阅读说明：本技术 一种由原油生产烯烃、芳烃及中间相沥青基碳纤维的组合工艺方法 (Combined process method for producing olefin, aromatic hydrocarbon and mesophase pitch-based carbon fiber from crude oil ) 是由 郭春垒 范景新 李犇 李健 臧甲忠 李福双 吴青 赵云 董子超 郭健 张雪梅 于 2021-09-20 设计创作，主要内容包括：本发明提供了一种由原油生产低碳烯烃、芳烃及中间相沥青基碳纤维的组合工艺方法。该组合工艺方法先将原油进行切割,轻馏分经过加氢精制后通过吸附分离进行非芳烃(烷烃+烯烃)与芳烃组分的分离,针对组分特性配套烯烃、芳烃增产加工工艺,以最大化生产低碳烯烃和芳烃。重馏分经定向改质单元,转化为富含烯烃和芳烃的改质产物,改质汽柴油经加氢精制后返回吸附分离单元,改质重产物中富含多环芳烃,经超临界水改质、碳纤维加工工艺后生产优质中间相沥青基碳纤维。本发明组合工艺方法具有原料适应性强、化学品收率高、氢耗低、操作条件缓和等优势,可用于工业化生产。(The invention provides a combined process method for producing low-carbon olefin, aromatic hydrocarbon and mesophase pitch-based carbon fiber from crude oil. The combined process method comprises the steps of cutting crude oil, subjecting light fractions to hydrofining, separating non-aromatic hydrocarbons (alkane and olefin) from aromatic hydrocarbons through adsorption separation, and matching olefin and aromatic hydrocarbon yield increasing processing technology according to component characteristics so as to produce low-carbon olefin and aromatic hydrocarbon to the maximum extent. The heavy fraction is converted into a modified product rich in olefin and aromatic hydrocarbon through a directional modification unit, the modified gasoline and diesel oil is returned to an adsorption separation unit after being hydrofined, the modified heavy product is rich in polycyclic aromatic hydrocarbon, and high-quality mesophase pitch-based carbon fiber is produced after supercritical water modification and carbon fiber processing technologies. The combined process method has the advantages of strong raw material adaptability, high chemical yield, low hydrogen consumption, mild operation conditions and the like, and can be used for industrial production.)

1. A combined process for producing olefins, aromatics and mesophase pitch-based carbon fibers from crude oil, comprising the steps of:

1) crude oil enters a crude oil fraction cutting unit firstly, and is rectified and separated to obtain gasoline and diesel oil fractions with the temperature of less than or equal to 375 ℃, heavy oil fractions with the temperature of more than 375 ℃ and externally thrown heavy oil rich in polycyclic aromatic hydrocarbon;

2) the heavy oil fraction obtained in the step 1) enters a heavy oil directional modification unit, and under the action of a directional modification catalyst, under the conditions of reaction temperature of 350-650 ℃, pressure of 0.1-1.0 MPa and steam/oil mass ratio of 0.1: 1-10: 1, directional decarburization, demetalization and cracking modification reaction of heavy components are carried out, so as to obtain hydrogen, a fulvene gas, modified fulvene distillate oil and coke;

3) returning the modified fulvene distillate oil obtained in the step 2) to the crude oil fraction cutting unit in the step 1) for fraction cutting;

4) the externally thrown heavy oil obtained in the step 1) enters a supercritical water treatment unit, is treated for 0.5-2 hours under the conditions that the reaction pressure is 24-35 MPa, the temperature is 380-480 ℃ and the water-oil mass ratio is 0.5: 1-3: 1, and is subjected to deep removal of asphaltenes, colloids and sulfides to obtain a mesophase asphalt raw material;

5) feeding the mesophase pitch raw material obtained in the step 4) into a carbon fiber processing unit, and carrying out processing technologies including melt spinning, oxidation, carbonization and graphitization to obtain mesophase pitch-based carbon fibers;

6) the gasoline and diesel oil fraction obtained in the step 1) enters a gasoline and diesel oil selective hydrofining unit, and is subjected to reaction at the temperature of 120-260 ℃, the pressure of 3.0-6.0 MPa and the mass space velocity of 1.0-2.0 h under the action of a selective hydrofining catalyst^-1Removing colloid, diene and alkaline nitrogen impurities under the condition that the volume ratio of hydrogen to oil is 400: 1-800: 1 to obtain fuel gas and refined gasoline and diesel oil rich in olefin;

7) the refined gasoline and diesel oil obtained in the step 6) enters a gasoline and diesel oil adsorption separation unit, and is subjected to adsorption temperature of 40-150 ℃, pressure of 0.2-1.0 MPa and mass space velocity of 0.5-1.5 h under the action of an adsorbent^-1Under the condition of (1), separating aromatic hydrocarbon components and non-aromatic hydrocarbon components of the gasoline and diesel oil to obtain aromatic hydrocarbon adsorption components and alkene-rich non-aromatic hydrocarbon adsorption components;

8) the adsorbed alkene-rich non-aromatic components obtained in the step 7) enter an alkene yield increasing unit, and under the action of an alkene yield increasing catalyst, catalytic cracking reaction is carried out under the conditions of reaction temperature of 480-600 ℃, pressure of 0.1-0.3 MPa, agent-oil ratio of 8: 1-15: 1 and steam-oil mass ratio of 0.2: 1-10: 1, so as to obtain alkene-rich gas, cracked aromatic-rich gasoline and coke;

9) the aromatic hydrocarbon adsorbing component obtained in the step 6) and the cracked aromatic-rich gasoline and diesel oil obtained in the step 8) 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 4.0-8.0 MPa, and the volume airspeed is 1.0-2.0 h^-1And performing selective cracking reaction under the condition that the volume ratio of hydrogen to oil is 800: 1-1200: 1 to obtain fuel gas, saturated liquefied gas, light aromatic hydrocarbon and C₉/C₁₀Aromatic hydrocarbons;

in the heavy oil directional modification unit in the step 2), heavy oil macromolecules undergo a directional modification reaction, the conversion rate of heavy oil is more than or equal to 70 wt%, the olefin content in the converted gasoline and diesel oil product is 40-60 wt%, the aromatic hydrocarbon content is 20-40 wt%, and the polycyclic aromatic hydrocarbon content in the converted heavy oil is 60-85 wt%.

2. The method of claim 1, wherein the crude oil in step 1) is at least one of a paraffinic, a mesogenic, and a naphthenic base crude oil.

3. The method of claim 1, wherein the heavy oil directional upgrading unit in step 2) is in the form of one of a moving bed, a dense fluidized bed, and a riser reactor.

4. The method of claim 1, wherein the directional modification catalyst in step 2) is a supported catalyst containing a heavy metal scavenger and a basic auxiliary agent, wherein the carrier is at least one of white carbon black, a mesoporous high silica molecular sieve, attapulgite, silica gel, alumina, kaolin, montmorillonite, clay and diatomite, the active component of the heavy metal scavenger is one or more of Bi, Ce, Sn, Cr and La, and the active component of the basic auxiliary agent is at least one of Li, Na, Ca, Mg, K and Ba.

5. The method according to claim 1, wherein the selective hydrorefining catalyst in step 6) is a metal-supported catalyst, wherein the carrier is one or more of macroporous alumina, silica and amorphous silica-alumina, and the supported metal component is one or more of Ni, Mo, Co and W.

6. The method as claimed in claim 1, wherein the gasoline and diesel oil adsorption separation unit in step 7) 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, activated carbon and silica gel.

7. The method according to claim 1, wherein the olefin production increasing unit in the step 8) adopts a reactor form of one of a riser, a reducing riser, a downer and a downer reducing reactor, and the olefin production increasing catalyst is at least one of fully crystalline high silicon beta, mercerized, ZSM-5, APO-5, TS-1, MCM-22 and Y, IM-5 molecular sieves.

8. The method according to claim 1, wherein the aromatic hydrocarbon yield increasing catalyst in the step 9) is a metal modified composite molecular sieve catalyst, the molecular sieve is at least two of Y, mercerized zeolite, beta, ZSM-5, MCM-22 and MCM-48, and the metal modified component is at least one of Ni, Mo, Zn, Pt, Pd, Re, Sn, W and Co.

Technical Field

The invention relates to the technical field of production of low-carbon olefin, aromatic hydrocarbon and mesophase pitch-based carbon fibers, in particular to a combined process method for producing olefin, aromatic hydrocarbon and mesophase pitch-based carbon fibers from crude oil.

Background

With the vigorous development of new energy technologies, the fossil energy status is greatly challenged. The traditional refining industrial structure mainly produces high-quality gasoline and diesel oil, the transformation difficulty to the chemical industry is large, the chemical industry product rate can only reach about 45%, a large amount of gasoline and diesel oil still need to be produced, the product sale faces great difficulty, and the seeking of a revolutionary industry transformation upgrading technology is imperative. The technology of directly preparing chemicals from crude oil is an important means for industrial transformation, and has become a hot spot of current research.

The method for directly preparing chemicals from crude oil overturns the traditional processing concept, has the remarkable advantages of short flow, low energy consumption, low investment, high chemical yield and the like, and breaks through the existing pattern of the global petrochemical industry, thereby having revolutionary influence on the refining industry. At present, the most representative foreign technologies for directly producing chemicals from crude oil are the exxonmobil technology and the saudi amat technology, and the domestic representative technologies mainly include the crude oil catalytic cracking technology developed by the institute of petrochemical and chemical engineering science and the Chinese petroleum university.

The exxon meifu company applies serial patents at home and abroad, such as US20050261538A1, US007488459B2, CN200580016314.X, CN200780047937.2 and the like, at first, the technical innovation point is 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, compared with the traditional naphtha cracking process, 100-200 dollars can be earned for each 1 ton of ethylene produced, and the process has great competitive advantage. However, the raw materials of the technology are limited to paraffin-based crude oil, and a large amount of heavy oil by-produced still needs to be sent to a traditional refinery for treatment.

Saudi America technology includes both thermal crude oil chemical (TC2CTM) technology and catalytic crude oil chemical (CC2CTM) technology. Related patents of a TC2CTM technical route include US20130248416A1, US20130228495A1, US20160312132A1, CN201380006638.X, CN201780078205.3 and CN201880020904.7, crude oil is directly processed by adopting an integrated hydrotreating, steam cracking and coking process to produce olefin, aromatic hydrocarbon petrochemical products and petroleum coke, the route aims at that the raw material is paraffin-based crude oil, the yield of the steam cracking raw material is improved by a hydrogenation method, so that the yield of ethylene is increased, and the petroleum coke is produced from heavy oil which is not converted by a coking process. Related patents of the CC2CTM technical route include US2013033165, CN201380015214.X and the like, crude oil hydrocracking, steam cracking and high-severity catalytic cracking are adopted to increase the yield of low-carbon olefin and aromatic hydrocarbon, and the traditional processing technology with high cost such as grafting hydrocracking and the like is still needed.

Patents published by the institute of petrochemical and chemical science, such as CN201810523356.1, CN110540869A, CN110540866A, etc., firstly cut crude oil into light and heavy fractions, and then perform catalytic cracking to produce low-carbon olefins, which is implemented by using a double-riser reactor of a set of catalytic cracking apparatus, and the two risers are respectively fed with different distillate oil. The technology requires the raw material to be paraffin base crude oil, and if the raw material is intermediate base or naphthenic base, the cut heavy fraction needs to be hydrogenated firstly.

The university of petroleum in china promulgated two technological routes: one is that crude oil or heavy oil fraction enters two reactors to be catalytically cracked after being cut (CN109575982A), the technical route is basically consistent with the stone hospital route, and the raw material is mainly limited to paraffin base crude oil; the other is a crude oil integrated pretreatment, acid catalytic cracking and hydrotreatment process (CN201810341186.5, CN201810341227.0 and US16386872), the route mainly aims at poor crude oil, a large amount of heavy oil circulates in a system, the energy consumption of the system is high, and the externally thrown heavy oil cannot be utilized.

In summary, the existing crude oil processing technologies mainly include several technical routes of steam cracking, catalytic cracking and hydrocracking, and are high in raw material dependence and mainly suitable for paraffin-based crude oil or heavy oil raw materials. In addition, the product mainly comprises olefin and aromatic hydrocarbon, the yield of chemicals is 40-70%, the yield is further improved, and the variety of the chemicals needs to be further expanded.

Disclosure of Invention

The invention mainly solves the problems of poor raw material adaptability, low chemical yield and the like of the existing technology for preparing chemicals from crude oil, integrates the processes of heavy oil directional modification, gasoline and diesel oil adsorption separation, aromatic hydrocarbon yield increase, olefin yield increase, carbon fiber yield increase and the like, provides a combined process method for producing olefin, aromatic hydrocarbon and mesophase pitch-based carbon fiber from crude oil, and converts the crude oil into low-carbon olefin, aromatic hydrocarbon and carbon fiber to the maximum extent.

In order to solve the technical problems, the invention adopts the following technical scheme:

the invention provides a combined process method for producing olefin, aromatic hydrocarbon and mesophase pitch-based carbon fiber from crude oil, which comprises the following steps:

1) crude oil enters a crude oil fraction cutting unit firstly, and is rectified and separated to obtain gasoline and diesel oil fractions (less than or equal to 375 ℃), heavy oil fractions (more than 375 ℃), and externally thrown heavy oil rich in polycyclic aromatic hydrocarbon;

2) the heavy oil fraction obtained in the step 1) enters a heavy oil directional modification unit, and under the action of a directional modification catalyst, under the conditions of reaction temperature of 350-650 ℃, pressure of 0.1-1.0 MPa and steam/oil mass ratio of 0.1: 1-10: 1, directional decarburization, demetalization and cracking modification reaction of heavy components are carried out, so as to obtain hydrogen, a fulvene gas, modified fulvene distillate oil and coke;

3) returning the modified fulvene distillate oil obtained in the step 2) to the crude oil fraction cutting unit in the step 1) for fraction cutting;

4) the externally thrown heavy oil obtained in the step 1) enters a supercritical water treatment unit, is treated for 0.5-2 hours under the conditions that the reaction pressure is 24-35 MPa, the temperature is 380-480 ℃ and the water-oil mass ratio is 0.5: 1-3: 1, and is subjected to deep removal of asphaltenes, colloids and sulfides to obtain a mesophase asphalt raw material;

5) feeding the mesophase pitch raw material obtained in the step 4) into a carbon fiber processing unit, and carrying out processing technologies such as melt spinning, oxidation, carbonization, graphitization and the like to obtain mesophase pitch-based carbon fibers;

6) the gasoline and diesel oil fraction obtained in the step 1) enters a gasoline and diesel oil selective hydrofining unit, and is subjected to reaction at the temperature of 120-260 ℃, the pressure of 3.0-6.0 MPa and the mass space velocity of 1.0-2.0 h under the action of a selective hydrofining catalyst^-1Removing impurities such as colloid, alkadiene, alkaline nitrogen and the like under the condition that the volume ratio of hydrogen to oil is 400: 1-800: 1 to obtain fuel gas and refined gasoline and diesel oil rich in olefin;

7) the refined gasoline and diesel oil obtained in the step 6) enters a gasoline and diesel oil adsorption separation unit, and is subjected to adsorption temperature of 40-150 ℃, pressure of 0.2-1.0 MPa and mass space velocity of 0.5-1.5 h under the action of an adsorbent^-1Under the condition of (1), separating aromatic hydrocarbon components and non-aromatic hydrocarbon components of the gasoline and diesel oil to obtain aromatic hydrocarbon adsorption components and alkene-rich non-aromatic hydrocarbon adsorption components;

8) the adsorbed alkene-rich non-aromatic components obtained in the step 7) enter an alkene yield increasing unit, and under the action of an alkene yield increasing catalyst, catalytic cracking reaction is carried out under the conditions of reaction temperature of 480-600 ℃, pressure of 0.1-0.3 MPa, agent-oil ratio of 8: 1-15: 1 and steam-oil mass ratio of 0.2: 1-10: 1, so as to obtain alkene-rich gas, cracked aromatic-rich gasoline and coke;

9) the aromatic hydrocarbon adsorbing component obtained in the step 6) and the cracked aromatic-rich gasoline and diesel oil obtained in the step 8) 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 4.0-8.0 MPa, and the volume airspeed is 1.0-2.0 h^-1And performing selective cracking reaction on the hydrogen-oil volume ratio of 800: 1-1200: 1 to obtain fuel gas, saturated liquefied gas and light aromatic hydrocarbons (benzene, toluene and xylene))、C₉/C₁₀Aromatic hydrocarbons;

in the heavy oil directional modification unit in the step 2), heavy oil macromolecules undergo a directional modification reaction, the conversion rate of the heavy oil is more than or equal to 70 wt%, the olefin content in the converted gasoline and diesel oil product is 40-60 wt%, the aromatic hydrocarbon content is 20-40 wt%, and the polycyclic aromatic hydrocarbon content in the converted heavy oil is 60-85 wt%.

In the above integrated process of the present invention, the crude oil in step 1) is preferably at least one of paraffin-based, intermediate-based and naphthenic-based crude oil.

The reactor adopted by the heavy oil directional upgrading unit in the step 2) is in the form of one of a moving bed, a dense-phase fluidized bed and a riser reactor. The directional modification catalyst is a supported catalyst containing a heavy metal trapping agent and an alkaline auxiliary agent, wherein the carrier comprises but is not limited to at least one of white carbon black, a mesoporous high-silicon molecular sieve, attapulgite, silica gel, alumina, kaolin, montmorillonite, clay and diatomite, the active component of the heavy metal trapping agent comprises but is not limited to one or more of Bi, Ce, Sn, Cr and La, and the active component of the alkaline auxiliary agent comprises but is not limited to at least one of Li, Na, Ca, Mg, K and Ba.

The selective hydrofining catalyst in the step 6) is a metal supported catalyst, wherein the carrier is one or more of macroporous alumina, silicon oxide and amorphous silicon-aluminum, and the supported metal component is one or more of Ni, Mo, Co and W.

In the step 7), the gasoline and diesel oil adsorption separation unit adopts a fixed bed or a simulated moving bed, and the adsorbent is at least one of a mesoporous high-silicon molecular sieve, activated carbon, argil, white carbon black, activated carbon and silica gel.

In the olefin yield increasing unit in the step 8), the adopted reactor form is 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 fully crystalline high-silicon beta, mercerized, ZSM-5, APO-5, TS-1, MCM-22 and Y, IM-5 molecular sieves.

In the step 9), the aromatic hydrocarbon yield-increasing catalyst 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 modified component is at least one of Ni, Mo, Zn, Pt, Pd, Re, Sn, W and Co.

Compared with the prior art, the integrated process method for producing low-carbon aromatic hydrocarbon and olefin to the maximum extent, provided by the invention, has the following beneficial effects:

1) the raw material adaptability is strong, and the processing process is simple: the heavy oil is modified into high-quality chemical production raw materials (rich in olefin and aromatic hydrocarbon) by adopting the heavy oil directional modification unit, and 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 upgrading unit enriches polycyclic aromatic hydrocarbon into upgraded heavy oil, and is a high-quality carbon fiber production raw material. The modified gasoline and diesel oil is subjected to adsorption separation to realize separation of non-aromatic hydrocarbon (alkane and olefin) and aromatic hydrocarbon components, and is converted into low-carbon olefin and aromatic hydrocarbon by matching a subsequent processing unit according to component characteristics, wherein the total chemical yield reaches 70-80%.

Drawings

FIG. 1 is a schematic flow diagram of a combined process for producing olefins, aromatics and mesophase pitch-based carbon fibers from crude oil according to the present invention.

In the figure, 1 is a crude oil fraction cutting unit, 2 is a heavy oil directional modification unit, 3 is a supercritical water treatment unit, 4 is a carbon fiber processing unit, 5 is a gasoline and diesel oil selective hydrogenation refining unit, 6 is a gasoline and diesel oil adsorption separation unit, 7 is an olefin yield increasing unit, and 8 is an aromatic hydrocarbon yield increasing unit.

Detailed Description

The following embodiments are further described with reference to the drawings, but the present invention is not limited thereto.

As shown in fig. 1: crude oil enters a crude oil fraction cutting unit 1 for rectification and separation to obtain gasoline and diesel oil fractions (less than or equal to 375 ℃), heavy oil fractions (more than 375 ℃), and externally thrown heavy oil rich in polycyclic aromatic hydrocarbon;

the heavy oil fraction enters a heavy oil directional modification unit 2, and is subjected to directional decarburization, demetalization and cracking modification reaction of heavy components under the action of a directional modification catalyst to obtain hydrogen, a fulvene gas, modified fulvene distillate oil and coke; the modified fulvene distillate oil returns to the crude oil fraction cutting unit 1 for fraction cutting;

the externally thrown heavy oil enters a supercritical water treatment unit 3 to carry out deep removal of asphaltene, colloid and sulfide, the obtained mesophase pitch raw material enters a carbon fiber processing unit 4, and the mesophase pitch-based carbon fiber is obtained after processing technologies such as melt spinning, oxidation, carbonization and graphitization;

the gasoline and diesel oil fraction enters a gasoline and diesel oil selective hydrofining unit 5, and colloid, diene and alkaline nitrogen impurities are removed under the action of a selective hydrofining catalyst to obtain fuel gas and refined gasoline and diesel oil rich in olefin; the obtained refined gasoline and diesel oil enters a gasoline and diesel oil adsorption separation unit 6, and under the action of an adsorbent and under the condition of adsorption separation, the aromatic hydrocarbon component and the non-aromatic hydrocarbon component of the gasoline and diesel oil are separated to obtain an adsorbed aromatic hydrocarbon component and an adsorbed fulvene non-aromatic hydrocarbon component;

the obtained adsorbed rich-alkene non-aromatic components enter an alkene yield increasing unit 7, and catalytic cracking reaction is carried out under the action of an alkene yield increasing catalyst to obtain rich-alkene gas, cracked rich-aromatic gasoline and diesel oil and coke;

the absorbed aromatic hydrocarbon component and the obtained cracked rich aromatic gasoline and diesel oil enter an aromatic hydrocarbon yield increasing unit 8 together, and are subjected to selective cracking reaction under the action of an aromatic hydrocarbon yield increasing catalyst to obtain fuel gas, saturated liquefied gas, light aromatic hydrocarbons (benzene, toluene and xylene) and C9/C10 aromatic hydrocarbons.

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 heavy oil directional modification unit: the reactor adopts a riser reactor, the directional modification catalyst adopts Bi-Ca-K/coarse silica gel (based on the catalyst, the Bi content is 2.5 wt%, the Ca content is 5.0 wt%, the K content is 8.0 wt%, and the balance is coarse 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, the Ni content is 8wt percent, the Mo content is 4.0wt percent, and the balance isMacroporous alumina) under the following reaction conditions: the temperature is 120 ℃, the pressure is 3.0MPa, and the mass space velocity is 2.0h^-1And the volume ratio of hydrogen to oil is 600: 1.

Gasoline and diesel oil adsorption separation unit: adopting a simulated moving bed process, wherein the adsorbent is white carbon black, and the separation conditions are as follows: the adsorption temperature is 90 ℃, the pressure is 0.5MPa, and the mass space velocity is 1.0h^-1。

An olefin stimulation unit: adopting a descending bed reactor, wherein 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 agent-oil ratio is 10:1, and the steam-oil mass ratio is 1: 1.

An aromatic hydrocarbon yield increasing unit: the catalyst is a bimetal modified composite molecular sieve catalyst (based on the catalyst, the Ni content is 12 wt%, the Mo content is 4 wt%, the Y molecular sieve content is 40 wt%, the beta molecular sieve content is 20 wt%, the ZSM-5 molecular sieve content is 10 wt%, 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^-1Hydrogen-oil volume ratio of 900:1

Supercritical water modification unit: the reaction conditions are as follows: the reaction is carried out for 0.5h under the conditions that the reaction pressure is 25MPa, the temperature is 390 ℃, and the water-oil mass ratio is 0.8: 1.

A carbon fiber processing unit: the oxidation temperature is 250 ℃, the carbonization temperature is 1150 ℃ and the graphitization temperature is 2450 ℃.

The material balance of the above process is shown in Table 2.

Example 2

The properties of the intermediate base crude oil from a refinery are shown in Table 1.

A heavy oil directional modification unit: the reactor adopts a dense-phase fluidized bed, the directional modification catalyst adopts Bi-Ca-K/white carbon black (taking the catalyst as a reference, the Bi content is 4.0 wt%, the Ca content is 10.0 wt%, the K content is 5.0 wt%, 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 + alumina (based on the catalyst, the Ni content is 10 wt%, the Co content is 4.0 wt%, and the balance is amorphous silicon aluminum + alumina), and the reaction conditions are as follows: temperature 140 ℃ and pressure 30MPa, mass airspeed of 1.5h^-1And the volume ratio of hydrogen to oil is 500: 1.

Gasoline and diesel oil adsorption separation unit: a fixed bed process is adopted, the adsorbent is a mesoporous high-silicon SBA-15 molecular sieve, and the separation conditions are as follows: the adsorption temperature is 120 ℃, the pressure is 0.5MPa, and the mass space velocity is 0.5h^-1。

An olefin stimulation unit: adopting a descending bed reducing reactor, wherein the catalyst is a high-silicon ZSM-5+ Y molecular sieve catalyst, and the reaction conditions are as follows: the reaction temperature is 600 ℃, the pressure is 0.1MPa, the agent-oil ratio is 15:1, and the steam-oil mass ratio is 0.8: 1.

An aromatic hydrocarbon yield increasing unit: the catalyst is a bimetal modified composite molecular sieve catalyst (based on the catalyst, the Ni content is 12 wt%, the Pt content is 0.2 wt%, the beta molecular sieve content is 55 wt%, the ZSM-5 molecular sieve is 15 wt%, and the balance is alumina), and the reaction conditions are as follows: the temperature is 420 ℃, the pressure is 6.0MPa, and the volume space velocity is 1.5h^-1And the volume ratio of hydrogen to oil is 1200: 1.

Supercritical water modification unit: the reaction conditions are as follows: the reaction is carried out for 0.8h under the conditions of the reaction pressure of 28MPa, the temperature of 420 ℃ and the water-oil mass ratio of 0.5: 1.

A carbon fiber processing unit: the oxidation temperature is 250 ℃, the carbonization temperature is 1150 ℃ and the graphitization temperature is 2450 ℃.

The material balance of the above process is shown in Table 2.

Example 3

Naphthenic base crude oil of a certain refinery is used as a raw material, and the properties of the raw material are shown in table 1.

A heavy oil 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 used as a reference, the Ce content is 3.0 wt%, the Ca content is 15.0 wt%, the Mg content is 3.0 wt%, and the balance is molecular sieve + 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 10 wt%, the Mo content is 5.0 wt%, the Co content is 4.0 wt%, and the balance is alumina), and the reaction conditions are as follows: the temperature is 150 ℃, the pressure is 4.0MPa, and the mass space velocity is 1.5h^-1And the volume ratio of hydrogen to oil is 600: 1.

Gasoline and diesel oil adsorption separation unit: adopting a simulated moving bed process, wherein the adsorbent is activated carbon, and the separation conditions are as follows: the adsorption temperature is 100 ℃, the pressure is 0.8MPa, and the mass space velocity is 1.5h^-1。

An olefin stimulation unit: adopting a descending bed reducing reactor, wherein the catalyst is a high-silicon ZSM-5+ Y molecular sieve catalyst, and the reaction conditions are as follows: the reaction temperature is 560 ℃, the pressure is 0.2MPa, the agent-oil ratio is 12:1, and the steam-oil mass ratio is 0.6: 1.

An aromatic hydrocarbon yield increasing unit: the catalyst is a bimetal modified composite molecular sieve catalyst (based on the catalyst, the Ni content is 12 wt%, the Pt content is 0.3 wt%, the beta molecular sieve content is 40 wt%, the ZSM-5 molecular sieve is 20 wt%, 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^-1And the volume ratio of hydrogen to oil is 1000: 1.

Supercritical water modification unit: the reaction conditions are as follows: the reaction is carried out for 1.5h under the conditions that the reaction pressure is 30MPa, the temperature is 420 ℃ and the water-oil mass ratio is 1.5: 1.

A carbon fiber processing unit: the oxidation temperature is 250 ℃, the carbonization temperature is 1150 ℃ and the graphitization temperature is 2450 ℃.

The material balance of the above process is shown in Table 2.

TABLE 1 EXAMPLES 1 TO 3 Properties of raw materials

Raw materials	Example 1	Example 2	Example 3
				Density, g/cm3	0.862	0.90	0.935
API°	32.8	24.6	15.2
				Wax content, wt.%	28.6	10.8	5.8
Freezing point, deg.C	30	-2	-12
				Carbon residue in wt%	3.28	6.0	11.4
Colloid + asphaltene, wt.%	7.45	11.4	22.6
				Sulfur content, ug/g	1800	2600	28000
Nitrogen content, ug/g	2100	3200	5100
				Metal content, ug/g	16	35	140

TABLE 2 examples 1-3 Material balances

As shown in Table 2, the total yield of chemicals (olefin, aromatic hydrocarbon and carbon fiber) in paraffin-based crude oil, intermediate-based crude oil and naphthenic base crude oil can reach 73-76% by the method of the invention, and the total hydrogen consumption is only 1.2-1.64 wt%.