Automotive diesel, method of making and system for making

Abstract

The application provides a vehicle diesel oil, a preparation method and a preparation system thereof. The preparation method comprises the following steps: sequentially performing a first hydrorefining reaction, a first atmospheric distillation and a first vacuum distillation on a Fischer-Tropsch synthesis oil to obtain a first bottom product and a first top product; sequentially performing a hydrocracking reaction, a second atmospheric distillation and a second vacuum distillation on the first bottom product to obtain a side product and a second top product; mixing the first top product and the second top product to perform a steam cracking reaction to obtain a gasoline fraction; performing multiple hydrorefining and distillation on the gasoline fraction to obtain C 9+ oil products; performing blending on the C 9+ oil products and the side product to obtain the vehicle diesel oil, which can obtain the vehicle diesel oil with high density and lubricity of a distillation fraction, and meets the national standard, and has certain production and application value.

Description

Technical Field

[0001] This invention relates to the field of diesel fuel production technology, and more specifically, to a type of automotive diesel fuel, its preparation method, and its preparation system. Background Technology

[0002] Current technologies using Fischer-Tropsch synthetic oils can only produce diesel component oils. Because the intermediate products—indirectly liquefied oils (products of hydrorefining and hydrocracking of Fischer-Tropsch synthetic oils (waxes))—are mainly composed of n-alkanes and isoalkanes, with very few aromatics and cycloalkanes, the resulting diesel component oils have low distillate density and poor lubricity, making them unsuitable for use as automotive diesel fuel meeting national standards. Therefore, finding a way to prepare automotive diesel fuel meeting national standards using Fischer-Tropsch synthetic oils is crucial for both the application areas of Fischer-Tropsch synthetic oils and the production and application of automotive diesel fuels. Summary of the Invention

[0003] The main objective of this invention is to provide a type of automotive diesel fuel, its preparation method, and preparation system, in order to solve the problem that existing technologies cannot produce automotive diesel fuel that meets national standards using Fischer-Tropsch synthetic oil.

[0004] To achieve the above objectives, according to a first aspect of the present invention, a method for preparing automotive diesel fuel is provided, the method comprising: S1, subjecting Fischer-Tropsch synthetic oil to a first hydrorefining reaction, a first atmospheric distillation, and a first vacuum distillation sequentially to obtain a first bottom product and a first top product; S2, subjecting the first bottom product to a hydrocracking reaction, a second atmospheric distillation, and a second vacuum distillation sequentially to obtain a side-stream product and a second top product; S3, mixing the first top product and the second top product and subjecting them to a steam cracking reaction to obtain a gasoline fraction; S4, subjecting the gasoline fraction to multiple hydrorefining and distillations to obtain C 9+ Oil; S5, will C 9+ The oil and side-stream products are blended to obtain automotive diesel fuel; the bottom product of the first tower includes C. 20+ The refined wax has a first-top product consisting of refined LPG and refined naphtha, and a second-top product consisting of cracked LPG and cracked naphtha; side products include C 10 -C 21 The isomeric alkanes have a distillation range of 160-365℃ for the side-stream products.

[0005] Further, the temperature of the first hydrorefining reaction is 300-400℃; preferably, the pressure of the first hydrorefining reaction is 4.5-9.5 MPa; preferably, the volume hourly space velocity of the first hydrorefining reaction is 1-4 h⁻¹; preferably, the hydrogen-to-oil volume ratio of the first hydrorefining reaction is 300-700:1; preferably, the temperature of the first atmospheric distillation is 250-400℃; preferably, the pressure of the first atmospheric distillation is 0.1-1 MPa; preferably, the temperature of the first vacuum distillation is 200-350℃; preferably, the pressure of the first vacuum distillation is 0.01-0.02 MPa; preferably, the refined LPG is C1-C4 n-alkanes; preferably, the refined naphtha is C5-C6. 10 n-alkanes.

[0006] Further, the hydrocracking reaction temperature is 280~450℃; preferably, the hydrocracking reaction pressure is 6~13MPa; preferably, the volume hourly space velocity (VHSV) of the hydrocracking reaction is 1~3.5hl; preferably, the hydrogen-to-oil volume ratio of the hydrocracking reaction is 400~800:1; preferably, the second atmospheric distillation temperature is 250~400℃; preferably, the second atmospheric distillation pressure is 0.1~1.0MPa; preferably, the second vacuum distillation temperature is 200~350℃; preferably, the second vacuum distillation pressure is 0.01~0.02MPa; preferably, the cracked LPG is C1-C4 isoalkanes; preferably, the cracked naphtha is C5-C4... 10 Isomerized alkanes.

[0007] Furthermore, the temperature of the steam cracking reaction is 820~890℃; preferably, the pressure of the steam cracking reaction is 0.1~0.5MPa; preferably, the dilution steam ratio of the steam cracking reaction is 0.2~0.8.

[0008] Further, S4 includes: subjecting the gasoline fraction to a second hydrorefining reaction and a third atmospheric distillation to obtain C. 9+ Fraction; C 9+ The fraction underwent a third hydrogenation purification reaction and a fourth atmospheric distillation to obtain C. 9+ The oil product; preferably, the temperature of the second hydrorefining reaction is 80~250℃; preferably, the pressure of the second hydrorefining reaction is 2.0~4.0MPa; preferably, the volume hourly space velocity of the second hydrorefining reaction is 1.0~3.0hl; preferably, the hydrogen-to-oil volume ratio of the second hydrorefining reaction is 300~800:1; preferably, the temperature of the third atmospheric distillation is 140~200℃; preferably, the pressure of the third atmospheric distillation is 0.01~1.0MPa.

[0009] Furthermore, the temperature of the third hydrorefining reaction is 200~350℃; preferably, the pressure of the third hydrorefining reaction is 2.0~6.0MPa; preferably, the volume hourly space velocity of the third hydrorefining reaction is 0.5~3h-l; preferably, the hydrogen-to-oil volume ratio of the third hydrorefining reaction is 400~800:1; preferably, the temperature of the fourth atmospheric distillation is 180~280℃; preferably, the pressure of the fourth atmospheric distillation is 0.01~1.0MPa.

[0010] Furthermore, S5 includes: C 9+ After mixing the oil and side-stream products, an anti-wear agent is added and blended to obtain automotive diesel fuel; preferably, C 9+ The mass ratio of oil to side-stream products is 50-66:50-34; preferably, the anti-wear agent is selected from fatty acid type anti-wear agents or fatty acid ester type anti-wear agents; preferably, the amount of anti-wear agent is ≤180ppm; preferably, the mixing temperature is 55-65℃.

[0011] To achieve the above objectives, according to a second aspect of the present invention, a preparation system for carrying out the above-described method for preparing automotive diesel fuel is provided. The preparation system includes: a first hydrorefining unit, a hydrocracking unit, a steam cracking unit, a gasoline fraction hydrorefining unit, and a diesel blending unit; wherein the first hydrorefining unit includes a feed inlet, a bottom outlet, and a top outlet; the hydrocracking unit includes a feed inlet, a top outlet, and a side-stream product outlet; the steam cracking unit includes a feed inlet and a gasoline fraction outlet; and the gasoline fraction hydrorefining unit includes a feed inlet and a C... 9+ The oil product outlet; the diesel blending unit includes an inlet; the bottom outlet of the first hydrorefining unit is connected to the inlet of the hydrocracking unit; the top outlets of the first hydrorefining unit and the hydrocracking unit are respectively connected to the inlet of the steam cracking unit; the gasoline fraction outlet of the steam cracking unit is connected to the inlet of the gasoline fraction hydrorefining unit; the C... 9+ The oil product outlet and the side-stream product outlet of the hydrocracking unit are connected to the feed inlet of the diesel blending unit, respectively.

[0012] Furthermore, the gasoline fraction hydrorefining unit also includes a second hydrorefining unit and a third hydrorefining unit; wherein, the second hydrorefining unit includes an inlet and a C... 9+ The fraction outlet, the third hydrorefining unit includes the feed inlet and C 9+ Oil product outlet; the gasoline fraction outlet of the steam cracking unit is connected to the inlet of the second hydrorefining unit; the C of the second hydrorefining unit... 9+ The fraction outlet is connected to the inlet of the third hydrorefining unit; the C of the third hydrorefining unit... 9+The oil product outlet and the side-stream product outlet of the hydrocracking unit are respectively connected to the feed inlet of the diesel blending unit; preferably, the preparation system further includes: a Fischer-Tropsch synthesis unit; the Fischer-Tropsch synthesis oil outlet of the Fischer-Tropsch synthesis unit is connected to the feed inlet of the first hydrorefining unit.

[0013] To achieve the above objectives, according to a second aspect of the present invention, a diesel fuel for vehicles prepared using the above-described preparation method or preparation system is provided, wherein the wear track diameter of the diesel fuel is ≤460 μm; preferably, the density of the diesel fuel for vehicles is 810-845 kg / m³. 3 .

[0014] By applying the technical solution of this invention and utilizing the preparation method of this application, C is obtained through steam cracking. 9+ The fraction is then hydrogenated and purified, due to C 9+ The fraction is rich in aromatics and has a high density. Hydrorefining removes sulfur impurities from the product, and blending it with side-stream products yields automotive diesel fuel with high density and lubricity, which meets national standards and has certain production and application value. Attached Figure Description

[0015] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 A schematic diagram of a system for diesel fuel preparation according to Embodiments 1-3 of the present invention is shown; The above figures include the following reference numerals: 01. First hydrorefining unit; 02. Hydrocracking unit; 03. Steam cracking unit; 04. Diesel blending unit; 05. Second hydrorefining unit; 06. Third hydrorefining unit; 07. Fischer-Tropsch synthesis unit. Detailed Implementation

[0016] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0017] Definitions: Diesel component oil: Diesel component oil produced by coal indirect liquefaction-Fischer-Tropsch synthesis process; its national standard is GB / T29720-2013 "Coal-based Fischer-Tropsch Synthetic Diesel Component Oil".

[0018] Diesel fuel for vehicles: diesel fuel for vehicles with compression ignition engines that is derived from petroleum or contains additives to improve performance. Diesel fuel for vehicles that is blended with biodiesel is not applicable. The national standard for diesel fuel for vehicles is GB 19147-2016 "Diesel Fuel for Vehicles".

[0019] As mentioned in the background art, existing diesel fuels prepared by hydrogenation and distillation of Fischer-Tropsch synthetic oils have low fraction density and poor lubricity, and can only be used as diesel component oils, not as automotive diesel fuels conforming to GB 19147-2016. Therefore, to provide an automotive diesel fuel with higher fraction density and lubricity, in the first typical embodiment of this application, a method for preparing automotive diesel fuel is provided. The method includes: S1, subjecting Fischer-Tropsch synthetic oils to a first hydrorefining reaction, a first atmospheric distillation, and a first vacuum distillation sequentially to obtain a first bottom product and a first top product; S2, subjecting the first bottom product to a hydrocracking reaction, a second atmospheric distillation, and a second vacuum distillation sequentially to obtain a side-stream product and a second top product; S3, mixing the first top product and the second top product for a steam cracking reaction to obtain a gasoline fraction; S4, subjecting the gasoline fraction to multiple hydrorefining and distillation processes to obtain C... 9+ Oil; S5, will C 9+ Oil products and side-stream products are blended to obtain diesel fuel; the first bottom product includes C. 20+ The refined wax has a first-top product consisting of refined LPG and refined naphtha, and a second-top product consisting of cracked LPG and cracked naphtha; side products include C 10 -C 21 The isomeric alkanes have a distillation range of 160-365℃ for the side-stream products.

[0020] Using the method for preparing automotive diesel fuel according to this application, the bottom product obtained by hydrorefining the Fischer-Tropsch synthesis product is subjected to hydrocracking. The top product of the hydrocracking tower and the top product of the hydrorefining tower are then subjected to steam cracking to obtain a gasoline fraction (rich in aromatics and high density). This gasoline fraction is then subjected to multiple hydrorefining and atmospheric distillation processes to desulfurize and saturate some olefins and aromatics, yielding C425. 9+ Oil, then C 9+ Qualified automotive diesel products can be obtained by blending oil with side-stream products from hydrocracking.

[0021] Excessive diene content leads to decreased oxidation stability in automotive diesel fuel, making it prone to polymerization and precipitation, thus affecting combustion performance and mechanical wear. Therefore, it is necessary to reduce the diene content in automotive diesel fuel by hydrogenating the unsaturated hydrocarbons in the Fischer-Tropsch synthesis oil to control the unsaturated hydrocarbon content at a low level, followed by distillation to further separate the products. Atmospheric distillation separates components with lower boiling points, while vacuum distillation can separate components with higher boiling points under low pressure. To further efficiently obtain the distilled product after hydrorefining, in a preferred embodiment, the temperature of the first hydrorefining reaction is 300-400°C; preferably, the pressure of the first hydrorefining reaction is 4.5-9.5 MPa; preferably, the volume hourly space velocity (VHSV) of the first hydrorefining reaction is 1-4 h⁻¹. -1 Preferably, the hydrogen-to-oil volume ratio in the first hydrorefining reaction is 300-700:1; preferably, the temperature of the first atmospheric distillation is 250-400℃; preferably, the pressure of the first atmospheric distillation is 0.1-1 MPa; preferably, the temperature of the first vacuum distillation is 200-350℃; preferably, the pressure of the first vacuum distillation is 0.01-0.02 MPa; preferably, the refined LPG is C1-C4 n-alkanes; preferably, the refined naphtha is C5-C... 10 n-alkanes.

[0022] The top, side stream, and bottom products obtained after the first hydrogenation purification, first atmospheric distillation, and first vacuum distillation mainly consist of n-alkanes. The first bottom product includes C... 20+ The refined wax; the top products of the first column include refined LPG and refined naphtha. Refined LPG consists of <C5 hydrocarbons, primarily n-alkanes; refined naphtha is mainly C5-C6 hydrocarbons. 10 The hydrocarbons are mainly n-alkanes. The large hydrocarbon molecules in the bottom product of the first column need to be hydrocracking to obtain alkanes with shorter carbon chains.

[0023] To obtain alkanes with shorter carbon chains, the bottom product of the first column, which contains a large amount of long-chain hydrocarbons, needs to be hydrocracking, and the preliminarily separated components are obtained by distillation. To further efficiently obtain the distilled product after hydrocracking, in a preferred embodiment, the hydrocracking reaction temperature is 280–450°C; preferably, the hydrocracking reaction pressure is 6–13 MPa; preferably, the volume hourly space velocity (VHSV) of the hydrocracking reaction is 1–3.5 h⁻¹. -lPreferably, the hydrogen-to-oil volume ratio in the hydrocracking reaction is 400-800:1; preferably, the temperature of the second atmospheric distillation is 250-400°C; preferably, the pressure of the second atmospheric distillation is 0.1-1.0 MPa; preferably, the temperature of the second vacuum distillation is 200-350°C; preferably, the pressure of the second vacuum distillation is 0.01-0.02 MPa; preferably, the cracked LPG is C1-C4 isoalkanes; preferably, the cracked naphtha is C5-C... 10 Isomerized alkanes.

[0024] The top, side stream, and bottom products obtained after hydrocracking, second atmospheric distillation, and second vacuum distillation mainly consist of isoparaffins. Specifically, the second top product includes cracked LPG and cracked naphtha; the cracked LPG is composed of <C5 hydrocarbons, while the cracked naphtha is primarily composed of C5-C6 hydrocarbons. 10 Hydrocarbons. Side-stream products are mainly diesel fuel components, including first-stage cracking atmospheric distillation products, second-stage cracking atmospheric distillation products, and first-stage cracking sub-zero distillation products, primarily isomeric alkanes, with a distillation range of 160-365℃. Among them, the first-stage cracking atmospheric distillation products are mainly C 10 -C 14 Alkanes; the main cracking products are C2O4. 14 -C 18 Alkanes; cracking products are mainly C 18 -C 21 Alkanes.

[0025] Steam cracking is a process in which petroleum hydrocarbons such as ethane or petroleum fractions (naphtha (gasoline), diesel oil, etc.) undergo molecular breakage and dehydrogenation reactions under high temperature and in the presence of steam, accompanied by small amounts of polymerization and condensation reactions. The main purpose of steam cracking is to produce ethylene, byproducts such as propylene and butadiene, and light aromatics such as benzene, toluene, and xylene, as well as a small amount of heavy aromatics.

[0026] To obtain a gasoline fraction with a high aromatic content, LPG and naphtha are subjected to steam cracking. To further efficiently obtain the steam cracking products, in a preferred embodiment, the steam cracking reaction temperature is 820–890°C; preferably, the steam cracking reaction pressure is 0.1–0.5 MPa; preferably, the dilution steam ratio for the steam cracking reaction is 0.2–0.8. The steam cracking products include ethylene, propylene, and a gasoline fraction, with the gasoline fraction mainly consisting of C5-C... 12 Hydrocarbons include alkenes, alkanes, cycloalkanes, and aromatics. Some alkenes contain unstable dienes, while aromatics can serve as effective components to increase the density of automotive diesel fractions and improve their quality.

[0027] Because a sulfurizing agent needs to be added during steam cracking to protect the reaction unit and prevent carbon buildup and coking in the furnace tubes, sulfur-containing impurities are present in the reaction solution. Furthermore, since the olefin content in automotive diesel fuel should not be too high, the unsaturated hydrocarbons in the gasoline fraction need to be hydrogenated for saturation. In a preferred embodiment, S4 includes: subjecting the gasoline fraction to a second hydrogenation refining reaction and a third atmospheric distillation to obtain C. 9+ Fraction; C 9+ The fraction underwent a third hydrogenation purification reaction and a fourth atmospheric distillation to obtain C. 9+ Oil products.

[0028] In this process, the gasoline fraction undergoes hydrorefining, which removes some sulfur and nitrogen compounds and hydrogenates unstable dienes to obtain saturated alkanes, while the aromatics remain unsaturated. The resulting product after atmospheric distillation contains a high proportion of C6-C8 aromatics. Furthermore, to further refine the C6-C8 aromatics from the third atmospheric distillation... 9+ Sulfur and olefins are removed from the distillate, and C 9+ The fraction is further hydrotreated for desulfurization, saturation of some olefins and a small amount of aromatics, to obtain C 9+ Oil products. C 9+ The oil is mainly C9-C. 12 Hydrocarbons, including alkanes, cycloalkanes, aromatics and less alkenes, with a distillation range ≥160°C, can be used to blend with diesel component oils to obtain automotive diesel fuel.

[0029] To obtain C more efficiently 9+ In a preferred embodiment, the temperature of the second hydrorefining reaction is 80–250°C; preferably, the pressure of the second hydrorefining reaction is 2.0–4.0 MPa; preferably, the volume hourly space velocity (VHSV) of the second hydrorefining reaction is 1.0–3.0 h⁻¹. -l Preferably, the hydrogen-to-oil volume ratio of the second hydrorefining reaction is 300-800:1; preferably, the temperature of the third atmospheric distillation is 140-200℃; preferably, the pressure of the third atmospheric distillation is 0.01-1.0 MPa.

[0030] To obtain C more efficiently 9+ In a preferred embodiment, the temperature of the third hydrorefining reaction is 200-350°C; preferably, the pressure of the third hydrorefining reaction is 2.0-6.0 MPa; preferably, the volume hourly space velocity (VHSV) of the third hydrorefining reaction is 0.5-3 h⁻¹. -l Preferably, the hydrogen-to-oil volume ratio in the third hydrorefining reaction is 400-800:1; preferably, the temperature of the fourth atmospheric distillation is 180-280°C; preferably, the pressure of the fourth atmospheric distillation is 0.01-1.0 MPa.

[0031] To further obtain automotive diesel fuel with higher lubricity, an anti-wear agent can be added during the blending process. In a preferred embodiment, S5 includes: adding C... 9+ After mixing the oil and side-stream products, an anti-wear agent is added and blended to obtain diesel fuel; preferably, C 9+ The mass ratio of oil to side-stream products is 50-66:50-34; preferably, the anti-wear agent is selected from fatty acid-based or fatty acid ester-based anti-wear agents; preferably, the amount of anti-wear agent is ≤180ppm; preferably, the mixing temperature is 55-65℃. Because C 9+ The oil contains a relatively high amount of aromatics. When blended with diesel component oil, it can produce automotive diesel with a high fraction density that meets national standards and can be widely produced and used.

[0032] Anti-wear agents primarily function to prevent scratches, seizing, and wear. Dissolving in diesel fuel, they rely on physical and chemical adsorption to form a robust, directional adsorption film on the friction surface for lubrication. Diesel fuel anti-wear agents are mainly classified into two types: fatty acid type and fatty acid ester type. Fatty acid type diesel fuel anti-wear agents are primarily long-chain unsaturated fatty acid compounds, such as linoleic acid, tall oil acid, ricinoleic acid, tall oil fatty acids, or soybean oil fatty acids. Fatty acid ester type diesel fuel anti-wear agents are primarily long-chain unsaturated fatty acid ester compounds, such as polyglycerol polyricinoleate, long-chain fatty acid methyl esters, oleic acid monoglyceride, linoleic acid monoglyceride, polyglycerol polyricinoleate, or polyphosphate esters.

[0033] In a second typical embodiment of this application, a preparation system for the above-described diesel fuel preparation method is provided. This preparation system includes: a first hydrorefining unit 01, a hydrocracking unit 02, a steam cracking unit 03, a gasoline fraction hydrorefining unit, and a diesel blending unit 04. The first hydrorefining unit 01 includes a feed inlet, a bottom outlet, and a top outlet; the hydrocracking unit 02 includes a feed inlet, a top outlet, and a side-stream product outlet; the steam cracking unit 03 includes a feed inlet and a gasoline fraction outlet; and the gasoline fraction hydrorefining unit includes a feed inlet and a C... 9+ The diesel blending unit 04 includes an inlet and an outlet for oil products. The bottom outlet of the first hydrorefining unit 01 is connected to the inlet of the hydrocracking unit 02. The top outlets of the first hydrorefining unit 01 and the hydrocracking unit 02 are respectively connected to the inlet of the steam cracking unit 03. The gasoline fraction outlet of the steam cracking unit 03 is connected to the inlet of the gasoline fraction hydrorefining unit. The C... 9+ The oil product outlet and the side-stream product outlet of the hydrocracking unit 02 are respectively connected to the feed inlet of the diesel blending unit 04.

[0034] Specifically, the first hydrorefining unit 01 carries out the first hydrorefining reaction, the first atmospheric distillation, and the first vacuum distillation; the hydrocracking unit 02 carries out the hydrocracking reaction, the second atmospheric distillation, and the second vacuum distillation; the steam cracking unit 03 carries out the steam cracking reaction; the gasoline fraction hydrorefining unit carries out the hydrorefining reaction and atmospheric distillation; and the diesel blending unit 04 carries out the blending of automotive diesel fuel.

[0035] To further remove sulfur-containing substances and unsaturated hydrocarbons from the gasoline fraction, in a preferred embodiment, the gasoline fraction hydrorefining unit further includes a second hydrorefining unit 05 and a third hydrorefining unit 06; wherein, the second hydrorefining unit 05 includes an inlet and a C 9+ The fraction outlet, the third hydrorefining unit 06 includes an inlet and a C 9+ Oil product outlet; the gasoline fraction outlet of steam cracking unit 03 is connected to the inlet of the second hydrorefining unit 05; the C of the second hydrorefining unit 05 9+ The fraction outlet is connected to the inlet of the third hydrorefining unit 06; the C of the third hydrorefining unit 06 9+ The oil product outlet and the side-stream product outlet of the hydrocracking unit 02 are respectively connected to the feed inlet of the diesel blending unit 04. The second hydrorefining unit 05 conducts the second hydrorefining reaction and the third atmospheric distillation, while the third hydrorefining unit 06 conducts the third hydrorefining reaction and the fourth atmospheric distillation.

[0036] In order to continuously connect the preparation process of Fischer-Tropsch synthetic oil with the preparation of automotive diesel, in a preferred embodiment, the preparation system further includes: a Fischer-Tropsch synthesis unit 07; the Fischer-Tropsch synthetic oil outlet of the Fischer-Tropsch synthesis unit 07 is connected to the inlet of the first hydrorefining unit 01.

[0037] In a third typical embodiment of this application, a type of automotive diesel fuel prepared using the above-described preparation method or system is provided, wherein the wear track diameter of the automotive diesel fuel is ≤460μm. The automotive diesel fuel obtained through the technical solution of this application has a high aromatic content and its fraction has a high density, which meets the national standard for automotive diesel fuel and has significant implications for production and application.

[0038] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0039] The reaction system for preparing automotive diesel fuel in the following embodiments of this application is as follows: Figure 1 As shown, the first bottom product in the preparation process includes >C 20+The refined wax, with the first column top product including refined LPG and refined naphtha, the refined LPG being C1-C4 n-alkanes and the refined naphtha being C5-C6 n-alkanes. 10 The second column's overhead products include cracked LPG and cracked naphtha; the cracked LPG consists of C1-C4 isoalkanes, and the cracked naphtha consists of C5-C6 isoalkanes. 10 Isomeric alkanes; side-line products include C 10 -C 21 The isoalkanes have a side-stream product distillation range of 160-365℃; the gasoline fraction mainly includes C5-C64... 12 Hydrocarbons, including alkenes, alkanes, cycloalkanes, and aromatics; C 9+ The fractions mainly include C9-C 12 Hydrocarbons, including alkenes, alkanes, cycloalkanes, and aromatics; C 9+ Oil products mainly include C9-C 12 Hydrocarbons, including alkanes, cycloalkanes, aromatics, and fewer alkenes.

[0040] Example 1

[0041] 1) The Fischer-Tropsch synthesis reaction is carried out in Fischer-Tropsch synthesis unit 07. The process and parameters of the Fischer-Tropsch synthesis include: the synthesis of Fischer-Tropsch synthesis oil (liquid hydrocarbons or hydrocarbons) from syngas under iron-based catalyst and at 2.75 MPa and 270 °C. 2) The Fischer-Tropsch synthetic oil obtained from the Fischer-Tropsch synthesis is subjected to a first hydrorefining reaction in the first hydrorefining unit 01, followed by a first atmospheric distillation and a first vacuum distillation. The conditions for the first hydrorefining reaction include: a temperature of 350°C, a pressure of 8 MPa, and a volume hourly space velocity of 2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 350:1; the conditions for the first atmospheric distillation include a temperature of 340℃ and a pressure of 0.15MPa; the conditions for the first vacuum distillation include a temperature of 310℃ and a pressure of 0.01MPa. 3) The first bottom product obtained in step 2) is subjected to hydrocracking in hydrocracking unit 02, followed by a second atmospheric distillation and a second vacuum distillation. The conditions for the hydrocracking reaction include: a temperature of 360°C, a pressure of 8 MPa, and a volume hourly space velocity of 2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500:1; the conditions for the second atmospheric distillation include a temperature of 310℃ and a pressure of 0.1MPa; the conditions for the second vacuum distillation include a temperature of 300℃ and a pressure of 0.01MPa. 4) The first top product obtained in step 2) and the second top product obtained in step 3) are mixed and then subjected to steam cracking reaction in steam cracking unit 03, and then the gasoline fraction is separated. The conditions for the steam cracking reaction include: temperature of 840℃, pressure of 0.2MPa, and dilution steam ratio of 0.5.

[0042] 5) The gasoline fraction is subjected to a second hydrorefining reaction and a third atmospheric distillation in the second hydrorefining unit 05. The resulting second bottom product is then subjected to a third hydrorefining reaction and a fourth atmospheric distillation in the third hydrorefining unit 06. The conditions for the second hydrorefining reaction include: a temperature of 80°C, a pressure of 2.7 MPa, and a volume hourly space velocity of 2 h⁻¹. -1 The hydrogen-to-oil volume ratio was 300:1; the conditions for the third atmospheric distillation included a temperature of 180℃ and a pressure of 0.1 MPa; the conditions for the third hydrorefining reaction included a temperature of 305℃, a pressure of 2.5 MPa, and a volume hourly space velocity of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500:1; the conditions for the fourth atmospheric distillation include: a temperature of 265℃ and a pressure of 0.1MPa. 6) The third bottom product obtained in step 5) and the side stream product obtained in step 3) are blended in diesel blending unit 04 at a ratio of 66:34. Then, an anti-wear agent is added for blending to obtain diesel product. The total amount of the third bottom product obtained in step 5) and the side stream product obtained in step 3) is used as the basis. The anti-wear agent is a fatty acid ester type anti-wear agent with polyglycerol polyricinoleate as the main component and the amount of anti-wear agent is 170 ppm.

[0043] Example 2

[0044] 1) The Fischer-Tropsch synthesis reaction is carried out in Fischer-Tropsch synthesis unit 07. The process and parameters of the Fischer-Tropsch synthesis include: the synthesis of syngas into liquid hydrocarbons or hydrocarbons under the conditions of catalyst, 2.60 MPa and 280 °C. 2) The Fischer-Tropsch synthetic oil obtained from the Fischer-Tropsch synthesis is subjected to a first hydrorefining reaction in the first hydrorefining unit 01, followed by a first atmospheric distillation and a first vacuum distillation. The conditions for the first hydrorefining reaction include: a temperature of 355°C, a pressure of 7 MPa, and a volume hourly space velocity of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1; the conditions for the first atmospheric distillation include a temperature of 330℃ and a pressure of 0.1MPa; the conditions for the first vacuum distillation include a temperature of 320℃ and a pressure of 0.015MPa. 3) The first bottom product obtained in step 2) is subjected to hydrocracking in hydrocracking unit 02, followed by a second atmospheric distillation and a second vacuum distillation. The conditions for the hydrocracking reaction include: a temperature of 365°C, a pressure of 7 MPa, and a volume hourly space velocity of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1; the conditions for the second atmospheric distillation include a temperature of 320℃ and a pressure of 0.15MPa; the conditions for the second vacuum distillation include a temperature of 305℃ and a pressure of 0.015MPa. 4) The first overhead product obtained in step 2) and the second overhead product obtained in step 3) are mixed and then subjected to steam cracking reaction in steam cracking unit 03, and then the gasoline fraction is separated. The conditions for the steam cracking reaction include: temperature of 820℃, pressure of 0.35MPa, and dilution steam ratio of 0.3. 5) The gasoline fraction is subjected to a second hydrorefining reaction and a third atmospheric distillation in the second hydrorefining unit 05. The resulting second bottom product is then subjected to a third hydrorefining reaction and a fourth atmospheric distillation in the third hydrorefining unit 06. The conditions for the second hydrorefining reaction are: temperature 95℃, pressure 2.6MPa, and volume hourly space velocity 1.0 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1; the conditions for the third atmospheric distillation included a temperature of 165℃ and a pressure of 0.15 MPa; the conditions for the third hydrorefining reaction included a temperature of 300℃, a pressure of 5 MPa, and a volume hourly space velocity of 1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1; the conditions for the fourth atmospheric distillation include: a temperature of 270℃ and a pressure of 0.15MPa. 6) The third bottom product obtained in step 5) and the side stream product obtained in step 3) are blended in diesel blending unit 04 at a ratio of 60:40. Then, an anti-wear agent is added for blending to obtain diesel product. The total amount of the third bottom product obtained in step 5) and the side stream product obtained in step 3) is used as the basis. The anti-wear agent is a fatty acid ester type anti-wear agent, the main components of which are triethanolamine oleate and glycerol oleate. The amount of anti-wear agent is 170 ppm.

[0045] Example 3

[0046] 1) The Fischer-Tropsch synthesis reaction is carried out in Fischer-Tropsch synthesis unit 07. The process and parameters of the Fischer-Tropsch synthesis include: synthesis of liquid hydrocarbons or hydrocarbons from syngas under the conditions of catalyst, 3.0 MPa and 260 °C. 2) The Fischer-Tropsch synthetic oil obtained from the Fischer-Tropsch synthesis is subjected to a first hydrorefining reaction in the first hydrorefining unit 01, followed by a first atmospheric distillation and a first vacuum distillation. The conditions for the first hydrorefining reaction include: a temperature of 360°C, a pressure of 6 MPa, and a volume hourly space velocity of 1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500:1; the conditions for the first atmospheric distillation include a temperature of 340℃ and a pressure of 0.2MPa; the conditions for the first vacuum distillation include a temperature of 330℃ and a pressure of 0.02MPa. 3) The first bottom product obtained in step 2) is subjected to hydrocracking in hydrocracking unit 02, followed by a second atmospheric distillation and a second vacuum distillation. The conditions for the hydrocracking reaction include: a temperature of 368°C, a pressure of 6 MPa, and a volume hourly space velocity of 1.5 h⁻¹.-1 The hydrogen-to-oil volume ratio is 500:1; the conditions for the second atmospheric distillation include a temperature of 325℃ and a pressure of 0.2MPa; the conditions for the second vacuum distillation include a temperature of 310℃ and a pressure of 0.02MPa. 4) The first top product obtained in step 2) and the second top product obtained in step 3) are mixed and then subjected to steam cracking reaction in steam cracking unit 03, and then the gasoline fraction is separated. The conditions for the steam cracking reaction include: temperature of 850℃, pressure of 0.15MPa, and dilution steam ratio of 0.4. 5) The gasoline fraction is subjected to a second hydrorefining reaction and a third atmospheric distillation in the second hydrorefining unit 05. The resulting second bottom product is then subjected to a third hydrorefining reaction and a fourth atmospheric distillation in the third hydrorefining unit 06. The conditions for the second hydrorefining reaction include: a temperature of 100°C, a pressure of 2.4 MPa, and a volume hourly space velocity of 3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 800:1; the conditions for the third atmospheric distillation included a temperature of 170℃ and a pressure of 0.2 MPa; the conditions for the third hydrorefining reaction included a temperature of 330℃, a pressure of 2.0 MPa, and a volume hourly space velocity of 0.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1; the conditions for the fourth atmospheric distillation include: a temperature of 275℃ and a pressure of 0.2MPa. 6) The third bottom product obtained in step 5) and the side stream product obtained in step 3) are blended in diesel blending unit 04 in a ratio of 50:50 to obtain diesel product. The total amount of the third bottom product obtained in step 5) and the side stream product obtained in step 3) is used as the basis. The anti-wear agent is a fatty acid type anti-wear agent, the main components of which are polyricinoleic acid and polyglycerol. The amount of anti-wear agent is 180 ppm.

[0047] Comparative Example 1: Existing methods for preparing diesel component oils using Fischer-Tropsch synthetic oils

[0048] The specific method is as follows: Steps S1 and S2 are the same as in Example 1, except for steps S3, S4, and S5. The side-stream products (cracking atmospheric first line, cracking atmospheric second line, and cracking deionized first line) are the Fischer-Tropsch synthetic diesel component oils.

[0049] Comparative Example 2

[0050] Except for S4, all other steps are the same as in Example 1. The specific steps of S4 in this comparative example are as follows: The gasoline fraction undergoes only the second hydrorefining reaction and the third atmospheric distillation, without the third hydrorefining reaction and the fourth atmospheric distillation. The resulting second bottom product and the side stream product obtained in step 3) are blended with diesel fuel in a ratio of 66:34, and then an anti-wear agent is added for further blending to obtain the diesel fuel product.

[0051] Test case

[0052] The performance of the diesel products obtained in Examples 1, 2, and 3, and Comparative Examples 1 and 2, was tested using existing methods. The results are shown in Tables 1 and 2. Among them, C... 9+ The aromatic hydrocarbon content of the fraction is generally around 70%, and the carbon number is mainly C8-C. 12 The main components are ethylbenzene, xylene, trimethylbenzene, etc. As can be seen from the results in Tables 1 and 2, the diesel fuel produced using the method of this invention meets national standards.

[0053] Table 1:

[0054] Table 2:

[0055] As can be seen from the above description, the embodiments of the present invention achieve the following technical effects: using the preparation method of this application, C is obtained through steam cracking. 9+ The fraction is then hydrogenated and purified, due to C 9+ The fraction is rich in aromatics and has a high density. Hydrorefining removes sulfur impurities from the product, and blending it with side-stream products yields automotive diesel fuel with high density and lubricity, which meets national standards and has certain production and application value.

[0056] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing automotive diesel fuel, characterized in that, The preparation method includes: S1, the Fischer-Tropsch synthetic oil is subjected to a first hydrorefining reaction, a first atmospheric distillation and a first vacuum distillation in sequence to obtain the first bottom product and the first top product; S2, the first bottom product of the column is subjected to hydrocracking reaction, second atmospheric distillation and second vacuum distillation in sequence to obtain side stream product and second top product of the column; S3, the first and second overhead products of the column are mixed and subjected to steam cracking reaction to obtain gasoline fraction; S4, the gasoline fraction is subjected to a second hydrorefining reaction and a third atmospheric distillation to obtain C. 9+ Fraction; the C 9+ The fraction underwent a third hydrogenation purification reaction and a fourth atmospheric distillation to obtain C. 9+ Oil products; S5, the C 9+ After mixing the oil and the side-stream product, an anti-wear agent is added and blended to obtain the automotive diesel fuel; The first bottom product includes C 20+ The refined wax, wherein the first overhead product comprises refined LPG and refined naphtha, and the second overhead product comprises cracked LPG and cracked naphtha; the side-stream product comprises C 10 -C 21 The isomeric alkanes, wherein the distillation range of the side-stream products is 160-365°C; The refined LPG is a C1-C4 n-alkanes; the refined naphtha is a C5-C6 alkane. 10 n-alkanes; The cracked LPG is a C1-C4 isoalkanes; the cracked naphtha is a C5-C4 isoalkanes. 10 Isomerized alkanes; The temperature of the second hydrorefining reaction is 80~250℃, the pressure is 2.0~4.0 MPa, and the volume hourly space velocity (VHSV) is 1.0~3.0 h⁻¹. -l The hydrogen-to-oil volume ratio in the second hydrorefining reaction is 300-800:1; The temperature of the third atmospheric distillation is 140~200℃; the pressure of the third atmospheric distillation is 0.1-0.2 MPa; The temperature of the third hydrorefining reaction is 200~350℃, the pressure of the third hydrorefining reaction is 2.0~6.0 MPa, and the volume hourly space velocity of the third hydrorefining reaction is 0.5~3 h⁻¹. -l The hydrogen-to-oil volume ratio of the third hydrorefining reaction is 400-800:1; The temperature of the fourth atmospheric distillation is 180~280℃; the pressure of the fourth atmospheric distillation is 0.1-0.2 MPa. The C 9+ The mass ratio of the oil to the side-stream product is 50-66:50-34; The temperature for blending is 55-65℃.

2. The preparation method according to claim 1, characterized in that, The temperature of the first hydrogenation refining reaction is 300~400℃; The pressure of the first hydrorefining reaction is 4.5~9.5 MPa; The volume hourly space velocity (VHSV) of the first hydrogenation purification reaction is 1–4 h⁻¹. -1 ; The hydrogen-to-oil volume ratio in the first hydrorefining reaction is 300-700:

1.

3. The preparation method according to claim 1, characterized in that, The temperature of the first atmospheric distillation is 250~400℃; The pressure of the first atmospheric distillation is 0.1-0.2 MPa.

4. The preparation method according to claim 1, characterized in that, The temperature of the first vacuum distillation is 200~350℃; The pressure of the first vacuum distillation is 0.01~0.02 MPa.

5. The preparation method according to claim 1, characterized in that, The temperature of the hydrocracking reaction is 280~450℃; The pressure of the hydrocracking reaction is 6~13 MPa; The volume hourly space velocity (VHSV) of the hydrocracking reaction is 1–3.5 h⁻¹. -l ; The hydrogen-to-oil volume ratio in the hydrocracking reaction is 400-800:

1.

6. The preparation method according to claim 1, characterized in that, The temperature for the second atmospheric distillation is 250~400℃; The pressure of the second atmospheric distillation is 0.1-0.2 MPa.

7. The preparation method according to claim 1, characterized in that, The temperature for the second vacuum distillation is 200~350℃; The pressure of the second vacuum distillation is 0.01~0.02 MPa.

8. The preparation method according to claim 1, characterized in that, The temperature of the steam cracking reaction is 820~890℃; The pressure of the steam cracking reaction is 0.1~0.5 MPa; The dilution steam ratio for the steam cracking reaction is 0.2 to 0.

8.

9. The preparation method according to claim 1, characterized in that, The anti-wear agent is selected from fatty acid type anti-wear agents or fatty acid ester type anti-wear agents; The amount of the anti-wear agent is ≤180ppm.

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