CN106467761B - A kind of method that heavy oil separation is combined with catalytic cracking - Google Patents
A kind of method that heavy oil separation is combined with catalytic cracking Download PDFInfo
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Abstract
The invention discloses the method that a kind of separation of heavy oil is combined with catalytic cracking, this method includes：A, heavy oil is subjected to separating treatment, obtains S components, A1 components, A2 components and A3 components；B, S components, A1 components, A2 components and the A3 components of gained in step a are subjected to catalytic cracking reaction respectively, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.This method carries out catalytic cracking reaction respectively by the way that heavy oil is carried out the obtained S components of separating treatment, A1 components, A2 components and A3 components, has higher gasoline and liquefied gas yield and lower gasoline sulfur nitrogen content.
Description
Technical field
The present invention relates to the methods that a kind of separation of heavy oil is combined with 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 a kind of method that is combined with catalytic cracking of heavy oil separation, this method is by by heavy oil
It carries out the obtained S components of separating treatment, A1 components, A2 components and A3 components and 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 a kind of method that heavy oil separation is combined with catalytic cracking, this method
Including：A, heavy oil is subjected to separating treatment, obtains S components, A1 components, A2 components and A3 components；Wherein, with total matter of S components
On the basis of amount, the mass fraction of saturated hydrocarbons is more than 90 mass % in the S components；It is described on the basis of the gross mass of A1 components
The mass fraction of mononuclear aromatics is more than 60 mass % in A1 components；It is single in the A2 components on the basis of the gross mass of A2 components
The mass fraction of cycloaromatics is less than 40 mass %, and the mass fraction of double ring arene is more than 30 mass %, bicyclic Yi Shang aromatic hydrocarbons and glue
The total mass fraction of matter is less than 45 mass %；On the basis of the gross mass of A3 components, in the A3 components bicyclic Yi Shang aromatic hydrocarbons and
The total mass fraction of colloid is more than 50 mass %；B, the S components of gained in step a are subjected to the first catalytic cracking reaction, obtained
Dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；The A1 components of gained in step a are subjected to the second Catalytic Cracking Unit of Measure
Should, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；The A2 components of gained in step a are subjected to the 3rd catalysis
Cracking reaction obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；The A3 components of gained in step a are carried out the
Four catalytic cracking reactions obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel 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 A1 components, the mass fraction of mononuclear aromatics is more than 70 mass % in the A1 components；With A2 groups
On the basis of the gross mass divided, the mass fraction of mononuclear aromatics is less than 30 mass %, the quality point of double ring arene in the A2 components
It counts and is more than 35 mass %, the total mass fraction of bicyclic Yi Shang aromatic hydrocarbons and colloid is less than 40 mass %；Using the gross mass of A3 components as
Benchmark, the total mass fraction of bicyclic Yi Shang aromatic hydrocarbons and colloid is more than 60 mass % in the A3 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 aromatic hydrocarbons and C are used5-C6Alkane volume ratio be 1：Second stationary phase of solvent washing of (15-25), obtains
The A1 components and the 3rd stationary phase；Then aromatic hydrocarbons and C are used5-C6Alkane volume ratio be 1：The solvent washing the 3rd of (3-5) is solid
Determine phase, obtain the A2 components and the 4th stationary phase；Then it is 1 with aromatic hydrocarbons and monohydric alcohol volume ratio：The solvent punching of (0.8-1.5)
The 4th stationary phase is washed, obtains the A3 components；Wherein, the stationary phase contains the aluminium oxide of load silver, with the load silver
On the basis of the gross mass of aluminium oxide, 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 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 3rd catalytic cracking reaction is described in step b：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 the 4th catalytic cracking reaction is described in step b：Temperature is 480-540 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 in heavy oil, A1 components, A2 components and A3 components is realized based on isolation technics, for power
Scholarship and moral conduct be the S components, A1 components, A2 components and the A3 components that differ greatly can respectively under most matched catalytic cracking condition into
Row individually reaction, had not only eliminated influencing each other between different hydrocarbons, but also each hydrocarbon system can be made anti-under conditions of optimization
It answers, the utilization rate of hydrogen in heavy oil is improved, so as to save petroleum resources.
2nd, 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.
3rd, heavy oil is carried out separating treatment by the present invention, reduces the sulphur nitrogen content in S components, A1 components and A2 components, and
Further reduce S components, the sulphur nitrogen content of A1 components and A2 components through catalytic cracking products obtained therefrom.
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 a kind of flow diagram of 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 a kind of method that heavy oil separation is combined with catalytic cracking, and this method includes：A, heavy oil is carried out
Separating treatment obtains S components, A1 components, A2 components and A3 components；Wherein, on the basis of the gross mass of S components, the S components
The mass fraction of middle saturated hydrocarbons is more than 90 mass %, preferably greater than 95 mass %；On the basis of the gross mass of A1 components, the A1
The mass fraction of mononuclear aromatics is more than 60 mass %, preferably greater than 70 mass % in component；On the basis of the gross mass of A2 components,
The mass fraction of mononuclear aromatics is less than 40 mass %, preferably smaller than 30 mass %, the quality point of double ring arene in the A2 components
Number is more than 30 mass %, preferably greater than 35 mass %, and the total mass fraction of bicyclic Yi Shang aromatic hydrocarbons and colloid is excellent less than 45 mass %
Choosing is less than 40 mass %；On the basis of the gross mass of A3 components, the gross mass of bicyclic Yi Shang aromatic hydrocarbons and colloid in the A3 components
Fraction is more than 50 mass %, preferably greater than 60 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；The A1 components of gained in step a are carried out the second catalysis to split
Change reaction, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；The A2 components of gained in step a are carried out the 3rd
Catalytic cracking reaction obtains dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil；By in step a gained A3 components into
The 4th catalytic cracking reaction of row, obtains dry gas, liquefied 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 A1 components, A2 components and A3 components, and the present invention is no longer superfluous
It states, the colloid contained by A3 components refers to the normal heptane solvent of residual oil isolating saturated hydrocarbons and virtue by aluminium oxide liquid chromatogram
The component obtained after hydrocarbon, for details, reference can be made to《Catalytic cracking chemistry and technique》, permitted close friend and write, 2013, Science Press, for example,
RIPP10-90 test methods may be employed and carry out separation determination, since heavy oil composition and residual oil can use saturated hydrocarbons, virtue
Hydrocarbon, resin and asphalt are bound, therefore the colloid in heavy oil can also be so defined.It is currently preferred that meeting
Under conditions of each component definition, separating treatment should be such that alkane and cycloalkane is enriched in S components as far as possible, mononuclear aromatics
It concentrates in A1 components, double ring arene is concentrated in A2 components, and bicyclic Yi Shang aromatic hydrocarbons and colloid are concentrated in A3 components, reduces four
Intersection between person.
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 heavy oil being separated into S components, A1 components, A2 components and A3
The process of component can be selected from solvent extraction processing, Solid Phase Extraction processing and at least one of membrane separation method, no
Same method for separating and processing can be used alone, and can also be used in series.The solvent extraction processing is preferably selected from solvent essence
At least one of system extraction, supercritical fluid extraction and ion liquid abstraction, may be employed single solvent extraction, can also use
Multi-solvent extracts mode, it is preferred to use multi-solvent extracts mode.Solid phase described in the Solid Phase Extraction processing can include dividing
From equipment such as column, vacuum systems, following steps are preferably included：Stationary phase is sent into after the heavy oil first is used dilution dilution agent
In, obtain the first stationary phase；Then C is used5-C6Alkane rinse first stationary phase, obtain the S components and second and fix
Phase；Then aromatic hydrocarbons and C are used5-C6Alkane volume ratio be 1：Second stationary phase of solvent washing of (15-25), obtains the A1 components
With the 3rd stationary phase；Then aromatic hydrocarbons and C are used5-C6Alkane volume ratio be 1：The 3rd stationary phase of solvent washing of (3-5), obtains institute
State A2 components and the 4th stationary phase；Then it is 1 with aromatic hydrocarbons and monohydric alcohol volume ratio：The solvent washing the 4th of (0.8-1.5) is fixed
Phase obtains the A3 components；Wherein, the stationary phase contains the aluminium oxide of load silver, with the total of the aluminium oxide of the load silver
On the basis of quality, the mass fraction of the silver of load is 0.5-12 mass %.The stationary phase can also contain to be flowed to according to fluid
Silica gel positioned at the aluminium oxide upstream of the load silver and the aluminium oxide positioned at the aluminium oxide downstream of the load silver；With quality
Meter, the matter of the silica gel, the aluminium oxide of the load silver and the aluminium oxide positioned at the aluminium oxide downstream of the load silver
Amount is than that can be 1：(2.5-5.0)：(0-1.2)；Wherein, the specific surface area of the aluminium oxide can be 50-300 meters2/ gram, hole
Volume can be 0.1-0.55 mls/g, and the specific surface of the silica gel 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 volume of the diluent and heavy oil it
Than that can be (1-10)：1；The aromatic hydrocarbons can be benzene and/or toluene, and the monohydric alcohol can be methanol and/or ethyl alcohol；With matter
Gauge, 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 15-20
Hour-1, oil ratio is (1-10)：1, be preferably (2-6)：1.The condition of the second catalytic cracking reaction can be described in step b：
Temperature is 420-520 DEG C, is preferably 480-520 DEG C, when mass space velocity is 2-20 small-1, when being preferably 15-20 small-1, oil ratio
For (1-10)：1, be preferably (2-6)：1.The condition of the 3rd catalytic cracking reaction can be described in step b：Temperature is 480-
540 DEG C, be preferably 480-520 DEG C, when mass space velocity is 2-20 small-1, when being preferably 15-20 small-1, oil ratio is (2-30)：1,
Preferably (2-6)：1.The condition of the 4th catalytic cracking reaction can be described in step b：Temperature is 480-540 DEG C, is preferably
480-520 DEG C, when mass space velocity is 2-20 small-1, when being preferably 15-20 small-1, oil ratio is (2-30)：1, be preferably (2-6)：
1。
A kind of specific embodiment of the method for the present invention is as shown in Figure 1：
Will heavy oil carry out separating treatment after obtained S components, A1 components, A2 components and A3 components, by the S components of gained,
A1 components, A2 components and A3 components carry out the first catalytic cracking reaction, the second catalytic cracking reaction, the 3rd Catalytic Cracking Unit of Measure respectively
Dry gas, liquefied gas, gasoline, diesel oil, coke and cracked fuel oil should be obtained with the 4th catalytic cracking reaction.Meanwhile it can will be hydrogenated with
Cracking tail oil carries out the first catalytic cracking reaction together with after the mixing of S components.
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 6890 GC of Agilent (TCD detectors) on-line analysis；After liquid product collection from
Line is weighed, carry out respectively simulation distillation and gasoline detailed hydrocarbon analyze (being tested using RIPP81-90 test methods), gasoline and
The fraction cut point of diesel oil is respectively 221 DEG C and 343 DEG C；Green coke catalyst draw off after in 2000 carbon and sulfur analytical instruments of multi EA
Upper progress coke and analysis of sulfur content (being tested using RIPP106-90 test methods), all product qualities, which sum it up, calculates object
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.
S components, A1 components, A2 components and the hydrocarbon system of A3 components and HCW composition are carried out using RIPP10-90 test methods
Test.
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 separated with heavy oil in the method that catalytic cracking is combined
The implementation of unit.(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 ions, using nitre
It is prepared by sour silver dipping method), (specific surface area is 479 meters to upper strata filling 30g silica gel2/ gram, pore volume is 0.349 ml/g)；
Splitter lower end is connected with pumped vacuum systems.The total volume of stationary phase is 150mL.Take vacuum distillate (VGO, Tahe Crude Oil
Sinopec northwest branch company system in Tahe Oilfield is derived from, Tahe decompression wax is obtained through true boiling point distillation in Research Institute of Petro-Chemical Engineering
Oil) sample 10.20g (11.19mL), it is dissolved in 30mL n-hexanes, is first soaked in above-mentioned splitter and loaded with the n-hexane of 100mL
Stationary 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：N-hexane volume ratio is 1：19 solvent washing goes out A1 components, 255mL toluene：N-hexane volume ratio is 1：4
Solvent washing goes out middle A2 components, 255mL toluene：Ethyl alcohol volume ratio is 1：1 solvent washing goes out A3 components.Using rotary evaporator
The solvent being evaporated in S components, A1 components, A2 components and A3 components obtains 4.94 grams of S components, 1.56 grams of A1 components, A2 components
1.52 grams, A3 component 1.83g, lose 0.35 gram.The subfraction after feedstock oil and separation used in embodiment, comparative example
Basic physical properties data are listed in table 1, and subfraction S, hydrocarbon system's composition data of subfraction A1, A2 and A3 are listed in table 2.
Embodiment 2
As shown in Figure 1, in reaction temperature it is 500 by S components, A1 components, A2 components and the A3 components of the gained of embodiment 1
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, the second catalytic cracking, the 3rd respectively
Catalytic cracking and the 4th catalytic cracking；Conversion ratio, total liquid yield, the yield of light oil of raw material also have six kinds of primary products to do air-liquid
Change the yield of gas, gasoline, diesel oil, cracked fuel 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 in comparative example 1, by S components,
A1 components, A2 components and A3 components are after the liquefied gas obtained by catalytic cracking, gasoline summarize respectively respectively, liquefied gas, gasoline yield
Summarized results 2 is respectively higher than liquefied gas, the gasoline yield that wax oil directly carries out catalytic cracking, while sulfur content and nitrogen in gasoline
Content is significantly lower than the content of sulfur in gasoline and nitrogen content of the direct catalytic cracking of wax oil, illustrates that method using the present invention is first by heavy oil
It carries out separating treatment and carries out catalytic cracking again, obtained high-value product yield and property are better than directly being catalyzed heavy oil
The product of cracking.
Embodiment 3
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 5.
As can be seen from Table 5, 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
Shown in table 4.
Table 1 is heavy oil feedstock and the fundamental property of each hydrocarbon system's component.
| Project | S | A1 | A2 | A3 | VGO | HCW |
| Density (100 DEG C)/(gcm-3) | 0.8086 | 0.8653 | 0.9265 | 0.9766 | 0.8825 | 0.7911 |
| Viscosity (100 DEG C)/(mm2·s-1) | 4.829 | 6.717 | 10.462 | 33.803 | 9.8463 | 3.571 |
| Carbon residue, % | <0.05 | <0.05 | 0.21 | 4.28 | 0.48 | <0.05 |
| Weight (C), % | 85.90 | 87.22 | 87.14 | 84.08 | 86.07 | 85.59 |
| Weight (H), % | 13.92 | 12.30 | 10.36 | 9.19 | 11.99 | 14.34 |
| n(H)/n(C) | 1.94 | 1.69 | 1.43 | 1.31 | 1.67 | 2.03 |
| Weight (S)/(μ g.g-1) | 67 | 4500 | 4600 | 46400 | 17000 | 10 |
| Weight (N)/(μ g.g-1) | 1.7 | 7.0 | 266 | 8000 | 1800 | 1.0 |
| Boiling point range/DEG C | 350~478 | 357~525 | 365~520 | 392~558 | 350~559 | 350~496 |
Table 2 is that the hydrocarbon system of S, A1, A2, A3 and HCW form, and data unit is attached most importance to % for mass percent in table.
| Hydrocarbon types | S | A1 | A2 | A3 | HCW |
| Total saturated hydrocarbons | 97.4 | 0 | 0 | 0 | 99.4 |
| Total aromatic hydrocarbons | 2.6 | 100.0 | 100.0 | 60.0 | 0.6 |
| Total mononuclear aromatics | 2.6 | 74.3 | 24.7 | 9.4 | 0.6 |
| Total double ring arene | 0 | 13.2 | 37.1 | 11.1 | 0 |
| Bicyclic Yi Shang aromatic hydrocarbons | 0 | 12.5 | 38.2 | 39.5 | 0 |
| Colloid | 0 | 0.0 | 0.0 | 40.0 | 0 |
| Total weight | 100 | 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 when small (12 aging) | 69 |
Table 4 is embodiment 2 and the experimental data of comparative example 1.
Table 5 is the experimental data of embodiment 3.
| Project | Embodiment 3 |
| 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 (13)
1. a kind of method that heavy oil separation is combined with catalytic cracking, this method include：
A, heavy oil is subjected to separating treatment, obtains S components, A1 components, A2 components and A3 components；Wherein, with the gross mass of S components
On the basis of, the mass fraction of saturated hydrocarbons is more than 90 mass % in the S components；On the basis of the gross mass of A1 components, the A1
The mass fraction of mononuclear aromatics is more than 60 mass % in component；It is monocyclic in the A2 components on the basis of the gross mass of A2 components
The mass fraction of aromatic hydrocarbons is less than 40 mass %, and the mass fraction of double ring arene is more than 30 mass %, bicyclic Yi Shang aromatic hydrocarbons and colloid
Total mass fraction be less than 45 mass %；On the basis of the gross mass of A3 components, bicyclic Yi Shang aromatic hydrocarbons and glue in the A3 components
The total mass fraction of matter is more than 50 mass %；Separating treatment described in step a is selected from solvent extraction processing, Solid Phase Extraction processing
At least one of with membrane separation method；
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；The A1 components of gained in step a are subjected to the second catalytic cracking reaction, obtain dry gas, liquefied gas, gasoline, bavin
Oil, coke and cracked fuel oil；By in step a gained A2 components carry out the 3rd catalytic cracking reaction, obtain dry gas, liquefied gas,
Gasoline, diesel oil, coke and cracked fuel oil；By in step a gained A3 components carry out the 4th catalytic cracking reaction, obtain dry gas,
Liquefied gas, gasoline, diesel oil, coke and cracked fuel oil.
2. the method according to claim 1, wherein, on the basis of the gross mass of S components, the quality of saturated hydrocarbons in the S components
Fraction is more than 95 mass %；On the basis of the gross mass of A1 components, the mass fraction of mononuclear aromatics is more than 70 in the A1 components
Quality %；On the basis of the gross mass of A2 components, the mass fraction of mononuclear aromatics is less than 30 mass % in the A2 components, bicyclic
The mass fraction of aromatic hydrocarbons is more than 35 mass %, and the total mass fraction of bicyclic Yi Shang aromatic hydrocarbons and colloid is less than 40 mass %；With A3 groups
On the basis of the gross mass divided, the total mass fraction of bicyclic Yi Shang aromatic hydrocarbons and colloid is more than 60 mass % in the A3 components.
3. according to the method for claim 1 or 2, this method further includes：Hydrocracking tail oil is subjected to institute together with the S components
State the first catalytic cracking reaction.
4. the method according to claim 1, wherein, the heavy oil for initial boiling point 350 DEG C or more straight run vacuum distillate and/
Or initial boiling point is more than 350 DEG C of fraction obtained by secondary processing process.
5. method according to claim 4, wherein, the secondary processing process is selected from hydroprocessing processes, was hydrocracked
At least one of journey, catalytic cracking process and solvent deasphalting process.
6. the method according to claim 1, wherein, the solvent extraction processing is selected from solvent refining extraction, supercritical fluid
At least one of extraction and ion liquid abstraction.
7. the 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 aromatic hydrocarbons and C are used5-C6Alkane volume ratio be 1：
Second stationary phase of solvent washing of (15-25), obtains the A1 components and the 3rd stationary phase；Then aromatic hydrocarbons and C are used5-C6Alkane
Volume ratio is 1：The 3rd stationary phase of solvent washing of (3-5), obtains the A2 components and the 4th stationary phase；Then aromatic hydrocarbons and one are used
First alcohol volume ratio is 1：The 4th stationary phase of solvent washing of (0.8-1.5), obtains the A3 components；Wherein, the stationary phase contains
There is the aluminium oxide of 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 %.
8. method according to claim 7, wherein, the stationary phase also contains the oxygen for being located at the load silver according to fluid flow direction
The silica gel and the aluminium oxide positioned at the aluminium oxide downstream of the load silver for changing aluminium upstream；In mass, the silica gel, described negative
It is 1 to carry the aluminium oxide of 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, described
The specific surface of silica gel is 250-850 meters2/ gram, pore volume is 0.25-0.99 mls/g.
9. method according to claim 7, wherein, the diluent is C5-C6Alkane, by volume, the diluent with again
The ratio between volume of oil is (1-10)：1；The aromatic hydrocarbons is benzene and/or toluene, and the monohydric alcohol is methanol and/or ethyl alcohol；With quality
The mass ratio of meter, the stationary phase and the heavy oil is (8-30)：1.
10. the method according to claim 1, wherein, the condition of the first catalytic cracking reaction is described in step b：Temperature is
420-520 DEG C, when mass space velocity is 2-20 small-1, oil ratio is (1-10)：1.
11. the method according to claim 1, wherein, the condition of the second catalytic cracking reaction is described in step b：Temperature is
420-520 DEG C, when mass space velocity is 2-20 small-1, oil ratio is (1-10)：1.
12. the method according to claim 1, wherein, the condition of the 3rd catalytic cracking reaction is described in step b：Temperature is
480-540 DEG C, when mass space velocity is 2-20 small-1, oil ratio is (2-30)：1.
13. the method according to claim 1, wherein, the condition of the 4th catalytic cracking reaction is described in step b：Temperature is
480-540 DEG C, when mass space velocity is 2-20 small-1, oil ratio is (2-30)：1.
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