CN106467756A - A kind of processing of heavy oil combined method - Google Patents
A kind of processing of heavy oil combined method Download PDFInfo
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- CN106467756A CN106467756A CN201510520761.4A CN201510520761A CN106467756A CN 106467756 A CN106467756 A CN 106467756A CN 201510520761 A CN201510520761 A CN 201510520761A CN 106467756 A CN106467756 A CN 106467756A
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Abstract
The invention discloses a kind of processing of heavy oil combined method, the method includes：A, heavy oil is carried out separating treatment, obtain SA1A2 component and A3 component；Wherein, on the basis of the gross mass of SA1A2 component, in described SA1A2 component, the total mass fraction of saturated hydrocarbons, mononuclear aromatics and double ring arene is more than 80 mass %；On the basis of the gross mass of A3 component, in described A3 component, the total mass fraction of bicyclic above aromatic hydrocarbons and colloid is more than 50 mass %；B, the SA1A2 component of gained in step a is carried out the first catalytic cracking reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.The method carries out catalytic cracking reaction respectively by the SA1A2 component obtained by heavy oil is carried out separating treatment and A3 component, has higher gasoline and liquefied gas yield and lower gasoline sulfur nitrogen content.
Description
Technical field
The present invention relates to a kind of processing of heavy oil combined method.
Background technology
Catalytic cracking process is the secondary operations means of most important light materialization of heavy oil, is liquefied petroleum
The important production process of the light-end products such as gas, gasoline, diesel oil, is to improve constantly heavy oil conversion performance to add
Work process, is also constantly to pursue a goal the process of product selectivity.
It is derived from atmospheric and vacuum distillation unit at present and enter the raw material of heavy oil catalytically cracking equipment processing not from fraction
Make a distinction on composition and its reactivity worth, be all in the form of mixing refining, various raw materials to be mixed
Enter catalytic cracking unit, and and converted under the conditions of same process, not in same reactor
The reactivity worth difference of the different hydro carbons of with good grounds structure takes Optimized Measures respectively.Substantial amounts of easy in raw material
Hydro carbons in conversion together feeds reaction with non-hydrocarbons, condensed-nuclei aromatics, certainly will be in same reaction zone
Interior generation harmful competition absorption, the reaction of the raw material strong to cracking performance produces retardation, thus affecting
The reaction conversion of whole raw material.The reaction rate of the preferable convertible hydrocarbons of reactivity worth is higher, warmer
Just high conversion ratio can be realized under the process conditions of sum, and substantial amounts of condensed ring non-hydrocarbons, condensed ring
Aromatic hydrocarbons and glial response speed are low, need harsher process conditions and longer response time can be only achieved
Preferably conversion level.The distinct hydro carbons of multiple crackings is in same reactor and same process condition
Under reacted, the reactivity worth difference of different hydrocarbons and reaction step inconsistent, reaction can be caused deep
Degree does not optimize and interferes, and has had a strong impact on the catalytic cracking transformation efficiency of whole raw material.
On the developing way of conventional catalytic cracking process and catalyst, continue to along increase heavy oil
Conversion per pass ability is development goal.These technology are mostly by technological operation optimization parameter and catalyst
To strengthen heavy oil catalytic cracking reaction process although these methods can only improve light oil to a certain extent
Yield, improves the distribution of catalytic cracking production.But for processing inferior raw material, only urged by adjustment
Agent composition and technological parameter are often attended to one thing and lose sight of another, and increasing would generally be along with while heavy oil conversion performance
Being significantly increased of dry gas and coke yield, so undoubtedly will lead to heavy oil conversion selectivity to be deteriorated, that is, turn
Obvious contradiction is there is it is difficult to realize the hydrocarbon distribution of hydro carbons between rate and dry gas and coke selectivity
Optimization and oil product maximize.
In heavy oil catalytic cracking process, raw material oil nature, catalyst performance, process conditions (temperature,
Agent oil quality ratio, air speed etc.) etc. factor all product slates are had a major impact, wherein raw material hydro carbons composition
Remain the basis of product slates.Heavy oil feedstock is carried out separate and can carry to a certain extent according to boiling point
The conversion capability of high heavy oil, and improve its products distribution.According to boiling point, raw oil is cut into and relatively easily splits
Change fraction and relatively difficult cracked distillate can weaken the harmful effect of difficult cracked distillate to a certain extent, be
Easily cracked distillate provides a preferable reaction environment, improves product yield and product slates.CN
It is classification point that 102102029 A disclose with 500-540 DEG C, carbon residue gravimetric value for 2～4%, by heavy oil
Raw material is divided into quality raw materials and inferior raw material, its result compared with traditional handicraft, heavy oil classification after, product
Distribution is obviously improved, and yield of light oil improves, and coke and dry gas yield reduce.Button root woods etc. (button root woods,
Chen Jie. the research of Catalytic Cracking of Shengli Vacuun Residue. oil refining design, 1995,25 (2):6-10) profit
With supercritical fluid extraction precision segregation apparatuss, catalytically cracked material is cut into comparative good-quality according to boiling point
With raw material inferior, Shengli VR is divided into 15 components and has investigated the catalytic cracking of front 13 fractions
Performance, experiment shows to become weight with fraction, and yield of light oil reduces successively, and coke yield gradually rises.
Heavy oil is cut into different narrow of boiling spread by the method such as true boiling point distillation or supercritical fluid extraction
Fraction, although boiling spread can be cut very narrow, each narrow fraction remains the mixture of various hydro carbons.
For different fcc raw materials, the larger difference of boiling range scope and chemical constitution and composition determines it
Reactivity worth there is larger difference.It is big that various hydro carbons absorbability on a catalyst presses its strong and weak order
Cause can arrange as follows：Condensed-nuclei aromatics>Condensed ring cycloalkane>Alkene>The mononuclear aromatics of monoalkyl side chain>Cycloalkanes
Hydrocarbon>Alkane.According to the sequence arrangement of chemical reaction rate, then substantially situation is as follows：Alkene>Big point
The mononuclear aromatics of sub- monoalkyl side chain>Isoparaffin and cycloalkane>The monocyclic virtue of small molecule monoalkyl side chain
Hydrocarbon>N-alkane>Condensed-nuclei aromatics.As can be seen that various hydro carbons, non-hydrocarbons are in catalysis in raw material
There is very big difference in the absorption on agent surface and cracking capability, the non-hydrocarbons of condensed ring, condensed-nuclei aromatics and
Condensed ring cycloalkane high adsorption capacity and reaction rate is low, and carry mononuclear aromatics and the macromole of longer side chain
Isoparaffin, cycloalkane absorbability is weak and reaction rate is high, and this has resulted in competing between different hydrocarbons
Strive absorption and the retardation to reaction.High adsorption capacity and the low condensed ring non-hydrocarbons chemical combination of reaction rate
, once occupying catalyst surface first, their reaction rates are slow for thing, condensed-nuclei aromatics, are difficult to be desorbed, or even
Condensation becomes coke and covers in catalyst surface, causes catalyst to inactivate, has had a strong impact on other and be easy to split
Change the reaction rate of hydro carbons.
Based on this, various heavy oil feedstocks do not fed as one " overall ", to take into full account wide boiling range
The larger difference that in heavy oil feedstock, different component cracking performance exists, can will be poor for cracking performance in raw oil
Different larger component carries out catalytic cracking after carrying out separating respectively.
Traditional catalytically cracked material is mainly the vacuum distillate that in refinery, atmospheric and vacuum distillation unit provides.Decompression
Wax oil fraction can be divided into different hydrocarbon system's component such as non-aromatic components and virtue according to the difference of hydrocarbon structure
Hydrocarbon component, saturated hydrocarbon component and aromatic component (without colloid), but the mononuclear aromatics in aromatic component,
The reflex action in catalytic cracking process of double ring arene and polycyclic aromatic hydrocarbon still has larger difference, and current grinds
Study carefully to rarely have in report and carry out catalytic cracking reaction by after aromatic hydrocarbons separation and concentration from raw material of different number of rings
Research.
At present, market to oil product continuous lighting, high quality and the requirement cleaning and oil supply
The aggravation of contradictions of increasingly heaviness, in poor quality, and light, the middle matter oil to high value for China's economic development
The demand of product is continuously increased.Therefore, as how more economical rational cost realizes heavy oil lighting, institute
Obtain product and can meet the oil Refining Technologies of the constantly petrol and diesel oil product specification of harshness again having become domestic and international oil refining
One of technology of technological development business's focus development.
The arene content of catalytic cracking diesel oil is high, and Cetane number is low, and engine ignition poor performance belongs to bad
The diesel oil blending component of matter, has a strong impact on diesel product quality, Shi Ge enterprise diesel product quality upgrading
One of biggest obstacle.Weighted BMO spaces are carried out to faulty wax oil raw material, aromatic hydrocarbons obtains different degrees of saturation,
Except desulfuration, nitrogen, metal impurities, it is re-used as the raw material of catalytic cracking, can be raw according to producing needs
Produce quality product and the intermediate products such as diesel oil, gasoline, such that it is able to improve its Catalytic Cracking Performance, significantly
Improve the structure of product.CN 1896192 A discloses a kind of wax oil hydrogenation process and catalytic cracking is two-way
Method, wax oil enters hydrotreater together with heavy catalytic cycle oil and catalytic cracking diesel oil and reacts
After obtain the products such as gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenation tail oil, wherein hydrogenation tail oil enters
Catalytic cracking unit reacts, and the method increases light oil yield, reduces coke yield, reduce simultaneously
The arene content of diesel oil and sulfur content simultaneously improve its Cetane number.
Similarly, CN101434865A is also disclosed a kind of heavy distillate hydrotreating and is split with catalysis
Change united method.But these methods are all directly by second-rate catalytic cracking heavy oil and catalytic cracking diesel oil
Mixed with the wax oil raw material containing a large amount of saturated hydrocarbons, the saturated hydrocarbons in wax oil are in hydroprocessing processes
Due on catalyst the effect of acid centre and be easy to be cracked into lighter hydrocarbons, cause gas yield increase, simultaneously
Generate hydrogenation heavy oil proportion less, as catalytic cracking unit charging when lightweight oily yield decline.
Therefore, there is space to be modified in current processing of heavy oil technique.
Content of the invention
It is an object of the invention to provide a kind of processing of heavy oil combined method, the method is by carrying out point heavy oil
SA1A2 component obtained by processing and A3 component carry out catalytic cracking reaction respectively, have higher
Gasoline and liquefied gas yield and lower gasoline sulfur nitrogen content.
To achieve these goals, the present invention provides a kind of processing of heavy oil combined method, and the method includes：
A, heavy oil is carried out separating treatment, obtain SA1A2 component and A3 component；Wherein, with SA1A2 group
On the basis of the gross mass divided, in described SA1A2 component, saturated hydrocarbons, mononuclear aromatics and double ring arene is total
Mass fraction is more than 80 mass %；On the basis of the gross mass of A3 component, bicyclic in described A3 component
The total mass fraction of above aromatic hydrocarbons and colloid is more than 50 mass %；B, by the SA1A2 of gained in step a
Component carries out the first catalytic cracking reaction, obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracking
Heavy oil.
Preferably, wherein, on the basis of the gross mass of SA1A2 component, described SA1A2 component is embezzled
It is more than 85 mass % with the total mass fraction of hydrocarbon, mononuclear aromatics and double ring arene；Total matter with A3 component
On the basis of amount, in described A3 component, the total mass fraction of bicyclic above aromatic hydrocarbons and colloid is more than 55 mass %.
Preferably, the method also includes step c：Gained A3 component in step a is carried out the second catalysis
Cracking reaction.
Preferably, the method also includes step d：Gained A3 component in step a is urged in hydrotreating
Carry out hydrotreating reaction in the presence of agent, obtain hydrogenated oil.
Preferably, the method also includes step e：Gained hydrogenated oil in step d is carried out the 3rd urge
Change cracking reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
Preferably, the method also includes：The diesel oil that obtains described first catalytic cracking reaction and/or split
Change at least a portion of heavy oil and diesel oil that described 3rd catalytic cracking reaction obtains and/or cracked fuel oil
At least a portion carry out described hydrotreating reaction together with described A3 component.
Preferably, the method also includes step f：By in gained hydrogenated oil in step d and step a
Gained SA1A2 component carries out described first catalytic cracking reaction together, obtains dry gas, liquefied gas, vapour
Oil, diesel oil, coke and cracked fuel oil.
Preferably, the method also includes：The diesel oil that obtains described first catalytic cracking reaction and/or split
At least a portion changing heavy oil carries out described hydrotreating reaction together with described A3 component.
Preferably, the method also includes：Hydrocracking tail oil is carried out together with described SA1A2 component
Described first catalytic cracking reaction.
Preferably, wherein, described heavy oil be straight run vacuum distillate more than 350 DEG C for the initial boiling point and/
Or secondary processing process gained initial boiling point is more than 350 DEG C of fraction.
Preferably, wherein, described secondary processing process be selected from hydroprocessing processes, hydrocracking process,
At least one in catalytic cracking process and solvent deasphalting process.
Preferably, wherein, separating treatment described in step a is selected from solvent extraction process, Solid-Phase Extraction
Process and at least one in membrane separation method.
Preferably, wherein, described solvent extraction is processed as selected from solvent refining extraction, supercritical fluid extraction
Take and at least one in ion liquid abstraction.
Preferably, wherein, described Solid-Phase Extraction processes and comprises the following steps：First described heavy oil is adopted dilute
Send in fixing phase after releasing dilution agent, obtain the first fixing phase；Then aromatic hydrocarbons and C5-C6Alkane volume
Than for 1：(3-5) the first fixing phase described in solvent washing, obtains described SA1A2 component and second admittedly
Determine phase；Then aromatic hydrocarbons and monohydric alcohol volume ratio is used to be 1：(0.8-1.5) solvent washing second fixing phase,
Obtain described A3 component；Wherein, described fixing phase contains the aluminium oxide of load silver, with described load silver
The gross mass of aluminium oxide on the basis of, the mass fraction of the silver of load is 0.5-12 mass %.
Preferably, wherein, described fixing phase also contains the oxidation being located at described load silver according to fluid flow direction
The silica gel of aluminum upstream and the aluminium oxide being located at the silver-colored aluminium oxide downstream of described load；In mass, described
The aluminium oxide of silica gel, the aluminium oxide of described load silver and the described aluminium oxide downstream positioned at described load silver
Mass ratio be 1：(2.5-5.0)：(0-1.2)；Wherein, the specific surface area of described aluminium oxide is 50-300
Rice2/ gram, pore volume is 0.1-0.55 ml/g, and the specific surface of described silica gel is 250-850 rice2/ gram,
Pore volume is 0.25-0.99 ml/g.
Preferably, wherein, described diluent is C5-C6Alkane, by volume, described diluent with
The ratio of the volume of heavy oil is (1-10)：1；Described aromatic hydrocarbons is benzene and/or toluene, and described monohydric alcohol is methanol
And/or ethanol；In mass, described fixing phase and the mass ratio of described heavy oil are (8-30)：1.
Preferably, wherein, described in step b, the condition of the first catalytic cracking reaction is：Temperature is
420-520 DEG C, mass space velocity is 2-20 hour-1, oil ratio is (1-10)：1.
Preferably, wherein, described in step c, the condition of the second catalytic cracking reaction is：Temperature is
480-540 DEG C, mass space velocity is 2-20 hour-1, oil ratio is (2-30)：1.
Preferably, wherein, the condition of hydrotreating reaction described in step d is：Hydrogen dividing potential drop is 3-12
MPa, reaction temperature is 280-360 DEG C, and hydrotreating catalyst is the aromatic hydrogenation not containing acid site
Saturation catalyst；The initial boiling point of hydrogenated oil described in step d is 155-175 DEG C.
Preferably, wherein, described in step e, the condition of the 3rd catalytic cracking reaction is：Temperature is
450-540 DEG C, mass space velocity is 2-20 hour-1, oil ratio is (2-30)：1.
Compared with prior art, the present invention is advantageous in that：
1st, achieve the separation of SA1A2 component and A3 component in heavy oil based on isolation technics, for dynamic
The SA1A2 component that mechanical behavior differs greatly and A3 component can be respectively in the catalytic cracking bars of coupling
Individually reacted under part, both eliminated influencing each other between different hydrocarbons, every kind of hydrocarbon system can be made again
Reacting under the conditions of optimized, improve the utilization rate of hydrogen in heavy oil, thus saving petroleum resources.
2nd, the solution of the present invention can be connected a hydrotreating list before the catalytic cracking unit of A3 component
Unit, to realize two kinds of purposes：First, hydrogen addition technology is selective hydrogenation, and A3 component occurs hydrogenation de-
Sulfur, hydrodenitrogeneration reaction, and selectivity saturation polycyclic aromatic hydrocarbon and colloid, appropriate saturated bicyclic aromatic hydrocarbons, single
PAH saturation is few, and does not almost have acid site, the fractional saturation of generation or full saturation on catalyst
Macromolecule hydrocarbon is farthest retained, and producing low-sulphur oil for catalytic cracking unit provides high-quality former
Material, can control catalytic gasoline sulfur nitrogen content by controlling the reaction depth of hydrotreating unit simultaneously；Its
Secondary, all return to and add from the catalytic cracking diesel oil of different catalytic cracking unit outflows and catalytic cracking heavy oil
Hydrogen processing unit, as catalytic cracking unit after the appropriateness hydrogenation saturated reaction of bicyclic above aromatic hydrocarbons therein
Charging, for catalytic cracking unit produce high-knock rating gasoline provide high-quality charging.
Catalytic cracking diesel oil and catalytic cracking heavy oil can be returned by the 3, method being provided by the present invention
Hydrotreating unit carries out cracking again after being hydrogenated with, catalytic cracking conversion per pass first does not pursue high conversion
Rate, and pursue the total conversion of whole process, catalytic cracking unit do not produce arene content high, 16
The low catalytic diesel oil of alkane value, reduces the yield of dry gas and coke, improves liquefied gas and high-octane rating vapour
The yield of oil；Secondly the fractionating system of catalytic cracking reaction effluent only fractionates out the lightweights such as gasoline fraction and produces
Product, the theoretical cam curve needed for fractionating column substantially reduces；Finally to the raw material rich in polycyclic aromatic hydrocarbon and colloid
Play diluting effect, the two is more prone to make the conveying of mixed material oil after certain proportion mixing.
4th, increased catalytic cracking process material choice scope, improve the hydrogen utilization rate in raw material, change
It has been apt to products distribution, improved gasoline yield and productivity of propylene, make product restructuring more flexible.
5th, idetified separation process, hydrotreating and catalytic cracking technology are more reasonably integrated, for oil refining
Efficient and refined oil product the rationalization of production process provides a new approach.
6th, heavy oil is carried out separating treatment by the present invention, reduces the sulfur nitrogen content in SA1A2 component, and
Reduce the sulfur nitrogen content of SA1A2 group lease making catalytic cracking products obtained therefrom further, in addition, high-sulfur nitrogen contains
The A3 component of amount, can carry out hydrotreating reaction and carry out removing sulfur nitrogen, thus reducing catalytic cracking
Sulfur nitrogen content in product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.?
In accompanying drawing：
Fig. 1 is the schematic flow sheet of the first specific embodiment of the inventive method；
Fig. 2 is the schematic flow sheet of the inventive method second specific embodiment；
Fig. 3 is the schematic flow sheet of the third specific embodiment of the inventive method.
Specific embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.It should be appreciated that
Specific embodiment described herein is merely to illustrate and explains the present invention, is not limited to this
Bright.
The present invention provides a kind of processing of heavy oil combined method, and the method includes：A, by heavy oil carry out separate
Process, obtain SA1A2 component and A3 component；Wherein, on the basis of the gross mass of SA1A2 component,
In described SA1A2 component, the total mass fraction of saturated hydrocarbons, mononuclear aromatics and double ring arene is more than 80 matter
Amount %, preferably greater than 85 mass %；On the basis of the gross mass of A3 component, double in described A3 component
The total mass fraction of the above aromatic hydrocarbons of ring and colloid is more than 50 mass %, preferably greater than 55 mass %；B, general
In step a, the SA1A2 component of gained carries out the first catalytic cracking reaction, obtain dry gas, liquefied gas,
Gasoline, diesel oil, coke and cracked fuel oil.
According to the present invention, in described SA1A2 component, mainly contain the saturation including alkane and cycloalkane
Hydrocarbon and mononuclear aromatics and double ring arene, described aromatic hydrocarbons is well-known to those skilled in the art, this
Bright repeat no more；In A3 component, contained colloid refers to for the normal heptane solvent of residual oil to pass through aluminium oxide
The component that liquid chromatograph obtains after isolating saturated hydrocarbons and aromatic hydrocarbons, specifically can be found in《Catalytic cracking chemistry with
Technique》, perhaps friendly work, 2013, Science Press, it is for instance possible to use RIPP10-90 test side
Method carries out separation determination, because heavy oil composition can be using saturated hydrocarbons, aromatic hydrocarbons, colloid and drip with residual oil
Blue or green matter is bound, and therefore the colloid in heavy oil can also be so defined.Currently preferred is to accord with
Under conditions of closing the definition of each component, separating treatment should make alkane, cycloalkane, monocyclic virtue as far as possible
Hydrocarbon and double ring arene are enriched in SA1A2 component, and bicyclic above aromatic hydrocarbons and colloid are farthest enriched with
In A3 component, reduce intersection therebetween.
Present invention aims to different hydrocarbons competitive Adsorption in Conventional catalytic cracking reactor at present,
The hydro carbons of difficult cracking such as polycyclic aromatic hydrocarbon and colloid produce strong adsorption in catalyst surface and are but difficult to cracking, right
The cracking reaction of saturated hydrocarbons produces retardation, leads to quite a few easy cracking hydrocarbons not sufficiently reactive just
It is stripped and enters into the problem gone in product, gained A3 component in step a can be carried out by the present invention
Two catalytic cracking reactions.
According to the present invention, because the degree of unsaturation of A3 component is higher, therefore the method can also include walking
Rapid d：Gained A3 component in step a is carried out hydrotreating in the presence of hydrotreating catalyst anti-
Should, obtain hydrogenated oil.In the present invention, hydrotreating is to make double ring arene, multi-ring by hydrogenation
There is different degrees of saturation in aromatic hydrocarbons and colloid, and as few as possible being saturated of mononuclear aromatics, to the greatest extent may be used simultaneously
Can how to retain the aromatic hydrocarbons after hydrogenation, the therefore hydrotreating of employing is preferably selective hydrogenation and processes, and obtains
To product be mainly hydrogenated oil, and its yield be preferably not less than 70-99 weight %.Described hydrogenation
Generate oil and refer to the distillate that boiling point is 150 DEG C -600 DEG C about, with HT-A3 labelling, preferably hydrogenation life
The initial boiling point becoming oil is 150 DEG C -250 DEG C, more preferably 155 DEG C -175 DEG C.The present invention can be by controlling
During hydrotreating, the yield of hydrogenated oil to be controlling the degree of hydro-upgrading, so that it is guaranteed that during hydro-upgrading
Both it had been not result in that gas yield was too high, and led to lose too many light oil it is also possible to guarantee follow-up catalysis
Cracking is easily carried out.
According to the present invention, described hydrogenated oil is a kind of good catalyst cracking raw material, the therefore party
Method also includes step e：Gained hydrogenated oil in step d is carried out the 3rd catalytic cracking reaction, obtains
Dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；And may further include step f：
Gained hydrogenated oil in step d is carried out described first together with gained SA1A2 component in step a
Catalytic cracking reaction, obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
According to the present invention, in order to further with the diesel oil of catalytic cracking reaction gained and cracked fuel oil, real
Existing diesel oil and the full conversion of cracked fuel oil, therefore the method can also include after step e：Will be described
The diesel oil that first catalytic cracking reaction obtains and/or at least a portion of cracked fuel oil and the described 3rd are urged
The diesel oil that change cracking reaction obtains and/or at least a portion of cracked fuel oil are carried out together with described A3 component
Described hydrotreating reaction.The method can also include after step f：By described first Catalytic Cracking Unit of Measure
The diesel oil that should obtain and/or at least a portion of cracked fuel oil carry out described hydrogenation together with described A3 component
Process reaction.The diesel oil of catalytic cracking gained is primarily referred to as 221 DEG C in catalytic cracking full distillate product
- 343 DEG C about fraction, the cracked fuel oil of gained refer mainly in catalytic cracking full distillate product 350 DEG C with
Upper fraction.Wherein, in the diesel oil of catalytic cracking gained, bicyclic above arene content can account for 40 mass %
More than, further up to 50 mass % more than, this part fraction return hydrotreating unit carry out appropriateness
Saturation, proceeds cracking reaction subsequently into catalytic cracking unit, provides for generating high-knock rating gasoline
High-quality feeds；Mass fraction in hydrotreating unit mixed feeding for the diesel oil of the present invention may range from greatly
In 0 to 50 weight %, more preferably higher than 0 to 30 weight %.In described cracked fuel oil bicyclic and more than
Arene content can reach more than 40 mass %, further up to 50 mass % more than, this part fraction returns
Return hydrotreating unit and carry out appropriate saturation, increase hydrogen content, subsequently into catalytic cracking unit continue into
Row cracking reaction, provides high-quality charging for generating high-knock rating gasoline.The cracked fuel oil of the present invention is in hydrogenation
Mass fraction in processing unit mixed feeding ranges preferably from and weighs % more than 0 to 50, and more preferably greater than 0
To 30 weight %.
According to the present invention it is possible to hydrocracking tail oil be carried out together with described SA1A2 component described
One catalytic cracking reaction.Described hydrocracking tail oil refers to uncracked full produced by hydrocracking reaction
And hydrocarbon.
According to the present invention, described heavy oil is well-known to those skilled in the art, can exist for initial boiling point
More than 350 DEG C of straight run vacuum distillate and/or secondary processing process gained initial boiling point evaporating more than 350 DEG C
Point, described initial boiling point refers to the minima of oil distillation.Wherein, described secondary processing process can be
In hydroprocessing processes, hydrocracking process, catalytic cracking process and solvent deasphalting process extremely
Few one kind.
According to the present invention, separating treatment described in step a refer to by heavy oil be separated into SA1A2 component and
The process of A3 component, can be to process and membrane separation side selected from solvent extraction process, Solid-Phase Extraction
At least one in method, different method for separating and processing can be used alone it is also possible to be used in series.Institute
State solvent extraction process and be preferably selected from solvent refining extraction, supercritical fluid extraction and ion liquid abstraction
In at least one, single solvent extraction can be adopted, it would however also be possible to employ multi-solvent extract mode, preferably adopt
Extract mode with multi-solvent.Solid phase described in described Solid-Phase Extraction process can include detached dowel, vacuum
The equipment such as system, preferably include following steps：First described heavy oil is sent into fixation using after dilution dilution agent
Xiang Zhong, obtains the first fixing phase；Then aromatic hydrocarbons and C5-C6Alkane volume ratio be 1：(3-5) molten
Described first fixing phase is rinsed in agent, obtains described SA1A2 component and the second fixing phase；Then use aromatic hydrocarbons
It is 1 with monohydric alcohol volume ratio：(0.8-1.5) solvent washing second fixing phase, obtains described A3 component；
Wherein, described fixing phase contains the aluminium oxide of load silver, and the gross mass with the aluminium oxide of described load silver is
Benchmark, the mass fraction of the silver of load is 0.5-12 mass %.Described fixing phase can also contain according to stream
Direction of flow is located at the silica gel of aluminium oxide upstream of described load silver and the aluminium oxide being located at described load silver
The aluminium oxide in downstream；In mass, described silica gel, described load silver aluminium oxide and described positioned at institute
The mass ratio stating the aluminium oxide in aluminium oxide downstream of load silver can be 1：(2.5-5.0)：(0-1.2)；Its
In, the specific surface area of described aluminium oxide can be 50-300 rice2/ gram, pore volume can be 0.1-0.55 milli
Rise/gram, the specific surface of described silica gel can be 250-850 rice2/ gram, pore volume can be 0.25-0.99
Ml/g.Described diluent can be C5-C6Alkane, by volume, described diluent and heavy oil
The ratio of volume can be (1-10)：1；Described aromatic hydrocarbons can be benzene and/or toluene, and described monohydric alcohol is permissible
For methanol and/or ethanol；In mass, described fixing phase and the mass ratio of described heavy oil can be (8-30)：
1.
According to the present invention, described catalytic cracking reaction is well-known to those skilled in the art, and the present invention is not
Repeat again.According to the difference of reaction raw materials, the condition of catalytic cracking reaction can be different, for example, step
Described in b, the condition of the first catalytic cracking reaction can be：Temperature is 420-520 DEG C, preferably
480-520 DEG C, mass space velocity is 2-20 hour-1, preferably 15-20 hour-1, oil ratio is (1-10)：
1, preferably (2-6)：1.Described in step c, the condition of the second catalytic cracking reaction can be：Temperature
For 480-540 DEG C, preferably 480-520 DEG C, mass space velocity is 2-20 hour-1, preferably 15-20 is little
When-1, oil ratio is (2-30)：1, preferably (2-6)：1.3rd catalytic cracking described in step e
Reaction condition can be：Temperature is 450-540 DEG C, preferably 480-520 DEG C, and mass space velocity is 2-20
Hour-1, preferably 15-20 hour-1, oil ratio is (2-30)：1, preferably (2-6)：1.
According to the present invention, described hydrotreating reaction is well-known to those skilled in the art, and the present invention is not
Repeat again.The condition of hydrotreating reaction described in step d is：Hydrogen dividing potential drop is 3-12 MPa, preferably
For 4-8 MPa, reaction temperature is 280-360 DEG C, and hydrotreating catalyst is the virtue not containing acid site
Hydrocarbon hydrocatalyst for saturating；The initial boiling point of hydrogenated oil described in step d is 155-175 DEG C.
The three kind specific embodiments of the inventive method are provided below, but the present invention is not limited to this.
The first specific embodiment of the present invention is as shown in Figure 1：
Heavy oil is carried out having obtained SA1A2 component and A3 component after separating treatment, by the SA1A2 of gained
Component and A3 component carry out the first catalytic cracking reaction and the second catalytic cracking reaction respectively, obtain dry gas,
Liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.Meanwhile, can be by hydrocracking tail oil and SA1A2
Carry out the first catalytic cracking reaction together after component mixing.
The second specific embodiment of the present invention is as shown in Figure 2：
Heavy oil is carried out having obtained SA1A2 component and A3 component after separating treatment, by the SA1A2 of gained
Component carries out the first catalytic cracking reaction, obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracking
Heavy oil；Gained A3 component is carried out hydrotreating reaction, the hydrogenated oil obtaining carries out the 3rd catalysis
Cracking reaction, obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；Bavin by gained
Oil and cracked fuel oil carry out hydrotreating reaction, obtain hydrogenated oil.Meanwhile, can will be hydrocracked
Tail oil mix with SA1A2 component after together with carry out the first catalytic cracking reaction.
The third specific embodiment of the present invention is as shown in Figure 3：
Heavy oil is carried out having obtained SA1A2 component and A3 component after separating treatment, by gained A3 component
Carry out hydrotreating reaction, the hydrogenated oil obtaining carries out the first catalysis together with SA1A2 component and splits
Change reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；Diesel oil by gained
Carry out hydrotreating reaction with cracked fuel oil, obtain hydrogenated oil.Meanwhile, tail will can be hydrocracked
Oil mix with SA1A2 component after together with carry out the first catalytic cracking reaction with hydrogenated oil.
The present invention will be further illustrated by embodiment below, but the present invention will not therefore be taken office
What limits.Reagent and instrument that the embodiment of the present invention is adopted, if no special instructions, are this area normal
The instrument of rule and reagent.
The catalytic cracking reaction taken in the embodiment of the present invention and comparative example produces in KTI company of the U.S.
Carry out on ACE Model AP device, in experiment, catalyst loading amount is 9g, reaction temperature is 500 DEG C,
Mass space velocity is 16 hours-1, agent/oil quality ratio (C/O) is 4.After experiment parameter is stable, enter anti-
Answer program, catalyst is in self gravitation and N2Effect is lower to enter reactor, and raw oil promotes in plunger displacement pump
Lower edge charging tubule enters in reactor catalyst fluidized-bed layer, contacts instead with the catalyst granules of fluidisation state
Should, adopt N simultaneously2Stripping 600-900s.Product is by N2Circulation of qi promoting is entered in the liquid receipts bottle bringing -10 DEG C into
Liquid separates, and gaseous product is collected and completed by Agilent 6890 GC (TCD detector) on-line analyses group
Become；Weighed off line after liquid product collection, is simulated distillation respectively and gasoline detailed hydrocarbon analysis (adopts
RIPP81-90 method of testing is tested), the fraction cut point of gasoline and diesel oil be respectively 221 DEG C and
343℃；Green coke catalyst carries out coke and sulfur content after drawing off on multi EA 2000 carbon and sulfur analytical instrument
Analysis (being tested using RIPP106-90 method of testing), all product qualities add and calculate material puts down
Weighing apparatus.
In embodiment and comparative example using the trade mark that Sinopec catalyst company limited produces it is
, as experiment catalyst, its micro-activity can be by existing skill for the catalytic cracking catalyst of MLC-500
RIPP92-90 measuring method measurement in art, basic physical properties are listed in table 3.
The 500mL essence that the hydroprocessing processes of embodiment produce in Yantai Ke Li Chemical Equipment Co., Ltd.
Carry out in close autoclave, this reactor heating power is 1.5K weight, and dischargeable capacity is 0.5L,
High rotating speed 1500rpm.A certain amount of A3 is added in reactor, the catalyst being adopted is petrochemical industry
In the sulphided state catalyst of 40～60 mesh, the trade mark is RIB-429 to the granularity that research institute produces.Use hydrogen
By after air displacement in kettle, unlatching speed of agitator is 338rpm to gas, starts simultaneously at temperature programming to reaction
Temperature is 340 DEG C, and after reaching design temperature, hydrogen dividing potential drop is adjusted to 5MPa, and speed of agitator is 985rpm,
After response time terminates for 12h reaction, ON cycle condensed water cooling down, to room temperature, uses N2Displacement
Gas reactor is vented for several times afterwards, carries out fraction cutting to the product liquid of product liquid in kettle, is hydrogenated with
Generate oily HT-A3.
SA1A2 component, hydrocarbon system's composition of A3 component, HT-A3 component and HCW adopt RIPP10-90
Method of testing is tested.
The RIPP method of testing of the present invention be selected from《Petrochemical Engineering Analysis method (RIPP test method)》,
Yang Cui surely waits and compiles, Science Press, and 1990.
Embodiment 1
The present embodiment is used for heavy oil separative element in the processing of heavy oil combined method that the present invention provides is described
Implementation.In detached dowel, (specific surface area is 152 meters to bottom filling 30g neutral alumina2/ gram,
Pore volume is 0.213 ml/g), the aluminium oxide of middle filling 110g load silver ion (divide by the quality of silver
Number is 7.05 mass %, using the preparation of silver nitrate dipping method), 30g silica gel (specific surface is loaded on upper strata
Amass as 479 meters2/ gram, pore volume is 0.349 ml/g)；By detached dowel lower end and pumped vacuum systems phase
Even.The cumulative volume of fixing phase is 150mL.(VGO, Tahe Crude Oil takes from China to take vacuum distillate
Petrochemical industry northwest branch company system in Tahe Oilfield, obtains Tahe in Research Institute of Petro-Chemical Engineering through true boiling point distillation and subtracts
Pressure wax oil) sample 10.15g (11.13mL), it is dissolved in 30mL normal hexane, first just using 100mL
The fixing phase of filling in the above-mentioned detached dowel of hexane moistening, then the hexane solution of above-mentioned oil sample is added to point
In post.Use 255mL toluene respectively：Normal hexane volume ratio is 1：4 solvent washing goes out SA1A2
Component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out A3 component.Using rotation
Vaporizer is evaporated the solvent in SA1A2 component and A3 component, obtains SA1A2 component 7.98, A3
Component 1.92g, 0.25 gram of loss.Raw oil used in embodiment, comparative example and the Asia after separation
The basic physical properties data of component is listed in table 1, and hydrocarbon system's composition data of subfraction SA1A2, A3 is listed in table 2.
Embodiment 2
As shown in figure 1, the SA1A2 component of embodiment 1 gained and A3 component are split as catalysis
Change raw material, reaction temperature be 500 DEG C, agent oil quality ratio for 4, air speed is 16 hours-1Under conditions of
Carry out the first catalytic cracking reaction and the second catalytic cracking reaction, its conversion ratio, total liquid yield, light oil are received
Rate, also six kinds of primary product dry gas, liquefied gas, gasoline, yields of diesel oil, cracked fuel oil and coke,
Sulfur content in gasoline and nitrogen content, as shown in table 4.
From table 4, data can be seen that compared with the experimental result of the direct catalytic cracking of VGO, will
SA1A2 and A3 component is after the liquefied gas of catalytic cracking gained, gasoline collect respectively respectively, liquefied gas,
Gasoline yield summarized results 1 are respectively higher than liquefied gas, the gasoline yield that wax oil directly carries out catalytic cracking,
Sulfur content in gasoline and nitrogen content contain less than the content of sulfur in gasoline of the direct catalytic cracking of wax oil and nitrogen simultaneously
Amount, heavy oil is first carried out carrying out catalytic cracking, institute after separating treatment using the method for the present invention by this explanation again
The high-value product yield obtaining and property are superior to heavy oil directly carries out the product of catalytic cracking.
Embodiment 3
As shown in Fig. 2 by the SA1A2 component of embodiment 1 gained reaction temperature be 500 DEG C, agent oil
Mass ratio is 4, and air speed is 16 hours-1Under conditions of carry out the first catalytic cracking；A3 group by gained
Divide and carry out hydrotreating in accurate autoclave, the initial boiling point obtaining is 160 DEG C of hydrogenated oils
(HT-A3, hydrocarbon system composition as shown in table 2), reaction temperature be 500 DEG C, agent oil quality ratio for 4,
Air speed is 16 hours-1Under conditions of carry out the 3rd catalytic cracking；First catalytic cracking and the 3rd catalysis are split
Change the catalytic cracking diesel oil of gained and catalytic cracking heavy oil all returns hydrotreating and uses；The conversion of raw material
Rate, total liquid yield, yield of light oil, also six kinds of primary product dry gas, liquefied gas, gasoline, diesel oil,
Cracked fuel oil and the yield of coke, the sulfur content in gasoline and nitrogen content, as shown in table 5.
From table 5, data can be seen that the experimental result with the direct catalytic cracking of VGO in comparative example 1
Compare, by SA1A2 component in embodiment 2 and HT-A3 component respectively the liquefied gas of catalytic cracking gained,
After gasoline collects respectively, liquefied gas, gasoline yield summarized results 2 are respectively higher than wax oil and are directly catalyzed
The liquefied gas of cracking, gasoline yield, the sulfur content in gasoline is significantly lower than the direct catalytic cracking of wax oil simultaneously
Content of sulfur in gasoline, illustrate, using the method for the present invention, heavy oil first carries out separating treatment and hydrotreating
Carry out catalytic cracking afterwards again, obtained high-value product yield and property are better than directly being urged heavy oil
Change the product of cracking.
Embodiment 4
As shown in figure 3, the A3 component of embodiment 1 gained is hydrogenated with accurate autoclave
Process, the initial boiling point obtaining is 160 DEG C of hydrogenated oils (HT-A3, hydrocarbon system's composition is as shown in table 2),
HT-A3 together with the S component of embodiment 1 gained reaction temperature be 500 DEG C, agent oil quality ratio for 4,
Air speed is 16 hours-1Under conditions of carry out the first catalytic cracking；The catalysis of the first catalytic cracking gained is split
Change diesel oil and catalytic cracking heavy oil returns hydrotreating and uses；The conversion ratio of raw material, total liquid yield, light oil
Yield, also six kinds of primary product dry gas, liquefied gas, gasoline, products of diesel oil, cracked fuel oil and coke
Rate, the sulfur content in gasoline and nitrogen content, as shown in table 6.
From table 6, data can be seen that compared with the experimental result of the direct catalytic cracking of VGO, SA1A2
The liquefied gas of catalytic cracking, gasoline yield are respectively higher than wax oil and are directly catalyzed together with HT-A3 component
The liquefied gas of cracking, gasoline yield, the sulfur content in gasoline and nitrogen content are direct significantly lower than wax oil simultaneously
The content of sulfur in gasoline of catalytic cracking and nitrogen content, illustrate first to carry out heavy oil separating using the method for the present invention
Carry out catalytic cracking again, obtained product yield and property are better than directly to after process and hydrotreating
Heavy oil carries out the product of catalytic cracking.
Embodiment 5
By the SA1A2 component of embodiment 1 gained and hydrocracking tail oil, (HCW, from petrochemical industry
Research institute is hydrocracked middle- scale device, and as shown in table 1, hydrocarbon system's composition is as shown in table 2 for fundamental property)
With 1：The mixture of 1 mass ratio mixing, reaction temperature be 500 DEG C, agent oil quality ratio for 4, empty
Speed is 16 hours-1Under conditions of carry out catalytic cracking reaction, its conversion ratio, total liquid yield, yield of light oil,
Also has six kinds of primary product dry gas, liquefied gas, gasoline, yields of diesel oil, cracked fuel oil and coke, vapour
Sulfur content in oil and nitrogen content are as shown in table 7.
As can be seen from Table 7, split carrying out catalysis after SA1A2 component and hydrocracking tail oil mixing
Change, gained liquefied gas and gasoline products yield are high and sulfur in gasoline nitrogen content is low.
Comparative example 1
By VGO directly as catalytically cracked material, enter catalytic cracking unit, in reaction temperature be
500 DEG C, agent oil quality ratio for 4, air speed is 16 hours-1Under conditions of carry out catalytic cracking reaction, its
Conversion ratio, total liquid yield, yield of light oil, also six kinds of primary product dry gas, liquefied gas, gasoline, bavins
Yield, the sulfur content in gasoline and the nitrogen content such as table 4 of oil, cracked fuel oil and coke, shown in 5,6.
Table 1 heavy oil feedstock and the fundamental property of each hydrocarbon system component.
Table 2 is hydrocarbon system's composition of SA1A2, A3, HT-A3 and HCW, and in table, data unit is matter
Amount percent is attached most importance to %.
| Hydrocarbon types | SA1A2 | A3 | HT-A3 | HCW |
| Total saturated hydrocarbons | 59.6 | 0 | 22.7 | 99.4 |
| Total aromatic hydrocarbons | 40.4 | 60.0 | 77.3 | 0.6 |
| Total mononuclear aromatics | 20.3 | 9.4 | 29.2 | 0.6 |
| Total double ring arene | 10.0 | 11.1 | 23.4 | 0 |
| Bicyclic above aromatic hydrocarbons | 10.1 | 39.5 | 24.7 | 0 |
| Colloid | 0 | 40.0 | 0 | 0 |
| Amount to | 100 | 100 | 100 | 100 |
Table 3 is the basic physical properties of MLC-500
| Project | MLC-500 |
| Physical property | |
| Specific surface area/(m2·g-1) | 122 |
| Pore volume/(cm3·g-1) | 0.184 |
| Granularity, mesh | 70～270 |
| Chemical composition (w), % | |
| Na2O | 0.25 |
| Al2O3 | 56.4 |
| SiO2 | 36.9 |
| RE2O3 | 3.7 |
| Micro-activity (12 hours aging) | 69 |
Table 4 is the experimental data of embodiment 2 and comparative example 1.
Table 5 is the experimental data of embodiment 3 and comparative example 1.
Table 6 is the experimental data of embodiment 4 and comparative example 1.
| Project | Embodiment 4 | Comparative example 1 |
| Raw material | SA1A2+(HT-A3) | VGO |
| Reaction temperature/DEG C | 500 | 500 |
| Air speed/h-1 | 16 | 16 |
| Catalyst | MLC-500 | MLC-500 |
| Oil ratio (C/O) | 4 | 4 |
| Conversion ratio (weight), % | 73.74 | 61.11 |
| Yield of light oil (weight), % | 89.50 | 64.52 |
| Total liquid yield (weight), % | 73.13 | 76.71 |
| Product yield (weight), % | ||
| Dry gas | 0.97 | 1.26 |
| Liquefied gas | 16.37 | 12.19 |
| Gasoline | 54.29 | 44.44 |
| Diesel oil | 18.84 | 20.08 |
| Cracked fuel oil | 7.41 | 18.81 |
| Coke | 2.12 | 3.23 |
| Gasoline property | ||
| Sulfur content (weight), μ g/g | 6.59 | 209.5 |
| Nitrogen content (weight), μ g/g | 3.47 | 7.38 |
Table 7 is the experimental data of embodiment 5.
| Project | Embodiment 5 |
| Raw material | SA1A2+HCW |
| Reaction temperature/DEG C | 500 |
| Air speed/h-1 | 16 |
| Catalyst | MLC-500 |
| Oil ratio (C/O) | 4 |
| Conversion ratio (weight), % | 86.07 |
| Yield of light oil (weight), % | 71.73 |
| Total liquid yield (weight), % | 94.20 |
| Product yield (weight), % | |
| Dry gas | 0.83 |
| Liquefied gas | 22.46 |
| Gasoline | 61.13 |
| Diesel oil | 10.61 |
| Cracked fuel oil | 3.32 |
| Coke | 1.65 |
| Total | 100 |
| Gasoline property | |
| Sulfur content (weight), μ g/g | 3.75 |
| Nitrogen content (weight), μ g/g | 0.02 |
Claims (20)
1. a kind of processing of heavy oil combined method, the method includes：
A, heavy oil is carried out separating treatment, obtain SA1A2 component and A3 component；Wherein, with SA1A2
On the basis of the gross mass of component, saturated hydrocarbons, mononuclear aromatics and double ring arene in described SA1A2 component
Total mass fraction is more than 80 mass %；On the basis of the gross mass of A3 component, double in described A3 component
The total mass fraction of the above aromatic hydrocarbons of ring and colloid is more than 50 mass %；
B, the SA1A2 component of gained in step a is carried out the first catalytic cracking reaction, obtain dry gas,
Liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
2. combined method according to claim 1, wherein, on the basis of the gross mass of SA1A2 component,
In described SA1A2 component, the total mass fraction of saturated hydrocarbons, mononuclear aromatics and double ring arene is more than 85 matter
Amount %；On the basis of the gross mass of A3 component, in described A3 component, bicyclic above aromatic hydrocarbons and colloid is total
Mass fraction is more than 55 mass %.
3. combined method according to claim 1, the method also includes step c：By gained in step a
A3 component carries out the second catalytic cracking reaction.
4. combined method according to claim 1, the method also includes step d：By gained in step a
A3 component carries out hydrotreating reaction in the presence of hydrotreating catalyst, obtains hydrogenated oil.
5. combined method according to claim 4, the method also includes step e：By gained in step d
Hydrogenated oil carries out the 3rd catalytic cracking reaction, obtains dry gas, liquefied gas, gasoline, diesel oil, coke
And cracked fuel oil.
6. combined method according to claim 5, the method also includes：By described first catalytic cracking
React the diesel oil obtaining and/or at least a portion of cracked fuel oil and described 3rd Catalytic Cracking Unit of Measure is deserved
To diesel oil and/or at least a portion of cracked fuel oil carry out described hydrotreating together with described A3 component
Reaction.
7. combined method according to claim 4, the method also includes step f：By gained in step d
Hydrogenated oil carries out described first catalytic cracking reaction together with gained SA1A2 component in step a,
Obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
8. combined method according to claim 7, the method also includes：By described first catalytic cracking
React the diesel oil obtaining and/or at least a portion of cracked fuel oil carries out described adding together with described A3 component
Hydrogen processes reaction.
9. the combined method according to any one in claim 1-8, the method also includes：Will
Hydrocracking tail oil carries out described first catalytic cracking reaction together with described SA1A2 component.
10. combined method according to claim 1, wherein, described heavy oil be initial boiling point 350 DEG C with
On straight run vacuum distillate and/or secondary processing process gained initial boiling point be more than 350 DEG C of fraction.
11. combined methods according to claim 10, wherein, described secondary processing process be selected from plus
At least one in hydrogen processing procedure, hydrocracking process, catalytic cracking process and solvent deasphalting process.
12. combined methods according to claim 1, wherein, separating treatment described in step a be selected from
At least one in solvent extraction process, Solid-Phase Extraction process and membrane separation method.
13. combined methods according to claim 12, wherein, described solvent extraction is processed as selected from molten
Agent refines at least one in extraction, supercritical fluid extraction and ion liquid abstraction.
14. combined methods according to claim 12, wherein, it is following that described Solid-Phase Extraction processes inclusion
Step：
First described heavy oil is sent in fixing phase using after dilution dilution agent, obtain the first fixing phase；Then
Aromatic hydrocarbons and C5-C6Alkane volume ratio be 1：(3-5) described in solvent washing, the first fixing phase, obtains
Described SA1A2 component and the second fixing phase；Then aromatic hydrocarbons and monohydric alcohol volume ratio is used to be 1：(0.8-1.5)
Solvent washing second fixing phase, obtain described A3 component；Wherein, described fixing phase contains load silver
Aluminium oxide, by described load silver aluminium oxide gross mass on the basis of, the mass fraction of the silver of load is
0.5-12 mass %.
15. combined methods according to claim 14, wherein, described fixing phase also contains according to fluid
Flow direction is located at the silica gel of aluminium oxide upstream of described load silver and under the aluminium oxide of described load silver
The aluminium oxide of trip；In mass, described silica gel, described load silver aluminium oxide and described positioned at described
The mass ratio of the aluminium oxide in aluminium oxide downstream of load silver is 1：(2.5-5.0)：(0-1.2)；Wherein, institute
The specific surface area stating aluminium oxide is 50-300 rice2/ gram, pore volume is 0.1-0.55 ml/g, described silica gel
Specific surface be 250-850 rice2/ gram, pore volume is 0.25-0.99 ml/g.
16. combined methods according to claim 14, wherein, described diluent is C5-C6Alkane,
By volume, described diluent and the ratio of the volume of heavy oil are (1-10)：1；Described aromatic hydrocarbons be benzene and/
Or toluene, described monohydric alcohol is methanol and/or ethanol；In mass, described fixing phase and described heavy oil
Mass ratio is (8-30)：1.
17. combined methods according to claim 1, wherein, the first Catalytic Cracking Unit of Measure described in step b
The condition answered is：Temperature is 420-520 DEG C, and mass space velocity is 2-20 hour-1, oil ratio is (1-10)：
1.
18. combined methods according to claim 3, wherein, the second Catalytic Cracking Unit of Measure described in step c
The condition answered is：Temperature is 480-540 DEG C, and mass space velocity is 2-20 hour-1, oil ratio is (2-30)：
1.
19. combined methods according to claim 4, wherein, hydrotreating reaction described in step d
Condition is：Hydrogen dividing potential drop is 3-12 MPa, and reaction temperature is 280-360 DEG C, and hydrotreating catalyst is not
Hydrocatalyst for saturating arylhydrocarbon containing acid site；The initial boiling point of hydrogenated oil described in step d is
155-175℃.
20. combined methods according to claim 5, wherein, the 3rd Catalytic Cracking Unit of Measure described in step e
The condition answered is：Temperature is 450-540 DEG C, and mass space velocity is 2-20 hour-1, oil ratio is (2-30)：
1.
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