C5-C 10 Systems and methods for the production of alkanes from benzene and aviation kerosene-based aromatic hydrocarbons

Abstract

The present application provides a kind of C5-C 10 Alkanes are converted into benzene and aviation kerosene-based aromatic hydrocarbons by a system and method, which includes an aromatization reaction device for high-temperature catalytic conversion of gaseous C5-C 10 alkane raw materials to obtain aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen; a gas-liquid separation device for cooling the gas output by the aromatization reaction device to cause gas-liquid phase separation, and separating benzene from the liquid phase; an alkylation reaction device for high-temperature treatment of the gas phase and liquid phase mixture output by the gas-liquid separation device to convert C2-C4 olefins and aromatic hydrocarbons into aviation kerosene-based aromatic hydrocarbons; and a gas separation device for separating the unreacted gas phase output by the alkylation reaction device to obtain dry gas, and inputting the remaining unreacted gas phase material into the aromatization reaction device for recycling. The system provided by the present application realizes the conversion of C5-C 10 alkanes to obtain a benzene yield of 60-70% and an aviation kerosene-based aromatic hydrocarbon yield of 20-25%, achieving simultaneous mass production of benzene and aviation kerosene-based aromatic hydrocarbons.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrocarbon conversion, in particular to a method for converting C5-C 10 System and method for preparing alkanes into benzene and aviation kerosene-based aromatics. Background Art

[0002] C5-C 10 Alkanes. Among them, except C8-C 10 In addition to being used for gasoline, most mixed C5-alkanes do not have a good utilization route. The accumulated amount of this part of resources in my country alone reaches tens of millions of tons per year. In an era when gasoline consumption is approaching saturation, there is an urgent need to develop new utilization channels.

[0003] With the development of the aviation industry, my country's annual consumption of jet fuel has exceeded 5,000 tons. Currently, European and American countries have established green jet fuel standards, but the relevant production technology is lacking. In addition to the conversion of CO2 to green hydrogen, biomass-based syngas and the Fischer-Tropsch route can also produce green jet fuel. However, the Fischer-Tropsch route often produces alkanes, making it impossible to produce jet fuel containing approximately 20% aromatics.

[0004] Benzene is a versatile aromatics feedstock, with annual consumption exceeding 10 million tons in China. Existing technology allows the production of green aromatics from green methanol (e.g., derived from CO2 and green hydrogen). However, this route tends to produce a small amount of benzene, with a higher concentration of xylenes or polymethylbenzenes (PMBs). Mixed xylenes are a gasoline blending component. Polymethylbenzenes have a high melting point and cannot be directly used in jet fuel.

[0005] At the same time, in principle, polymethylbenzenes or aviation kerosene-based aromatics (C9-C 14 Monocyclic aromatic hydrocarbons (with various asymmetric alkyl side chains) are obtained by alkylation of benzene, toluene, and olefins, or by direct hydrocarbon pool conversion. Therefore, the technology for mass production of benzene directly conflicts with the technology for mass production of aviation kerosene-based aromatics. Summary of the Invention

[0006] In view of the above problems existing in the prior art, the present invention provides a C5-C 10 System and method for preparing alkanes into benzene and aviation kerosene-based aromatics, through which gaseous C5-C 10 The alkane raw materials are sequentially subjected to aromatization conversion, separation, alkylation conversion and recycling, and aromatization to produce benzene and alkylation to produce aviation kerosene-based aromatics are respectively realized in two reactors.

[0007] The specific content of the invention is as follows:

[0008] In the first aspect, the present invention provides a C5-C10 The system for converting alkanes into benzene and aviation kerosene-based aromatics includes:

[0009] Aromatization reaction unit 1, used for gaseous C5-C 10 The alkane feedstock is subjected to high temperature catalytic conversion to obtain reaction products such as aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen;

[0010] The gas-liquid separation device 2 is used to cool the aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen output from the aromatization reaction device 1, so as to cause gas-liquid phase separation to obtain gas phase and liquid phase substances, and to separate the target product benzene from the liquid phase;

[0011] The alkylation reaction unit 3 is used to perform high-temperature treatment on the gas-liquid mixture output from the gas-liquid separation unit 2 to convert the C2-C4 olefins and aromatics therein into the target product, aviation kerosene-based aromatics;

[0012] The gas separation device 4 is used to separate the unreacted gas phase output from the alkylation reaction device 3 to obtain H2, methane and ethane, and input the remaining unreacted gas phase materials into the aromatization reaction device 1 for recycling.

[0013] Optionally, the aromatization reaction device includes a raw gas inlet 5;

[0014] A reaction product transmission channel 6 is provided between the aromatization reaction device 1 and the gas-liquid separation device 2;

[0015] The gas-liquid separation device 2 includes a benzene output outlet 8;

[0016] A gas-phase transmission channel 7 and a liquid-phase transmission channel 9 are provided between the gas-liquid separation device 2 and the alkylation reaction device 3. The gas-phase transmission channel 7 and the liquid-phase transmission channel 9 share an inlet on the side of the alkylation reaction device 3;

[0017] The alkylation reaction unit 3 includes an aviation kerosene-based aromatics output outlet 10;

[0018] An unreacted gas phase output channel 11 is provided between the alkylation reaction device 3 and the gas separation device 4;

[0019] The gas separation device 4 includes a dry gas output outlet 12;

[0020] A circulation pipeline 13 is provided between the gas separation device 4 and the aromatization reaction device 1 .

[0021] In the second aspect, the present invention provides a C5-C 10 A method for converting alkanes into benzene and aviation kerosene-based aromatics, the method being applicable to the system described in the first aspect above, the method comprising the following steps:

[0022] S1, the aromatization reaction device 1 is loaded with a metal-molecular sieve catalyst, and preheated to 520-600 ° C, and the metal-molecular sieve catalyst is loaded therein, and then the gaseous C5-C 10 Alkane raw materials, under the action of metal-molecular sieve catalyst, are converted into gaseous C5-C 10 The alkane feedstock is subjected to high temperature catalytic conversion to obtain reaction products such as aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen;

[0023] S2, using a gas-liquid separation device 2 to cool the reaction product output from the aromatization reaction device, so that it undergoes gas-liquid phase separation to obtain gas phase and liquid phase substances, and separating the target product benzene from the liquid phase substances;

[0024] S3, the alkylation reaction unit 3 is loaded with a molecular sieve catalyst, and the gas phase and liquid phase mixture output from the gas-liquid separation unit 2 is subjected to high temperature treatment by the alkylation reaction unit 3 to convert the C2-C4 olefins and aromatics therein into the target product, aviation kerosene-based aromatics;

[0025] S4. Using the gas separation device 4 to separate the unreacted gas phase output from the alkylation reaction device to obtain the target product dry gas, and the remaining unreacted gas phase is input into the aromatization reaction device.

[0026] Optionally, in step S1, the mass fraction of the metal in the metal-molecular sieve catalyst is 1%-10%;

[0027] Wherein, the metal is one or more of zinc, gallium, molybdenum, copper, manganese, and silver;

[0028] The molecular sieve is one or more of MFI, Y, and β.

[0029] Optionally, in step S1, the gaseous C5-C 10 The alkane raw material is C5-C 10 Alkanes are vaporized at 200-300°C; the gaseous C5-C 10 The contact reaction time of the alkane raw material and the metal-molecular sieve catalyst is 5-25s;

[0030] The aromatization reaction device 1 is a fixed bed or a fluidized bed.

[0031] Optionally, in step S2, the gaseous substances are C1-C4 hydrocarbons and hydrogen, and enter the alkylation reaction device 3 through the gas phase transmission channel 7;

[0032] The liquid phase substance is C5-C 12 Hydrocarbons, the target product benzene is separated from the liquid phase by distillation and extraction, and the remaining liquid phase material enters the alkylation reaction device 3 through the liquid phase transmission channel 9.

[0033] Optionally, in step S3, the molecular sieve catalyst is one or more of MFI, Y, and β molecular sieves;

[0034] The temperature of the high temperature treatment is 200-350°C.

[0035] Optionally, it is characterized in that, in step S3, the alkylation reaction device 3 is a fixed bed or a fluidized bed.

[0036] Optionally, it is characterized in that the gaseous C5-C 10 The alkane feedstock is derived from petroleum cracking or reforming; or

[0037] Coal-based, natural gas or biomass-based synthesis gas obtained through Fischer-Tropsch synthesis; or

[0038] Directly synthesized from CO2 and green hydrogen.

[0039] Optionally, it is characterized in that the yield of the target product is based on gaseous C5-C 10 The alkane feedstock is represented as follows:

[0040] Benzene: 60-70%;

[0041] Aviation kerosene-based aromatics: 20-25%;

[0042] Dry gas: 5-15%.

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

[0044] The present invention provides a C5-C 10 The system for converting alkanes into benzene and aviation kerosene-based aromatics includes: an aromatization reaction unit 1 for converting gaseous C5-C 10 The alkane raw material is subjected to high-temperature catalytic conversion to obtain reaction products such as aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen; the gas-liquid separation device 2 is used to cool the aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen output from the aromatization reaction device 1, so that they undergo gas-liquid phase separation to obtain gas phase and liquid phase substances, and separate the target product benzene from the liquid phase; the alkylation reaction device 3 is used to perform high-temperature treatment on the gas phase and liquid phase mixture output from the gas-liquid separation device 2, so that the C2-C4 olefins and aromatic hydrocarbons therein are converted into the target product aviation kerosene-based aromatic hydrocarbons; the gas separation device 4 is used to separate the unreacted gas phase output from the alkylation reaction device 3 to obtain H2, methane and ethane, and the remaining unreacted gas phase substances are input into the aromatization reaction device 1 for recycling. Through the system provided by the present invention, the production of C5-C 10 The yield of benzene finally converted from alkanes is 60-70%, and the yield of aviation kerosene-based aromatics is 20-25% (based on the total material balance of the entire process), realizing the simultaneous large-scale production of benzene and aviation kerosene-based aromatics.

[0045] In addition, the present invention provides C5-C 10 Compared with the current petrochemical route for preparing benzene (naphtha reforming), the method for converting alkanes into benzene and aviation kerosene-based aromatics is based on C5-C 10 The present invention can produce 2-3 times more benzene than the existing technology by using alkane raw materials; compared with the existing technology of producing multiple mixed aromatic hydrocarbons in one reactor, the ratio of benzene to aviation kerosene-based aromatic hydrocarbons in the present invention is significantly higher by 2-5 times; compared with the existing technology of separating olefins and alkanes from mixed light hydrocarbons, the present invention automatically converts olefins through the alkylation process, saving about 85-90% of separation energy consumption; compared with the current alkylation route of pure olefins and aromatics, the present invention uses mixed light hydrocarbons (C5-C 10 Alkanes), effectively reducing the raw material concentration and the total heat release of the reaction by about 20-50%, simplifying the reactor design and saving 40-60% of the investment cost in the alkylation unit. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0047] Figure 1 The embodiment of the present invention provides a method for converting C5-C 10 Schematic diagram of the system structure for preparing alkanes into benzene and aviation kerosene-based aromatics;

[0048] Figure 2 The embodiment of the present invention provides a method for converting C5-C 10 Flow chart of the process for preparing alkanes into benzene and aviation kerosene-based aromatics.

[0049] Among them, 1. aromatization reaction unit; 2. gas-liquid separation unit; 3. alkylation reaction unit; 4. gas separation unit; 5. raw gas inlet; 6. reaction product transmission channel; 7. gas phase transmission channel; 8. benzene output outlet; 9. liquid phase transmission channel; 10. aviation kerosene-based aromatics output outlet; 11. unreacted gas phase output channel; 12. dry gas output outlet; 13. circulation pipeline 13. DETAILED DESCRIPTION

[0050] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means a limitation on the present invention and its application or use. Based on the embodiments of the present invention, any product that is identical or similar to the present invention and is obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts falls within the scope of protection of the present invention. In addition, all other embodiments obtained by ordinary technicians in this field without carrying out creative work fall within the scope of protection of the present invention.

[0051] Where specific experimental steps or conditions are not specified in the examples, the conventional experimental steps or conditions described in the prior art in the art may be used. Reagents and other instruments used, for which the manufacturer is not specified, are commercially available conventional reagent products. Furthermore, the accompanying drawings are merely schematic illustrations of embodiments of the present invention and are not necessarily drawn to scale. Identical reference numerals in the figures denote identical or similar parts, and their repeated descriptions will be omitted. Some block diagrams shown in the accompanying drawings are functional entities and do not necessarily correspond to physically or logically independent entities.

[0052] Technologies, methods and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, such technologies, methods and equipment should be considered part of the authorization specification.

[0053] In the description of the present invention, it should be understood that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0054] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0055] The first object of the present invention is to provide a method for converting C5-C 10 System for converting alkanes into benzene and aviation kerosene-based aromatics, Figure 1 The embodiment of the present invention provides a method for converting C5-C 10 Schematic diagram of the system structure for preparing alkanes into benzene and aviation kerosene-based aromatics, such as Figure 1 As shown, the system comprises: an aromatization reaction unit 1, a gas-liquid separation unit 2, an alkylation reaction unit 3 and a gas separation unit 4 connected in sequence. The gas separation unit 4 is connected to the aromatization reaction unit 1 through a circulation pipeline.

[0056] Among them, the aromatization reaction device 1 is used to 10 The alkane feedstock is subjected to high-temperature catalytic conversion to obtain reaction products, aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen; the gas-liquid separation device 2 is used to cool the aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen output from the aromatization reaction device 1, so that they undergo gas-liquid phase separation to obtain gas phase and liquid phase substances, and separate the target product benzene from the liquid phase; the alkylation reaction device 3 is used to perform high-temperature treatment on the gas phase and liquid phase mixture output from the gas-liquid separation device 2, so that the C2-C4 olefins and aromatic hydrocarbons therein are converted into the target product, aviation kerosene-based aromatic hydrocarbons; the gas separation device 4 is used to separate the unreacted gas phase output from the alkylation reaction device 3 to obtain H2, methane and ethane, and the remaining unreacted gas phase substances are re-input into the aromatization reaction device 1 through a circulation pipeline for recycling.

[0057] Specifically, the raw gas inlet 5 is used to deliver gaseous C5-C 10 Alkane raw materials; gaseous C5-C 10 The alkane raw material contacts with the pre-filled and preheated metal-molecular sieve catalyst in the aromatization reaction unit 1. Under the action of the catalyst, C5-C 10 Alkanes undergo aromatization reaction to produce aromatics, C1-C4 hydrocarbons and hydrogen. The yield of aromatics is about 50-65%, the selectivity of benzene in aromatics is 40-60%, and the rest is C6-C 12 Hydrocarbons (aromatic hydrocarbons, olefins and alkanes, cycloalkanes mixtures without benzene).

[0058] Furthermore, a reaction product transmission channel 6 is provided between the aromatization reaction device 1 and the gas-liquid separation device 2. The aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen of the aromatization reaction are all transported to the gas-liquid separation device 2 through the reaction product transmission channel 6 for cooling, and the aromatization reaction products are separated into a gas phase (C1-C4 hydrocarbons and hydrogen) and a liquid phase (C5-C 12 hydrocarbons), and the gas phase (C1-C4 hydrocarbons and hydrogen) is transmitted to the alkylation reaction unit 3 through the gas phase transmission channel 7, and the separated liquid phase (C5-C 12 The remaining liquid phase other than benzene is output to the gas-liquid separation device 2 through the liquid phase transmission channel 9, and is combined with the gaseous product and then transmitted to the alkylation reaction device 3.

[0059] Furthermore, the alkylation reaction unit 3 is preheated to 200-350°C in advance, and the liquid phase entering therein is vaporized, and the C2-C4 olefins therein are alkylated with aromatic hydrocarbons (such as toluene, xylene, ethylbenzene or polymethylbenzenes) at 200-350°C to produce aviation kerosene-based aromatic hydrocarbons (C9-C 14) and exits the alkylation reaction unit 3 through outlet 10 as a product. Unreacted H2 and C1-C4 alkanes enter the gas separation unit 4 through the unreacted gas phase output channel 11 for further separation. The resulting H2, methane, and ethane exit the system through the dry gas output outlet 12 as products. The C3-C4 alkanes enter the aromatization reaction unit 1 through the circulation line 13 to continue the reaction. The above steps are repeated to achieve a continuous process.

[0060] Through the system provided by the present invention, C5-C 10 The yield of benzene obtained by aromatization of alkanes is 60-70%, and the yield of aviation kerosene-based aromatics obtained by alkylation conversion is 20-25%. In addition, the yield of dry gas (H2, methane and ethane) is also obtained in the range of 5-15%, thus achieving the simultaneous large-scale production of benzene and aviation kerosene-based aromatics.

[0061] The second object of the present invention is to provide a method for converting C5-C 10 A method for converting alkanes into benzene and aviation kerosene-based aromatics, which is applicable to the system of the first aspect above, Figure 2 The embodiment of the present invention provides a method for converting C5-C 10 Flow chart of the method for preparing alkanes into benzene and aviation kerosene-based aromatics, such as Figure 2 As shown, the method includes:

[0062] S1, the aromatization reaction device 1 is loaded with a metal-molecular sieve catalyst, and preheated to 520-600 ° C, and the metal-molecular sieve catalyst is loaded therein, and then the gaseous C5-C 10 Alkane raw materials, under the action of metal-molecular sieve catalyst, are converted into gaseous C5-C 10 The alkane feedstock is subjected to high temperature catalytic conversion to obtain reaction products such as aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen;

[0063] S2, using a gas-liquid separation device 2 to cool the reaction product output from the aromatization reaction device, so that it undergoes gas-liquid phase separation to obtain gas phase and liquid phase substances, and separating the target product benzene from the liquid phase substances;

[0064] S3, the alkylation reaction unit 3 is loaded with a molecular sieve catalyst, and the gas phase and liquid phase mixture output from the gas-liquid separation unit 2 is subjected to high temperature treatment by the alkylation reaction unit 3 to convert the C2-C4 olefins and aromatics therein into the target product, aviation kerosene-based aromatics;

[0065] S4. Use the gas separation device 4 to separate the unreacted gas phase output from the alkylation reaction device to obtain the target product dry gas (H2, methane and ethane), and input the remaining unreacted gas phase into the aromatization reaction device.

[0066] In some embodiments, in step S1, the mass fraction of the metal in the metal-molecular sieve catalyst is 1%-10%; wherein the metal is one or more of zinc, gallium, molybdenum, copper, manganese, and silver; and the molecular sieve is one or more of MFI, Y, and β.

[0067] In some embodiments, gaseous C5-C 10 The alkane raw material is C5-C 10 Alkanes are vaporized at 200-300℃; gaseous C5-C 10 The contact reaction time between the alkane raw material and the metal-molecular sieve catalyst is 5-25 seconds;

[0068] The aromatization reaction unit 1 is a fixed bed or a fluidized bed.

[0069] In some embodiments, in step S2, the gas phase material is C1-C4 hydrocarbon and hydrogen, and enters the alkylation reaction device 3 through the gas phase transmission channel 7; the liquid phase material is C5-C 12 Hydrocarbons are separated from the liquid phase by distillation and extraction to obtain the target product benzene, and the remaining liquid phase material enters the alkylation reaction device 3 through the liquid phase transmission channel 9.

[0070] In some embodiments, in step S3, the molecular sieve catalyst is one or more of MFI, Y, and β molecular sieves, and the temperature of the high temperature treatment is 200-350°C.

[0071] In some embodiments, in step S3, the alkylation reaction unit 3 is a fixed bed or a fluidized bed.

[0072] In some embodiments, gaseous C5-C 10 The alkane feedstock is derived from petroleum cracking or reforming; or

[0073] Coal-based, natural gas or biomass-based synthesis gas obtained through Fischer-Tropsch synthesis; or

[0074] Directly synthesized from CO2 and green hydrogen.

[0075] In some embodiments, the yield of the target product is based on the gaseous C5-C 10 The alkane feedstock is represented as follows: benzene: 60-70%; aviation kerosene-based aromatics: 20-25%; dry gas (H2, methane and ethane): 5-15%.

[0076] In order to make those skilled in the art understand the present invention more clearly, the following examples are provided to illustrate the method of converting C5-C 10 The system and method for preparing alkanes into benzene and aviation kerosene-based aromatics are described in detail.

[0077] Example 1

[0078] Connect units 1-4 as described in claim 1 to form a complete system. Load a metal-molecular sieve-based catalyst (zinc / MCM-41, with a zinc content of 10% by mass) into unit 1, and a molecular sieve catalyst (ZSM-5) into unit 3. Preheat unit 1 to 580°C; preheat unit 3 to 270°C.

[0079] C5-C 10 The alkane feedstock (derived from petroleum cracking or reforming) is vaporized at 280°C and fed into device 1 (using a fluidized bed reactor) through inlet 5. It reacts for 5 seconds under the action of a metal-molecular sieve-based catalyst to produce aromatics, C1-C4 hydrocarbons, and hydrogen. The aromatics yield is approximately 50%, with a selectivity of 60% for benzene in aromatics, and the remainder being C6-C 12 Hydrocarbons (aromatic hydrocarbons, olefins and alkanes, cycloalkanes mixtures without benzene).

[0080] The gas product of device 1 is passed into device 2 through transmission channel 6, and is first cooled to separate the gaseous product (C1-C4 hydrocarbons and hydrogen) and the liquid phase (C5-C 12 The gaseous product enters the device 3 through the gas phase transmission channel 7. Then the liquid phase (C5-C 12 The benzene is separated and extracted through distillation and extraction, and is discharged from outlet 8 as a product. Liquid hydrocarbons other than benzene exit device 2 through liquid phase transmission channel 9, merge with the gaseous products, and enter device 3 (using a fluidized bed reactor).

[0081] In device 3, C2-C4 olefins in the gaseous product react with aromatic hydrocarbons (such as toluene, xylene, ethylbenzene or polymethylbenzenes) at 350°C to produce aviation kerosene-based aromatic hydrocarbons (C9-C 14 ), exits the device 3 through the outlet 10 and is used as a product.

[0082] Unreacted H₂ and C₁-C₄ alkanes in unit 3 are passed through output channel 11 to unit 4 for further separation. Dry gas (H₂, methane, and ethane) exits through outlet 12 and is used as the product. C₃-C₄ alkanes exit through recycle line 13, circulate to inlet 5, and enter unit 1 for further reaction. These steps are repeated to achieve a continuous process.

[0083] Under steady-state operation, the benzene yield based on the feedstock is 70%, 25% is aviation kerosene-based aromatics, and 5% is dry gas (H2, methane and ethane).

[0084] Example 2

[0085] Connect units 1-4 as described in claim 1 to form a complete system. Load a metal-molecular sieve-based catalyst (molybdenum / manganese / 60% ZSM-5 / 39% Y molecular sieve, with molybdenum and manganese content of 0.5% by mass) into unit 1, and load a molecular sieve catalyst (β molecular sieve) into unit 3. Preheat unit 1 to 550°C; preheat unit 3 to 220°C.

[0086] C5-C 10 The alkane feedstock (derived from coal-based synthesis gas and prepared by the Fischer-Tropsch synthesis route) is vaporized at 300°C and introduced into device 1 (using a fluidized bed reactor) through inlet 5. It reacts for 25 seconds under the action of a metal-molecular sieve-based catalyst to produce aromatics, C1-C4 hydrocarbons and hydrogen. The aromatics yield is about 58%, the selectivity of benzene in aromatics is 40%, and the remainder is C6-C 12 Hydrocarbons (aromatic hydrocarbons, olefins and alkanes, cycloalkanes mixtures without benzene).

[0087] The gas product of device 1 is passed into device 2 through transmission channel 6, and is first cooled to separate the gaseous product (C1-C4 hydrocarbons and hydrogen) and the liquid phase (C5-C 12 The gaseous product enters the device 3 through the gas phase transmission channel 7. Then the liquid phase (C5-C 12 The benzene is separated and extracted through distillation and extraction, and is discharged from outlet 8 as a product. Liquid hydrocarbons other than benzene exit device 2 through liquid phase transmission channel 9, merge with the gaseous products, and enter device 3 (using a fluidized bed reactor).

[0088] In device 3, C2-C4 olefins in the gaseous product react with aromatic hydrocarbons (such as toluene, xylene, ethylbenzene or polymethylbenzenes) at 200°C to produce aviation kerosene-based aromatic hydrocarbons (C9-C 14 ), exits the device 3 through the outlet 10 and is used as a product.

[0089] Unreacted H₂ and C₁-C₄ alkanes in unit 3 are passed through output channel 11 to unit 4 for further separation. Dry gas (H₂, methane, and ethane) exits through outlet 12 and is used as the product. C₃-C₄ alkanes exit through recycle line 13, circulate to inlet 5, and enter unit 1 for further reaction. These steps are repeated to achieve a continuous process.

[0090] Under steady-state operation, the benzene yield based on the feedstock is 60%, 25% is aviation kerosene-based aromatics, and 15% is dry gas (H2, methane and ethane).

[0091] Example 3

[0092] Connect devices 1-4 as described in claim 1 to form a complete system. Load a metal-molecular sieve-based catalyst (zinc / gallium / MCM-22, with zinc and gallium content of 3% and 2% by mass, respectively) into device 1, and load a molecular sieve catalyst (β molecular sieve) into device 3. Preheat device 1 to 600°C; preheat device 3 to 350°C.

[0093] C5-C 10 The alkane feedstock (derived from natural gas-based synthesis gas, prepared via the Fischer-Tropsch synthesis route) is vaporized at 200°C and introduced into device 1 (using a fluidized bed reactor) via inlet 5. It reacts for 15 seconds under the action of a metal-molecular sieve-based catalyst to produce aromatics, C1-C4 hydrocarbons, and hydrogen. The aromatics yield is approximately 65%, with a selectivity of 50% for benzene in the aromatics, and the remainder being C6-C 12 Hydrocarbons (aromatic hydrocarbons, olefins and alkanes, cycloalkanes mixtures without benzene).

[0094] The gas product of device 1 is passed into device 2 through transmission channel 6, and is first cooled to separate the gaseous product (C1-C4 hydrocarbons and hydrogen) and the liquid phase (C5-C 12 The gaseous product enters the device 3 through the gas phase transmission channel 7. Then the liquid phase (C5-C 12 The benzene is separated and extracted through distillation and extraction, and is discharged from outlet 8 as a product. Liquid hydrocarbons other than benzene exit device 2 through liquid phase transmission channel 9, merge with the gaseous products, and enter device 3 (using a fluidized bed reactor).

[0095] In device 3, C2-C4 olefins in the gaseous product react with aromatic hydrocarbons (such as toluene, xylene, ethylbenzene or polymethylbenzenes) at 280°C to produce aviation kerosene-based aromatic hydrocarbons (C9-C 14 ), exits the device 3 through the outlet 10 and is used as a product.

[0096] Unreacted H₂ and C₁-C₄ alkanes in unit 3 are passed through output channel 11 to unit 4 for further separation. Dry gas (H₂, methane, and ethane) exits through outlet 12 and is used as the product. C₃-C₄ alkanes exit through recycle line 13, circulate to inlet 5, and enter unit 1 for further reaction. These steps are repeated to achieve a continuous process.

[0097] Example 4

[0098] Connect devices 1-4 as described in claim 1 to form a complete system. Load a metal-molecular sieve-based catalyst (zinc / copper / 20% β molecular sieve / 75% ZSM-5, with zinc and copper content of 4% and 1% by mass, respectively) into device 1, and load a molecular sieve catalyst (β molecular sieve) into device 3. Preheat device 1 to 520°C; preheat device 3 to 250°C.

[0099] C5-C 10 The alkane feedstock (derived from biomass-based synthesis gas, prepared via the Fischer-Tropsch synthesis route) is vaporized at 300°C and introduced into device 1 (using a fixed bed reactor) via inlet 5. A contact reaction occurs for 22 seconds over a metal-molecular sieve-based catalyst to produce aromatics, C1-C4 hydrocarbons, and hydrogen. The aromatics yield is approximately 61%, with a selectivity of 53% for benzene in the aromatics group, and the remainder being C6-C 12 Hydrocarbons (aromatic hydrocarbons, olefins and alkanes, cycloalkanes mixtures without benzene).

[0100] The gas product of device 1 is passed into device 2 through transmission channel 6, and is first cooled to separate the gaseous product (C1-C4 hydrocarbons and hydrogen) and the liquid phase (C5-C 12 The gaseous product enters the device 3 through the gas phase transmission channel 7. Then the liquid phase (C5-C 12 The benzene is separated and extracted through distillation and extraction, and is discharged from outlet 8 as a product. Liquid hydrocarbons other than benzene exit device 2 through liquid phase transmission channel 9, merge with the gaseous products, and enter device 3 (using a fluidized bed reactor).

[0101] In device 3, C2-C4 olefins in the gaseous product react with aromatic hydrocarbons (such as toluene, xylene, ethylbenzene or polymethylbenzenes) at 290°C to produce aviation kerosene-based aromatic hydrocarbons (C9-C 14 ), exits the device 3 through the outlet 10 and is used as a product.

[0102] Unreacted H₂ and C₁-C₄ alkanes in unit 3 are passed through output channel 11 to unit 4 for further separation. Dry gas (H₂, methane, and ethane) exits through outlet 12 and is used as the product. C₃-C₄ alkanes exit through recycle line 13, circulate to inlet 5, and enter unit 1 for further reaction. These steps are repeated to achieve a continuous process.

[0103] Under steady-state operation, the benzene yield based on the feedstock is 67%, 26% is aviation kerosene-based aromatics, and 7% is dry gas (H2, methane and ethane).

[0104] Example 5

[0105] Connect devices 1-4 as described in claim 1 to form a complete system. Load a metal-molecular sieve-based catalyst (zinc / silver / 56% Y molecular sieve / 40.5% MCM-22, with zinc and silver content of 3% and 0.5% by mass, respectively) into device 1, and load a molecular sieve catalyst (50% ZSM-5 molecular sieve, 50% β molecular sieve) into device 3. Preheat device 1 to 570°C; preheat device 3 to 270°C.

[0106] C5-C 10The alkane feedstock (derived from biomass-based synthesis gas, alkanes obtained by Fischer-Tropsch synthesis) is vaporized at 290°C and introduced into device 1 (using a fluidized bed reactor) through inlet 5. It reacts for 18 seconds under the action of a metal-molecular sieve-based catalyst to produce aromatics, C1-C4 hydrocarbons and hydrogen. The aromatics yield is about 59%, the selectivity of benzene in aromatics is 59%, and the remainder is C6-C 12 Hydrocarbons (aromatic hydrocarbons, olefins and alkanes, cycloalkanes mixtures without benzene).

[0107] The gas product of device 1 is passed into device 2 through transmission channel 6, and is first cooled to separate the gaseous product (C1-C4 hydrocarbons and hydrogen) and the liquid phase (C5-C 12 The gaseous product enters the device 3 through the gas phase transmission channel 7. Then the liquid phase (C5-C 12 The benzene is separated and extracted through distillation and extraction, and is discharged from outlet 8 as a product. Liquid hydrocarbons other than benzene exit device 2 through liquid phase transmission channel 9, merge with the gaseous products, and enter device 3 (using a fluidized bed reactor).

[0108] In device 3, C2-C4 olefins in the gaseous product react with aromatic hydrocarbons (such as toluene, xylene, ethylbenzene or polymethylbenzenes) at 305°C to produce aviation kerosene-based aromatic hydrocarbons (C9-C 14 ), exits the device 3 through the outlet 10 and is used as a product.

[0109] Unreacted H₂ and C₁-C₄ alkanes in unit 3 are passed through output channel 11 to unit 4 for further separation. Dry gas (H₂, methane, and ethane) exits through outlet 12 and is used as the product. C₃-C₄ alkanes exit through recycle line 13, circulate to inlet 5, and enter unit 1 for further reaction. These steps are repeated to achieve a continuous process.

[0110] Under steady-state operation, the benzene yield based on the feedstock is 62%, 25% is aviation kerosene-based aromatics, and 13% is dry gas (H2, methane and ethane).

[0111] Example 6

[0112] Connect devices 1-4 as described in claim 1 to form a complete system. Load a metal-molecular sieve-based catalyst (molybdenum / zinc / ZSM-11, with 5% molybdenum and zinc by mass in the catalyst) into device 1, and load a molecular sieve catalyst (20% ZSM-5, 50% Y molecular sieve, 30% β molecular sieve) into device 3. Preheat device 1 to 540°C; preheat device 3 to 290°C.

[0113] C5-C 10The alkane feedstock (derived from the direct synthesis of CO2 and green hydrogen) is vaporized at 300°C and introduced into device 1 (using a fluidized bed reactor) through inlet 5. It reacts for 16 seconds under the action of a metal-molecular sieve-based catalyst to produce aromatics, C1-C4 hydrocarbons, and hydrogen. The aromatics yield is approximately 62.5%, with a selectivity of 45% for benzene in the aromatics, and the remainder being C6-C 12 Hydrocarbons (aromatic hydrocarbons, olefins and alkanes, cycloalkanes mixtures without benzene).

[0114] The gas product of device 1 is passed into device 2 through transmission channel 6, and is first cooled to separate the gaseous product (C1-C4 hydrocarbons and hydrogen) and the liquid phase (C5-C 12 The gaseous product enters the device 3 through the gas phase transmission channel 7. Then the liquid phase (C5-C 12 The benzene is separated and extracted through distillation and extraction, and is discharged from outlet 8 as a product. Liquid hydrocarbons other than benzene exit device 2 through liquid phase transmission channel 9, merge with the gaseous products, and enter device 3 (using a fluidized bed reactor).

[0115] In device 3, C2-C4 olefins in the gaseous product react with aromatic hydrocarbons (such as toluene, xylene, ethylbenzene or polymethylbenzenes) at 276°C to produce aviation kerosene-based aromatic hydrocarbons (C9-C 14 ), exits the device 3 through the outlet 10 and is used as a product.

[0116] Unreacted H₂ and C₁-C₄ alkanes in unit 3 are passed through output channel 11 to unit 4 for further separation. Dry gas (H₂, methane, and ethane) exits through outlet 12 and is used as the product. C₃-C₄ alkanes exit through recycle line 13, circulate to inlet 5, and enter unit 1 for further reaction. These steps are repeated to achieve a continuous process.

[0117] Under steady-state operation, the benzene yield based on the feedstock is 68%, 20% is aviation kerosene-based aromatics, and 12% is dry gas (H2, methane and ethane).

[0118] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification.

[0119] For simplicity of description, the method embodiments are described as a series of actions. However, those skilled in the art should be aware that the present invention is not limited by the order of the actions described, as certain steps can be performed in other orders or simultaneously according to the present invention. Furthermore, those skilled in the art should also be aware that the embodiments described in this specification are preferred embodiments, and the actions and components involved are not necessarily required for the present invention.

[0120] The above is a method of converting C5-C 10 A system and method for preparing benzene and aviation kerosene-based aromatics from alkanes are described in detail. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only intended to help understand the method and core concept of the present invention. At the same time, for those skilled in the art, based on the concept of the present invention, there may be changes in the specific implementation methods and application scope. In summary, the contents of this specification should not be understood as limiting the present invention.

Claims

1. A method of converting C5-C 10 A method for converting alkanes into benzene and aviation kerosene-based aromatics, characterized in that: The method uses C5-C 10 The conversion of alkanes into benzene and aviation kerosene-based aromatics is achieved by a system comprising: Aromatization reaction unit, gas-liquid separation unit, alkylation reaction unit, gas separation unit; The aromatization reaction device includes a raw gas inlet; a reaction product transmission channel is provided between the aromatization reaction device and the gas-liquid separation device; the gas-liquid separation device includes a benzene output outlet; a gas-phase transmission channel and a liquid-phase transmission channel are provided between the gas-liquid separation device and the alkylation reaction device, and the gas-phase transmission channel and the liquid-phase transmission channel share an inlet on the alkylation reaction device side; The alkylation reaction unit includes an outlet for outputting aviation kerosene-based aromatics; an unreacted gas phase output channel is provided between the alkylation reaction unit and the gas separation unit; the gas separation unit includes a dry gas output outlet; and a circulation pipeline is provided between the gas separation unit and the aromatization reaction unit; The method comprises the following steps: S1. The aromatization reaction device is loaded with metal-molecular sieve catalyst and preheated to 520-600℃, and then the gaseous C5-C 10 Alkane raw materials, under the action of metal-molecular sieve catalyst, are converted into gaseous C5-C 10 The alkane raw material is subjected to high temperature catalytic conversion to obtain the reaction products of aromatic hydrocarbons, C1-C4 hydrocarbons and hydrogen; the gaseous C5-C 10 The contact reaction time between the alkane feedstock and the metal-molecular sieve catalyst is 5-25 s; the mass fraction of the metal in the metal-molecular sieve catalyst is 1%-10%; wherein the metal is one or more of zinc, gallium, molybdenum, copper, manganese, and silver; and the molecular sieve is one or more of MFI, Y, and β; S2, using a gas-liquid separation device to cool the reaction product output from the aromatization reaction device, so that it undergoes gas-liquid phase separation to obtain gas phase material and liquid phase material, and separating the target product benzene from the liquid phase material; the gas phase material is C1-C4 hydrocarbons and hydrogen, and enters the alkylation reaction device through the gas phase transmission channel; the liquid phase material is C5-C 12 Hydrocarbons, the target product benzene is separated from the liquid phase material by distillation and extraction, and the remaining liquid phase material enters the alkylation reaction device through the liquid phase transmission channel; S3. The alkylation reaction unit is loaded with a molecular sieve catalyst, and the gas and liquid mixture output from the gas-liquid separation unit is subjected to high-temperature treatment by the alkylation reaction unit to convert the C2-C4 olefins and aromatics therein into the target product, aviation kerosene-based aromatics; the high-temperature treatment temperature is 200-350° C.; the molecular sieve catalyst is one or more of MFI, Y, and β molecular sieves; S4, using a gas separation device to separate the unreacted gas phase output from the alkylation reaction unit to obtain the target product dry gas, and input the remaining unreacted gas phase into the aromatization reaction unit; The yield of the target product based on the gaseous C5-C10 alkane feedstock is expressed as follows: Benzene: 60-70%; Aviation kerosene-based aromatics: 20-25%; Dry gas: 5-15%.

2. The method of claim 1 wherein C5-C 10 A method for converting alkanes into benzene and aviation kerosene-based aromatics, characterized in that: In step S1, the gaseous C5-C 10 The alkane raw material is C5-C 10 The alkane is obtained by vaporizing at 200-300°C; the aromatization reaction device is a fixed bed or a fluidized bed.

3. The method of claim 1 wherein C5-C 10 A method for converting alkanes into benzene and aviation kerosene-based aromatics, characterized in that: In step S3, the alkylation reaction device is a fixed bed or a fluidized bed.

4. The method of claim 1 wherein C5-C 10 A method for converting alkanes into benzene and aviation kerosene-based aromatics, characterized in that: The gaseous C5-C 10 The alkane feedstock is derived from petroleum cracking or reforming; or Coal-based, natural gas or biomass-based synthesis gas obtained through Fischer-Tropsch synthesis; or Directly synthesized from CO2 and green hydrogen.

Images