component outlet, C8 component outlet and C9 + component outlet provided, The cracking and aromatic compound conversion unit has an inlet, C4 - component outlet, C5 component outlet, C6-C7 component outlet, C8 component outlet and C9 + component outlet provided, The aromatic compound purification unit has an inlet, C4 - component outlet, C5 component outlet, C6-C7 component outlet, C8 aromatic hydrocarbon outlet and C9 + component outlet provided, The light hydrocarbon conversion unit has an inlet and a conversion product outlet provided, The light gasoline mixing unit has an inlet and a mixed gasoline outlet provided, The C6-C7 component outlet and the C9 + component outlet of the aromatization unit communicate with the inlet of the cracking and aromatic compound conversion unit, Optionally, at least one of the C8 component outlets of the C8 component outlet of the aromatization unit and the C8 component outlet of the cracking and aromatic compound conversion unit communicates with the inlet of the aromatic compound purification unit, and the C4 - component outlet of the aromatization unit, the C4 of the cracking and aromatic compound conversion unit- Component outlet and the C4 of the aromatic compound purification unit - At least one C4 of the component outlets - The component outlet communicates with the inlet of the light hydrocarbon conversion unit, Optionally, at least one C5 component outlet of the C5 component outlet of the aromatization unit, the C5 component outlet of the cracking and aromatic compound conversion unit, and the C5 component outlet of the aromatic compound purification unit communicates with the inlet of the light gasoline mixing unit, The C6-C7 component outlet and the C9 of the cracking and aromatic compound conversion unit + Component outlet and, optionally, at least one of the component outlets of the C6-C7 component outlet and the C9 of the aromatic compound purification unit + The component outlet communicates with the inlet of the cracking and aromatic compound conversion unit.

[0073] In a preferred embodiment, the aromatic compound purification unit may be an aromatic compound extraction and separation unit, a non-aromatic compound selective decomposition unit, or a combination thereof.

[0074] In a preferred embodiment, the light hydrocarbon conversion unit may be a steam cracking unit, a dehydrogenation unit, or a combination thereof.

[0075] According to the present application, the aromatization unit may include an aromatization reactor and a separation device. Here, the aromatization reactor may be in the form of a fixed bed or a moving bed generally used in the art, such as an axial fixed bed reactor. Further, the separation device may be in the form of a distillation column, a rectification column, or a fractionation column generally used in the art, for example, in the form of an atmospheric rectification column or a pressurized rectification column.

[0076] According to this application, the cracking and aromatic compound conversion unit may include a cracking and aromatic compound conversion reactor and a separation device. Here, the cracking and aromatic compound conversion reactor may be a fixed-bed reactor with intermediate quenching or a single-stage fixed-bed reactor, which are commonly used in the art. The separation device may be a distillation column, rectification column, or fractionation column, which are commonly used in the art, such as an atmospheric pressure rectification column.

[0077] According to this application, the aromatic compound extraction and separation unit may include an extraction separator and a separation device. Here, the extraction separator may be in the form of a liquid-liquid extractor, an extraction distillation column, or the like, commonly used in the art, for example, an extraction distillation column using a sulfolane solvent. The separation device may be in the form of a distillation column, a rectification column, or a fractionation column, commonly used in the art, for example, an atmospheric pressure rectification column or a pressurized rectification column.

[0078] According to this application, the non-aromatic compound selective decomposition unit may include a decomposition reactor and a separation device. Here, the decomposition reactor may be in the form of a fixed-bed reactor commonly used in the art, such as a radial fixed-bed reactor or a fixed-bed reactor with multistage quenching. The separation device may be in the form of a distillation column, rectification column, or fractionation column commonly used in the art, for example, an atmospheric pressure rectification column or a pressurized rectification column.

[0079] According to this application, the steam decomposition unit may be in the form of a gas decomposition furnace commonly used in the art, such as an ultrashort residence time decomposition furnace or a short residence time decomposition furnace.

[0080] According to this application, the dehydrogenation unit may be in the form of a dehydrogenation reactor commonly used in the art, such as a fixed-bed reactor.

[0081] According to this application, in one preferred embodiment, the supply inlet and outlet of each unit communicate with the supply inlet and outlet of the associated unit via a pipeline, as necessary. More preferably, valves are independently located on each pipeline to regulate the flow rate.

[0082] When used for processing gasoline fractions, the system of this application can effectively and directionally convert gasoline fractions (such as catalytic gasoline fractions and LPG) to one or more C8 aromatic hydrocarbons, while generating light olefins and high-quality light gasoline as by-products. As a result, efficient and comprehensive utilization can be achieved.

[0083] Examples The present application will be further described below with reference to several embodiments, but the present application is not limited to these embodiments.

[0084] (Example of preparation of the aromatic compound conversion catalyst of this application) All reagents used in the following preparation examples are commercially available and have reagent-grade purity.

[0085] In the following preparation example, the NH3-TPD pattern of the obtained catalyst was measured by the following method: 100 mg of a sample ground to 20-40 mesh was weighed, heated to 500°C at a heating rate of 10°C / min under a nitrogen stream (30 ml / min), purged at a constant temperature for 30 minutes, cooled to 100°C after heat treatment, NH3 gas was introduced to adsorb ammonia, and the ammonia adsorption was maintained for 10 minutes. Then, the process was switched to a helium purge (30 ml / min) for 1 hour, heated to 600°C with a temperature programming of a heating rate of 10°C / min, and the signal of NH3 concentration in the effluent was detected by TCD.

[0086] In the following preparation examples, the moderate-to-strong acid content of the catalyst was calculated according to the peak area of ​​its NH3-TPD pattern within the temperature range of 200-400°C. The ratio of the moderate-to-strong acid content to the total acid content of the catalyst is the ratio of the peak area within the temperature range of 200-400°C to the total peak area within the temperature range of 100-600°C of its NH3-TPD pattern.

[0087] In the following preparation examples, the TEM images of the obtained catalysts were characterized by high-resolution field emission transmission electron microscopy. Elemental analysis was performed using an energy scattering X-ray analyzer mounted on the transmission electron microscope, with an operating voltage of 200 kV.

[0088] Preparation Example 1 20 g of mordenite was taken, supersaturated with ammonium molybdate solution, and the resulting material was spray-dried at 150°C. It was then roasted at 400°C for 3 hours in an air atmosphere to obtain a modified molecular sieve. 7.7 g of alumina was taken, isotope-impregnated with strontium nitrate, and dried at 150°C for 10 hours to obtain modified alumina. The modified molecular sieve and modified alumina were kneaded and molded, then roasted at 550°C for 2 hours to obtain catalyst A with a molybdenum content of 1% by weight and a strontium content of 1.0% by weight. The composition and properties of the obtained catalyst are shown in Table 1, and the NH3-TPD pattern of the obtained catalyst is shown in Figure 3.

[0089] Figure 4 shows the TEM elemental analysis of the obtained catalyst. The upper left image shows the TEM phase image of the combined molecular sieve and alumina, the upper center image shows the distribution of Al elements, the upper right image shows the distribution of Si elements, the lower left image shows the distribution of Mo elements, and the lower center image shows the distribution of Sr elements. From the composition of the obtained catalyst, it can be seen that the silicon-rich portion (see upper right image) corresponds to mordenite, and the aluminum-rich portion (see upper center image) corresponds to the alumina additive. Furthermore, from the distribution of Mo elements (see lower left image), it can be seen that Mo elements are mainly distributed on the surface of the mordenite in the catalyst, and Sr elements (see lower center image) are mainly distributed on the surface of the alumina additive.

[0090] Preparation Example 2 15 g of mordenite and 5 g of ZSM-5 molecular sieve were mixed and supersaturated with ammonium molybdate solution. The resulting mixture was dried at 120°C for 10 hours, and then roasted at 450°C for 3 hours in an air atmosphere to obtain modified molecular sieve. 7.7 g of alumina was taken, impregnated with bismuth nitrate in an isovolumetric manner, dried at 120°C for 10 hours, and then roasted at 400°C for 3 hours in an air atmosphere to obtain modified alumina. The modified molecular sieve and modified alumina were kneaded and molded, and roasted at 500°C for 6 hours to obtain catalyst B with a molybdenum content of 3% by weight and a bismuth content of 5% by weight. The composition and properties of the obtained catalyst are shown in Table 1.

[0091] Preparation Example 3 15 g of mordenite and 5 g of ZSM-5 molecular sieve were taken, uniformly mixed, and then supersaturated with ammonium molybdate solution. The resulting product was dried at 120°C for 10 hours, and then roasted at 500°C for 3 hours in an air atmosphere to obtain modified molecular sieve. 7.7 g of alumina was taken, impregnated with cerium nitrate in an isovolumetric manner, dried at 120°C for 10 hours, and then roasted at 400°C for 3 hours in an air atmosphere to obtain modified alumina. The modified molecular sieve and modified alumina were kneaded and molded, and the resulting product was roasted at 550°C for 2 hours to obtain catalyst C with a molybdenum content of 13% by weight and a cerium content of 8.0% by weight. The composition and properties of the obtained catalyst are shown in Table 1.

[0092] Preparation Example 4 15 g of mordenite and 5 g of ZSM-5 molecular sieve were mixed and supersaturated with ammonium molybdate solution. The resulting mixture was spray-dried at high speed at 160°C and then roasted at 500°C for 3 hours to obtain modified molecular sieve. 7.7 g of alumina was taken, impregnated with bismuth nitrate in an isovolumetric manner, dried at 160°C for 10 hours, and then roasted at 500°C for 3 hours in an air atmosphere to obtain modified alumina. The modified molecular sieve and modified alumina were kneaded and molded, and roasted at 500°C for 6 hours to obtain catalyst D with a molybdenum content of 3% by weight and a bismuth content of 5% by weight. The composition and properties of the obtained catalyst are shown in Table 1.

[0093] Preparation Example 5 15 g of mordenite and 5 g of ZSM-5 molecular sieve were mixed and supersaturated with ammonium molybdate solution. The resulting mixture was roasted at 500°C for 3 hours to obtain modified molecular sieve. 7.7 g of alumina was taken, impregnated with bismuth nitrate in an isovolume, dried at 160°C for 10 hours, and then roasted at 500°C for 3 hours in an air atmosphere to obtain modified alumina. The modified molecular sieve and modified alumina were kneaded and molded, and roasted at 550°C for 3 hours to obtain catalyst E with a molybdenum content of 3% by weight and a bismuth content of 5% by weight. The composition and properties of the obtained catalyst are shown in Table 1.

[0094] Preparation Example 6 15 g of β molecular sieve and 5 g of ZSM-5 molecular sieve were uniformly mixed and supersaturated with ammonium perrhenate solution. The resulting mixture was dried at 120°C for 10 hours, and then roasted at 500°C for 3 hours in an air atmosphere to obtain modified molecular sieve. 7.7 g of alumina was taken, impregnated with germanium chloride in an isotope, dried at 120°C for 10 hours, and then roasted at 500°C for 3 hours in an air atmosphere to obtain modified alumina. The modified molecular sieve and modified alumina were kneaded and molded, and roasted at 550°C for 2 hours to obtain catalyst F with a rhenium content of 1% by weight and a germanium content of 3.0% by weight. The composition and properties of the obtained catalyst are shown in Table 1.

[0095] Preparation Example 7 15 g of ZSM-12 molecular sieve and 5 g of ZSM-5 molecular sieve were uniformly mixed and impregnated with an isovolume ammonium molybdate solution. The resulting product was dried at 120°C for 10 hours, and then roasted at 400°C for 3 hours in an air atmosphere to obtain a modified molecular sieve. 4 g of alumina and 3.5 g of magnesia were taken, uniformly mixed, and then impregnated with zirconium chloride. The resulting product was dried at 120°C for 10 hours, and then roasted at 400°C for 3 hours in an air atmosphere to obtain a modified oxide. The modified molecular sieve and the modified oxide were kneaded and molded, and the resulting product was roasted at 500°C for 4 hours to obtain catalyst G with a molybdenum content of 8 wt% and a zirconium content of 5.0 wt%. The composition and properties of the obtained catalyst are shown in Table 1.

[0096] Preparation Example 8 Catalyst I was prepared as described in Preparation Example 1, except that 18 g of mordenite and 2 g of ZSM-5 molecular sieve were uniformly mixed and impregnated with an isovolume solution of ammonium molybdate and ammonium tungstate. The composition and properties of the obtained catalyst are shown in Table 1.

[0097] Preparation Example 9 Catalyst J was prepared as described in Preparation Example 1, except that 18 g of mordenite and 2 g of ZSM-5 molecular sieve were uniformly mixed and then impregnated with an isovolume solution of ammonium molybdate, ammonium tungstate, and ammonium perrhenate. The composition and properties of the obtained catalyst are shown in Table 1.

[0098] Preparation Example 10 Catalyst M was prepared as described in Preparation Example 1, except that 18 g of mordenite and 2 g of ZSM-5 molecular sieve were uniformly mixed, impregnated with an isovolume ammonium molybdate solution, dried at 120°C for 10 hours, and then roasted at 400°C for 3 hours in a mixed atmosphere of air and water vapor (air:water vapor = 20:1 volume ratio) to obtain a modified molecular sieve. The composition and properties of the obtained catalyst are shown in Table 1.

[0099] Preparation Example 11 Catalyst N was prepared as described in Preparation Example 1, except that 18 g of mordenite and 2 g of ZSM-5 molecular sieve were uniformly mixed, impregnated with an isovolume ammonium molybdate solution, dried at 120°C for 10 hours, and then roasted at 400°C for 3 hours in a mixed atmosphere of air and water vapor (air:water vapor = 5:1 volume ratio) to obtain a modified molecular sieve. The composition and properties of the obtained catalyst are shown in Table 1.

[0100] Preparation Example 12 Catalyst O was prepared as described in Preparation Example 1, except that 18 g of mordenite and 2 g of ZSM-5 molecular sieve were uniformly mixed, impregnated with an isovolumetric ammonium molybdate solution, and the resulting product was dried at 120°C to obtain a modified molecular sieve; 7.7 g of alumina was impregnated with strontium nitrate at an isovolumetric level, dried at 150°C to obtain modified alumina; and the modified molecular sieve and modified alumina were kneaded and molded, then roasted at 550°C for 2 hours to obtain a catalyst. The composition and properties of the obtained catalyst are shown in Table 1.

[0101] Preparation Example 13 Catalyst P was prepared as described in Preparation Example 1, except that 20 g of mordenite was taken and impregnated with an isovolumetric solution of ammonium molybdate and ammonium tungstate. The composition and properties of the obtained catalyst are shown in Table 1.

[0102] Preparation Example 14 Catalyst Q was prepared as described in Preparation Example 1, except that 20 g of ZSM-5 molecular sieve was taken and impregnated with isovolumetric solutions of ammonium molybdate and ammonium tungstate. The composition and properties of the obtained catalyst are shown in Table 1.

[0103] Preparation Example 15 Catalyst R was prepared as described in Preparation Example 1, except that 20 g of β molecular sieve was taken and impregnated with isovolumetric solutions of ammonium molybdate and ammonium tungstate. The composition and properties of the obtained catalyst are shown in Table 1.

[0104] Preparation Example 16 Catalyst S was prepared as described in Preparation Example 1, except that 20 g of MCM-22 molecular sieve was taken and impregnated with an isovolumetric solution of ammonium molybdate and ammonium tungstate. The composition and properties of the obtained catalyst are shown in Table 1.

[0105] Preparation Example 17 Catalyst T was prepared as described in Preparation Example 1, except that 18 g of MCM-22 molecular sieves and 2 g of ZSM-5 molecular sieves were taken and impregnated with isovolumetric solutions of ammonium molybdate and ammonium tungstate. The composition and properties of the obtained catalyst are shown in Table 1.

[0106] Preparation Example 18 Catalyst U was prepared as described in Preparation Example 1, except that an equal amount of kaolin was used instead of alumina as an oxide auxiliary agent. The composition and properties of the obtained catalyst are shown in Table 1.

[0107] [Table 1] JPEG0007829569000002.jpg243169

[0108] (Example of a method for processing gasoline fractions) Examples 1 and 2 below illustrate the implementation of the processing method of this invention using conventional catalysts. Unless otherwise specified, each catalyst used was prepared by conventional methods known in the art.

[0109] Example 1 Refer to the flowchart shown in Figure 1. Catalytic cracking gasoline (100 tons / hour) is desulfurized and denitrified, then passed through an aromatization unit for aromatization, and the resulting product is processed according to its boiling point range into C4 - Component, C5 component, C6-C7 component, C8 component, C9 + The components were separated. C4 in the product - The components were used as decomposition raw materials for steam decomposition. Component C5, having a low olefin content and high isoparaffin content, was used as a high-quality light gasoline blend component. Component C8 was sent to a non-aromatic compound cracking unit to produce (one or more) high-purity C8 aromatic hydrocarbons. Components C6-C7 and C9 +The components were sent to the cracking and aromatic compound conversion unit to increase the yield of light hydrocarbons and C8 aromatic hydrocarbons. From the cracking and aromatic compound conversion unit, C4 was obtained as a byproduct. - The components were used as fuel for steam cracking. Component C5 was used as a high-quality light gasoline blending component for gasoline blending. Component C8 was sent to a non-aromatic compound cracking unit to produce (one or more) high-purity C8 aromatic hydrocarbons. Unreacted C6-C7 and C9 components. + The components were recycled to the cracking and aromatic compound conversion unit. In the non-aromatic compound cracking unit, the non-aromatic hydrocarbons in the C8 components were further decomposed to produce (one or more) high-purity C8 aromatic hydrocarbons and decomposed light hydrocarbons. Here, (one or more) C8 aromatic hydrocarbons were recovered as products and converted to C4 - The components are used as steam decomposition raw materials, component C5 is used as a high-quality light gasoline blending component, and C6 + The heavy fractions were partially or completely recycled to cracking and aromatic compound conversion units.

[0110] In the aromatization unit, the catalyst used was a Zn-modified ZSM-5 molecular sieve, with a Zn content (calculated as a metallic element) of 2 wt%, a ZSM-5 molecular sieve content of 70 wt%, and the remainder being alumina. The reaction temperature was 500°C, the reaction pressure was 0.5 MPa, and the space velocity per watt of feed was 1.5 h. -1 The following conditions were observed. In the cracking and aromatic compound conversion unit, the catalyst used was Pt-modified mordenite, with a Pt content (calculated as a metallic element) of 0.05 wt%, a mordenite content of 70 wt%, and the remainder being alumina. The reaction temperature was 350°C, the reaction pressure was 3.0 MPa, and the space velocity per watt of feed was 3.0 h. -1 The molar ratio of hydrogen to hydrocarbons was 3.0. In the non-aromatic compound cracking unit, the catalyst used was the ZSM-5 molecular sieve catalyst. The reaction temperature was 450°C, the reaction pressure was 3.0 MPa, and the space velocity per hour of feed was 1.0 h.-1 The molar ratio of hydrogen to hydrocarbons was 4.0.

[0111] The characteristics of the catalytic cracking gasoline feedstocks, the reaction conditions for each unit, and the product yield of the integrated unit are shown in Tables 2, 3, and 4, respectively.

[0112] Example 2 Refer to the flowchart shown in Figure 2. Catalytic cracking gasoline (100 tons / hour) is desulfurized and denitrified, then passed through an aromatization unit for aromatization, and the resulting product is processed according to its boiling point range into C4 - Component, C5 component, C6-C7 component, C8 component, C9 + The components were separated. C4 in the product - The components were used as decomposition raw materials for steam decomposition. Component C5, having a low olefin content and high isoparaffin content, was used as a high-quality light gasoline blend component for light gasoline blending. Component C8 was sent to an aromatic compound extraction unit to produce (one or more) high-purity C8 aromatic hydrocarbons. Components C6-C7 and C9 + The components were sent to the cracking and aromatic compound conversion unit to increase the yield of light hydrocarbons and C8 aromatic hydrocarbons. From the cracking and aromatic compound conversion unit, C4 was obtained as a byproduct. - The components were used as fuel for steam decomposition. Component C5 was used as a high-quality light gasoline blend component. Component C8 was sent to an aromatic compound extraction unit to produce (one or more) high-purity C8 aromatic hydrocarbons. Unreacted C6-C7 and C9 components. + The components were recycled to the cracking and aromatic compound conversion unit. In the aromatic compound extraction unit, aromatic hydrocarbons and non-aromatic hydrocarbons were separated from the C8 component. Here, the C8 aromatic hydrocarbons were recovered as a product, and the non-aromatic hydrocarbons were partially or completely recycled to the cracking and aromatic compound conversion unit.

[0113] In the aromatization unit, the catalyst used was a Zn-modified ZSM-5 molecular sieve, with a Zn content (calculated as a metallic element) of 3 wt%, a ZSM-5 molecular sieve content of 70 wt%, and the remainder being alumina. The reaction temperature was 450°C, the reaction pressure was 1.0 MPa, and the space velocity per watt of feed was 1.0 h. -1 The following conditions were observed. In the cracking and aromatic compound conversion unit, the catalyst used was a Mo-modified β-zeolite with a Mo content (calculated as a metallic element) of 4 wt%, a β-zeolite content of 70 wt%, and the remainder being alumina. The reaction temperature was 380°C, the reaction pressure was 3.0 MPa, and the space velocity per watt of feed was 3.0 h. -1 The molar ratio of hydrogen to hydrocarbons was 3.0.

[0114] The characteristics of the catalytic cracking gasoline feedstocks, the reaction conditions for each unit, and the product yield of the integrated unit are shown in Tables 2, 3, and 4, respectively.

[0115] [Table 2]

[0116] [Table 3]

[0117] [Table 4]

[0118] As can be seen from the test results in Table 4, the method of this application can be applied to the treatment of gasoline fractions having various compositions. The yield of olefins and C8 aromatic hydrocarbons in the product can reach 70-80%.

[0119] Examples 3 to 20 below illustrate the implementation of the processing method of this application using the aromatic compound conversion catalyst of this application.

[0120] Examples 3-20 Prior to use, catalysts A to U obtained in Preparation Examples 1 to 18 were placed separately in reactors and reduced by introducing hydrogen gas at 450°C for 3 hours. Next, the gasoline raw material was processed in the same manner as in Example 1, except that the aromatic compound conversion catalyst used in Example 1 was replaced with catalysts A to U, and all other operating conditions were kept the same. The results are shown in Table 5.

[0121] Example 21 In Example 10, the steam decomposition unit was replaced with a dehydrogenation unit, and the dehydrogenation catalyst used was Cr2O3-modified alumina with a Cr content (calculated as a metallic element) of 8% by weight and the remainder being alumina. The dehydrogenation temperature was set to 560°C, the reaction pressure to 0.8 MPa, and the supply weight per hour space velocity to 2 h. -1 Except for keeping all other operating conditions the same, the gasoline raw material was processed as described in Example 10. The results are shown in Table 5.

[0122] [Table 5] JPEG0007829569000007.jpg255161JPEG0007829569000008.jpg28169

[0123] As can be seen from the test results in Table 5, the total yield of olefins and C8 aromatic hydrocarbons can be further increased by using the aromatic compound conversion catalyst of this application. In one preferred embodiment, the total yield of (C8 aromatic compound + ethylene + propylene) can be increased to 89% by weight or more.

[0124] While this 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 spirit of this application. Such modifications shall remain within the scope of this application.

[0125] Furthermore, the various technical features described in the embodiments above may be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, various possible combinations are not described in this application. However, such combinations are also within the scope of this application.

[0126] In addition, various embodiments of this application can be arbitrarily combined without departing from the spirit of this application. Such combined embodiments should be considered as part of the disclosures of this application. [Brief explanation of the drawing]

[0127] [Figure 1] This is a schematic flowchart of a preferred embodiment of the method described in this application. [Figure 2] This is a schematic flowchart of another preferred embodiment of the method relating to this application. [Figure 3] The NH3-TPD pattern of the catalyst obtained in Preparation Example 1 of this application is shown. [Figure 4] The TEM image of the catalyst obtained in Preparation Example 1 of this application is shown.

Claims

1. A method for processing gasoline fractions, Step I) The gasoline fraction is reacted in the aromatization unit, and the resulting reaction product is separated, C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, C ８ Ingredients and C ９ ＋ The process of obtaining a component, wherein the reaction occurring within the aromatization unit includes an aromatization reaction; Step II) The C from Step I ６ -C ７ component and the C ９ ＋ components are reacted in a cracking and aromatic compound conversion unit, and the resulting reaction product is separated to obtain C ４ － component, C ５ component, C ６ -C ７ component, C ８ component and C ９ ＋ components; wherein the reactions occurring in the cracking and aromatic compound conversion unit include a non-aromatic compound cracking reaction and a transalkylation reaction; Step III) C from Step I) ８ Components and the above C from step II) ８ At least one of the components C ８ The components are purified, and the resulting product is separated, C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, (one or more types) C ８ Aromatic hydrocarbons, and C ９ ＋ The process of obtaining the components; Process IV) From Process I) C ４ － Components, from step II) C ４ － Components and the C from step III) ４ － At least one of the components is C ４ － A step of subjecting at least a portion of the components to a steam decomposition or dehydrogenation reaction; Process V) From Process I) C ５ Components, from step II) C ５ Components and the C from step III) ５ At least one of the components is C ５ A process of using at least a portion of the components for gasoline blending; and, Process VI) Process II) C ６ -C ７ Components and the C ９ ＋ Components and, optionally, C from step III) ６ -C ７ Components and the C ９ ＋ A step of recycling at least a portion of at least one of the components to the cracking and aromatic compound conversion unit of step II) for further reaction. Methods that include...

2. A method for processing gasoline fractions, Step 1) The gasoline fraction is reacted in the presence of an aromatization catalyst, and the resulting reaction product is separated and C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, C ８ Ingredients and C ９ ＋ A step to obtain the components, wherein the reaction includes an aromatization reaction; Step 2) C from Step 1) ６ -C ７ Components and the C ９ ＋ The components are reacted in the presence of an aromatic compound conversion catalyst, and the resulting reaction product is separated, C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, C ８ Ingredients and C ９ ＋ A step to obtain the components, wherein the reaction includes a non-aromatic compound cracking reaction and a transalkylation reaction; Step 3) C from Step 1) ８ Components and the C from step 2) ８ At least one of the components C ８ The components are purified, and the resulting product is separated, C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, (one or more types) C ８ Aromatic hydrocarbons, and C ９ ＋ The process of obtaining the components; Step 4) subjecting at least a part of the C component from Step 1), the C component from Step 2), and the C component from Step 3) to steam cracking or dehydrogenation reaction; ４ － Step 4) subjecting at least a part of the C component from Step 1), the C component from Step 2), and the C component from Step 3) to steam cracking or dehydrogenation reaction; ４ － Step 4) subjecting at least a part of the C component from Step 1), the C component from Step 2), and the C component from Step 3) to steam cracking or dehydrogenation reaction; ４ － Step 4) subjecting at least a part of the C component from Step 1), the C component from Step 2), and the C component from Step 3) to steam cracking or dehydrogenation reaction; ４ － Step 4) subjecting at least a part of the C component from Step 1), the C component from Step 2), and the C component from Step 3) to steam cracking or dehydrogenation reaction; Step 5) C from Step 1) ５ Components, from step 2) the above C ５ Components and the C from step 3) ５ At least one of the components is C ５ A process of using at least a portion of the components for gasoline blending; and, Step 6) The C from step 2) ６ -C ７ component and the C ９ ＋ component, and optionally, the C from step 3) ６ -C ７ component and the C ９ ＋ At least a part of at least one of the components is recycled to step 2) in the presence of the aromatic compound conversion catalyst for further reaction Methods that include...

3. The gasoline fraction used in step I) or step 1) has one or more of the following characteristics, according to the method of claim 1 or 2: The boiling point range is 40 to 250°C; The aromatic compound content is 10 to 100% by weight; and, The gasoline must be selected from the group consisting of catalytically cracked gasoline, hydrocracked gasoline, ethylene-cracked gasoline, catalytically reformed gasoline, straight-run gasoline, LPG, mixtures thereof, and partial fractions thereof.

4. The aromatizing catalyst used in the aromatizing unit of step I), or the aromatizing catalyst used in step 1), is measured based on the weight of the catalyst, A molecular sieve in an amount of 50-90% by weight, selected from aluminosilicates, aluminogallosilicates, aluminosilicophosphates, aluminoferrosilicates, and combinations thereof, having a 10-membered ring pore structure or a 12-membered ring pore structure, A modified metal in an amount of 0.5 to 10% by weight, selected from the group consisting of Group IB metals, Group IIB metals, Group VIB metals, Group VIIB metals, and Group VIII metals, Including; and / or, The reaction conditions for step I) or step 1) are a reaction temperature of 400 to 600°C, a reaction pressure of 0.2 to 3 MPa, and 0.5 to 5 hours. －１ The method according to claim 1 or 2, comprising supplying weight per hour in spacetime.

5. The aromatic compound conversion catalyst used in the cracking and aromatic compound conversion unit of step II), or the aromatic compound conversion catalyst used in step 2), comprises an acidic molecular sieve component, an oxide additive, a first metal component immobilized on the acidic molecular sieve component, and a second metal component. The first metal of the first metallic component is selected from the group consisting of VB metals, VIB metals, VIIB metals, and combinations thereof. The second metal of the second metal component is a different metal from the first metal. The catalyst has a moderate acid content of 0.05 to 2.0 mmol / g and a ratio of moderate acid content to a total acid content of 60 to 99%; and / or, The reaction conditions for step II) or step 2) are a reaction temperature of 250 to 500°C, a reaction pressure of 1.5 to 6.5 MPa, a molar ratio of hydrogen to hydrocarbons of 1 to 10, and 0.5 to 5 hours. －１ The method according to claim 1 or 2, comprising supplying weight per hour in spacetime.

6. The first metal component is immobilized on the acidic molecular sieve component by physical mixing and / or chemical bonding. The method according to claim 5, wherein the second metal component is immobilized on the oxide additive by physical mixing and / or chemical bonding.

7. The method according to claim 5, wherein the aromatic compound conversion catalyst has, based on the total weight of the catalyst, a content of 40 to 90% by weight of an acidic molecular sieve component, a content of 5 to 40% by weight of an oxide additive, a content of 0.01 to 20% by weight of a first metal component, and a content of 0.01 to 20% by weight of a second metal component.

8. The aromatic compound conversion catalyst according to claim 5 has one or more of the following features: The acidic molecular sieve component is selected from an acidic molecular sieve component having an 8-membered ring pore structure, an acidic molecular sieve component having a 10-membered ring pore structure, or an acidic molecular sieve component having a 12-membered ring pore structure, and is selected from ZSM-5 molecular sieve, MCM-22 molecular sieve, MOR molecular sieve, β molecular sieve, ZSM-12 molecular sieve, and combinations thereof; The first metal is selected from the group consisting of Mo, Re, and W, or the first metal is a combination of two of Mo, Re, and W calculated as metallic elements in a weight mixing ratio of 0.1 to 10:1, or the first metal is a combination of Mo, Re, and W calculated as metallic elements in a weight ratio of Mo:Re:W = 1:0.1 to 0.4:0.1 to 0.6; The second metal is selected from the group consisting of Group IA metals, Group IIA metals, Group IIIA metals, Group IVA metals, Group VA metals, lanthanide metals, and combinations thereof; and, The oxide additive is selected from the group consisting of alumina, magnesia, kaolin, and combinations thereof.

9. The purification step of step III) or step 3) is C ８ The process involves subjecting the components to the extraction and separation of aromatic compounds, the selective decomposition of non-aromatic compounds, or a combination thereof; The purification step is C ８ The process includes subjecting the components to extraction and separation by extraction distillation using a sulfolane solvent; or, The purification step is C ８ The method according to claim 1 or 2, comprising the step of subjecting a component to selective decomposition of a non-aromatic compound in the presence of a catalyst comprising a molecular sieve component selected from the group consisting of ZSM-5 molecular sieve, MCM-22 molecular sieve, MOR molecular sieve, β molecular sieve, and combinations thereof, and a metal component selected from group VIB metals, group VIIB metals, and group VIII metals.

10. If the purification step of step III) or step 3) includes subjecting the C8 component to selective decomposition of non-aromatic compounds, The method according to claim 9, wherein the operating conditions for the selective decomposition of the non-aromatic compound include a reaction temperature of 300 to 600°C, a reaction pressure of 0.5 to 3.0 MPa, a molar ratio of hydrogen to hydrocarbons of 1 to 10, and a space velocity of feed weight per hour of 1 to 15 h⁻¹.

11. The operating conditions for the steam decomposition in step IV) or step 4) include a decomposition temperature of 600 to 1000°C, a residence time of 0.01 to 0.8 seconds, and a reaction pressure of 0.1 to 0.3 MPa; or, The method according to claim 1 or 2, wherein the operating conditions for the dehydrogenation reaction in step IV) or step 4) include a reaction temperature of 400 to 700°C, a space velocity of 0.5 to 10 mass per hour, and a reaction pressure of 0.1 to 2 MPa.

12. A system for carrying out the gasoline fraction processing method described in any one of claims 1 to 11, The gasoline fraction is reacted internally, and the resulting reaction products are separated, C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, C ８ Ingredients and C ９ ＋ A fragrance unit for obtaining components, The C from the aromaticization unit ６ -C ７ Components and the C ９ ＋ The components are reacted, and the resulting reaction product is separated, C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, C ８ Ingredients and C ９ ＋ A cracking and aromatic compound conversion unit for obtaining components, The C from the aromaticization unit ８ Components, and the C from the cracking and aromatic compound conversion unit. ８ At least one of the components C ８ The components are purified, and the resulting product is separated, C ４ － Ingredients, C ５ Ingredients, C ６ -C ７ Ingredients, (one or more types) C ８ Aromatic hydrocarbons, and C ９ ＋ A unit for purifying aromatic compounds to obtain components, The C from the aromaticization unit ４ － Components, the cracking and aromatic compound conversion unit, and the C ４ － Components, and optionally, C from the aromatic compound purification unit. ４ － At least one of the components is C ４ － A light hydrocarbon conversion unit for carrying out steam decomposition or dehydrogenation reactions on at least a portion of the components, The C from the aromaticization unit ５ Components, the cracking and aromatic compound conversion unit, and the C ５ Components, and optionally, C from the aromatic compound purification unit. ５ At least one of the components is C ５ A light gasoline blending unit for gasoline blending using at least a portion of the components, It is equipped with, Here, the aromaticization unit includes a gasoline fraction inlet, C ４ － component outlet, C ５ component outlet, C ６ -C ７ component outlet, C ８ Component outlet and C ９ ＋ An ingredient outlet is provided. The cracking and aromatic compound conversion unit includes an inlet, C ４ － component outlet, C ５ component outlet, C ６ -C ７ component outlet, C ８ Component outlet and C ９ ＋ An ingredient outlet is provided. The aforementioned aromatic compound purification unit includes an inlet, C ４ － component outlet, C ５ component outlet, C ６ -C ７ component outlet, C ８ Aromatic hydrocarbon outlet and C ９ ＋ An ingredient outlet is provided. The light hydrocarbon conversion unit is provided with an inlet and a conversion product outlet. The light gasoline mixing unit is provided with an inlet and a mixed gasoline outlet. The C of the aromaticization unit ６ -C ７ Component outlet and the C ９ ＋ The component outlet is in communication with the inlet of the cracking and aromatic compound conversion unit. The C of the aromaticization unit ８ The component outlet and the cracking and aromatic compound conversion unit C ８ At least one of the component outlets C ８ The component outlet is in communication with the inlet of the aromatic compound purification unit, and the C of the aromaticization unit ４ － Component outlet, the cracking and aromatic compound conversion unit C ４ － The component outlet and the C of the aromatic compound purification unit ４ － At least one of the component outlets C ４ － The component outlet is in communication with the inlet of the light hydrocarbon conversion unit. The C of the aromaticization unit ５ Component outlet, the cracking and aromatic compound conversion unit C ５ The component outlet and the C of the aromatic compound purification unit ５ At least one of the component outlets C ５ The component outlet is in communication with the inlet of the light gasoline mixing unit. The C of the cracking and aromatic compound conversion unit ６ -C ７ Component outlet and the C ９ ＋ The component outlet and optionally the C of the aromatic compound purification unit. ６ -C ７ Component outlet and the C ９ ＋ A system wherein at least one of the component outlets is in communication with the inlet of the cracking and aromatic compound conversion unit.

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