CN113956124B - Integrated process method for producing low-carbon olefin, aromatic hydrocarbon and high-quality carbon material - Google Patents
Integrated process method for producing low-carbon olefin, aromatic hydrocarbon and high-quality carbon material Download PDFInfo
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Abstract
The invention provides an integrated process method for producing low-carbon olefin, aromatic hydrocarbon and high-quality carbon materials. The method comprises the steps of carrying out directional modification on raw oil, wherein the modified gasoline and diesel oil products are rich in olefins, separating non-aromatic hydrocarbon (alkane and olefin) from aromatic hydrocarbon components through adsorption separation, and matching olefin and aromatic hydrocarbon yield increasing processing technology aiming at component characteristics so as to maximize production of low-carbon olefin and aromatic hydrocarbon. The modified heavy oil is rich in polycyclic aromatic hydrocarbon and can produce high-quality carbon materials. The method has the advantages of strong raw material adaptability, high chemical yield, low hydrogen consumption, mild operating conditions and the like, and can be used for industrial production.
Description
Technical Field
The invention relates to the technical field of production of low-carbon olefin, aromatic hydrocarbon and carbon materials, in particular to an integrated process method for producing low-carbon olefin, aromatic hydrocarbon and high-quality carbon materials.
Background
With the great development of new energy technology, fossil energy status is greatly challenged. The traditional refining industrial structure mainly produces high-quality gasoline and diesel oil, the difficulty of transforming to chemical industry is high, the chemical product rate can only reach about 45%, a large amount of gasoline and diesel oil still needs to be produced, the product sales faces a great dilemma, and the revolutionary industry transformation upgrading technology is imperative. The technology of directly preparing chemicals from crude oil and heavy oil is an important means for industry transformation, and has become a hot spot of current research.
The crude oil directly prepares chemical routes, overturns the traditional processing concept, has the remarkable advantages of short flow, low energy consumption, small investment, high chemical yield and the like, breaks the existing pattern of the global petrochemical industry, and has revolutionary influence on the refining industry. At present, the most representative crude oil direct production chemical technology abroad is the Exxon Mobil technology and the Sade America technology, and the domestic representative technology mainly comprises crude oil catalytic cracking technology developed by China petrochemical science institute and China petroleum university.
The Exxon Mobil company applies for series of patents at home and abroad, such as US20050261538A1, US007488459B2, CN200580016314.X, CN200780047937.2 and the like, and has the technical innovation that crude oil is directly supplied to a steam cracking furnace, and a flash tank is added between a convection section and a radiation section of the cracking furnace, so that 100-200 dollars can be earned for producing 1 ton of ethylene compared with the traditional naphtha cracking process, and the method has a larger competitive advantage. However, the raw materials of the technology are limited to paraffin-based crude oil, and a large amount of heavy oil as a byproduct still needs to be sent to a traditional refinery for treatment.
Sauter amera technology includes both hot crude oil production chemical (TC 2 CTM) technology and catalytic crude oil production chemical (CC 2 CTM) technology. Related patents of TC2CTM technical routes are US20130248416A1, US20130228495A1, US20160312132A1, CN20138006638. X, CN201780078205.3, CN201880020904.7 and the like, crude oil is directly processed by adopting integrated hydrotreating, steam cracking and coking processes to produce olefin and aromatic hydrocarbon petrochemical products and petroleum coke, the routes are aimed at petroleum-based crude oil serving as raw materials, steam cracking raw material yield is improved by a hydrogenation means, so that ethylene yield is increased, and unconverted heavy oil is produced into petroleum coke by a coking process. Related patents of CC2CTM technical routes include US2013033165, CN201380295614. X and the like, and the traditional processing technology with high cost such as grafting hydrocracking is still needed by adopting crude oil hydrocracking, steam cracking and high-severity catalytic cracking to increase the yield of low-carbon olefin and aromatic hydrocarbon.
The patent published by the institute of petrochemical industry and petrochemical industry such as CN201810523356.1 and CN110540869A, CN110540866A cuts crude oil into light and heavy fractions, and then carries out catalytic cracking to produce light olefins, and the two risers are respectively fed with different distillate oil by adopting a double riser reactor of a catalytic cracking device. The technology requires paraffin-based crude oil as a raw material, and if the raw material is intermediate or cycloalkyl, the cut heavy fraction needs to be hydrogenated first.
Two technical routes are published by the university of petroleum in China: one is that crude oil or heavy oil fraction enters two reactors for catalytic cracking (CN 109575982A) after being cut, the technical route is basically consistent with the route of Dan Ke yards, and the raw materials are mainly limited to paraffin-based crude oil; the other is a crude oil integrated raw material pretreatment, acid catalytic cracking and hydrotreating process (CN 201810341186.5, CN201810341227.0, US 16386872), the route mainly aims at poor crude oil, a large amount of heavy oil circulates in the system, the energy consumption of the system is high, and the outward-thrown heavy oil cannot be utilized.
In summary, the existing crude oil or heavy oil processing technology mainly comprises several technical routes of steam cracking, catalytic cracking and hydrocracking, has strong raw material dependence, and is mainly applicable to paraffin-based crude oil or heavy oil raw materials. In addition, the product takes olefin and aromatic hydrocarbon as main materials, the yield of chemicals is between 40 and 70 percent, and a further improvement space is provided, so that the types of the chemicals are required to be further expanded.
Disclosure of Invention
The invention mainly solves the problems of poor raw material adaptability, low chemical yield and relatively single chemical variety existing in the existing crude oil or heavy oil chemical preparation technology, integrates process units such as directional modification of the raw oil, adsorption separation of gasoline and diesel hydrocarbons, aromatic hydrocarbon yield increase, olefin yield increase, supercritical water modification of heavy oil, carbon material yield increase and the like, and maximally converts the oil into low-carbon olefin, aromatic hydrocarbon and high-quality carbon material.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
the invention provides an integrated process method for producing low-carbon olefin, aromatic hydrocarbon and high-quality carbon materials, which comprises the following steps:
1) The raw oil is subjected to directional decarburization, demetallization and cracking modification reaction of heavy components under the conditions of a reaction temperature of 350-650 ℃ and a pressure of 0.1-1.0 MPa and a steam/oil mass ratio of 0.1:1-10:1 under the action of a directional modification catalyst to obtain hydrogen, rich-alkene gas, modified rich-alkene distillate and coke;
2) The modified fulvene distillate oil obtained in the step 1) enters a modified distillate oil cutting unit, and is subjected to rectification separation to obtain gasoline and diesel oil fractions rich in olefins (less than or equal to 350 ℃) and heavy distillate oil rich in polycyclic aromatic hydrocarbons (more than 350 ℃);
3) The gasoline and diesel oil fraction obtained in the step 2) enters a gasoline and diesel oil selective hydrofining unit, and under the action of a selective hydrofining catalyst, the reaction temperature is 80-260 ℃ and the pressure is high2.5-4.5 MPa, and mass airspeed of 1.0-2.0 h -1 Removing colloid, diene and basic nitrogen impurities under the condition that the volume ratio of hydrogen to oil is 300:1-600:1 to obtain fuel gas and refined gasoline and diesel oil rich in olefin;
4) The heavy distillate oil obtained in the step 2) enters a supercritical water modification unit, is treated for 0.5 to 2 hours under the conditions of the reaction pressure of 24 to 35MPa, the temperature of 380 to 480 ℃ and the water-oil mass ratio of 0.5:1 to 5:1, and is subjected to deep removal of solid impurities, asphaltenes, colloid, sulfides and other impurities to obtain modified heavy oil distillate oil;
5) The modified heavy oil fraction obtained in the step 4) enters a carbon material yield increasing unit to obtain high-quality needle coke, carbon fiber, graphite and other carbon materials;
6) The refined gasoline and diesel oil fraction obtained in the step 3) enters a gasoline and diesel oil adsorption separation unit, and under the action of an adsorbent, the adsorption temperature is 40-150 ℃, the pressure is 0.2-1.0 MPa, and the mass airspeed is 0.5-1.5 h -1 Under the condition of (1) separating the gasoline and diesel aromatic hydrocarbon component from the non-aromatic hydrocarbon component to obtain an adsorbed aromatic hydrocarbon component and an adsorbed fulvene non-aromatic hydrocarbon component;
7) Introducing the non-aromatic components of the adsorbed fulvene obtained in the step 6) into an olefin yield increasing unit, and carrying out catalytic cracking reaction under the conditions of 480-600 ℃ of reaction temperature, 0.1-0.3 MPa of pressure, 8:1-15:1 of catalyst-oil ratio and 0.2:1-10:1 of steam/oil mass ratio under the action of an olefin yield increasing catalyst to obtain the fulvene gas, cracked aromatic gasoline-enriched diesel oil and coke;
8) The adsorbed aromatic hydrocarbon component obtained in the step 6) and the cracked aromatic hydrocarbon-rich diesel oil obtained in the step 7) enter an aromatic hydrocarbon yield increasing unit together, and under the action of an aromatic hydrocarbon yield increasing catalyst, the reaction temperature is 360-460 ℃, the pressure is 3.5-8.0 MPa, and the volume space velocity is 1.0-2.0 h -1 Under the condition that the hydrogen-oil volume ratio is 600:1-1200:1, the selective cracking reaction is carried out to obtain fuel gas, saturated liquefied gas, light aromatic hydrocarbon (benzene, toluene and dimethylbenzene) and C 9 /C 10 Aromatic hydrocarbons;
the raw material directional modification unit in the step 1) is characterized in that heavy oil macromolecules in raw material oil undergo directional modification reaction, the conversion rate of the heavy oil is more than or equal to 70wt%, the olefin content in a converted gasoline and diesel product is 40-60 wt%, the aromatic hydrocarbon content is 20-40 wt%, and the polycyclic aromatic hydrocarbon content in the heavy oil is 60-85 wt%.
The raw oil in the step 1) is at least one of paraffin-based crude oil, intermediate base crude oil, naphthenic base crude oil, wax oil, atmospheric residuum, vacuum residuum, oil sand asphalt and deasphalted oil; the reactor is one of a moving bed, a dense-phase fluidized bed and a riser reactor; the adopted directional modification catalyst is a supported catalyst containing a heavy metal capturing agent and an alkaline auxiliary agent, wherein the carrier comprises at least one of white carbon black, mesoporous high silicon molecular sieve, attapulgite clay, silica gel, alumina, kaolin, montmorillonite clay and kieselguhr, the heavy metal capturing agent active component comprises one or more of Bi, ce, sn, cr, la, and the alkaline auxiliary agent active component comprises at least one of Li, na, ca, mg, K, ba.
The process adopted by the gasoline and diesel oil adsorption separation unit in the step 6) is a fixed bed or a simulated moving bed, and the adsorbent is at least one of mesoporous high-silicon molecular sieve, activated carbon, clay, white carbon black, activated carbon and silica gel.
The olefin yield increasing unit in the step 7) adopts one of a riser, a reducing riser, a downer and a downer reducing reactor, and the olefin yield increasing catalyst is at least one of full-crystal high-silicon beta, mercerizing, ZSM-5, APO-5, TS-1, MCM-22 and Y, IM-5 molecular sieves.
The aromatic hydrocarbon yield increasing catalyst in the step 8) is a metal modified composite molecular sieve catalyst, the molecular sieve is at least two of Y, mercerization, beta, ZSM-5, MCM-22 and MCM-48, and the metal modifying component is at least one of Ni, mo, zn, pt, pd, re, sn, W, co.
Compared with the prior art, the integrated process method for producing the low-carbon olefin, the aromatic hydrocarbon and the high-quality carbon material has the following beneficial effects:
1) The raw material adaptability is strong, and the processing process is simple: the crude oil directional modification unit is adopted to modify crude oil or heavy oil into high-quality chemical production raw materials (rich in olefin and aromatic hydrocarbon), so that the dependence of high chemical yield on paraffin-based raw materials is broken.
2) The chemical species are various, and the chemical yield is high: the directional modification unit enriches the polycyclic aromatic hydrocarbon into modified heavy oil, and is a high-quality carbon material production raw material. The modified gasoline and diesel oil realizes the separation of non-aromatic hydrocarbon (alkane and olefin) and aromatic hydrocarbon components through an adsorption separation unit, and is converted into low-carbon olefin and aromatic hydrocarbon by a subsequent processing unit matched with the component characteristics, and the total chemical yield reaches 70-80%.
Drawings
FIG. 1 is a schematic flow chart of an integrated process for producing light olefins, aromatic hydrocarbons and high quality carbon materials.
Detailed Description
The implementation and effects of the method according to the present invention will be further described with reference to specific examples, but the present invention is not limited thereto.
Example 1
Paraffin-based crude oil from a refinery is used as a raw material, and the properties of the raw material are shown in Table 1.
A raw material directional modification unit: the reactor adopts a riser reactor, the directional modification catalyst adopts Bi-Ca-K/coarse pore silica gel (based on the catalyst, the Bi content is 2.5wt%, the Ca content is 5.0wt%, the K content is 8.0wt%, and the balance is coarse pore silica gel), and the reaction conditions are as follows: the temperature is 580 ℃, the pressure is 0.1MPa, and the steam/oil mass ratio is 1.0:1.
A gasoline and diesel selective hydrofining unit: the catalyst adopts Ni-Mo/macroporous alumina (based on the catalyst, ni content is 8.5wt percent, mo content is 4.0wt percent, and the balance is macroporous alumina), and the reaction conditions are as follows: the temperature is 165 ℃, the pressure is 3.0MPa, and the mass airspeed is 1.0h -1 Hydrogen oil volume ratio 400:1.
Supercritical water upgrading unit: the reaction conditions are as follows: the reaction pressure is 25MPa, the temperature is 390 ℃, and the water-oil mass ratio is 0.8:1 for 0.5h.
A carbon material yield increasing unit: the reaction temperature of the coking device is 510 ℃ and the reaction pressure is 0.15MPa.
Gasoline and diesel adsorption separation unit: adopting a simulated moving bed process, wherein the adsorbent is white carbon black, and separatingThe conditions are as follows: adsorption temperature 90 ℃, pressure 0.5MPa and mass space velocity 0.5h -1 。
An olefin stimulation unit: the catalyst is a high-silicon ZSM-5+beta+MCM-22 molecular sieve catalyst, and the reaction conditions are as follows: the reaction temperature is 580 ℃, the pressure is 0.2MPa, the catalyst-oil ratio is 10:1, and the steam-oil mass ratio is 1:1.
Aromatic hydrocarbon yield increasing unit: the catalyst is a bimetal modified composite molecular sieve catalyst (based on the catalyst, the Ni content is 12wt%, the Mo content is 4wt%, the Y-type molecular sieve content is 40wt%, the beta molecular sieve content is 20wt%, the ZSM-5 molecular sieve is 10wt%, and the balance is alumina), and the reaction conditions are as follows: the temperature is 400 ℃, the pressure is 5.0MPa, and the volume space velocity is 1.0h -1 The volume ratio of hydrogen to oil is 900:1.
The material balance by the above integration process is shown in table 2.
Example 2
The intermediate crude oil of a refinery is used as a raw material, and the properties of the raw material are shown in table 1.
A raw material directional modification unit: the reactor adopts a dense-phase fluidized bed, the directional modification catalyst adopts Bi-Ca-K/white carbon black (based on the catalyst, the Bi content is 4.0wt percent, the Ca content is 10.0wt percent, the K content is 5.0wt percent, and the balance is white carbon black), and the reaction conditions are as follows: the temperature is 480 ℃, the pressure is 0.2MPa, and the steam/oil mass ratio is 2.0:1.
A gasoline and diesel selective hydrofining unit: the catalyst adopts Ni-Co/amorphous silicon aluminum and aluminum oxide (based on the catalyst, the Ni content is 10wt percent, the Co content is 4.0wt percent, and the balance is amorphous silicon aluminum and aluminum oxide), and the reaction conditions are as follows: 230 ℃ and 4.0MPa, and 1.5h of mass airspeed -1 The volume ratio of hydrogen to oil is 500:1.
Supercritical water upgrading unit: the reaction conditions are as follows: the reaction pressure is 28MPa, the temperature is 420 ℃, and the water-oil mass ratio is 0.5:1 for 0.8h.
A carbon material yield increasing unit: the reaction temperature of the coking device is 510 ℃ and the reaction pressure is 0.15MPa.
Gasoline and diesel adsorption separation unit: adopting a simulated moving bed process, wherein the adsorbent is activated carbon, and the separation conditions are as follows: adsorption temperature 100 ℃, pressure 0.8MPa and empty massSpeed 1.5h -1 。
An olefin stimulation unit: the catalyst is a high-silicon ZSM-5+Y molecular sieve catalyst by adopting a downstream bed reducing reactor, and the reaction conditions are as follows: the reaction temperature is 560 ℃, the pressure is 0.2MPa, the catalyst-oil ratio is 12:1, and the steam-oil mass ratio is 0.6:1.
Aromatic hydrocarbon yield increasing unit: the catalyst is a bimetal modified composite molecular sieve catalyst (based on the catalyst, the Ni content is 12wt%, the Pt content is 0.3wt%, the beta molecular sieve content is 40wt%, the ZSM-5 molecular sieve is 20wt%, and the balance is alumina), and the reaction conditions are as follows: the temperature is 420 ℃, the pressure is 5.0MPa, and the volume space velocity is 1.5h -1 The volume ratio of hydrogen to oil is 1000:1.
The material balance by the above integration process is shown in table 2.
Example 3
Cycloalkyl crude oil from a refinery is used as a raw material, and the properties of the raw material are shown in Table 1.
A raw material directional modification unit: the reactor adopts a moving bed, the directional modification catalyst adopts a Ce-Ca-Mg/high silicon MCM-48 molecular sieve (the catalyst is taken as a reference, the Ce content is 3.0wt percent, the Ca content is 15.0wt percent, the Mg content is 3.0wt percent, and the balance is molecular sieve and binder), and the reaction conditions are as follows: the temperature is 500 ℃, the pressure is 0.5MPa, and the steam/oil mass ratio is 2.0:1.
A gasoline and diesel selective hydrofining unit: the catalyst adopts Ni-Mo-Co/alumina (based on the catalyst, the Ni content is 10wt%, the Mo content is 5.0wt%, the Co content is 4.0wt%, and the balance is alumina), and the reaction conditions are as follows: the temperature is 210 ℃, the pressure is 4.5MPa, and the mass airspeed is 1.0h -1 The volume ratio of hydrogen to oil is 600:1.
Supercritical water upgrading unit: the reaction conditions are as follows: the reaction pressure is 30MPa, the temperature is 420 ℃, and the water-oil mass ratio is 1.5:1 for 1.5h.
A carbon material yield increasing unit: the reaction temperature of the coking device is 510 ℃ and the reaction pressure is 0.15MPa.
Gasoline and diesel adsorption separation unit: the fixed bed process is adopted, the adsorbent is mesoporous high silicon SBA-15 molecular sieve, and the separation conditions are as follows: adsorption temperature 120 ℃, pressure 0.5MPa and mass space velocity 0.5h -1 。
An olefin stimulation unit: the catalyst is a high-silicon ZSM-5+Y molecular sieve catalyst by adopting a downstream bed reducing reactor, and the reaction conditions are as follows: the reaction temperature is 540 ℃, the pressure is 0.3MPa, the catalyst-oil ratio is 15:1, and the steam-oil mass ratio is 0.8:1.
Aromatic hydrocarbon yield increasing unit: the catalyst is a bimetal modified composite molecular sieve catalyst (based on the catalyst, the Ni content is 12wt%, the Pd content is 0.3wt%, the beta molecular sieve content is 50wt%, the ZSM-5 molecular sieve is 20wt%, and the balance is alumina), and the reaction conditions are as follows: temperature 450 ℃, pressure 7.0MPa and volume space velocity 1.5h -1 The volume ratio of hydrogen to oil is 1000:1.
The material balance by the above integration process is shown in table 2.
Example 4
The vacuum residuum of a refinery is used as a raw material, and the raw material properties are shown in table 1.
A raw material directional modification unit: the reactor adopts a descending bed, the directional modification catalyst adopts a Ce-Ca-Na/high-silicon MCM-48 molecular sieve (the catalyst is taken as a reference, the Ce content is 3.0wt percent, the Ca content is 10.0wt percent, the Na content is 3.0wt percent, and the balance is molecular sieve and binder), and the reaction conditions are as follows: the temperature is 480 ℃, the pressure is 0.5MPa, and the steam/oil mass ratio is 4.0:1.
A gasoline and diesel selective hydrofining unit: the catalyst adopts Ni-Co/amorphous silicon aluminum and aluminum oxide (based on the catalyst, the Ni content is 14wt percent, the Co content is 6.0wt percent, and the balance is amorphous silicon aluminum and aluminum oxide), and the reaction conditions are as follows: 230 ℃ and 4.0MPa, and 1.5h of mass airspeed -1 The volume ratio of hydrogen to oil is 600:1.
Supercritical water upgrading unit: the reaction conditions are as follows: the reaction pressure is 27MPa, the temperature is 400 ℃, and the water-oil mass ratio is 2:1 for 1.5h.
A carbon material yield increasing unit: the reaction temperature of the coking device is 510 ℃ and the reaction pressure is 0.15MPa.
Gasoline and diesel adsorption separation unit: the fixed bed process is adopted, the adsorbent is mesoporous high silicon SBA-15 molecular sieve, and the separation conditions are as follows: adsorption temperature 150 ℃, pressure 0.5MPa and mass space velocity 0.5h -1 。
An olefin stimulation unit: the catalyst is a high-silicon ZSM-5+beta molecular sieve catalyst, and the reaction conditions are as follows: the reaction temperature is 580 ℃, the pressure is 0.3MPa, the catalyst-oil ratio is 15:1, and the steam-oil mass ratio is 0.8:1.
Aromatic hydrocarbon yield increasing unit: the catalyst is a bimetal modified composite molecular sieve catalyst (based on the catalyst, the Ni content is 10wt%, the Pd content is 0.2wt%, the beta molecular sieve content is 40wt%, the Y molecular sieve is 20wt%, and the balance is alumina), and the reaction conditions are as follows: temperature 430 ℃, pressure 8.0MPa and volume space velocity 1.0h -1 The volume ratio of hydrogen to oil is 1000:1.
The material balance by the above integration process is shown in table 2.
Table 1 examples 1 to 4 raw material properties
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 |
| Density, g/cm 3 | 0.862 | 0.90 | 0.935 | 0.949 |
| API° | 32.8 | 24.6 | 15.2 | 14.3 |
| Wax content, wt% | 28.6 | 10.8 | 5.8 | 4.6 |
| Condensation point, DEG C | 30 | -2 | -12 | -15 |
| Carbon residue, wt% | 3.28 | 6.0 | 11.4 | 14.0 |
| Colloid + asphaltene, wt% | 7.45 | 11.4 | 22.6 | 25.2 |
| Sulfur content, ug/g | 1800 | 2600 | 28000 | 30000 |
| Nitrogen content, ug/g | 2100 | 3200 | 5100 | 4800 |
| Metal content, ug/g | 16 | 35 | 140 | 220 |
Table 2 examples 1 to 4 material balance
As shown in Table 2, the total yield of the chemicals (olefin + aromatic + carbon material) can reach 70-77% by the method of the invention, and the total hydrogen consumption is only 1.0-1.5 wt%.
Claims (6)
1. An integrated process method for producing low-carbon olefin, aromatic hydrocarbon and high-quality carbon materials is characterized in that after raw oil is directionally modified, a processing unit is selected according to product characteristics, chemical products are produced maximally, and the chemical product yield reaches 70-80%, and the method comprises the following steps:
1) The method comprises the steps of (1) carrying out directional decarburization, demetallization and cracking modification reaction of heavy components on raw oil under the conditions of a reaction temperature of 350-650 ℃ and a pressure of 0.1-1.0 MPa and a steam/oil mass ratio of 0.1:1-10:1 under the action of a directional modification catalyst to obtain hydrogen, a rich-alkene gas, modified rich-alkene distillate and coke;
2) The modified fulvene distillate oil obtained in the step 1) enters a modified distillate oil cutting unit, and is subjected to rectification separation to obtain an olefin-rich gasoline and diesel oil fraction which is less than or equal to 350 ℃ and a heavy distillate oil which is more than 350 ℃ and is rich in polycyclic aromatic hydrocarbon;
3) Step 2)The obtained gasoline and diesel oil fraction enters a gasoline and diesel oil selective hydrofining unit, and under the action of a selective hydrofining catalyst, the reaction temperature is 80-260 ℃, the pressure is 2.5-4.5 MPa, and the mass space velocity is 1.0-2.0 h -1 Removing colloid, diene and basic nitrogen impurities under the condition that the volume ratio of hydrogen to oil is 300:1-600:1 to obtain fuel gas and refined gasoline and diesel oil rich in olefin;
4) The heavy distillate oil obtained in the step 2) enters a supercritical water modification unit, is treated for 0.5-2 hours under the conditions of the reaction pressure of 24-35 MPa, the temperature of 380-480 ℃ and the water-oil mass ratio of 0.5:1-5:1, and is subjected to deep removal of solid impurities, asphaltene, colloid and sulfide impurities to obtain modified heavy oil distillate oil;
5) The modified heavy oil distillate oil obtained in the step 4) enters a carbon material yield increasing unit to obtain a high-quality carbon material;
6) The refined gasoline and diesel oil fraction obtained in the step 3) enters a gasoline and diesel oil adsorption separation unit, and under the action of an adsorbent, the adsorption temperature is 40-150 ℃, the pressure is 0.2-1.0 MPa, and the mass space velocity is 0.5-1.5 h -1 Under the condition of (1) separating the gasoline and diesel aromatic hydrocarbon component from the non-aromatic hydrocarbon component to obtain an adsorbed aromatic hydrocarbon component and an adsorbed fulvene non-aromatic hydrocarbon component;
7) Introducing the non-aromatic hydrocarbon component of the adsorbed fulvene obtained in the step 6) into an olefin yield increasing unit, and carrying out catalytic cracking reaction under the conditions of 480-600 ℃ of reaction temperature, 0.1-0.3 MPa of pressure, 8:1-15:1 of catalyst-oil ratio and 0.2:1-10:1 of steam/oil mass ratio under the action of an olefin yield increasing catalyst to obtain fulvene gas, cracked aromatic gasoline-enriched diesel oil and coke;
8) The adsorbed aromatic hydrocarbon component obtained in the step 6) and the cracked aromatic hydrocarbon-rich diesel oil obtained in the step 7) enter an aromatic hydrocarbon yield increasing unit together, and under the action of an aromatic hydrocarbon yield increasing catalyst, the reaction temperature is 360-460 ℃, the pressure is 3.5-8.0 MPa, and the volume space velocity is 1.0-2.0 h -1 Under the condition that the hydrogen-oil volume ratio is 600:1-1200:1, carrying out selective cracking reaction to obtain fuel gas, saturated liquefied gas, light aromatic hydrocarbon and C 9 /C 10 Aromatic hydrocarbons;
the raw material directional modification unit in the step 1) carries out directional modification reaction on heavy oil macromolecules in raw material oil, the conversion rate of the heavy oil is more than or equal to 70wt%, the olefin content in a converted gasoline and diesel product is 40-60 wt%, the aromatic hydrocarbon content is 20-40 wt%, and the polycyclic aromatic hydrocarbon content in the heavy oil is 60-85 wt%;
the directional modification catalyst in the step 1) is a supported catalyst containing a heavy metal capturing agent and an alkaline auxiliary agent, wherein the carrier is at least one of white carbon black, mesoporous high silicon molecular sieve, attapulgite, silica gel, kaolin, montmorillonite, clay and diatomite, the active component of the heavy metal capturing agent is one or more of Bi, ce, sn, cr, la, and the active component of the alkaline auxiliary agent is at least one of Li, na, ca, mg, K, ba.
2. The integrated process of claim 1, wherein the feedstock in step 1) is at least one of paraffinic crude oil, intermediate crude oil, naphthenic crude oil, wax oil, atmospheric residue, vacuum residue, oil sand bitumen, and deasphalted oil.
3. The integrated process of claim 1 wherein the feedstock orientation upgrading unit of step 1) is in the form of one of a moving bed, a dense fluid bed, and a riser reactor.
4. The integrated process according to claim 1, wherein the gas-oil adsorption separation unit in step 6) adopts a fixed bed or a simulated moving bed, and the adsorbent is at least one of mesoporous high silicon molecular sieve, activated carbon, clay, white carbon black and silica gel.
5. The integrated process of claim 1, wherein the olefin stimulation unit of step 7) is in the form of one of a riser, a variable diameter riser, a downer, and a downer variable diameter reactor, and the olefin stimulation catalyst is at least one of a fully crystalline high silica beta, mercerized, ZSM-5, APO-5, TS-1, MCM-22, Y, IM-5 molecular sieve.
6. The integrated process of claim 1 wherein the aromatic hydrocarbon stimulation catalyst of step 8) is a metal modified composite molecular sieve catalyst, the molecular sieve is at least two of Y, mercerized, β, ZSM-5, MCM-22, MCM-48, and the metal modifying component is at least one of Ni, mo, zn, pt, pd, re, sn, W, co.
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