CN106467759B - A kind of heavy oil pretreatment and the combined method of catalytic cracking - Google Patents
A kind of heavy oil pretreatment and the combined method of catalytic cracking Download PDFInfo
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Abstract
The invention discloses the combined method of a kind of pretreatment of heavy oil and catalytic cracking, this method includes：A, heavy oil is subjected to separating treatment, obtains S components and AR components；Wherein, on the basis of the gross mass of S components, the mass fraction of saturated hydrocarbons is more than 90 mass % in the S components；On the basis of the gross mass of AR components, the sum of the mass fraction of aromatic hydrocarbons and the mass fraction of colloid are more than 90 mass % in the AR components, and the mass fraction of the aromatic hydrocarbons is more than 50 mass %；B, the S components of gained in step a are subjected to the first catalytic cracking reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.Compared with prior art, method using the present invention carries out heavy oil processing and catalytic cracking reaction afterwards, has higher gasoline and liquefied gas yield and lower gasoline sulfur nitrogen content.
Description
Technical field
The present invention relates to the combined methods of a kind of pretreatment of heavy oil and catalytic cracking.
Background technology
Catalytic cracking process is the secondary operation means of most important light materialization of heavy oil, is liquefied petroleum gas, gasoline, bavin
The important production process of the light-end products such as oil is that the process of heavy oil conversion performance is continuously improved and constantly pursues a goal
The process of product selectivity.
Enter at present from atmospheric and vacuum distillation unit the raw material of heavy oil catalytically cracking equipment processing there is no from fractional composition and its
It is distinguished in reactivity worth, is all to be mixed various raw materials into catalytic cracking unit using the form for mixing refining, and
It is converted in same reactor and under the conditions of same process, there is no the reactivity worth according to the different hydro carbons of structure is poor
It is different to take Optimized Measures respectively.The hydro carbons for being largely easy to conversion in raw material is fed together with non-hydrocarbons, condensed-nuclei aromatics
Harmful competition absorption certainly will occur in same reaction zone for reaction, and the reaction of the raw material strong to cracking performance generates retardation,
So as to influence the reaction of entire raw material conversion.The reaction rate of the preferable convertible hydrocarbons of reactivity worth is higher, relatively mild
High conversion ratio can be realized under process conditions, and substantial amounts of condensed ring non-hydrocarbons, condensed-nuclei aromatics and glial response are fast
Rate is low, it is necessary to which harsher process conditions and longer reaction time can be only achieved preferable conversion level.A variety of cracking properties
Different hydro carbons is reacted in same reactor and under the conditions of same process, the reactivity worth difference of different hydrocarbons and reaction
Step it is inconsistent, reaction depth can be caused not optimize and interfered with each other, seriously affected entire raw material catalytic cracking conversion
Efficiency.
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 technologies are mostly anti-to strengthen heavy oil catalytic cracking by technological operation optimization parameter and catalyst
Process is answered, although these methods can only improve yield of light oil to a certain extent, improves the distribution of catalytic cracking production.It is but right
It for inferior raw material is processed, only often attends to one thing and lose sight of another by adjusting catalyst composition and technological parameter, increases heavy oil conversion energy
While power would generally being significantly increased with dry gas and coke yield, heavy oil conversion selectivity so will undoubtedly be caused to become
There is apparent contradictions between difference, i.e. conversion ratio and dry gas and coke selectivity, it is difficult to realize that the hydrocarbon distribution of hydro carbons is optimal
Change and oil product maximizes.
In heavy oil catalytic cracking process, raw material oil nature, catalyst performance, process conditions (temperature, agent oil quality ratio,
Air speed etc.) etc. factors all to product distribution have a major impact, wherein raw material hydro carbons composition be still product distribution basis.According to
Boiling point, which separates heavy oil feedstock, to improve the conversion capability of heavy oil to a certain extent, and improves the distribution of its product.It presses
Feedstock oil is cut into relatively easy cracked distillate and relatively difficult cracked distillate according to boiling point can weaken difficult cracking to a certain extent
The harmful effect of fraction provides a preferable reaction environment for easy cracked distillate, improves product yield and product distribution.CN
It is classification point that 102102029 A, which are disclosed using 500-540 DEG C, carbon residue gravimetric value as 2~4%, and heavy oil feedstock is divided into high-quality original
Material and inferior raw material, result is compared with traditional handicraft, and after heavy oil classification, product distribution is obviously improved, and yield of light oil improves,
Coke and dry gas yield reduce.(button root woods, the research of Chen Jie Catalytic Cracking of Shengli Vacuun Residue such as button root woods
Oil refining design, 1995,25 (2):6-10) utilize supercritical fluid extraction precision separator by catalytically cracked material according to boiling point
Comparative good-quality and raw material inferior are cut into, Shengli VR is divided into 15 components and has investigated the catalytic cracking of preceding 13 fractions
Performance, experiment show to reduce successively with fraction change weight, yield of light oil, and coke yield gradually rises.
Heavy oil is cut into the different narrow fraction of boiling spread by the methods of true boiling point distillation or supercritical fluid extraction, although
Boiling spread can cut very narrow, but each narrow fraction is still the mixture of various hydro carbons.For different fcc raw materials
Speech, boiling range scope and chemical constitution and the larger difference of composition determine their reactivity worth, and there are larger differences.Various hydro carbons
Adsorption capacity on a catalyst can substantially be arranged as follows by its strong and weak order：Condensed-nuclei aromatics>Condensed ring cycloalkane>Alkene>Single alkane
The mononuclear aromatics of base side chain>Cycloalkane>Alkane.It is arranged according to the sequence of chemical reaction rate, then substantially situation is as follows：Alkene
Hydrocarbon>The mononuclear aromatics of macromolecular monoalkyl side chain>Isoparaffin and cycloalkane>The mononuclear aromatics of small molecule monoalkyl side chain>Just
Structure alkane>Condensed-nuclei aromatics.As can be seen that the absorption and cracking of various hydro carbons in raw material, non-hydrocarbons in catalyst surface
There is very big difference in ability, the non-hydrocarbons of condensed ring, condensed-nuclei aromatics and condensed ring cycloalkane adsorption capacity be strong and reaction rate
It is low, and the mononuclear aromatics with longer side chain and macromolecular isoparaffin, cycloalkane adsorption capacity is weak and reaction rate is high, this is just
Cause the competitive Adsorption between different hydrocarbons and the retardation to reaction.Adsorption capacity is strong and condensed ring that reaction rate is low is non-
Hydrocarbon compound, condensed-nuclei aromatics once occupy catalyst surface first, their reaction rates are slow, are not easy to be desorbed or even be condensed into
Catalyst surface is covered in for coke, causes catalyst inactivation, has seriously affected other reaction rates for being easy to cracking hydrocarbons.
Based on this, do not fed using various heavy oil feedstocks as one " entirety ", take into full account the heavy oil feedstock of wide boiling range
Larger difference existing for middle different component cracking performance can separate the component that cracking performance in feedstock oil differs greatly
Carry out catalytic cracking respectively afterwards.
Traditional catalytically cracked material is mainly the vacuum distillate that atmospheric and vacuum distillation unit provides in refinery.Decompressed wax oil fraction
It can be divided into different hydrocarbon system's component such as non-aromatic component and aromatic component, saturated hydrocarbon component and virtue according to the difference of hydrocarbon structure
The hydrocarbon component (is free of colloid), but mononuclear aromatics, double ring arene and the polycyclic aromatic hydrocarbon in aromatic component are in catalytic cracking process
Reflex action still has larger difference, rarely has that separation and concentration is laggard from raw material by the aromatic hydrocarbons of different number of rings in current research report
The research of row catalytic cracking reaction.
At present, market is to the continuous lighting of oil product, high quality and the requirement cleaned and oil supply increasingly heavy
Change, the aggravation of contradictions of in poor quality, and China's economic development is continuously increased the demand of light, the middle matter oil product of high value.Cause
This, such as how more economical rational cost realizes that heavy oil lighting, acquired product can meet the petrol and diesel oil production of continuous harshness again
The oil Refining Technologies of product specification are into one of technology of domestic and international oil Refining Technologies developer focus development.
The arene content of catalytic cracking diesel oil is high, and Cetane number is low, engine ignition poor performance, belongs to diesel oil tune inferior
And component, diesel product quality is seriously affected, is one of the biggest obstacle of each enterprise's diesel product quality upgrading.To faulty wax oil
Raw material carries out weighted BMO spaces, and aromatic hydrocarbons obtains different degrees of saturation, except desulfuration, nitrogen, metal impurities, is re-used as catalytic cracking
Raw material, can be according to production needs, production diesel oil, quality products and the intermediate products such as gasoline, so as to improve its catalysis
Cracking performance significantly improves the structure of product.1896192 A of CN disclose a kind of wax oil hydrogenation processing and catalytic cracking is two-way
Method, wax oil together with heavy catalytic cycle oil and catalytic cracking diesel oil into hydrotreater reaction after obtain gas,
The products such as hydrotreated naphtha, hydrogenated diesel oil and hydrogenation tail oil, wherein hydrogenation tail oil enter catalytic cracking unit reaction, and this method carries
High light oil yield, reduces coke yield, while reduces the arene content of diesel oil and sulfur content and improve its hexadecane
Value.
Similarly, CN101434865A also discloses a kind of heavy distillate hydrotreating and catalytic cracking combined side
Method.But these methods are directly by second-rate catalytic cracking heavy oil and catalytic cracking diesel oil and the wax oil containing a large amount of saturated hydrocarbons
Raw material is mixed, and the saturated hydrocarbons in wax oil is easy to split in hydroprocessing processes due to the effect of acid centre on catalyst
Lighter hydrocarbons are melted into, gas yield is caused to increase, while the hydrogenation heavy oil proportion generated is smaller, during charging as catalytic cracking unit
Lightweight oily yield declines.
Therefore, there are spaces to be modified for current processing of heavy oil technique.
The content of the invention
The object of the present invention is to provide the combined methods of a kind of pretreatment of heavy oil and catalytic cracking, and this method is by by heavy oil
It carries out the obtained S components of separating treatment and AR components carries out catalytic cracking reaction respectively, there is higher gasoline and liquefied gas
Yield and lower gasoline sulfur nitrogen content.
To achieve these goals, the present invention provides the combined method of a kind of heavy oil pretreatment and catalytic cracking, this method
Including：A, heavy oil is subjected to separating treatment, obtains S components and AR components；Wherein, on the basis of the gross mass of S components, the S
The mass fraction of saturated hydrocarbons is more than 90 mass % in component；On the basis of the gross mass of AR components, aromatic hydrocarbons in the AR components
The sum of mass fraction and the mass fraction of colloid are more than 90 mass %, and the mass fraction of the aromatic hydrocarbons is more than 50 mass %；B, will
The S components of gained carry out the first catalytic cracking reaction in step a, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracking weight
Oil.
Preferably, wherein, on the basis of the gross mass of S components, the mass fraction of saturated hydrocarbons is more than 95 matter in the S components
Measure %；On the basis of the gross mass of AR components, the sum of the mass fraction of aromatic hydrocarbons and the mass fraction of colloid are big in the AR components
In 95 mass %, the mass fraction of the aromatic hydrocarbons is more than 55 mass %.
Preferably, this method further includes step c：Gained AR components in step a are subjected to the second catalytic cracking reaction.
Preferably, this method further includes step d：By gained AR components in step a under the action of hydrotreating catalyst
Hydrotreating reaction is carried out, obtains hydrogenated oil.
Preferably, this method further includes step e：Gained hydrogenated oil in step d is subjected to the 3rd catalytic cracking reaction,
Obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
Preferably, this method further includes：The diesel oil and/or cracked fuel oil that first catalytic cracking reaction is obtained are extremely
The diesel oil and/or at least a portion and the AR groups of cracked fuel oil that a few part and the 3rd catalytic cracking reaction obtain
Divide and carry out the hydrotreating reaction together.
Preferably, this method further includes step f：By gained hydrogenated oil in step d and gained S components one in step a
It rises and carries out first catalytic cracking reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
Preferably, this method further includes：The diesel oil and/or cracked fuel oil that first catalytic cracking reaction is obtained are extremely
It is a part of less to carry out the hydrotreating reaction together with the AR components.
Preferably, this method further includes：Hydrocracking tail oil is subjected to first catalytic cracking together with the S components
Reaction.
Preferably, wherein, the heavy oil is straight run vacuum distillate and/or secondary operation of the initial boiling point at 350 DEG C or more
Initial boiling point is more than 350 DEG C of fraction obtained by process.
Preferably, wherein, the secondary processing process is selected from hydroprocessing processes, hydrocracking process, catalytic cracking
At least one of process and solvent deasphalting process.
Preferably, wherein, separating treatment described in step a is selected from solvent extraction processing, Solid Phase Extraction processing and film point
From at least one of processing method.
Preferably, wherein, the solvent extraction processing is selected from solvent refining extraction, supercritical fluid extraction and ionic liquid
At least one of body extraction.
Preferably, wherein, the Solid Phase Extraction processing comprises the following steps：After the heavy oil first is used dilution dilution agent
It is sent into stationary phase, obtains the first stationary phase；Then C is used5-C6Alkane rinse first stationary phase, obtain the S components
With the second stationary phase；Then it is 1 with aromatic hydrocarbons and monohydric alcohol volume ratio：Second stationary phase of solvent washing of (0.8-1.5), obtains institute
State AR components；Wherein, the stationary phase contains the aluminium oxide of load silver, using the gross mass of the aluminium oxide of the load silver as base
Standard, the mass fraction of the silver of load is 0.5-12 mass %.
Preferably, wherein, the stationary phase also contains is located at the silver-colored aluminium oxide upstream of the load according to fluid flow direction
Silica gel and the aluminium oxide positioned at the aluminium oxide downstream of the load silver；In mass, the oxidation of the silica gel, the load silver
The mass ratio of aluminium and the aluminium oxide positioned at the aluminium oxide downstream of the load silver is 1：(2.5-5.0)：(0-1.2)；Its
In, the specific surface area of the aluminium oxide is 50-300 meters2/ gram, pore volume is 0.1-0.55 mls/g, the ratio table of the silica gel
Face is 250-850 meters2/ gram, pore volume is 0.25-0.99 mls/g.
Preferably, wherein, the diluent is C5-C6Alkane, by volume, the volume of the diluent and heavy oil it
Than for (1-10)：1；The aromatic hydrocarbons is benzene and/or toluene, and the monohydric alcohol is methanol and/or ethyl alcohol；In mass, it is described solid
Fixed is mutually (8-30) with the mass ratio of the heavy oil：1.
Preferably, wherein, the condition of the first catalytic cracking reaction is described in step b：Temperature is 420-520 DEG C, quality
When air speed is 2-20 small-1, oil ratio is (1-10)：1.
Preferably, wherein, the condition of the second catalytic cracking reaction is described in step c：Temperature is 480-540 DEG C, quality
When air speed is 2-20 small-1, oil ratio is (2-30)：1.
Preferably, wherein, the condition of hydrotreating reaction is described in step d：Hydrogen partial pressure be 3-12 megapascal, reaction temperature
For 280-360 DEG C, hydrotreating catalyst is the hydrocatalyst for saturating arylhydrocarbon for not containing acid site；It is hydrogenated with described in step d
The initial boiling point of generation oil is 155-175 DEG C.
Preferably, wherein, the condition of the 3rd catalytic cracking reaction is described in step e：Temperature is 450-540 DEG C, quality
When air speed is 2-20 small-1, oil ratio is (2-30)：1.
Compared with prior art, it is of the invention to be advantageous in that：
1st, the separation of S components and AR components in heavy oil is realized based on isolation technics, is differed greatly for dynamic behavior
S components and AR components can individually be reacted under most matched catalytic cracking condition respectively, both eliminate different hydrocarbons
Between influence each other, and each hydrocarbon system can be made to be reacted under conditions of optimization, improve the utilization rate of hydrogen in heavy oil, from
And save petroleum resources.
2nd, the solution of the present invention can connect a hydrotreating unit before the catalytic cracking unit of AR components, to realize
Two kinds of purposes：First, hydrogen addition technology is selective hydrogenation, and hydrodesulfurization, hydrodenitrogeneration reaction occur for AR components, and selectively full
With polycyclic aromatic hydrocarbon and colloid, appropriate saturated bicyclic aromatic hydrocarbons, mononuclear aromatics saturation is few, and almost without acid site on catalyst,
The macromolecule hydrocarbon of the fractional saturation of generation or full saturation is retained to the greatest extent, and low-sulfur vapour is produced for catalytic cracking unit
Oil provides quality raw materials, while can control catalytic gasoline sulphur nitrogen content by controlling the reaction depth of hydrotreating unit；Its
Secondary, the catalytic cracking diesel oil and catalytic cracking heavy oil flowed out from different catalytic cracking units may return to hydrotreating list
Member, the appropriateness of bicyclic Yi Shang aromatic hydrocarbons therein are hydrogenated with the charging after saturated reaction as catalytic cracking unit, are catalytic cracking list
Member production high-knock rating gasoline provides high-quality charging.
3rd, by method provided by the invention, catalytic cracking diesel oil and catalytic cracking heavy oil can be returned to hydrotreating list
Member carries out cracking again after being hydrogenated with, catalytic cracking conversion per pass does not pursue high conversion first, and pursues the total of whole process
Conversion ratio does not produce the catalytic diesel oil that arene content is high, Cetane number is low in catalytic cracking unit, reduces dry gas and coke
Yield improves the yield of liquefied gas and high-knock rating gasoline；Secondly the fractionating system of catalytic cracking reaction effluent is only fractionated
Go out the light-end products such as gasoline fraction, the theoretical cam curve needed for fractionating column substantially reduces；Finally to being rich in polycyclic aromatic hydrocarbon and colloid
Raw material play diluting effect, the two is more prone to the conveying of mixed raw material oil after being mixed with certain proportion.
4th, catalytic cracking process raw material range of choice is added, improves the hydrogen utilization rate in raw material, improves product point
Cloth improves gasoline yield and productivity of propylene, makes product restructuring more flexible.
5th, idetified separation process, hydrotreating and catalytic cracking technology more reasonably integrate, high for oil refining production process
The rationalization of effectization and refined oil product provides a new approach.
6th, heavy oil is carried out separating treatment by the present invention, is reduced the sulphur nitrogen content in S components, and is further reduced S components
Sulphur nitrogen content through catalytic cracking products obtained therefrom, in addition, the AR components of high-sulfur nitrogen content, can carry out hydrotreating reaction progress
Sulphur nitrogen is removed, so as to reduce the sulphur nitrogen content in catalytic cracking product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is together for explaining the present invention, but be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the flow diagram of the first specific embodiment of the method for the present invention；
Fig. 2 is the flow diagram of second of specific embodiment of the method for the present invention；
Fig. 3 is the flow diagram of the third specific embodiment of the method for the present invention.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides the combined method of a kind of heavy oil pretreatment and catalytic cracking, and this method includes：A, heavy oil is carried out
Separating treatment obtains S components and AR components；Wherein, on the basis of the gross mass of S components, the quality of saturated hydrocarbons in the S components
Fraction is more than 90 mass %, preferably greater than 95 mass %；On the basis of the gross mass of AR components, the matter of aromatic hydrocarbons in the AR components
It measures the sum of fraction and the mass fraction of colloid and is more than 90 mass %, preferably greater than 95 mass %, the mass fraction of the aromatic hydrocarbons is big
In 50 mass %, preferably greater than 55 mass %；B, the S components of gained in step a are subjected to the first catalytic cracking reaction, are done
Air-liquid gas, gasoline, diesel oil, coke and cracked fuel oil.
According to the present invention, the saturated hydrocarbons including alkane and cycloalkane is mainly contained in the S components, remaining can be virtue
Hydrocarbon；Contained aromatic hydrocarbons is well-known to those skilled in the art in the AR components, and the present invention repeats no more, and contained colloid is
Refer to and the normal heptane solvent of residual oil is isolated into the component obtained after saturated hydrocarbons and aromatic hydrocarbons by aluminium oxide liquid chromatogram, specifically may be used
Referring to《Catalytic cracking chemistry and technique》, permitted close friend and write, 2013, Science Press, for example, RIPP10-90 tests may be employed
Method carries out separation determination, since heavy oil composition and residual oil can use saturated hydrocarbons, aromatic hydrocarbons, resin and asphalt to carry out boundary
It is fixed, therefore the colloid in heavy oil can also be so defined.It is currently preferred that under conditions of each component definition is met,
Separating treatment should be such that alkane and cycloalkane is enriched in S components as far as possible, and aromatic hydrocarbons and colloid are enriched in AR to the greatest extent
In component, intersection therebetween is reduced.
It is an object of the invention to be directed to different hydrocarbons competitive Adsorption in current Conventional catalytic cracking reactor, difficult cracking
Hydro carbons such as polycyclic aromatic hydrocarbon and colloid generate strong adsorption in catalyst surface and are but difficult to cracking, and the cracking reaction of saturated hydrocarbons is generated
Retardation causes quite a few easy cracking hydrocarbons is not sufficiently reactive to be just stripped the problem of entering in product, this hair
Bright that S components and AR components can separately be carried out to catalytic cracking, i.e. this method can also include step c：By gained AR in step a
Component carries out the second catalytic cracking reaction.
According to the present invention, since the degree of unsaturation of AR components is higher, this method can also include step d：By step a
Middle gained AR components carry out hydrotreating reaction under the action of hydrotreating catalyst, obtain hydrogenated oil.In the present invention
Hydrotreating is and the mononuclear aromatics in order to by hydrogenation double ring arene, polycyclic aromatic hydrocarbon and colloid be made to occur different degrees of saturation
As few as possible is saturated, while retains the aromatic hydrocarbons after hydrogenation as much as possible, therefore the hydrotreating used is preferably to select
Property hydrotreating, obtained product is mainly hydrogenated oil, and its yield is preferably not less than 70-99 weight %.The hydrogenation
Generation oil refers to the distillate that boiling point is 150 DEG C -600 DEG C or so, is marked with HT-AR, the initial boiling point of preferably hydrogenated oil is
150 DEG C -250 DEG C, more preferably 155 DEG C -175 DEG C.The yield of hydrogenated oil when the present invention can be by controlling hydrotreating
The degree of hydro-upgrading is controlled, so that it is guaranteed that will not both cause the gas yield too high during hydro-upgrading, causes loss too many
Light oil can also ensure that subsequent catalytic cracking easily carries out.
According to the present invention, the hydrogenated oil is a kind of good catalyst cracking raw material, therefore this method further includes
Step e：By in step d gained hydrogenated oil carry out the 3rd catalytic cracking reaction, obtain dry gas, liquefied gas, gasoline, diesel oil,
Coke and cracked fuel oil；And it may further include step f：By gained hydrogenated oil in step d and gained S groups in step a
Divide and carry out first catalytic cracking reaction together, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
According to the present invention, in order to further utilize catalytic cracking reaction obtained by diesel oil and cracked fuel oil, realize diesel oil and
The full conversion of cracked fuel oil, therefore this method can also include after step e：First catalytic cracking reaction is obtained
The diesel oil and/or cracked fuel oil that at least a portion and the 3rd catalytic cracking reaction of diesel oil and/or cracked fuel oil obtain
At least a portion carry out the hydrotreating reaction together with the AR components；This method can also include after step f：It will
The diesel oil and/or at least a portion of cracked fuel oil that first catalytic cracking reaction obtains carry out institute together with the AR components
State hydrotreating reaction.Diesel oil obtained by catalytic cracking is primarily referred to as in catalytic cracking full distillate product 221 DEG C -343 DEG C or so
Fraction, the cracked fuel oil of gained refers mainly to 350 DEG C or more fractions in catalytic cracking full distillate product.Wherein, catalytic cracking institute
Bicyclic Yi Shang arene content can account for more than 40 mass % in the diesel oil obtained, and further up to more than 50 mass %, this part evaporates
Divide and return to the appropriate saturation of hydrotreating unit progress, continue cracking reaction subsequently into catalytic cracking unit, for generation height
Octane rating gasoline provides high-quality charging；Mass fraction of the diesel oil of the present invention in hydrotreating unit mixed feeding may range from
% heavy more than 0 to 50, more preferably higher than 0 to 30 heavy %.Bicyclic and above arene content can reach in the cracked fuel oil
More than 40 mass %, further up to more than 50 mass %, this part fraction returns to hydrotreating unit and carries out appropriate saturation, increases
Content is hydrogenated with, continues cracking reaction subsequently into catalytic cracking unit, high-quality charging is provided for generation high-knock rating gasoline.
Mass fraction of the cracked fuel oil of the present invention in hydrotreating unit mixed feeding ranges preferably from % heavy more than 0 to 50, more
Preferably greater than 0 to 30 heavy %.
According to the present invention it is possible to hydrocracking tail oil is subjected to first catalytic cracking reaction together with the S components.
The hydrocracking tail oil refers to uncracked saturated hydrocarbons caused by hydrocracking reaction.
According to the present invention, the heavy oil is well-known to those skilled in the art that can be initial boiling point at 350 DEG C or more
Initial boiling point is more than 350 DEG C of fraction obtained by straight run vacuum distillate and/or secondary processing process, and the initial boiling point refers to oil product
The minimum value of boiling range.Wherein, the secondary processing process can be to be split selected from hydroprocessing processes, hydrocracking process, catalysis
At least one of change process and solvent deasphalting process.
According to the present invention, separating treatment described in step a refers to the process of heavy oil being separated into S components and AR components, can
Think selected from least one of solvent extraction processing, Solid Phase Extraction processing and membrane separation method, different separating treatments
Method can be used alone, and can also be used in series.The solvent extraction processing is preferably selected from solvent refining and extracts, is overcritical
Single solvent extraction may be employed at least one of fluid extraction and ion liquid abstraction, can also use multi-solvent extraction side
Formula, it is preferred to use multi-solvent extracts mode.Solid phase described in the Solid Phase Extraction processing can include splitter, vacuum system
Etc. equipment, preferably include following steps：The heavy oil is first obtained into the first fixation using being sent into after dilution dilution agent in stationary phase
Phase；Then C is used5-C6Alkane rinse first stationary phase, obtain the S components and the second stationary phase；Then with aromatic hydrocarbons and
Monohydric alcohol volume ratio is 1：Second stationary phase of solvent washing of (0.8-1.5), obtains the AR components；Wherein, the stationary phase
Aluminium oxide containing load silver, on the basis of the gross mass of the aluminium oxide of the load silver, the mass fraction of the silver of load is
0.5-12 mass %.The stationary phase can also contain the silica gel for the aluminium oxide upstream for being located at the load silver according to fluid flow direction
And the aluminium oxide positioned at the aluminium oxide downstream of the load silver；In mass, the silica gel, it is described load silver aluminium oxide with
And the mass ratio of the aluminium oxide positioned at the aluminium oxide downstream of the load silver can be 1：(2.5-5.0)：(0-1.2)；Its
In, the specific surface area of the aluminium oxide can be 50-300 meters2/ gram, pore volume can be 0.1-0.55 mls/g, the silicon
The specific surface of glue can be 250-850 meters2/ gram, pore volume can be 0.25-0.99 mls/g.The diluent can be C5-
C6Alkane, by volume, the ratio between volume of the diluent and heavy oil can be (1-10)：1；The aromatic hydrocarbons can be benzene
And/or toluene, the monohydric alcohol can be methanol and/or ethyl alcohol；In mass, the stationary phase and the mass ratio of the heavy oil
Can be (8-30)：1.
According to the present invention, the catalytic cracking reaction is well-known to those skilled in the art that the present invention repeats no more.Root
According to the difference of reaction raw materials, the condition of catalytic cracking reaction can be different, for example, the first catalytic cracking reaction described in step b
Condition can be：Temperature is 420-520 DEG C, is preferably 480-520 DEG C, when mass space velocity is 2-20 small-1, it is preferably 5-20 small
When-1, oil ratio is (1-10)：1, be preferably (4-10)：1；The condition of the second catalytic cracking reaction can be described in step c：
Temperature is 480-540 DEG C, when mass space velocity is 2-20 small-1, when being preferably 5-20 small-1, oil ratio is (2-30)：1, be preferably
(4-10)：1；The condition of the 3rd catalytic cracking reaction can be described in step e：Temperature is 450-540 DEG C, is preferably 480-
520 DEG C, when mass space velocity is 2-20 small-1, when being preferably 5-20 small-1, oil ratio is (2-30)：1, be preferably (4-10)：1.
According to the present invention, the hydrotreating reaction is well-known to those skilled in the art that the present invention repeats no more.Step
The condition of hydrotreating reaction is described in rapid d：Hydrogen partial pressure is 3-12 megapascal, preferably 4-8 megapascal, reaction temperature 280-
360 DEG C, hydrotreating catalyst is the hydrocatalyst for saturating arylhydrocarbon for not containing acid site；Hydrogenated oil described in step d
Initial boiling point be 155-175 DEG C.
Three kinds of specific embodiments of the method for the present invention are provided below, but the present invention is not limited thereto.
The first specific embodiment of the present invention is as shown in Figure 1：
S components and AR components have been obtained after heavy oil is carried out separating treatment, the S components of gained and AR components have been carried out respectively
First catalytic cracking reaction and the second catalytic cracking reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
Meanwhile can hydrocracking tail oil be subjected to the first catalytic cracking reaction together with after the mixing of S components.
Second of specific embodiment of the present invention is as shown in Figure 2：
S components and AR components have been obtained after heavy oil is carried out separating treatment, the S components of gained are subjected to the first catalytic cracking
Reaction, obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；Gained AR components are subjected to hydrotreating reaction, are obtained
The hydrogenated oil arrived carries out the 3rd catalytic cracking reaction, obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；
The diesel oil of gained and cracked fuel oil are subjected to hydrotreating reaction, obtain hydrogenated oil.It meanwhile can be by hydrocracking tail oil
The first catalytic cracking reaction is carried out together with after the mixing of S components.
The third specific embodiment of the present invention is as shown in Figure 3：Will heavy oil carry out separating treatment after obtained S components and
Gained AR components are carried out hydrotreating reaction by AR components, and obtained hydrogenated oil and S components carry out the first catalysis and split together
Change reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；The diesel oil of gained and cracked fuel oil are added
Hydrogen processing reaction, obtains hydrogenated oil.Meanwhile after hydrocracking tail oil and S components can be mixed together with being hydrogenated to
Oil carries out the first catalytic cracking reaction.
It will be further illustrated the present invention below by embodiment, but the present invention is not therefore subject to any restriction.
Reagent and instrument used by the embodiment of the present invention are the instrument and reagent of this field routine unless otherwise specified.
The ACE Model that the catalytic cracking reaction taken in the embodiment of the present invention and comparative example is produced in KTI companies of the U.S.
It is carried out on AP devices, catalyst loading amount is 9g in experiment, and reaction temperature is 500 DEG C, when mass space velocity is 16 small-1, agent/oil
Amount is 4 than (C/O).After experiment parameter is stablized, into response procedures, catalyst is in self gravitation and N2Effect is lower into reaction
Device, feedstock oil promote lower edge charging tubule to enter in reactor catalyst fluidized-bed layer in plunger pump, the catalyst with fluidizing state
Particle haptoreaction, while using N2Strip 600-900s.Reaction product is by N2It brings -10 DEG C of liquid into and receives progress gas-liquid point in bottle
From gaseous product, which is collected, to be completed to be made of Agilent 6890GC (TCD detectors) on-line analysis；It is offline after liquid product collection
It weighs, carries out simulation distillation respectively and gasoline detailed hydrocarbon analyzes (being tested using RIPP81-90 test methods), gasoline and bavin
The fraction cut point of oil is respectively 221 DEG C and 343 DEG C；Green coke catalyst draw off after on 2000 carbon and sulfur analytical instruments of multi EA
Coke and analysis of sulfur content (being tested using RIPP106-90 test methods) are carried out, all product qualities, which sum it up, calculates material
Balance.
The trade mark that Sinopec catalyst Co., Ltd produces is used to be split for the catalysis of MLC-500 in embodiment and comparative example
Change catalyst as experiment catalyst, micro-activity can be measured by RIPP92-90 measuring methods of the prior art,
Basic physical properties are listed in table 3.
The 500mL precision reaction under high pressures that the hydroprocessing processes of embodiment are produced in Yantai Ke Li Chemical Equipment Co., Ltd.s
It is carried out in kettle, which is 1.5K heavy, dischargeable capacity 0.5L, maximum speed 1500rpm.A certain amount of AR is added
Enter in reaction kettle, used catalyst is catalyzed for the granularity of Research Institute of Petro-Chemical Engineering's production in the sulphided state of 40~60 mesh
Agent, trade mark RIB-429.With hydrogen by after air displacement in kettle, unlatching speed of agitator is 338rpm, starts simultaneously at temperature programming
It it is 340 DEG C to reaction temperature, after reaching design temperature, hydrogen partial pressure is adjusted to 5MPa, speed of agitator 985rpm, and the reaction time is
After reaction, ON cycle condensed water cooling down to room temperature uses N to 12h2Displacement gas reactor is vented afterwards for several times, in kettle
The product liquid of product liquid carries out fraction cutting, obtains hydrogenated oil HT-AR.
S components, AR components, hydrocarbon system's composition of HT-AR components and HCW are tested using RIPP10-90 test methods.
The present invention RIPP test methods be selected from《Petrochemical Engineering Analysis method (RIPP test methods)》, Yang Cui is fixed etc.
It compiles, Science Press, 1990.
Embodiment 1
The present embodiment separates for illustrating that heavy oil provided by the invention is pre-processed with heavy oil in the combined method of catalytic cracking
The implementation of processing.(specific surface area is 152 meters to bottom filling 30g neutral aluminas in splitter2/ gram, pore volume is
0.213 ml/g), (silver-colored mass fraction is 7.05 mass % to the aluminium oxide of centre filling 110g load silver, using silver nitrate
It is prepared by dipping method), (specific surface area is 479 meters to upper strata filling 30g silica gel2/ gram, pore volume is 0.349 ml/g)；It will divide
It is connected from column lower end with pumped vacuum systems.The total volume of stationary phase is 150mL.Take decompressed wax oil (VGO, during Tahe Crude Oil is derived from
State's petrochemical industry northwest branch company system in Tahe Oilfield, Tahe decompressed wax oil is obtained in Research Institute of Petro-Chemical Engineering through true boiling point distillation) sample
Product 10.13g (11.11mL), is dissolved in 30mL n-hexanes, is first consolidated with what is loaded in the above-mentioned splitter of n-hexane wetting of 100mL
Determine phase, then the hexane solution of above-mentioned oil sample is added in splitter.S components are flushed out with 170mL n-hexanes respectively,
255mL toluene：Ethyl alcohol volume ratio is 1：1 solvent washing goes out AR components.It is evaporated using rotary evaporator in S components and AR components
Solvent, obtain 4.92 grams of S components, 5.08 grams of AR components lose 0.13 gram.Feedstock oil used in embodiment, comparative example
Table 1 is listed in the basic physical properties data of the component after separation, and S components, hydrocarbon system's composition data of AR components are listed in table 2, S in heavy oil
Constituent mass content is that the mass content of 49.2 mass %, AR components is 50.8 mass %.
Embodiment 2
As shown in Figure 1, using the S components of 1 gained of embodiment and AR components as catalytically cracked material, in reaction temperature
For 500 DEG C, agent oil quality ratio be 4, air speed for 16 it is small when-1Under conditions of carry out the first catalytic cracking reaction and the second catalytic cracking
Reaction, conversion ratio, total liquid yield, yield of light oil also have six kinds of primary product dry gas, liquefied gas, gasoline, diesel oil, cracking weight
The yield of oil and coke, sulfur content and nitrogen content in gasoline, as shown in table 4.
It can be seen from the data in Table 4 that compared with the experimental result of the direct catalytic cracking of VGO, S and AR components are urged respectively
After liquefied gas, gasoline obtained by change cracking summarize respectively, liquefied gas, gasoline yield summarized results 1, which are respectively higher than VGO, directly to carry out
The liquefied gas of catalytic cracking, gasoline yield, while sulfur content in gasoline and nitrogen content are less than the vapour of the direct catalytic cracking of wax oil
Oily sulfur content and nitrogen content, this illustrates that method using the present invention carries out catalytic cracking again after heavy oil is first carried out separating treatment,
Obtained high-value product yield and property are superior to directly carry out heavy oil the product of catalytic cracking.
Embodiment 3
As shown in Fig. 2, by the S components of the gained of embodiment 1 reaction temperature be 500 DEG C, agent oil quality ratio is 4, air speed is
16 it is small when-1Under conditions of carry out the first catalytic cracking；The AR components of gained are subjected to hydrotreating in accurate autoclave,
Obtained initial boiling point is 160 DEG C of hydrogenated oils (HT-AR, hydrocarbon system's composition are as shown in table 2), reaction temperature be 500 DEG C, agent oil
Mass ratio is 4, when air speed is 16 small-1Under conditions of carry out the 3rd catalytic cracking；By the first catalytic cracking and the 3rd catalytic cracking
The catalytic cracking diesel oil and catalytic cracking heavy oil of gained return to hydrotreating and use；Conversion ratio, total liquid yield, the light oil of raw material are received
Rate, also has the yield of six kinds of primary product dry gas, liquefied gas, gasoline, diesel oil, cracked fuel oil and coke, the sulfur content in gasoline
And nitrogen content, as shown in table 5.
It can be seen from the data in Table 5 that compared with the experimental result of the direct catalytic cracking of VGO in comparative example 1, by embodiment
After the liquefied gas obtained by catalytic cracking, gasoline summarize respectively respectively, liquefied gas, gasoline yield are converged for S components and HT-AR components in 2
Overall result 2 is respectively higher than wax oil and directly carries out liquefied gas, the gasoline yield of catalytic cracking, while sulfur content in gasoline and nitrogen contain
Amount illustrates that method using the present invention is advanced by heavy oil significantly lower than the content of sulfur in gasoline and nitrogen content of the direct catalytic cracking of wax oil
Catalytic cracking is carried out after row separating treatment and hydrotreating again, obtained high-value product yield and property are better than directly to
Heavy oil carries out the product of catalytic cracking.
Embodiment 4
As shown in figure 3, the AR components of 1 gained of embodiment are carried out hydrotreating in accurate autoclave, obtain
Initial boiling point is 160 DEG C of hydrogenated oils (HT-AR, hydrocarbon system's composition are as shown in table 2), the S components one of HT-AR and 1 gained of embodiment
Rise reaction temperature be 500 DEG C, agent oil quality ratio is 4, air speed for 16 it is small when-1Under conditions of carry out the first catalytic cracking；By
Catalytic cracking diesel oil and catalytic cracking heavy oil obtained by one catalytic cracking return to hydrotreating and use；The conversion ratio of raw material, total liquid
It receives, yield of light oil, also has the yield of six kinds of primary product dry gas, liquefied gas, gasoline, diesel oil, cracked fuel oil and coke, gasoline
In sulfur content and nitrogen content, as shown in table 6.
It can be seen from the data in Table 6 that compared with the experimental result of the direct catalytic cracking of VGO, S and HT-AR components are together
The liquefied gas of catalytic cracking, gasoline yield are respectively higher than liquefied gas, the gasoline yield that wax oil directly carries out catalytic cracking, while vapour
Sulfur content and nitrogen content in oil are significantly lower than the content of sulfur in gasoline and nitrogen content of the direct catalytic cracking of wax oil, illustrate using this hair
Bright method carries out catalytic cracking, obtained product yield and property again after heavy oil first to be carried out to separating treatment and hydrotreating
It is of fine quality in directly by heavy oil carry out catalytic cracking product.
Embodiment 5
By the S components of 1 gained of embodiment and hydrocracking tail oil, (HCW is hydrocracked from Research Institute of Petro-Chemical Engineering
Middle- scale device, fundamental property is as shown in table 1, and hydrocarbon system's composition is as shown in table 2) with 1：The mixture of 1 mass ratio mixing is reacting
Temperature is 500 DEG C, agent oil quality ratio is 4, when air speed is 16 small-1Under conditions of carry out catalytic cracking reaction, conversion ratio, total liquid
It receives, yield of light oil, also has the yield of six kinds of primary product dry gas, liquefied gas, gasoline, diesel oil, cracked fuel oil and coke, gasoline
In sulfur content and nitrogen content, as shown in table 7.
As can be seen from Table 7, will S components and hydrocracking tail oil mix after carry out catalytic cracking, gained liquefied gas and
Gasoline products yield is high and sulfur in gasoline nitrogen content is low.
Comparative example 1
It is 500 DEG C, agent oil quality in reaction temperature into catalytic cracking unit by VGO directly as catalytically cracked material
Than for 4, air speed for 16 it is small when-1Under conditions of carry out catalytic cracking reaction, conversion ratio, total liquid yield, yield of light oil also have six
Kind of primary product dry gas, liquefied gas, gasoline, diesel oil, the yield of cracked fuel oil and coke, sulfur content and nitrogen content in gasoline are such as
Table 4,5, shown in 6.
Table 1 is decompressed wax oil (VGO) and its S component and the fundamental property of AR components that are isolated to and is hydrocracked
The fundamental property of tail oil (HCW).
| Project | S | AR | VGO | HCW |
| Density (100 DEG C)/(gcm-3) | 0.8086 | 0.9300 | 0.8825 | 0.7911 |
| Viscosity (100 DEG C)/(mm2·s-1) | 4.829 | 19.012 | 9.8463 | 3.571 |
| Carbon residue, % | <0.05 | 1.83 | 0.48 | <0.05 |
| W (C), % | 85.90 | 85.90 | 86.07 | 85.59 |
| W (H), % | 13.92 | 10.42 | 11.99 | 14.34 |
| n(H)/n(C) | 1.94 | 1.45 | 1.67 | 2.03 |
| w(S)/(μg.g-1) | 67 | 21754 | 17000 | 10 |
| w(N)/(μg.g-1) | 1.7 | 3372.8 | 1800 | 1.0 |
| Boiling range scope/DEG C | 350~478 | 350~558 | 350~559 | 350~496 |
Table 2 is that the hydrocarbon system of S components, AR components, HT-AR and HCW form, and data unit is that mass percent is in table
Weight %.
| Component | S | AR | HT-AR | HCW |
| Total saturated hydrocarbons | 97.4 | 0 | 27.8 | 99.4 |
| Alkane | 25.8 | 0 | 4.3 | 38.6 |
| Total cycloalkane | 71.6 | 0 | 23.5 | 60.8 |
| Total aromatic hydrocarbons | 2.6 | 83.6 | 72.2 | 0.6 |
| Colloid | 0 | 16.5 | 0.0 | 0.6 |
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 when small (12 aging) | 69 |
Table 4 is embodiment 2 and the experimental data of comparative example 1.
Table 5 is embodiment 3 and the experimental data of comparative example 1.
Table 6 is embodiment 4 and the experimental data of comparative example 1.
| Project | Embodiment 4 | Comparative example 1 |
| Raw material | S+(HT-AR) | 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), % | 78.14 | 61.11 |
| Yield of light oil (weight), % | 71.31 | 64.52 |
| Total liquid yield (weight), % | 90.50 | 76.71 |
| Product yield (weight), % | ||
| Dry gas | 0.90 | 1.26 |
| Liquefied gas | 19.19 | 12.19 |
| Gasoline | 56.46 | 44.44 |
| Diesel oil | 14.85 | 20.08 |
| Cracked fuel oil | 6.15 | 18.81 |
| Coke | 1.59 | 3.23 |
| Gasoline property | ||
| Sulfur content (weight), μ g/g | 1.1 | 209.5 |
| Nitrogen content (weight), μ g/g | 3.08 | 7.38 |
Table 7 is the experimental data of embodiment 5.
| Project | Embodiment 5 |
| Raw material | S+HCW |
| Reaction temperature/DEG C | 500 |
| Air speed/h-1 | 16 |
| Catalyst | MLC-500 |
| Oil ratio (C/O) | 4 |
| Conversion ratio (weight), % | 91.99 |
| Yield of light oil (weight), % | 70.95 |
| Total liquid yield (weight), % | 96.40 |
| Product yield (weight), % | |
| Dry gas | 0.82 |
| Liquefied gas | 25.45 |
| Gasoline | 64.49 |
| Diesel oil | 6.46 |
| Cracked fuel oil | 1.55 |
| Coke | 1.23 |
| It is total | 100 |
| Gasoline property | |
| Sulfur content (weight), μ g/g | 0.5 |
| Nitrogen content (weight), μ g/g | 0.02 |
Claims (14)
1. a kind of heavy oil pretreatment and the combined method of catalytic cracking, this method include：
A, heavy oil is subjected to separating treatment, obtains S components and AR components；Wherein, on the basis of the gross mass of S components, the S groups
The mass fraction of saturated hydrocarbons is more than 90 mass % in point；On the basis of the gross mass of AR components, the matter of aromatic hydrocarbons in the AR components
It measures the sum of fraction and the mass fraction of colloid and is more than 90 mass %, the mass fraction of the aromatic hydrocarbons is more than 50 mass %；
B, the S components of gained in step a are subjected to the first catalytic cracking reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke
And cracked fuel oil；
This method further includes step c or this method further includes step d：
Step c includes：Gained AR components in step a are subjected to the second catalytic cracking reaction；
Step d includes：Gained AR components in step a under the action of hydrotreating catalyst are subjected to hydrotreating reaction, are obtained
To hydrogenated oil；
On the basis of step d, the method further includes step e or step f：
Step e includes：Gained hydrogenated oil in step d is subjected to the 3rd catalytic cracking reaction, obtains dry gas, liquefied gas, vapour
Oil, diesel oil, coke and cracked fuel oil；
Step f includes：Gained hydrogenated oil in step d is carried out first catalysis together with gained S components in step a to split
Change reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；
Separating treatment described in step a is selected from least one of Solid Phase Extraction processing and membrane separation method.
2. combined method according to claim 1, wherein, on the basis of the gross mass of S components, saturated hydrocarbons in the S components
Mass fraction is more than 95 mass %；On the basis of the gross mass of AR components, the mass fraction and colloid of aromatic hydrocarbons in the AR components
The sum of mass fraction be more than 95 mass %, the mass fraction of the aromatic hydrocarbons is more than 55 mass %.
3. combined method according to claim 1, this method further include：The diesel oil that first catalytic cracking reaction is obtained
And/or at least a portion and the obtained diesel oil of the 3rd catalytic cracking reaction and/or cracked fuel oil of cracked fuel oil are extremely
It is a part of less to carry out the hydrotreating reaction together with the AR components.
4. combined method according to claim 1, this method further include：The diesel oil that first catalytic cracking reaction is obtained
And/or at least a portion of cracked fuel oil carries out the hydrotreating reaction together with the AR components.
5. according to the combined method described in any one in claim 1-4, this method further includes：By hydrocracking tail oil and institute
It states S components and carries out first catalytic cracking reaction together.
6. combined method according to claim 1, wherein, the heavy oil is straight run reduced pressure distillate of the initial boiling point at 350 DEG C or more
Initial boiling point is more than 350 DEG C of fraction obtained by oil and/or secondary processing process.
7. combined method according to claim 6, wherein, the secondary processing process is to be split selected from hydroprocessing processes, hydrogenation
At least one of change process, catalytic cracking process and solvent deasphalting process.
8. combined method according to claim 1, wherein, the Solid Phase Extraction processing comprises the following steps：
The heavy oil is first obtained into the first stationary phase using being sent into after dilution dilution agent in stationary phase；Then C is used5-C6Alkane
First stationary phase is rinsed, obtains the S components and the second stationary phase；Then it is 1 with aromatic hydrocarbons and monohydric alcohol volume ratio：
Second stationary phase of solvent washing of (0.8-1.5), obtains the AR components；Wherein, the stationary phase contains the oxidation of load silver
Aluminium, on the basis of the gross mass of the aluminium oxide of the load silver, the mass fraction of the silver of load is 0.5-12 mass %.
9. combined method according to claim 8, wherein, the stationary phase also contains is located at the load silver according to fluid flow direction
Aluminium oxide upstream silica gel and positioned at it is described load silver aluminium oxide downstream aluminium oxide；In mass, the silica gel, institute
It is 1 to state the aluminium oxide of load silver and the mass ratio of the aluminium oxide positioned at the aluminium oxide downstream of the load silver：(2.5-
5.0)：(0-1.2)；Wherein, the specific surface area of the aluminium oxide is 50-300 meters2/ gram, pore volume is 0.1-0.55 mls/g,
The specific surface of the silica gel is 250-850 meters2/ gram, pore volume is 0.25-0.99 mls/g.
10. combined method according to claim 8, wherein, the diluent is C5-C6Alkane, by volume, the dilution
The ratio between volume of agent and heavy oil is (1-10)：1；The aromatic hydrocarbons is benzene and/or toluene, and the monohydric alcohol is methanol and/or ethyl alcohol；
In mass, the mass ratio of the stationary phase and the heavy oil is (8-30)：1.
11. combined method according to claim 1, wherein, the condition of the first catalytic cracking reaction is described in step b：Temperature
For 420-520 DEG C, when mass space velocity is 2-20 small-1, oil ratio is (1-10)：1.
12. combined method according to claim 1, wherein, the condition of the second catalytic cracking reaction is described in step c：Temperature
For 480-540 DEG C, when mass space velocity is 2-20 small-1, oil ratio is (2-30)：1.
13. combined method according to claim 1, wherein, the condition of hydrotreating reaction is described in step d：Hydrogen partial pressure is
3-12 megapascal, reaction temperature are 280-360 DEG C, and hydrotreating catalyst is the aromatic hydrogenation saturation catalysis for not containing acid site
Agent；The initial boiling point of hydrogenated oil described in step d is 155-175 DEG C.
14. combined method according to claim 1, wherein, the condition of the 3rd catalytic cracking reaction is described in step e：Temperature
For 450-540 DEG C, when mass space velocity is 2-20 small-1, oil ratio is (2-30)：1.
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| CN101760239A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Utilization method of catalytic cracking diesel |
| CN102079987A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for separating heavy oils by solid phase extraction |
| CN102102029A (en) * | 2009-12-17 | 2011-06-22 | 中国石油大学(北京) | Catalytic cracking fractional and divisional transformation method and device for heavy oil |
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