Method and reaction system for producing spaceflight fuel base oil and solvent oil in high yield by using DCC byproduct oil

Abstract

The invention relates to a method for producing more aerospace fuel base oil and solvent oil by using DCC byproduct oil, which comprises the following steps: mixing DCC oil slurry, pulverized coal and a catalyst, mixing with hydrogen, hydrocracking, and separating to obtain light product oil and heavy product oil; the heavy product oil is subjected to hot low-pressure separation and vacuum tower separation to obtain tailings and vacuum wax oil, the vacuum wax oil and the light product oil are mixed and subjected to a hydrocracking reaction, product oil is obtained and separated, and hydrocracked naphtha, a diesel oil component and a wax oil component are obtained; mixing the diesel oil component, the hydrocracking naphtha, the DCC diesel oil, the DCC naphtha and hydrogen, and hydrofining to obtain a product; and carrying out a hydroisomerization reaction on the product to obtain a product, and separating the product to obtain the aerospace fuel base oil, solvent oil, light naphtha and heavy diesel oil components. According to the present invention, the comprehensive utilization and the efficient conversion of the DCC oil slurry, the DCC diesel oil and the DCC naphtha are achieved, the unexpected hydrogenation effect is achieved, and the high yield of the high energy density aerospace fuel base oil and the high yield of the solvent oil are achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of comprehensive processing and utilization of high-aromatic by-product oil, and specifically relates to a method and a reaction system for utilizing DCC by-product oil to produce more aerospace fuel base oil and solvent oil. Background Art

[0002] The DCC unit is a unit that performs deep catalytic cracking on heavy oil (atmospheric residue or vacuum residue) to produce more olefins, but it will produce a large amount of DCC slurry oil, DCC diesel and DCC naphtha as by-products, with yields of approximately 5-10%, 5-8% and 15-20% respectively. DCC slurry oil is rich in 3-4-ring aromatics, and DCC diesel is rich in 2-3-ring aromatics, but a considerable portion of DCC slurry oil and DCC diesel are used to produce ordinary oil products or as fuel, without achieving high added value.

[0003] With the rapid development of the aerospace industry, there is a demand for various types of spacecraft for supersonic, ultra-long-range, and unconventional climate flight missions. Such vehicles have high requirements on the energy density, freezing point and other properties of the aerospace fuels used. Conventional petroleum-based raw materials are difficult to achieve standard production. The high aromatic content of DCC slurry and DCC diesel makes them very suitable as raw materials for the production of high-performance aerospace fuels.

[0004] CN201510468820.8 discloses a DCC cracking light oil processing technology. The process modification design has a three-bed reactor, which mainly produces National IV and National V diesel blending components after deep hydrogenation and modification of the cracking light oil produced by the DCC device. However, the product of this patent is just an ordinary fuel oil product with low added value. It does not disclose or involve the technical solution of how to achieve high-calorific value, low-freezing-point aerospace fuel base oil and solvent oil.

[0005] CN201310241346.6 discloses a method for preparing coal-based military fuel and the military fuel prepared, including: cutting the raw oil into light distillate oil and heavy distillate oil by distillation; mixing the catalyst, sulfiding agent and solvent oil evenly to make catalyst oil slurry, mixing the catalyst oil slurry, heavy distillate oil and circulating oil with catalyst for hydrocracking, separating the reaction products to obtain a liquid-solid phase mixed flow, and separating the liquid-solid phase mixture to obtain light distillate oil; the light distillate oil is subjected to hydrofining or selective hydrogenation to obtain the generated oil, which is cooled and separated from the gas and liquid, and then enters the fractionation tower for product fractionation to obtain military fuel. However, the patent does not disclose or involve a technical solution on how to use DCC oil slurry and DCC diesel to achieve the production of high calorific value, low freezing point aerospace fuel base oil and solvent oil.

[0006] In summary, the shortcomings of the prior art are that there is no method for utilizing the high aromatic by-product oil of the DCC device to process and produce high energy density aerospace fuel base oil or solvent oil. The products of the prior art have low added value, and there is no technical solution to promote the deep hydrogenation and deep cracking reaction of DCC oil slurry and stable and efficient conversion. Summary of the invention

[0007] In order to overcome the deficiencies of the above-mentioned prior art, the object of the present invention is to provide a method for utilizing DCC by-product oil to produce more aerospace fuel base oil and solvent oil, and comprehensively utilize and process the DCC oil slurry, DCC diesel and DCC naphtha by-products of the DCC device, subject the DCC oil slurry to micro-scale mixed-phase bed hydrocracking jointly dominated by positive carbon ion reaction and free radicals, and integrate fixed-bed hydrocracking online, and couple micro-scale hydrorefining and micro-scale hydroisomerization offline to produce more high-energy-density aerospace fuel base oil and solvent oil.

[0008] A method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil, wherein the method comprehensively processes DCC slurry oil, DCC diesel, and DCC naphtha to prepare aerospace fuel base oil and solvent oil; specifically comprising: (1) DCC oil slurry, coal powder, and catalyst are mixed with hydrogen to carry out hydrocracking reaction and separated to obtain light product oil and heavy product oil; (2) The heavy product oil is separated by hot low fractionation and vacuum tower to obtain tailings and vacuum wax oil, the vacuum wax oil is mixed with the light product oil of step (1) and then subjected to hydrocracking reaction to obtain hydrocracking product oil, which is separated to obtain hydrocracked naphtha, diesel component and wax oil component; (3) The diesel component, hydrocracked naphtha, DCC diesel, DCC naphtha and hydrogen are mixed and subjected to a hydrotreating reaction to obtain a hydrotreating product; (4) The hydrorefined product is then subjected to a hydroisomerization reaction to obtain a hydroisomerization product, which is then separated to obtain aerospace fuel base oil, solvent oil, light naphtha and heavy diesel components.

[0009] Preferably, the catalyst in step (1) comprises a hydrotalcite Ni-Fe catalyst, a microscale amorphous silica-alumina and a microscale USY molecular sieve supported on a microscale porous carbon material; the mass proportion of the hydrotalcite Ni-Fe catalyst supported on the microscale porous carbon material is 50-90%, the Ni-Fe content accounts for 5-6% of the total amount of the hydrotalcite Ni-Fe catalyst supported on the microscale porous carbon material, the mass ratio is 9:1-8:2, the mass proportion of the microscale amorphous silica-alumina is 40-5%, and the mass proportion of the microscale USY molecular sieve is 10-5%; the specific surface area of ​​the hydrotalcite Ni-Fe catalyst of the microscale porous carbon material is 550-650m2 / g; Preferably, the specific conditions of the hydrocracking reaction in step (1) are: reaction temperature 460-472°C, reaction pressure 10-16 MPa, space velocity 0.3-0.6 h -1 , hydrogen-to-oil ratio is 1000-1400NL / kg; the mass ratio of the DCC oil slurry to coal powder is 75:25-65:35.

[0010] Preferably, the hydrocracking reaction in step (2) is carried out in a fixed bed reactor, wherein the fixed bed reactor is sequentially filled with a hydrorefining catalyst A, a hydrocracking catalyst and a hydrorefining catalyst B; the hydrorefining catalyst A is a Mo-Ni catalyst supported on macroporous alumina, the hydrocracking catalyst is an active metal Ni-Mo-W supported on a carrier USY molecular sieve and macroporous alumina; the hydrorefining catalyst B is a Mo-Co catalyst supported on macroporous alumina; the reaction conditions of the hydrocracking reaction are: a temperature of 380°C to 395°C, a reaction pressure of 10 to 16 MPa, and a space velocity of 0.8 to 1.2 h -1 , the hydrogen-to-oil ratio is 800-1000 NL / kg; the 95% distillation point of the vacuum wax oil in the step (2) is <520°C.

[0011] Preferably, the catalyst for the hydrofining reaction in step (3) is a special catalyst of two kinds of Mo, Ni, W and Co supported on neutral alumina, and the total amount of metals accounts for 30%-35% of the catalyst mass; the conditions of the hydrofining reaction are: temperature 240°C to 330°C, reaction pressure 10-16Mpa, space velocity 0.8-1.4h -1 , the hydrogen-to-oil ratio is 800-1000NL / kg.

[0012] Preferably, the catalyst for the hydroisomerization reaction in step (4) is an active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve, and an active metal Ni-W catalyst supported on carriers USY molecular sieve, SAPO-11 molecular sieve and alumina, and the content of the active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve accounts for 25-40% of the total catalyst; the active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve is calculated by mass percentage, the mass ratio of USY molecular sieve to carrier is 5% to 25%, and the mass ratio of ZSM-5 molecular sieve to carrier is 10%. The mass ratio of the carrier is 15% to 5%, the mass ratio of Pt to the carrier is 0.2-2.2%, and the balance is alumina; the catalyst loaded on the carrier USY molecular sieve, SAPO-11 molecular sieve and alumina and the active metal is Ni-W, according to the mass percentage, SAPO-11 accounts for 15-40% of the carrier, the mass ratio of USY molecular sieve to the carrier is 30-5%, the mass ratio of Ni-W to the carrier is 14-28%, and the balance is alumina, and the mass ratio of Ni to W is 4:1-2:1; the conditions of the hydroisomerization reaction are: temperature 230-330°C, reaction pressure 10-16MPa, hydrogen-to-oil ratio 800-1200Nm 3 / t, airspeed 0.3~0.8h- 1 The initial distillation point of the aerospace fuel base oil is not lower than 188°C and the final distillation point is not higher than 250°C; the initial distillation point of the solvent oil 25 is not lower than 140°C and the dry point is not higher than 200°C.

[0013] Preferably, the mass ratio of the DCC slurry oil, DCC diesel and DCC naphtha is 5:3:2; and the amount of the catalyst added in step (1) is 0.3% to 0.8% of the total amount of the DCC slurry oil and the coal powder.

[0014] A reaction system for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil, the system comprising a microscale hydrogen mixer A (11), a microscale mixed-phase bed hydrocracking reactor (21), a thermal high fraction unit (3), a thermal low fraction unit (4), a vacuum tower (5), a fixed bed hydrocracking reactor (22), a separation system A (1), a microscale hydrogen mixer B (12), a microscale hydrofining reactor (23), a microscale hydroisomerization reactor (24), and a separation system B (2) connected in sequence; The microscale hydrogen mixer A (11) is provided with a gas source and a liquid source, wherein the gas source is connected to a hydrogen pipeline, and the liquid source is connected to a DCC oil slurry, coal powder and a catalyst; The microscale hydrogen mixer B (12) is provided with a gas source and a liquid source, wherein the gas source is connected to a hydrogen pipeline, and the liquid source is connected to DCC diesel, DCC naphtha and light component and medium component outlet pipelines of the separation system A (1); The light component outlet of the thermal high fraction unit (3) and the liquid phase outlet pipeline of the vacuum tower (5) are connected to the inlet of the fixed bed hydrocracking reactor (22).

[0015] Preferably, the separation system (1) comprises a separation unit A (6) and an atmospheric pressure tower A (7), wherein the gas phase of the separation unit A (6) is connected to the gas source inlet of the microscale hydrogen mixer A (11), and the liquid phase of the separation unit A (6) is connected to the inlet of the atmospheric pressure tower A (7); the heavy component outlet of the atmospheric pressure tower A (7) is connected to the liquid source inlet of the microscale mixed phase bed hydrocracking reactor (21); The separation system B (2) comprises a separation unit B (8) and an atmospheric pressure tower B (9); the heavy component of the separation unit B (8) is connected to the atmospheric pressure tower B (9), and the heavy component of the atmospheric pressure tower B (9) is connected to the liquid source inlet of the microscale hydrogen mixer B (12).

[0016] Preferably, the height-to-diameter ratio of the scaled mixed-bed hydrocracking reactor (21) is 8:1 to 2:1.

[0017] Beneficial effects of the present invention: (1) In the micro-scale mixed-phase bed hydrocracking reaction, the enhanced hydrogenation and enhanced cracking are synergistic. On the one hand, the combination of the micro-scale mixed-phase bed reaction system, the cyclic processing of the ring-rich hydrocarbon components, and the hydrotalcite Ni-Fe catalyst of the micro-scale porous carbon material loaded with the external specific surface area has the conditions for enhanced hydrogenation. The components of amorphous silicon aluminum, Y-type molecular sieve and process conditions have the conditions for enhanced cracking. The enhanced hydrogenation and enhanced cracking are mutually promoted, changing the previous status quo that the hydrogenation of heavy hydrocarbons is simply dominated by free radicals, forming a reaction system dominated by free radical reactions and positive carbon ion reactions, promoting the efficient and directional conversion of DCC oil slurry and coal, producing unexpected reaction effects, and providing the prerequisite for the production of aerospace fuel base oil and solvent oil; (2) The technical solution provided by the present invention sequentially performs hydrorefining, aromatic hydroisomerization, and alkane hydroisomerization under process reaction conditions suitable for a microscale reaction system, especially the consecutive hydroisomerization reaction of aromatic hydroisomerization and alkane hydroisomerization, which effectively optimizes the calorific value and freezing point of aerospace fuel base oil; (3) The technical solution provided by the present invention realizes the comprehensive utilization and efficient conversion of DCC slurry oil, DCC diesel and DCC naphtha through system integration and coupling of different types of catalysts, reactors, process reaction conditions, process processing routes and other technical means, achieves unexpected hydrogenation effects, and realizes the high production of high-energy-density aerospace fuel base oil and solvent oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic diagram of a reaction system that utilizes DCC by-product oil to produce more aerospace fuel base oil and solvent oil.

[0019] Icons: 11—microscale hydrogen mixer A; 21—microscale mixed-bed hydrocracking reactor; 3—thermal high-fraction unit; 4—thermal low-fraction unit; 5—vacuum tower; 22—fixed-bed hydrocracking reactor; 6—separation unit A; 7—atmospheric tower A; 12—microscale hydrogen mixer B; 23—microscale hydrorefining reactor; 24—microscale hydroisomerization reactor; 8—separation unit B; 9—atmospheric tower B; 1—separation system A; 2—separation system B. DETAILED DESCRIPTION

[0020] Example 1 A reaction system for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil, the system comprising a microscale hydrogen mixer A11, a microscale mixed phase bed hydrocracking reactor 21, a thermal high fraction unit 3, a thermal low fraction unit 4, a vacuum tower 5, a fixed bed hydrocracking reactor 22, a separation system A1, a microscale hydrogen mixer B12, a microscale hydrofining reactor 23, a microscale hydroisomerization reactor 24, and a separation system B2 connected in sequence; The microscale hydrogen mixer A 11 is provided with a gas source and a liquid source, the gas source is connected to the hydrogen pipeline, and the liquid source is connected to the DCC slurry, coal powder and catalyst; The microscale hydrogen mixer B 12 is provided with a gas source and a liquid source, the gas source is connected to the hydrogen pipeline, and the liquid source is connected to the DCC diesel, DCC naphtha and atmospheric tower light A 15 light component and medium component outlet pipelines; The light components of the thermal high fraction unit 3 are mixed with the liquid phase of the vacuum tower 5 and connected to the inlet of the fixed bed hydrocracking reactor 22; At the beginning of the start-up, the DCC oil slurry, coal powder and catalyst are introduced into the microscale hydrogen mixer A11 in a certain proportion and mixed with hydrogen and then enter the microscale mixed phase bed hydrocracking reactor 21 for hydrocracking reaction. The reaction product is separated into light product oil and heavy product oil through the thermal high fraction unit 3. The heavy product oil is separated into tailings and vacuum wax oil after passing through the thermal low fraction unit 4 and the vacuum tower 5 in turn. The tailings are discharged from the bottom of the vacuum tower 5. The vacuum wax oil and the light product oil are mixed and then enter the fixed bed hydrocracking reactor 22 for hydrocracking reaction. The reaction product passes through the separation system A1 to obtain a heavy component wax oil component, a medium component diesel component and a light component hydrocracking naphtha. The medium component diesel component and the light component hydrocracking naphtha are mixed with DCC diesel and DCC naphtha and then enter the microscale hydrogen mixer B 12 is mixed with hydrogen and then introduced into a microscale hydrotreating reactor 23 for hydrotreating reaction to obtain a hydrotreating product. The hydrotreating product enters a microscale hydroisomerization reactor 24 for hydroisomerization reaction to obtain a hydroisomerization product. After passing through a separation system B2, aerospace fuel base oil, solvent oil, light naphtha and heavy diesel components are obtained.

[0021] Example 2 A reaction system for producing more aerospace fuel base oil and solvent oil by utilizing DCC by-product oil After the start-up system is stable, the heavy diesel component of the separation system B2 is connected to the inlet of the microscale hydrogen mixer B12 through the heavy component outlet pipeline, and re-participates in the reaction as a raw material; the heavy component wax oil component obtained by the separation system A1 is connected to the inlet liquid source of the microscale mixed bed hydrocracking reactor 21, and participates in the reaction as a raw material.

[0022] At the same time, the separation system 1 includes a separation unit A6 and an atmospheric tower A7, wherein the gas phase of the separation unit A6 is connected to the gas source inlet of the microscale hydrogen mixer A11, and the liquid phase of the separation unit A6 is connected to the atmospheric tower A7; the heavy component outlet of the atmospheric tower A7 is connected to the liquid source inlet of the microscale mixed-phase bed hydrocracking reactor 21; The separation system B2 comprises a separation unit B8 and an atmospheric tower B9; the heavy component of the separation unit B8 is connected to the atmospheric tower B (9), and the heavy component of the atmospheric tower B9 is connected to the liquid source inlet of the microscale hydrogen mixer B12; The rest is the same as in Example 1.

[0023] Example 3 A method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil, comprising the following steps: (1) DCC oil slurry and coal powder were mixed with hydrogen in a mass ratio of 65:35 and a catalyst amount of 0.3% of the total amount of DCC oil slurry and coal powder. The temperature of the micro-scale mixed bed hydrocracking reactor 21 was controlled at 460°C, the reaction pressure was 10 MPa, and the space velocity was 0.6 h / min.-1 , hydrogen-to-oil ratio of 1000NL / kg for hydrocracking reaction; (2) The reaction product is separated into light product oil and heavy product oil through the thermal high fractionation unit 3, and the heavy product oil is separated into tailings and vacuum wax oil after passing through the thermal low fractionation unit 4 and the vacuum tower 5 in turn; the vacuum wax oil has a 95% distillation point of less than 520°C, and the tailings are discharged from the bottom of the vacuum tower 5. The vacuum wax oil is mixed with the light product oil and then enters the fixed bed hydrocracking reactor 22. The temperature of the fixed bed hydrocracking reactor 22 is controlled to be 380°C, the reaction pressure to be 10MPa, and the space velocity to be 1.2h -1 , hydrogen-to-oil ratio is 800NL / kg; hydrogenation reaction is carried out in sequence through hydrofining catalyst A, hydrocracking catalyst and hydrofining catalyst B to produce hydrocracking product oil; the hydrocracking product oil enters separation unit 6 to separate circulating hydrogen and heavy hydrocracking product oil; the circulating hydrogen enters the hydrogen pipeline; the heavy hydrocracking product oil enters atmospheric tower A7 for fractionation to obtain light component hydrocracking naphtha, medium component diesel component and heavy component wax oil component; (3) DCC diesel, DCC naphtha, and the light component hydrocracking naphtha and the medium component diesel component obtained in step (2) are mixed in a mass ratio of 5:3:2, and then enter the microscale hydrogen mixer B12 to mix with hydrogen, and then enter the microscale hydrotreating reactor 23, and the reaction is controlled at 240°C, 10 MPa, and a space velocity of 1.4 h / min. -1 , the hydrogen-oil ratio is 800NL / kg, and a hydrorefining reaction is carried out over a catalyst in which Mo and Ni are supported on neutral alumina to obtain a hydrorefining product; (4) The hydrorefined product is introduced into the microscale hydroisomerization reactor 24, and the temperature is controlled at 230°C, the reaction pressure is 10 MPa, the hydrogen-oil ratio is 800 Nm3 / t, and the space velocity is 0.8 h -1 , and successively pass through an active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve and a Ni-W catalyst supported on carriers USY molecular sieve, SAPO-11 molecular sieve and alumina, to obtain a hydrogenation isomerization product, wherein the content of the active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve accounts for 25% of the total catalyst, and the hydrogenation isomerization product successively enters separation unit B 8 and atmospheric pressure tower B 9 for fractionation to obtain aerospace fuel base oil, solvent oil, light naphtha and heavy diesel oil components; The heavy diesel component obtained by fractionation in the atmospheric tower B9 is mixed with DCC diesel, DCC naphtha, light component hydrocracking naphtha, and medium component diesel component to participate in the reaction; The heavy wax oil component obtained by fractionation in the atmospheric tower A7 is connected to the inlet of the micro-scale mixed-phase bed hydrocracking reactor 21 to participate in the reaction as a raw material; The catalyst in step (1) is a hydrotalcite Ni-Fe catalyst, a microscale amorphous silicon-aluminum and a microscale USY molecular sieve supported on a microscale porous carbon material. In terms of mass percentage, the hydrotalcite Ni-Fe catalyst supported on the microscale porous carbon material accounts for 90% by mass, the microscale USY molecular sieve accounts for 5% by mass, and the microscale amorphous silicon-aluminum accounts for 5% by mass; wherein the active metal of the hydrotalcite Ni-Fe catalyst supported on the microscale porous carbon material accounts for 5%, the mass ratio is 2:8, and the specific surface area is 550 m 2 / g; In the step (2), the hydrotreating catalyst A is a Mo-Ni catalyst supported on macroporous alumina, the hydrocracking catalyst is an active metal Ni-Mo-W supported on a carrier USY molecular sieve and macroporous alumina; the hydrotreating catalyst B is a Mo-Co catalyst supported on macroporous alumina; In the step (3), the total amount of metal in the catalyst of Mo and Ni supported on neutral alumina accounts for 30% of the mass of the catalyst; In the step (4), the active metal Pt content in the active metal Pt catalyst loaded on the carriers USY molecular sieve, alumina and ZSM-5 molecular sieve is 0.2%, the USY molecular sieve accounts for 5%, the ZSM-5 molecular sieve accounts for 15%, and the balance is alumina; the active metal Ni-W catalyst loaded on the carriers USY molecular sieve, SAPO-11 molecular sieve and alumina, in terms of mass percentage, SAPO-11 accounts for 15% of the mass ratio of the carrier, USY molecular sieve accounts for 30% of the mass ratio of the carrier, the active metal Ni-W accounts for 14% of the mass ratio of the carrier, and the balance is alumina, and the mass ratio of Ni to W is 2:1; The micro-scale mixed-phase bed hydrocracking reactor 21 has a height-to-diameter ratio of 12:1; The initial distillation point of the aerospace fuel base oil is not lower than 188°C and the final distillation point is not higher than 250°C, and the initial distillation point of the solvent oil 25 is not lower than 140°C and the dry point is not higher than 200°C.

[0024] Example 4 A method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil. The DCC slurry and coal powder are in a mass ratio of 70:30, and the amount of catalyst added is 0.6% of the total amount of DCC slurry and coal powder; In step (1), the hydrotalcite Ni-Fe catalyst, microscale amorphous silicon-aluminum and microscale USY molecular sieve loaded on the microscale porous carbon material are, by weight percentage, 70% by weight of the hydrotalcite Ni-Fe catalyst loaded on the microscale porous carbon material, 10% by weight of the microscale USY molecular sieve, and 20% by weight of the microscale amorphous silicon-aluminum; wherein the active metal content of the hydrotalcite Ni-Fe catalyst loaded on the microscale porous carbon material is 6%, the mass ratio is 9:1, and the specific surface area is 600 m 2 / g; the temperature of the hydrocracking reaction in step (1) is 465°C, the reaction pressure is 14MPa, and the space velocity is 0.5h -1 , hydrogen-to-oil ratio 1200NL / kg; The conditions of the hydrocracking reaction in step (2) are: temperature of 390°C, reaction pressure of 14 MPa, space velocity of 1 h -1 , hydrogen-oil ratio is 1000NL / kg; In the step (3), the total amount of metal in the catalyst in which Mo and Ni are supported on neutral alumina accounts for 30% of the catalyst mass; the conditions for the hydrorefining reaction in the step (3) are: reaction temperature 280°C, reaction pressure 14MPa, space velocity 1h -1 , hydrogen-oil ratio is 1000NL / kg; The conditions for the hydroisomerization reaction in step (4) are a reaction temperature of 300°C, a reaction pressure of 14 MPa, a hydrogen-to-oil ratio of 1000 Nm 3 / t, airspeed 0.5h -1 ; The active metal Pt content in the active metal Pt catalyst loaded on the carriers USY molecular sieve, alumina and ZSM-5 molecular sieve is 1%, the USY molecular sieve accounts for 10%, the ZSM-5 molecular sieve accounts for 10%, and the balance is alumina; The active metal loaded on the carriers USY molecular sieve, SAPO-11 molecular sieve and alumina is Ni-W. In terms of mass percentage, SAPO-11 accounts for 30% of the mass ratio of the carrier, USY molecular sieve accounts for 20% of the mass ratio of the carrier, the active metal is Ni-W accounts for 16% of the mass ratio of the carrier, and the balance is alumina, and the mass ratio of Ni to W is 3:1; The content of the active metal Pt catalyst loaded on the carriers USY molecular sieve, alumina and ZSM-5 molecular sieve accounts for 30% of the total catalyst; The rest is the same as in Example 3.

[0025] Example 5 A method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil. The DCC slurry, coal powder and catalyst are in a mass ratio of 75:25, and the amount of catalyst added is 0.8% of the total amount of DCC slurry and coal powder. In step (1), the hydrotalcite Ni-Fe catalyst, microscale amorphous silicon-aluminum and microscale USY molecular sieve loaded on the microscale porous carbon material are, in terms of mass percentage, 50% by mass of the hydrotalcite Ni-Fe catalyst loaded on the microscale porous carbon material, 10% by mass of the microscale USY molecular sieve, and 40% by mass of the microscale amorphous silicon-aluminum; wherein the active metal content of the hydrotalcite Ni-Fe catalyst loaded on the microscale porous carbon material is 6%, the mass ratio is 9:1, and the specific surface area is 650 m 2 / g; the temperature of the hydrocracking reaction in step (1) is 472°C, the reaction pressure is 16MPa, and the space velocity is 0.3h -1 , hydrogen-to-oil ratio 1400NL / kg; The conditions of the hydrocracking reaction in step (2) are: temperature of 390°C, reaction pressure of 14 MPa, space velocity of 1 h -1 , hydrogen-oil ratio is 1000NL / kg; In the step (3), the total amount of metal in the catalyst in which Mo and Ni are supported on neutral alumina accounts for 30% of the catalyst mass; the conditions for the hydrofining reaction in the step (3) are: reaction temperature 395°C, reaction pressure 16MPa, space velocity 0.8h -1 , hydrogen-oil ratio is 1000NL / kg; The hydroisomerization reaction conditions in step (4) are as follows: reaction temperature 330°C, reaction pressure 16MPa, hydrogen to oil ratio 1200Nm 3 / t, airspeed 0.3h -1 ; The active metal Pt content in the active metal Pt catalyst supported on the carriers USY molecular sieve, alumina and ZSM-5 molecular sieve is 2.2%, the USY molecular sieve accounts for 25%, the ZSM-5 molecular sieve accounts for 5%, and the balance is alumina; The active metal supported on the carriers USY molecular sieve, SAPO-11 molecular sieve and alumina is Ni-W. In terms of mass percentage, SAPO-11 accounts for 40% of the mass ratio of the carrier, USY molecular sieve accounts for 5% of the mass ratio of the carrier, the active metal is Ni-W, and the balance is alumina. The mass ratio of Ni to W is 4:1; The content of the active metal Pt catalyst supported on the carriers USY molecular sieve, alumina and ZSM-5 molecular sieve accounts for 40% of the total catalyst; The rest is the same as in Example 3.

[0026] Comparative Example 1 The catalyst in step (1) is a hydrotalcite Ni-Fe catalyst supported on a micro-scale porous carbon material, with an active metal content of 6% and a specific surface area of ​​650 m 2 / g. The rest is the same as in Example 5.

[0027] Comparative Example 2 The catalyst for the hydroisomerization reaction in step (4) is an active metal Pt catalyst supported on carriers of USY molecular sieve, alumina and ZSM-5 molecular sieve, wherein the active metal Pt content is 2.2%, the USY molecular sieve accounts for 25%, the ZSM-5 molecular sieve accounts for 5%, and the balance is alumina. The rest is the same as in Example 5.

[0028] Comparative Example 3 The hydroisomerization reaction catalyst in step (4) is supported on a carrier of USY molecular sieve, SAPO-11 molecular sieve and alumina, and the active metal is Ni-W. In terms of mass percentage, SAPO-11 accounts for 40% of the mass ratio of the carrier, USY molecular sieve accounts for 5% of the mass ratio of the carrier, the active metal is Ni-W accounts for 28% of the mass ratio of the carrier, and the remainder is alumina. The mass ratio of Ni to W is 4:1. Other parts are the same as those in Example 5.

[0029] Comparative Example 4 The catalyst in step (1) is micro-scale amorphous silicon aluminum and micro-scale USY molecular sieve, and in terms of mass percentage, the mass percentage of micro-scale amorphous silicon aluminum is 80%, and the mass percentage of micro-scale USY molecular sieve is 20%. The rest is the same as in Example 5.

[0030] The raw materials used in Examples 3-5 and Comparative Examples 1-4 and the yields and properties of the products are shown in Tables 1 to 5. Table 1 DCC slurry properties Table 2 DCC diesel properties Table 3 DCC naphtha properties Table 4 Properties of coal powder 6 Table 5 Results of Examples 3-5 and Comparative Examples 1-4 .

Claims

1. A method for producing more aerospace fuel base oil and solvent oil by utilizing DCC by-product oil, characterized in that: The method is to prepare aerospace fuel base oil and solvent oil by comprehensive processing of DCC slurry oil, DCC diesel and DCC naphtha; specifically comprising: (1) DCC oil slurry, coal powder, and catalyst are mixed with hydrogen to carry out hydrocracking reaction and separated to obtain light product oil and heavy product oil; (2) The heavy product oil is separated by hot low fractionation and vacuum tower to obtain tailings and vacuum wax oil, the vacuum wax oil is mixed with the light product oil of step (1) and then subjected to hydrocracking reaction to obtain hydrocracking product oil, which is separated to obtain hydrocracked naphtha, diesel component and wax oil component; (3) The diesel component, hydrocracked naphtha, DCC diesel, DCC naphtha and hydrogen are mixed and subjected to a hydrotreating reaction to obtain a hydrotreating product; (4) The hydrorefined product is then subjected to a hydroisomerization reaction to obtain a hydroisomerization product, which is then separated to obtain aerospace fuel base oil, solvent oil, light naphtha and heavy diesel components.

2. The method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 1, characterized in that: The catalyst in step (1) comprises a hydrotalcite Ni-Fe catalyst, a microscale amorphous silicon-aluminum and a microscale USY molecular sieve supported on a microscale porous carbon material; the mass proportion of the hydrotalcite Ni-Fe catalyst supported on the microscale porous carbon material is 50-90%, the Ni-Fe content accounts for 5-6% of the total amount of the hydrotalcite Ni-Fe catalyst supported on the microscale porous carbon material, the mass ratio is 9:1-8:2, the mass proportion of the microscale amorphous silicon-aluminum is 40-5%, and the mass proportion of the microscale USY molecular sieve is 10-5%; the specific surface area of ​​the hydrotalcite Ni-Fe catalyst of the microscale porous carbon material is 550-650m 2 / g.

3. The method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 1, characterized in that: The specific conditions of the hydrocracking reaction in step (1) are: reaction temperature 460-472°C, reaction pressure 10-16 MPa, space velocity 0.3-0.6 h -1 , hydrogen-to-oil ratio is 1000-1400NL / kg; the mass ratio of the DCC oil slurry to coal powder is 75:25-65:

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4. The method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 1, characterized in that: The hydrocracking reaction in step (2) is carried out in a fixed bed reactor, wherein the fixed bed reactor is sequentially filled with a hydrorefining catalyst A, a hydrocracking catalyst and a hydrorefining catalyst B; the hydrorefining catalyst A is a Mo-Ni catalyst supported on macroporous alumina, the hydrocracking catalyst is an active metal Ni-Mo-W supported on a carrier USY molecular sieve and macroporous alumina; the hydrorefining catalyst B is a Mo-Co catalyst supported on macroporous alumina; the reaction conditions of the hydrocracking reaction are: a temperature of 380°C to 395°C, a reaction pressure of 10 to 16 MPa, and a space velocity of 0.8 to 1.2 h -1 , the hydrogen-to-oil ratio is 800-1000 NL / kg; the 95% distillation point of the vacuum wax oil in the step (2) is <520°C.

5. The method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 1, characterized in that: The catalyst for the hydrofining reaction in step (3) is a special catalyst of two kinds of Mo, Ni, W and Co supported on neutral alumina, and the total amount of metal accounts for 30%-35% of the catalyst mass; the conditions of the hydrofining reaction are: temperature 240℃~330℃, reaction pressure 10~16Mpa, space velocity 0.8~1.4h -1 , the hydrogen-oil ratio is 800~1000NL / kg.

6. The method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 1, characterized in that: The catalyst for the hydroisomerization reaction in step (4) is an active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve and an active metal Ni-W catalyst supported on carriers USY molecular sieve, SAPO-11 molecular sieve and alumina, wherein the content of the active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve accounts for 25-40% of the total catalyst; the active metal Pt catalyst supported on carriers USY molecular sieve, alumina and ZSM-5 molecular sieve is calculated by mass percentage, the mass ratio of USY molecular sieve to carrier is 5% to 25%, and the mass ratio of ZSM-5 molecular sieve to carrier is 10%. The mass ratio of Pt to the carrier is 15% to 5%, the mass ratio of Pt to the carrier is 0.2-2.2%, and the balance is alumina; the catalyst loaded on the carrier USY molecular sieve, SAPO-11 molecular sieve and alumina and the active metal is Ni-W. According to the mass percentage, SAPO-11 accounts for 15-40% of the carrier, the mass ratio of USY molecular sieve to the carrier is 30-5%, the mass ratio of Ni-W to the carrier is 14-28%, and the balance is alumina, and the mass ratio of Ni to W is 4:1 to 2:1; the conditions of the hydroisomerization reaction are: temperature 230-330°C, reaction pressure 10-16MPa, hydrogen-to-oil ratio 800-1200Nm 3 / t, airspeed 0.3~0.8h- 1 The initial distillation point of the aerospace fuel base oil is not lower than 188°C and the final distillation point is not higher than 250°C; the initial distillation point of the solvent oil 25 is not lower than 140°C and the dry point is not higher than 200°C.

7. The method for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 1, characterized in that: The mass ratio of the DCC slurry oil, DCC diesel and DCC naphtha is 5:3:2; the amount of catalyst added in step (1) is 0.3% to 0.8% of the total amount of DCC slurry oil and coal powder.

8. A reaction system for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil, characterized in that: The system comprises a microscale hydrogen mixer A (11), a microscale mixed-phase bed hydrocracking reactor (21), a thermal high fraction unit (3), a thermal low fraction unit (4), a vacuum tower (5), a fixed bed hydrocracking reactor (22), a separation system A (1), a microscale hydrogen mixer B (12), a microscale hydrofining reactor (23), a microscale hydroisomerization reactor (24), and a separation system B (2) which are connected in sequence; The microscale hydrogen mixer A (11) is provided with a gas source and a liquid source, wherein the gas source is connected to a hydrogen pipeline, and the liquid source is connected to a DCC oil slurry, coal powder and a catalyst; The microscale hydrogen mixer B (12) is provided with a gas source and a liquid source, wherein the gas source is connected to a hydrogen pipeline, and the liquid source is connected to DCC diesel, DCC naphtha and light component and medium component outlet pipelines of the separation system A (1); The light component outlet of the thermal high fraction unit (3) and the liquid phase outlet pipeline of the vacuum tower (5) are connected to the inlet of the fixed bed hydrocracking reactor (22).

9. The reaction system for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 8, characterized in that: The separation system (1) comprises a separation unit A (6) and an atmospheric tower A (7); the gas phase of the separation unit A (6) is connected to the gas source inlet of the microscale hydrogen mixer A (11), and the liquid phase of the separation unit A (6) is connected to the inlet of the atmospheric tower A (7); the heavy component outlet of the atmospheric tower A (7) is connected to the liquid source inlet of the microscale mixed phase bed hydrocracking reactor (21); The separation system B (2) comprises a separation unit B (8) and an atmospheric pressure tower B (9); the heavy component of the separation unit B (8) is connected to the atmospheric pressure tower B (9), and the heavy component of the atmospheric pressure tower B (9) is connected to the liquid source inlet of the microscale hydrogen mixer B (12).

10. The reaction system for producing more aerospace fuel base oil and solvent oil by utilizing DCC byproduct oil according to claim 9, characterized in that: The height-to-diameter ratio of the scale mixed-bed hydrocracking reactor (21) is 8:1 to 2:1.

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