CN107557067A - The catalysis conversion method and system of a kind of inferior feedstock oil - Google Patents
The catalysis conversion method and system of a kind of inferior feedstock oil Download PDFInfo
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- CN107557067A CN107557067A CN201610513794.0A CN201610513794A CN107557067A CN 107557067 A CN107557067 A CN 107557067A CN 201610513794 A CN201610513794 A CN 201610513794A CN 107557067 A CN107557067 A CN 107557067A
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Abstract
The invention discloses a kind of catalysis conversion method of inferior feedstock oil and system, this method includes：Inferior feedstock oil is subjected to catalytic conversion reaction by riser reactor and settler successively, gained reaction product is sent into product separative element and separated, and gained diesel oil carries out Aromatics Extractive Project and hydrotreating successively；Wherein, the extension diameter section in the middle part of riser reactor takes out partial catalyst, from settler infeed section regenerated catalyst.The present invention organically combines the techniques such as catalyzed conversion, Aromatics Extractive Project and hydrotreating and process unit, low-carbon alkene, light-weight fuel oil and heavy aromatics is produced to greatest extent from inferior feedstock oil, so as to realize that petroleum resources efficiently utilize.
Description
Technical field
The present invention relates to a kind of catalysis conversion method of inferior feedstock oil and system.
Background technology
Low-carbon alkene using ethene, propylene as representative is the most basic raw material of chemical industry, both at home and abroad it is more with
Natural gas or light petroleum fraction are raw material, and low-carbon is produced using steam cracking process in Ethylene Complex unit
Alkene.The a large amount of basic materials such as other alkene and aromatic hydrocarbons of by-product while ethene is produced, corresponding ethene life
The inevitable production with a variety of intermediate products and final products of production connects together.In addition to ethene is produced, about 70%
Propylene, 90% butadiene, 30% aromatic hydrocarbons be all from steam cracking by-product.Although steam cracking skill
Art passes through the development of decades, technology constantly improve, but still has high energy consumption, production cost height, CO2
Discharge capacity is limited to greatly with technologies such as product structure are not easy to adjust, if petrochemical plant is using traditional steam
Cracking ethylene preparation, propylene route, the shortage of lightweight material oil, inefficiency of production and cost mistake will be faced
High several big restraining factors.FCC is increasingly subject to weight because its adaptability to raw material is wide, operates the advantage such as flexible
Depending on.In the U.S., almost the 50% of propylene market demand all derives from FCC apparatus.Propylene enhancing
Catalytic cracking improved technology have developed rapidly.
Patent document EP0305720A2 discloses a kind of hydro carbons from inferior feedstock oil preparing low-carbon olefins
Method for transformation, raw material is petroleum distillate, residual oil or the crude oil of different boiling ranges, anti-in fluid bed or moving bed
Answer in device and use solid acid catalyst, in 500 DEG C~650 DEG C of temperature, pressure 1.5 × 105~3 × 105Pa、
0.2~2.0h of weight (hourly) space velocity (WHSV)-1, carry out catalytic conversion reaction under conditions of oil ratio 2~12, it is reacted
Catalyst recycles after coke burning regeneration in Returning reactor.The gross production rate of this method propylene and butylene can
To reach 40% or so, wherein productivity of propylene is up to 26.34%.
Patent document WO00/31215A1 discloses a kind of catalyst cracking method for producing alkene, this method
ZSM-5 and/or ZSM-11 zeolites are used to do active component, the catalysis using a large amount of inert substances as matrix
Agent, using VGO as raw material, productivity of propylene is less than 20 heavy %.
Patent document US4,422,925 discloses a variety of hydro carbons with different cracking performances and urged with hot recycling
The method that agent is contacted and converted, the hydro carbons described in this method at least contain a kind of gas alkane raw material and one
Kind liquid hydrocarbon raw material, this method has different cracking performances according to different hydrocarbon molecules, by reaction zone
It is divided into multiple reaction zones and carries out cracking reaction, with voluminous low-molecular olefine.
During due to production low-carbon alkene, the higher reaction severity operation of generally use, this causes catalytic cracking
Arene content is high in diesel oil, Cetane number is low, gum level is high, stability in storage is poor.For aromatic hydrocarbons
To say, the Cetane number of mononuclear aromatics is relatively low in diesel oil, and bicyclic or polycyclic aromatic hydrocarbon Cetane number is lower, and
Bicyclic above arene content is high in catalytic diesel oil, generally the method for hydrofinishing need to be used to improve hexadecane
Value, but because aromatic hydrocarbons stability is good, hydrogenation need to be carried out under relatively severe condition, required equipment investment and
Operating cost is big.
On the other hand, aromatic hydrocarbons is good industrial chemicals in catalytic diesel oil, and chemical plant utilizes and focused primarily upon
Both direction, first, each component is separated, it is used respectively, the more one pack system of current application
There are pseudocumene, mesitylene, durol and naphthalene；Second, by fractionation, blending ingredients are added respectively
To utilize.Blending ingredients can make heat carrier and lube oil additive, raw material and height as carbon materials
Boiling point aromatic solvent, make aromatic aldehyde resin applied to rubber, plastic processing industry and production light aromatic hydrocarbons, should
For Oilfield Chemicals.
Chinese patent CN1766059A discloses a kind of inferior heavy oil or slag oil treatment process, this method
Heavy oil or residual oil raw material are entered into solvent extraction apparatus first, the deasphalted oil of gained enters fixed bed hydrogenation
Processing unit carries out hydrotreating, and gained hydrogenation tail oil enters catalytic cracking unit, wherein the part of gained
Or whole slurry oils enter floating bed hydrogenation device together with obtaining deasphalted oil by solvent extraction, product is through dividing
From light fraction and unconverted tail oil is obtained, wherein unconverted tail oil is recycled to solvent extraction apparatus.The party
Although method combines catalytic cracking process, extraction process and hydrogenation technique, also have in heavy oil processing certain
Effect, but this method technological process is complicated, and liquid yield is low.
Catalytic cracking is the process units of most important heavy oil lighting.Inferior feedstock oil is directly catalyzed
Cracking is processed and includes that productivity of low carbon olefin hydrocarbon is low, olefin(e) centent is high in gasoline, diesel oil density the problem of produce
Greatly and diesel cetane-number is low etc., and therefore, gasoline and diesel oil can not be as merchantable gasolines and the tune of diesel oil
And the catalytic diesel oil of component, especially gained, even if carrying out hydrofinishing, Cetane number lifting amplitude is smaller,
Still reach to the specification index less than commercial Dissel oil.Catalytic cracking generation is carried out after inferior feedstock oil is hydrogenated again
The problem of be hydrogenation plant operating condition severity it is high, plant investment is of a relatively high；Secondly, gasoline is pungent
Alkane value will decrease, and have a strong impact on gasoline pool octane level.
In order to efficiently utilize inferior heavy oil resource, meet growing industrial chemicals such as low-carbon alkene and again
The demand of aromatic hydrocarbons, it is necessary to develop a kind of catalysis that inferior heavy oil raw material is converted into high value added product and turn
Change method.
The content of the invention
It is an object of the invention to provide a kind of catalysis conversion method of inferior feedstock oil and system, the present invention will
The techniques such as catalyzed conversion, Aromatics Extractive Project and hydrotreating and process unit organically combine, from inferior feedstock oil
Low-carbon alkene, light-weight fuel oil and heavy aromatics are produced to greatest extent, so as to realize that petroleum resources are efficiently sharp
With.
To achieve these goals, the present invention provides a kind of catalysis conversion method of inferior feedstock oil, the party
Method includes：A, by the inferior feedstock oil of preheating from be provided with from the bottom to top pre lift zone, the first conversion zone,
Riser reactor is sent into the middle and lower part of first conversion zone of the riser reactor of extension diameter section and outlet section
In contacted and from the bottom to top in institute with being transported to the first regenerated catalyst of the pre lift zone from regenerator
State and the first catalytic conversion reaction is carried out in the first conversion zone, extension diameter section and outlet section, obtain the first reaction production
Thing and half reclaimable catalyst；B, by the first reaction product of gained and half reclaimable catalyst in step a from institute
State outlet section top exit leave the riser reactor into settler the second conversion zone in enter
The catalytic conversion reaction of row second, obtains the second reaction product and reclaimable catalyst；C, by institute in step b
Obtain the second reaction product to send out the settler and be sent into the progress product separation of product separative element, done
Air-liquid gas, gasoline, diesel oil and slurry oil；Gained diesel oil is sent into Aromatics Extractive Project unit progress aromatic hydrocarbons to take out
Carry, obtain raffinate diesel oil and extract diesel oil out；Gained raffinate diesel oil is sent at hydrotreating unit and hydrogenation
Reason catalyst contacts and carries out hydrotreating, obtains hydrogenation and raffinates oil；Wherein, this method also includes：From
The middle and lower part of the extension diameter section is taken out the partial catalyst feeding regenerator and regenerated, by the regeneration
Second conversion zone of the settler is sent into partial regeneration agent in device as the second regenerated catalyst
That second catalyzed conversion is carried out together with from half reclaimable catalyst of the outlet section is anti-for middle and lower part
Should.
Preferably, the settler also includes the settling section and stripping being in fluid communication with second conversion zone
Section, the settling section are located above second conversion zone, and the stripping section is located at second conversion zone
Lower section, the settler are set in outside the middle and upper part of the riser reactor, and the outlet section
Top exit is located in second conversion zone；By the second reaction product of gained in step b through the sedimentation
The settler is sent out after Duan Jinhang gas solid separations and is sent into product separative element and produced described in step c
Thing separates, and gained reclaimable catalyst in step b is sent out into the settler simultaneously after stripping section stripping
The regenerator is sent into be regenerated.
Preferably, this method also includes：By lightweight material oil and/or cold shock medium from the outlet section
Middle and lower part is sent into the riser reactor and carries out first catalytic conversion reaction；Wherein, it is described light
Matter feedstock oil includes at least one of raffinating oil selected from liquefied gas, gasoline, diesel oil and hydrogenation, described cold
Swash medium be selected from liquefied gas, raw gasoline, stable gasoline, diesel oil, hydrogenation raffinate oil, heavy diesel fuel and water
At least one of.
Preferably, the condition of the Aromatics Extractive Project includes：The solvent of Aromatics Extractive Project is selected from furfural, diformazan
At least one of sulfoxide, dimethylformamide, MEA, ethylene glycol and 1,2-PD, institute
The volume ratio for stating solvent and 18 separating obtained diesel oil of product separative element is (0.5-5.0)：1, the virtue
The temperature of hydrocarbon extracting is 40-120 DEG C；The condition of the hydrotreating includes：Hydrogen dividing potential drop is 3.0-20.0 million
Pa, temperature are 300-450 DEG C, and hydrogen to oil volume ratio is (300-2000)：1, raffinate diesel fuel volume air speed
For 0.1-3.0 hours-1；The hydrotreating catalyst includes carrier and loaded on the carrier
Group vib metal and/or VIII base metal, the carrier are alumina support and/or silica-alumina supports.
Preferably, the condition of the first catalytic conversion reaction includes described in step a：Temperature is 510-650 DEG C,
Time is the 0.05-1.5 seconds, and oil ratio is (3-20)：1, water-oil factor is (0.03-0.8)：1, pressure is
130-450 kPas；The condition of the second catalytic conversion reaction includes described in step b：Temperature is
420-550 DEG C, the time is the 1.5-20 seconds.
Preferably, in terms of the weight of catalyst, the 1-20 of catalyst internal circulating load in riser reactor will be accounted for
Weight % catalyst takes out from the middle and lower part of the extension diameter section, will account for catalyst in riser reactor and follows
The 1-20 weight % of circular rector second regenerated catalyst is sent into second conversion zone.
Preferably, the inferior feedstock oil be selected from decompression residuum, reduced crude inferior, it is inferior plus
Hydrogen residual oil, coker gas oil, deasphalted oil, crude oil with high acid value, high metal crude oil, liquefied coal coil, oil
At least one of sand oil and shale oil.
Preferably, the density of the inferior feedstock oil is 900-1000 kgs/m3, carbon residue is 4-15 weight %,
Tenor is 15-600ppm, acid number 0.5-20.0mgKOH/g.
Preferably, the catalyst of first catalytic conversion reaction and/or the second catalytic conversion reaction is carried out
Including zeolite, inorganic oxide and optional clay；Counted by butt and on the basis of the weight of the catalyst,
The content of the zeolite is 1-50 % again, and the content of inorganic oxide weighs %, the content of clay for 5-99
For 0-70 weights %.
Preferably, the zeolite be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35,
At least one in ZSM-38, ZSM-48, ZRP, Rare Earth Y, rare earth hydrogen Y, super steady Y and high silicon Y
Kind, the inorganic oxide is silica and/or aluminum oxide, and the clay is kaolin and/or more water
Kaolin.
The present invention also provides a kind of catalytic conversion system of inferior feedstock oil, and the catalytic conversion system includes：
The riser reactor of pre lift zone, the first conversion zone, extension diameter section and outlet section is provided with from the bottom to top,
From top to bottom it is provided with the settler of settling section, the second conversion zone and stripping section, and product separative element,
Aromatics Extractive Project unit and hydrotreating unit；Wherein, the second conversion zone of the settler and the outlet
The top exit of section is in fluid communication.
Preferably, the pre lift zone is provided with the first regenerated catalyst inlet, under first conversion zone
Portion is provided with the first inferior raw material oil-in, and the middle and lower part of the extension diameter section is provided with catalyst outlet, institute
State the second conversion zone and be provided with the second regenerated catalyst inlet, reaction product is provided with the top of the settling section
Outlet, the stripping section be provided with reclaimable catalyst outlet, the feed(raw material)inlet of the product separative element with
Reacting product outlet at the top of the settling section is in fluid communication, and the diesel product of the product separative element goes out
The feed(raw material)inlet of mouth and Aromatics Extractive Project unit is in fluid communication, the raffinate diesel product of the Aromatics Extractive Project unit
Outlet and the feed(raw material)inlet of the hydrotreating unit are in fluid communication.
Preferably, the settler is set in outside the middle and upper part of the riser reactor, the outlet
The top exit of section is arranged in second conversion zone.
Preferably, the middle and lower part of the outlet section is provided with lightweight material oil and/or cold shock medium inlet.
Preferably, the catalytic conversion system also includes regenerator, the catalyst inlet of the regenerator and institute
State the catalyst outlet of extension diameter section and the reclaimable catalyst outlet of the stripping section, the regenerator
Catalyst outlet and the pre lift zone the first regenerated catalyst inlet and the second conversion zone the
Two regenerated catalyst inlets connect.
Preferably, the height of the riser reactor is 10-60 rice, and the internal diameter of the pre lift zone is
0.2-5 rice, the height of the pre lift zone account for the 5-10% of riser reactor height, first reaction
Section and the ratio between the internal diameter of pre lift zone are (0.5-1.5)：1, the height of first conversion zone accounts for riser
The ratio between internal diameter of the 50-70% of height for reactor, the extension diameter section and the first conversion zone is (1.2-5.0)：1,
The height of the extension diameter section accounts for the 5-10% of riser reactor height, the outlet section and the first conversion zone
The ratio between internal diameter be (0.8-1.5)：1, the height of the outlet section accounts for riser reactor height
10-30%.
The present invention has following beneficial effect compared with prior art：
1st, the catalyst of the first catalytic conversion reaction of part progress is taken out in extension diameter section, in the second conversion zone
The regenerated catalyst of part second is supplemented, on the premise of reaction severity is not increased, catalyst activity
The conversion level of inferior feedstock oil can be significantly improved by improving.
2nd, the second regenerated catalyst of supplement is advantageous to fortifying catalytic conversion reaction, and it is anti-to improve catalyzed conversion
Should be selective, the product yield such as liquefied gas and gasoline is improved, reduces undesirable thermal cracking.
3rd, diesel oil obtained by catalyzed conversion makes follow-up hydrogenation handle processed raw material oiliness through Aromatics Extractive Project
Matter is improved, and makes the regeneration intervals of hydrotreating catalyst increase, and improves hydrotreater
The regenerative operation cycle.In addition, the raffinate diesel oil after hydrogenation is rich in alkane and cycloalkane, it is especially suitable for again
Secondary carry out producing light olefins through catalytic conversion.
4th, the inventive method can improve the octane number of gained gasoline, and reduce dry gas, coke and slurry oil
Yield, so as to realize that petroleum resources efficiently utilize.
5th, the present invention reduces the linear speed of catalyst in extension diameter section, improves the density of catalyst in extension diameter section,
Catalyst is facilitated to take out.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing be for providing a further understanding of the present invention, and a part for constitution instruction, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 includes a kind of schematic flow sheet of embodiment of the inventive method, also includes the present invention
A kind of structural representation of embodiment of system.
Description of reference numerals
The pipeline of 1 pipeline, 2 riser reactor 3
The pipeline of 4 pipeline, 5 pipeline 6
The collection chamber of 7 outlet section, 8 settling section 9
The inclined tube of 10 stripping section, 11 pipeline 12
The pipeline of 13 regenerator, 14 pipeline 15
The product separative element of 16 inclined tube, 17 pipeline 18
The pipeline of 19 pipeline, 20 pipeline 21
The Aromatics Extractive Project unit of 22 pipeline, 23 pipeline 24
The pipeline of 25 pipeline, 26 pipeline 27
The pipeline of 28 pipeline, 29 hydrotreating unit 30
31 pipelines
I the first conversion zone II the second conversion zone III extension diameter sections
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that
Embodiment described herein is merely to illustrate and explain the present invention, and is not limited to this hair
It is bright.
The present invention provides a kind of catalysis conversion method of inferior feedstock oil, and this method includes：A, will preheating
Inferior feedstock oil from being provided with pre lift zone, the first conversion zone I, extension diameter section III and outlet from the bottom to top
Section 7 riser reactor 2 the first conversion zone I middle and lower part be sent into riser reactor 2 in from
Regenerator 13 is transported to the first regenerated catalyst contact of the pre lift zone and from the bottom to top described the
The first catalytic conversion reaction is carried out in one conversion zone I, extension diameter section III and outlet section 7, obtains the first reaction
Product and half reclaimable catalyst；B, by step a gained the first reaction product and half reclaimable catalyst from
The top exit of the outlet section 7 leaves the second conversion zone that the riser reactor 2 enters settler
The second catalytic conversion reaction is carried out in II, obtains the second reaction product and reclaimable catalyst；C, by step b
The middle reaction product of gained second, which sends out the settler and is sent into product separative element 18, carries out product separation,
Obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil；Gained diesel oil is sent into Aromatics Extractive Project unit 24
Aromatics Extractive Project is carried out, raffinate diesel oil is obtained and extracts diesel oil out；Gained raffinate diesel oil is sent into hydrotreating list
Member 29 contacts with hydrotreating catalyst and carries out hydrotreating, obtains hydrogenation and raffinates oil；Wherein, should
Method also includes：Partial catalyst, which is taken out, from the middle and lower part of the extension diameter section III is sent into the regenerator 13
Regenerated, using the partial regeneration agent in the regenerator 13 as described in the second regenerated catalyst feeding
The second conversion zone II of settler middle and lower part and half reclaimable catalyst one from the outlet section 7
Rise and carry out second catalytic conversion reaction.
According to the present invention, the reaction bed of fluidisation, one kind tool are could be formed with the first conversion zone II
Body embodiment, the settler also include with the second conversion zone II be in fluid communication settling section 8 and
Stripping section 10, the settling section 8 are located above the second conversion zone II, and the stripping section 10 is located at
Below the second conversion zone II, the settler be set in the riser reactor 2 middle and upper part it
Outside, and the top exit of the outlet section 7 is located in the second conversion zone II；By gained in step b
Second reaction product sends out the settler after the settling section 8 carries out gas solid separation and is sent into product point
Product separation described in step c is carried out from unit 18, by described in gained reclaimable catalyst warp in step b
Stripping section 10 sends out the settler and be sent into the regenerator 13 after stripping to be regenerated.
According to the present invention, in order to rationally utilize raw material and control temperature, the inventive method to include：
Lightweight material oil and/or cold shock medium are sent into the lifting tube reaction from the middle and lower part of the outlet section 7
First catalytic conversion reaction is carried out in device 2；Wherein, the lightweight material oil can be selected from liquefaction
Gas, gasoline, diesel oil and hydrogenation at least one of are raffinated oil, and the cold shock medium can be selected from liquefaction
Gas, raw gasoline, stable gasoline, diesel oil, hydrogenation are raffinated oil, at least one of heavy diesel fuel and water.Gently
The composition of matter feedstock oil and cold shock medium be able to can also be differed with identical, and the effect of cold shock medium is
The temperature of outlet section and subsequent reactions is controlled, such as can be normal temperature, lightweight material oil can pass through pre-
It is re-fed into after heat in the outlet section 7.In lightweight material oil and/or cold shock medium, the liquefied gas can
To be the liquefied gas obtained by the inventive method and/or the liquefied gas or liquefied gas obtained by other methods
In a certain component, for example, propane and C4Hydrocarbon；The gasoline can be gasoline obtained by the inventive method
And/or the gasoline obtained by other methods；The diesel oil can be diesel oil and/or other obtained by the inventive method
Diesel oil obtained by method；It can be that hydrogenation is raffinated oil obtained by the inventive method that the hydrogenation, which is raffinated oil, including
Or the diesel oil obtained by not including the inventive method and/or other methods；The boiling range of the gasoline and diesel oil can be with
It is adjusted according to actual needs, is not limited only to full range gasoline or diesel oil.
According to the present invention, Aromatics Extractive Project and hydrotreating are well-known to those skilled in the art, the present invention
Repeat no more, for example, the condition of the Aromatics Extractive Project can include：The solvent of Aromatics Extractive Project can be choosing
From in furfural, dimethyl sulfoxide, dimethylformamide, MEA, ethylene glycol and 1,2- propane diols extremely
Few one kind, the volume ratio of the solvent and 18 separating obtained diesel oil of product separative element can be
(0.5-5.0)：1, the temperature of the Aromatics Extractive Project can be 40-120 DEG C；The condition of the hydrotreating
It can include：Hydrogen dividing potential drop can be 3.0-20.0 MPas, and temperature can be 300-450 DEG C, hydrogen oil volume
Than that can be (300-2000)：1, raffinate diesel fuel volume air speed can be 0.1-3.0 hours-1；It is described to add
Hydrogen processing catalyst generally comprises the group vib metal and/or VIII of carrier and load on the carrier
Race's base metal, the VIII base metal can be selected from least one of nickel, cobalt and iron, institute
It can be alumina support and/or silica-alumina supports to state carrier.Hydrogenation gained hydrogenation is raffinated oil and can removed through stripping
Remove lighter hydrocarbons molecule, the hydrogenation after stripping raffinate oil can be recycled to the catalytic conversion system outlet section and
/ or other catalytic convention designs further reaction obtain purpose product low-carbon alkene and heavy aromatics.Other catalysis
Reforming unit can be conventional catalytic convention design and its various improved devices, more detailed description
It may refer to Chinese patent CN1232069A and CN1232070A.
According to the present invention, the catalyst and reclaimable catalyst taken out from extension diameter section can be sent to regenerator and carry out
Regenerate Posterior circle to use, this is well-known to those skilled in the art, the specific regeneration step of the inventive method
Suddenly can include：The partial catalyst and step that will be taken out in step b from the middle and lower part of the extension diameter section III
Send out in the reclaimable catalyst feeding regenerator 13 of the settler and regenerated in rapid c, obtained portion
Divide regenerative agent to be sent into the first conversion zone I from the pre lift zone to carry out as the first regenerated catalyst
First catalytic conversion reaction described in step a, obtained another part regenerative agent are sent into second reaction
In section II the second catalytic conversion reaction described in step b is carried out as the second regenerated catalyst.
According to the present invention, catalyzed conversion is well-known to those skilled in the art, and the present invention repeats no more.
First catalytic conversion reaction described in step a is mainly macromolecular cracking reaction, to remove inferior feedstock oil
At least one of middle metal, sulphur, nitrogen and aphthenic acids impurity, its condition can include：Temperature can be
510-650 DEG C, preferably 520-600 DEG C, time can be 0.05-1.5 seconds, preferably 0.1-0.5 seconds,
Oil ratio can be (3-20)：1, be preferably (5-15):1, water-oil factor can be (0.03-0.8)：1,
Preferably (0.05-0.5):1, pressure can be 130-450 kPas, and the gas velocity of riser reactor can be with
For the meter per second of 2 meter per second -30 (disregarding catalyst).The second catalytic conversion reaction is mainly described in step b
Cracking reaction, hydrogen transfer reaction and isomerization reaction, its condition can include：Temperature can be
420-550 DEG C, preferably 460-530 DEG C, time can be 1.5-20 seconds, preferably 2-10 seconds, agent
Oily ratio can be (3-20)：1, water-oil factor can be (0.03-0.8)：1, the gas velocity of the second conversion zone can
Think the meter per second of 0.1 meter per second -2 (disregarding catalyst).
According to the present invention, the catalyst for passing through the first catalytic conversion reaction in part is taken out in extension diameter section, the
Two conversion zones are supplemented the regenerated catalyst of part second, on the premise of reaction severity is not increased, catalysis
The raising of agent activity can significantly improve the conversion level of inferior feedstock oil；Meanwhile the regeneration catalyzing of supplement
Agent is advantageous to fortifying catalytic conversion reaction, improves catalytic conversion reaction selectivity, improves liquefied gas and gasoline
Deng product yield, undesirable thermal cracking is reduced.In terms of the weight of catalyst, it is anti-can will to account for riser
The 1-20 weight % of catalyst internal circulating load in device are answered, preferably account for 5-10 weight % catalyst from the expansion
Footpath section III middle and lower part is taken out, and can will account for the 1-20 weights of catalyst internal circulating load in riser reactor
% is measured, second regenerated catalyst for preferably accounting for 5-10 weight % is sent into the second conversion zone II；
For the ease of taking out catalyst, catalyst can be the 0.05-0.5 seconds in the extension diameter section residence time, be preferably
The 0.1-0.3 seconds.The catalyst internal circulating load is well-known to those skilled in the art, can use thermal balance
It is measured with the method for carbon (material) balance.
According to the present invention, inferior feedstock oil is known to those skilled in the art, for example, distinguished from source,
Can be heavy petroleum hydrocarbon and/or other mineral oil, wherein heavy petroleum hydrocarbon can be selected from decompression residuum
(VR), reduced crude (AR) inferior, hydrogenated residue inferior, coker gas oil, deasphalted oil, height
At least one of acid number crude oil and high metal crude oil；Other mineral oil can be selected from liquefied coal coil, oil
At least one of sand oil and shale oil.Distinguished from performance indications, the density of the inferior feedstock oil can
Think 900-1000 kgs/m3, preferably 930-960 kgs/m3, carbon residue can be 4-15 weight %,
Preferably 6-12 weight %, tenor can be 15-600ppm, preferably 15-100ppm, and acid number can
Think 0.5-20.0mgKOH/g, preferably 0.5-10.0mgKOH/g.
According to the present invention, urging for first catalytic conversion reaction and/or the second catalytic conversion reaction is carried out
Agent can include zeolite, inorganic oxide and optional clay；In terms of butt and with the weight of the catalyst
On the basis of amount, the content of the zeolite can be 1-50 weight %, and the content of inorganic oxide can be 5-99
Weight %, the content of clay can be 0-70 weights %.Wherein described zeolite is as active component, Ke Yiwei
Mesopore zeolite and/or optional large pore zeolite, mesopore zeolite can account for the 0-100 weight % of zeolite gross weight,
It is preferred that accounting for 20-80 weight %, large pore zeolite can account for the 0-100 weight % of zeolite gross weight, preferably account for 20-80
Weight %.Mesopore zeolite can be ZSM series zeolites and/or ZRP zeolites, and can be to above-mentioned mesopore zeolite
It is modified with the transition metal such as the nonmetalloids such as phosphorus and/or iron, cobalt, nickel, relevant ZRP boilings
More description may refer to United States Patent (USP) US5 to stone in detail, and 232,675, ZSM series zeolites can be choosing
From ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and its
One or more kinds of mixtures among the zeolite of its similar structures, relevant ZSM-5 are more detailed
Description may refer to United States Patent (USP) US3,702,886.Large pore zeolite can be selected from by rare earth
In the zeolite that super steady Y, the high silicon Y that Y (REY), rare earth hydrogen Y (REHY), distinct methods obtain are formed
One or more kinds of mixtures.Preferably, the zeolite can be selected from ZSM-5, ZSM-11,
ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZRP, Rare Earth Y, rare earth hydrogen Y,
At least one of super steady Y and high silicon Y.Inorganic oxide can be selected from oxidation as bonding agent
Silicon (SiO2) and/or aluminum oxide (Al2O3), clay can be kaolin and/or more as matrix (i.e. carrier)
Hydrokaolinite.
According to the present invention, urging for first catalytic conversion reaction and/or the second catalytic conversion reaction is carried out
Agent can also be the equilibrium catalyst that given up used in Conventional catalytic reforming unit.
According to the present invention, the first catalytic conversion reaction and the second catalytic conversion reaction of the invention can be applicable together
The catalyst of one type, can also be applied different type catalyst, and different type catalyst can be particle
The different catalyst of catalyst and/or apparent bulk density of different sizes.The different catalyst of granular size
And/or the different activity over catalysts component of apparent bulk density can also select different type zeolite respectively.
The catalyst of particle of different sizes and/or the catalyst of height apparent bulk density can respectively enter difference
Conversion zone, for example, the catalyst of the bulky grain containing ultrastable enters the first conversion zone, increase
Add cracking reaction, the short grained catalyst containing rare earth Y type zeolite enters the second conversion zone, increases hydrogen
Transfer reaction, the different catalyst of granular size regenerate in same stripper stripping and same regenerator, so
After isolate bulky grain and catalyst particle, catalyst particle enters the second conversion zone through cooling.
Grain catalyst of different sizes can be in a certain particle diameter boundary in 30-40 microns, and apparent bulk density is not
Same catalyst can be in 0.6-0.7g/cm3In a certain density boundary.
As shown in figure 1, the present invention also provides a kind of catalytic conversion system of inferior feedstock oil, the catalysis turns
Change system includes：Pre lift zone, the first conversion zone I, extension diameter section III and outlet section are provided with from the bottom to top
7 riser reactor 2, from top to bottom it is provided with settling section 8, the second conversion zone II and stripping section 10
Settler, and product separative element 18, Aromatics Extractive Project unit 24 and hydrotreating unit 29；Its
In, the second conversion zone II of the settler is in fluid communication with the top exit of the outlet section 7.
A kind of embodiment, the pre lift zone are provided with the first regenerated catalyst inlet, and described
One conversion zone I bottoms are provided with the first inferior raw material oil-in, and the middle and lower part of the extension diameter section III is set
There is catalyst outlet, the second conversion zone II is provided with the second regenerated catalyst inlet, the settling section
8 tops are provided with reacting product outlet, and the stripping section 10 is provided with reclaimable catalyst outlet, the production
The reacting product outlet of the feed(raw material)inlet of thing separative element 18 and the top of settling section 8 is in fluid communication,
The diesel product outlet of the product separative element 18 and the feed(raw material)inlet fluid of Aromatics Extractive Project unit 24 connect
It is logical, the raffinate diesel product outlet of the Aromatics Extractive Project unit 24 and the original of the hydrotreating unit 29
Expect that entrance is in fluid communication.
The conveying of the first reaction product and half reclaimable catalyst, the settler can be set in for convenience
Outside the middle and upper part of the riser reactor 2, the top exit of the outlet section 7 can be arranged on institute
State in the second conversion zone II.
According to the present invention, in order to rationally utilize raw material and controlling reaction temperature, in the outlet section 7
Bottom can be provided with lightweight material oil and/or cold shock medium inlet, the lightweight material oil and/or cold shock
Medium inlet is alternatively in fluid communication with the product exit of the hydrotreating unit 29.
According to the present invention, can be sent from the catalyst that extension diameter section takes out with the reclaimable catalyst for leaving stripping section
Carry out regenerating Posterior circle use to regenerator, therefore, the catalytic conversion system can also include regenerator 13,
The catalyst inlet of the regenerator 13 can be with the extension diameter section III catalyst outlet and the vapour
Carry the reclaimable catalyst outlet of section 10, the catalyst outlet of the regenerator 13 can with it is described pre-
First regenerated catalyst inlet of raising section and the second conversion zone II the second regenerated catalyst inlet connect
It is logical.
According to the present invention, riser reactor is well-known to those skilled in the art, its height and internal diameter
It can be set as needed, in general, the height of the riser reactor 2 can be 10-60
Rice, the internal diameter of the pre lift zone can be 0.2-5 rice, and the height of the pre lift zone can account for lifting
The ratio between the 5-10% of pipe reactor height, the internal diameter of the first conversion zone I and pre lift zone can be
(0.5-1.5)：1, the height of the first conversion zone I can account for the height of riser reactor 2
The ratio between 50-70%, the extension diameter section III and the first conversion zone I internal diameter can be (1.2-5.0)：1,
The height of the extension diameter section III can account for the 5-10% of riser reactor height, the outlet section 7 with
The ratio between first conversion zone I internal diameter can be (0.8-1.5)：1, the height of the outlet section 7 can account for
The 10-30% of riser reactor height.
Below in conjunction with a kind of embodiment of brief description of the drawings the inventive method, but the present invention is not
Therefore it is any way limited.
As shown in figure 1, pre-lift medium is entered through pipeline 1 by the bottom of riser reactor 2, from oblique
First regenerated catalyst of pipe 16 is upward along riser reactor 2 under the castering action of pre-lift medium
Motion, inferior feedstock oil injecting lift pipe reactor together with the atomizing steam from pipeline 4 through pipeline 3
2 first conversion zone I bottom, contacted and under with the first regenerated catalyst in riser reactor 2
It is supreme to carry out the first catalytic conversion reaction in the first conversion zone I, extension diameter section III and outlet section 7,
The first reaction product and half reclaimable catalyst are obtained, wherein, partial catalyst is taken out through pipe from extension diameter section III
Line 27 is sent into regenerator 13 and regenerated；Lightweight material oil and/or cold shock medium are managed through pipeline 5 with coming from
The middle and lower part that the atomizing steam of line 6 injects outlet section 7 together carries out the first catalytic conversion reaction.First is anti-
Product and half reclaimable catalyst is answered to enter the second conversion zone II from the top exit of outlet section 7, it is to be generated half
Under the collective effect of second regenerated catalyst of catalyst and supplement, the first reaction product is relatively low in coke content
Catalyst on occur the second catalytic conversion reaction, the second reaction product of generation enters in settling section 8
Cyclone separator, realizes the separation of catalyst fines and the second reaction product, and the second reaction product enters collection
Air chamber 9, catalyst fines return to settling section 8 by dipleg.Reclaimable catalyst flow direction stripping in settling section 8
Section 10, is contacted with the steam from pipeline 11.The oil gas being stripped off from reclaimable catalyst is through whirlwind point
From entering collection chamber 9 after device.Reclaimable catalyst after stripping enters regenerator 13, regeneration through inclined tube 12
Main wind is through pipeline 14 into regenerator 13, burning-off reclaimable catalyst and on the catalyst from pipeline 27
Coke, regenerated flue gas enter cigarette machine through pipeline 15.Regenerated catalyst after regeneration is through inclined tube 16 and pipeline
28 respectively enter riser reactor 2 and settler.
Oil gas in collection chamber 9 enters follow-up product separative element 18 by pipeline 17 and carries out product point
From isolated dry gas is drawn through pipeline 19, and liquefied gas is drawn through pipeline 20, and gasoline is through pipeline 21
Draw, diesel oil is transported to Aromatics Extractive Project unit 24 through pipeline 22, and slurry oil is drawn through pipeline 23.Diesel oil passes through
Cross Aromatics Extractive Project to obtain raffinate diesel oil and extract diesel oil out, extract diesel oil out and drawn through pipeline 26.Raffinate diesel oil
Hydrotreating unit 29 is transported to through pipeline 25 to contact and be hydrogenated with hydrotreating catalyst therein
Processing, gained light component are drawn through pipeline 31, and hydrogenation is raffinated oil is recycled to outlet section 7 through pipeline 30,
Further produce low-carbon alkene and heavy aromatics.
The present invention will be further illustrated by embodiment below, but therefore the present invention is not taken office
What is limited.
The embodiment of the present invention and comparative example octane number are determined using RIPP 85-90 methods, described RIPP
Standard method for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, nineteen ninety version.
Reaction product obtained by embodiment and comparative example is dry gas, liquefied gas, gasoline, slurry oil, coke and bavin
Oily (or being heavy aromatics), distribution of reaction products adds and is 100%.
Raw material used is that decompression residuum, hydrogenated residue inferior and high acid value are former in embodiment and comparative example
Oil, its property are as shown in table 1.
Catalytic converting catalyst GZ-1 preparation methods used are as follows in embodiment, and its property is listed in table 2：
1), by 20gNH4Cl is dissolved in 1000g water, to obtain in solution add 100g (butt) crystallization
Product ZRP-1 zeolites (Qilu Petrochemical Company's catalyst plant production, SiO2/Al2O3=30, content of rare earth
RE2O3=2.0 heavy %), after 90 DEG C exchange 0.5h, filter to obtain filter cake；Add 4.0g H3PO4(concentration
85%) with 4.5g Fe (NO3)3It is dissolved in 90g water, is mixed with dipping and dries with filter cake；Then in 550 DEG C of temperature
The lower calcination process of degree obtains phosphorous and iron MFI structure mesopore zeolite, its elementary analytical chemistry group for 2 hours
As 0.1Na2O·5.1Al2O3·2.4P2O5·1.5Fe2O3·3.8RE2O3·88.1SiO2。
2), with 250 kilograms of decationized Y sieve water, by 75.4 kilograms of halloysites, (Suzhou china clay company is industrial
Product, 71.6 heavy % of solid content) mashing, add (Shandong Aluminum Plant's industry of 54.8 kilograms of boehmites
Product, 63 heavy % of solid content), its pH is adjusted to 2-4 with hydrochloric acid, stirred, at 60-70 DEG C
Aging 1 hour is stood, holding pH is 2-4, cools the temperature to less than 60 DEG C, adds 41.5 kilograms of aluminium
Colloidal sol (Qilu Petrochemical Company's catalyst plant product, Al2O3Content is 21.7 heavy %), stir 40 minutes,
Obtain mixed serum.
3) the phosphorous and MFI structure mesopore zeolite of iron (butt is 2 kilograms) for, preparing step 1) with
And DASY zeolites (Qilu Petrochemical Company's catalyst plant industrial products, lattice constant 2.445-2.448nm,
Butt is 22.5 kilograms) it is added in the mixed serum that step 2) obtains, stir, be spray-dried
Shaping, is washed with ammonium dihydrogen phosphate (phosphorus content is 1 heavy %), washes away free Na+, it is drying to obtain
Catalytic converting catalyst GZ-1, % are phosphorous and the MFI structure mesopore of iron for 2 weights for the composition of the catalyst
Zeolite, 18 weight %DASY zeolites, 32 weight % boehmites, 7 heavy % Alumina gels and balance kaolin.
Hydrotreating catalyst preparation method used is summarized as follows in embodiment：Weigh ammonium metatungstate
((NH4)2W4O13·18H2O, chemistry are pure) and nickel nitrate (Ni (NO3)2·18H2O, chemistry are pure), use water
It is made into 200mL solution.Solution is added in 50 grams of alumina supports, it is small to impregnate 3 at room temperature
When, ultrasonication maceration extract is used in dipping process 30 minutes, cool down, filtering, be put into microwave
Dried about 15 minutes in stove.The composition of the catalyst is：30.0 weight %WO3, 3.1 weight %NiO and
Remainder alumina.
Conventional catalytic reforming catalyst used in comparative example is respectively GZ-1 and CGP-1, and its property is listed in
Table 2.
Embodiment 1
The embodiment is tested according to Fig. 1 flow, poor qualities of the decompression residuum A as catalyzed conversion
Feedstock oil, riser reactor middle- scale device (height of riser reactor 2 be 30 meters, in advance
The internal diameter of raising section is 0.8 meter, 1.5 meters of the height of pre lift zone, and the first conversion zone I internal diameters are 1 meter,
First conversion zone I height is 21 meters, and extension diameter section III internal diameter is 3 meters, extension diameter section III height
For 1.5 meters, the internal diameter of outlet section 7 is 0.8 meter, and the height of outlet section 7 is 6 meters, similarly hereinafter) it is enterprising
Row experiment, decompression residuum A enter the first conversion zone I bottoms, contacted with catalyst GZ-1 and first
The first catalytic conversion reaction occurs in conversion zone I, extension diameter section III and outlet section 7, the first catalyzed conversion is anti-
The condition answered is：First conversion zone I 600 DEG C of temperature, the 0.4 second reaction time of the first conversion zone,
Oil ratio 6, water-oil factor 0.25, catalyst are 0.1 second in extension diameter section III residence time, are carried wherein accounting for
In riser reactors 8% catalyst of catalyst internal circulating load leave extension diameter section III into regenerator 13 again
Raw, the hydrogenation of the circulation from lightweight material oil and/or cold shock medium inlet is raffinated oil (with decompression residuum A
Ratio be 0.05：1) the first catalytic conversion reaction is carried out into the middle and lower part of outlet section 7.Half is to be generated
Catalyst and the first reaction product leave the outlet section of riser reactor, into the second conversion zone II with mending
The second regenerated catalyst for accounting for catalyst internal circulating load 8% in the riser reactor mixing filled, in reaction temperature
The second catalytic conversion reaction is carried out under conditions of 530 DEG C of degree, 5 seconds reaction time, water-oil factor 0.25, is obtained
To the second reaction product and reclaimable catalyst separated in settling section, the second reaction product is sent into product point
Cut from unit by boiling range, so as to obtain dry gas, liquefied gas (including propylene, propane and C4Hydrocarbon,
Similarly hereinafter), gasoline, diesel oil and slurry oil.Gained diesel oil is sent into Aromatics Extractive Project unit 24, in diesel oil and chaff
Aldehyde ratio is 2, extracting section temperature carries out Aromatics Extractive Project under conditions of being 75 DEG C, extracts diesel oil carrying device out.
Raffinate diesel oil is sent into hydrotreating unit 29, in hydrogen dividing potential drop 18.0MPa, 350 DEG C of reaction temperature, hydrogen oil
Volume ratio 1500：1st, raffinate diesel fuel volume air speed 1.5 hours-1Reaction condition under carry out hydrotreating,
Hydrogenation, which is raffinated oil, is recycled back to above-mentioned middle- scale device.Operating condition and product distribution are listed in table 3 and table 4.
From table 4, it can be seen that the ethylene yield and productivity of propylene of embodiment 1 be respectively 2.84 weight % and
19.51%, 8.35 heavy % of heavy aromatics yield, high-knock rating gasoline yield is up to 33.75 heavy %.
Comparative example 1
The comparative example is the raw material directly as catalyzed conversion with vacuum residuum feed A, in medium-sized lifting
On pipe reactor device (riser reactor includes pre lift zone, conversion zone and outlet section from the bottom to top,
Total height is 30 meters, and the internal diameter of pre lift zone is 0.8 meter, 1.5 meters of the height of pre lift zone, conversion zone
Internal diameter is 1 meter, and the height of conversion zone is 22.5 meters, and the internal diameter of outlet section 7 is 0.8 meter, outlet section 7
Height be 6 meters, similarly hereinafter) tested, using catalyst GZ-1, in 530 DEG C of reaction temperature, anti-
Be 2.5 seconds between seasonable, oil ratio 6, water-oil factor carry out catalytic conversion reaction, gained under the conditions of being 0.25
Oil gas and catalyst with charcoal are directly separated in settling section, and product is cut in product separative element by boiling range
Cut, so as to obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil.Operating condition and product distribution are listed in
Table 3 and table 4.
From table 4, it can be seen that dry gas yied is up to 12.22 heavy %, productivity of propylene is only 9.03 heavy %,
Slurry oil yield is up to 10.10 heavy %, and octane number is low.Compared with Example 1, high added value product
Yield is greatly lowered, and causes the reduction of petroleum resources utilization ratio.
Embodiment 2
The embodiment is tested according to Fig. 1 flow, and hydrogenated residue B inferior is former as inferior feedstock oil
Material, is tested, hydrogenated residue inferior on the middle- scale device of the riser reactor used in embodiment 1
B enters the first conversion zone I bottoms, is contacted with catalyst CGP-1 and in the first conversion zone I, extension diameter section
The first catalytic conversion reaction is carried out in III and outlet section 7, the condition of the first catalytic conversion reaction is：First
Conversion zone I 600 DEG C of temperature, the 0.4 second reaction time of the first conversion zone, oil ratio 6, water-oil factor be
0.25, catalyst extension diameter section III residence time be 0.1 second, wherein 8% catalyst leave it is expanding
Section III regenerates into regenerator 13.Hydrogenation from lightweight material oil and/or cold shock medium inlet is raffinated oil
(ratio with hydrogenated residue B inferior is 0.05：1) first is carried out into the middle and lower part of outlet section 7 to urge
Change conversion reaction.Half reclaimable catalyst and the first reaction product leave outlet section 7 enter the second conversion zone with
The second regenerated catalyst for accounting for catalyst internal circulating load 8% in the riser reactor mixing of supplement, is reacting
530 DEG C of temperature, 5 seconds reaction time, water-oil factor carry out the second catalytic conversion reaction under conditions of being 0.25,
Obtained the second reaction product and reclaimable catalyst separates in settling section, and the second reaction product is sent into product
Separative element is cut by boiling range, so as to obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil.Will
Gained diesel oil is sent into Aromatics Extractive Project unit 24, in diesel oil and furfural than for bar that 2, extraction temperature is 75 DEG C
Aromatics Extractive Project is carried out under part, extracts diesel oil carrying device out.Raffinate diesel oil is sent into hydrotreating unit 29,
Hydrogen dividing potential drop 18.0MPa, 350 DEG C of reaction temperature, hydrogen to oil volume ratio 1500：1st, raffinate diesel fuel volume is empty
Speed 1.5 hours-1Reaction condition under carry out hydrotreating, hydrogenation, which is raffinated oil, is recycled back to above-mentioned middle- scale device.
Operating condition and product distribution are listed in table 5 and table 6.
As can be seen from Table 6, the ethylene yield of embodiment 2 and productivity of propylene be respectively 2.43 weight % and
20.42%, 8.91 heavy % of heavy aromatics yield, high octane gasoline yield is up to 30.42 heavy %.
Comparative example 2
The comparative example is the raw material directly as catalytic cracking with hydrogenated residue B inferior, in comparative example 1
Tested on middle scale riser reactor assembly used, using catalyst CGP-1, in reaction temperature
530 DEG C, the reaction time be 2.5 seconds, that catalyzed conversion is carried out under the conditions of oil ratio 6, water-oil factor are 0.25 is anti-
Should；Oil gas and catalyst with charcoal are separated in settling section, and product is cut in product separative element by boiling range
Cut, so as to obtain dry gas, liquefied gas, gasoline, diesel oil, slurry oil.Operating condition and product distribution are listed in
Table 5 and table 6.
As can be seen from Table 6, for dry gas yied up to 7.62 heavy %, productivity of propylene is only 6.84 heavy %, oil
Slurry yield is up to 12.70 heavy %, and octane number is low.Compared with Example 2, high added value product produces
Rate is greatly lowered, and causes the reduction of petroleum resources utilization ratio.
Embodiment 3
The embodiment is tested according to Fig. 1 flow, and crude oil with high acid value C is as catalyzed conversion
Inferior feedstock oil, tested on the middle- scale device of the riser reactor used in embodiment 1, peracid
Value crude oil C enter the first conversion zone I bottoms, contacted with catalyst GZ-1 and the first conversion zone I,
The first catalytic conversion reaction, the condition of the first catalytic conversion reaction occurs in extension diameter section III and outlet section 7
For：600 DEG C of the temperature of the top exit of outlet section 7,0.4 second reaction time, oil ratio 6, water-oil factor
0.25, catalyst is 0.1 second in extension diameter section III residence time, is catalyzed wherein accounting in riser reactor
The catalyst of agent internal circulating load 8% leaves extension diameter section III and regenerated into regenerator 13, from lightweight material oil
And/or it (is 0.05 with crude oil with high acid value C ratio that the hydrogenation of cold shock medium inlet, which is raffinated oil,：1) enter
The middle and lower part of outlet section 7 carries out the first catalytic conversion reaction.Half reclaimable catalyst and the first reaction product from
The outlet section of riser reactor is opened, is catalyzed into the second conversion zone and accounting in riser reactor for supplement
Agent internal circulating load 8% the second regenerated catalyst mixing, 530 DEG C of reaction temperature, 5 seconds reaction time,
The second catalytic conversion reaction is carried out under conditions of water-oil factor 0.25, obtained the second reaction product and to be generated is urged
Agent separates in settling section, and the second reaction product is sent into product separative element and cut by boiling range, from
And obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil.Gained diesel oil is sent into Aromatics Extractive Project unit 24,
Aromatics Extractive Project is carried out under conditions of diesel oil and furfural ratio are 2, extraction temperature is 75 DEG C, diesel oil is extracted out and send
Go out device.Raffinate diesel oil be sent into hydrotreating unit 29, hydrogen dividing potential drop 18.0MPa, 350 DEG C of reaction temperature,
Hydrogen to oil volume ratio 1500：1st, raffinate diesel fuel volume air speed 1.5 hours-1Reaction condition under carry out at hydrogenation
Reason, hydrogenation, which is raffinated oil, is recycled back to above-mentioned middle- scale device.Operating condition and product distribution are listed in table 7 and table 8.
As can be seen from Table 8, ethylene yield and productivity of propylene are respectively 2.31 weight % and 20.40%, weight
8.79 heavy % of aromatics yield, high octane gasoline yield is up to 29.94 heavy %.
Comparative example 3
The comparative example is the raw material directly as catalytic cracking with crude oil with high acid value C, used in comparative example 1
Middle scale riser reactor assembly on tested, using catalyst GZ-1,530 DEG C of reaction temperature,
Reaction time is 2.5 seconds, oil ratio 6, water-oil factor carry out catalytic conversion reaction under the conditions of being 0.25；Oil
Gas and catalyst with charcoal are separated in settling section, and product is cut in product separative element by boiling range, from
And obtain dry gas, liquefied gas, gasoline, diesel oil, slurry oil.Operating condition and product distribution are listed in the He of table 7
Table 8.
From table 7 and table 8 as can be seen that dry gas yied is up to 8.82 heavy %, productivity of propylene is only 6.70
Weight %, slurry oil yield are up to 13.07 heavy %, and octane number is low.Compared with Example 1, it is high additional
Value products collection efficiency is greatly lowered, and causes the reduction of petroleum resources utilization ratio.
From table 3-8 embodiment 1-3 and comparative example 1-3 comparison as can be seen that using present invention system
The catalysis conversion method of system can improve liquefied gas and gasoline yield, reduce dry gas, coke and slurry oil yield,
The octane number of gained gasoline is high simultaneously.
Table 1 is used the property of inferior feedstock oil by embodiment and comparative example
Table 2 is used the specific nature of catalyst by embodiment and comparative example
| Catalyst is numbered | GZ-1 | CGP-1 |
| Zeolite type | Mesopore and large pore zeolite | Mesopore and large pore zeolite |
| Chemical composition, weight % | ||
| Aluminum oxide | 40.0 | 56.3 |
| Sodium oxide molybdena | 0.29 | 0.19 |
| Iron oxide | 1.1 | / |
| Rare earth | 2.5 | 3.2 |
| Apparent density, kg/m3 | 750 | 630 |
| Pore volume, mL/g | 0.40 | 0.36 |
| Specific surface area, m2/g | 196 | 221 |
| Abrasion index, weight % | 1.5 | 1.7 |
| Screening composition, weight % | ||
| 0~40 micron | 20.2 | 13.1 |
| 40~80 microns | 50.1 | 41.8 |
| >80 microns | 29.7 | 45.1 |
Table 3 is the operating condition of embodiment 1 and comparative example 1
Table 4 is the product distribution of embodiment 1 and comparative example 1
| Project | Embodiment 1 | Comparative example 1 |
| Product is distributed, weight % | ||
| Dry gas | 5.67 | 12.22 |
| Wherein ethene | 2.84 | 3.66 |
| Liquefied gas | 40.65 | 23.75 |
| Wherein propylene | 19.51 | 9.03 |
| Gasoline | 33.75 | 30.62 |
| Diesel oil | / | 12.43 |
| Slurry oil | 4.03 | 10.10 |
| Coke | 7.55 | 10.88 |
| Heavy aromatics | 8.35 | / |
| It is total | 100 | 100 |
| Octane number | ||
| RON | 95.2 | 92.5 |
| MON | 82.7 | 78.1 |
Table 5 is the operating condition of embodiment 2 and comparative example 2
Table 6 is the product distribution of embodiment 2 and comparative example 2
| Embodiment 2 | Comparative example 2 | |
| Product is distributed, weight % | ||
| Dry gas | 4.85 | 7.62 |
| Wherein ethene | 2.43 | 2.52 |
| Liquefied gas | 42.55 | 25.34 |
| Wherein propylene | 20.42 | 6.84 |
| Gasoline | 30.42 | 26.43 |
| Diesel oil | / | 17.67 |
| Slurry oil | 4.34 | 12.70 |
| Heavy aromatics | 8.91 | / |
| Coke | 8.93 | 10.24 |
| It is total | 100 | 100 |
| Octane number | ||
| RON | 94.4 | 92.0 |
| MON | 81.6 | 81.1 |
Table 7 is the operating condition of embodiment 3 and comparative example 3
Table 8 is the product distribution of embodiment 3 and comparative example 3
| Project | Embodiment 3 | Comparative example 3 |
| Product is distributed, weight % | ||
| Dry gas | 4.62 | 8.82 |
| Wherein ethene | 2.31 | 2.91 |
| Liquefied gas | 42.50 | 28.66 |
| Wherein propylene | 20.40 | 6.70 |
| Gasoline | 29.94 | 28.34 |
| Diesel oil | / | 17.68 |
| Slurry oil | 5.07 | 13.07 |
| Carbon dioxide | 0.98 | 1.07 |
| Heavy aromatics | 8.79 | / |
| Coke | 8.10 | 11.18 |
| It is total | 100 | 100 |
| Octane number | ||
| RON | 94.8 | 91.0 |
| MON | 81.2 | 79.8 |
Claims (16)
1. a kind of catalysis conversion method of inferior feedstock oil, this method include：
A, by the inferior feedstock oil of preheating from be provided with from the bottom to top pre lift zone, the first conversion zone (I),
In the first conversion zone (I) of the riser reactor (2) of extension diameter section (III) and outlet section (7)
Bottom is sent into riser reactor (2) with being transported to the of the pre lift zone from regenerator (13)
One regenerated catalyst contacts and from the bottom to top in first conversion zone (I), extension diameter section (III) and outlet
The first catalytic conversion reaction is carried out in section (7), obtains the first reaction product and half reclaimable catalyst；
B, by the first reaction product of gained and half reclaimable catalyst in step a from the outlet section (7)
Top exit leaves the riser reactor (2) into progress in the second conversion zone (II) of settler
Second catalytic conversion reaction, obtain the second reaction product and reclaimable catalyst；
C, the second reaction product of gained in step b is sent out into the settler and is sent into product separative element
(18) product separation is carried out, obtains dry gas, liquefied gas, gasoline, diesel oil and slurry oil；By gained diesel oil
It is sent into Aromatics Extractive Project unit (24) and carries out Aromatics Extractive Project, obtains raffinate diesel oil and extract diesel oil out；By gained
Raffinate diesel oil is sent into hydrotreating unit (29) and is contacted with hydrotreating catalyst and carry out hydrotreating,
Hydrogenation is obtained to raffinate oil；
Wherein, this method also includes：Partial catalyst is taken out from the middle and lower part of the extension diameter section (III) to send
Enter the regenerator (13) to be regenerated, using the partial regeneration agent in the regenerator (13) as
The middle and lower part that two regenerated catalysts are sent into second conversion zone (II) of the settler is described with coming from
Half reclaimable catalyst of outlet section (7) carries out second catalytic conversion reaction together.
2. catalysis conversion method according to claim 1, wherein, the settler also include with
The settling section (8) and stripping section (10) that second conversion zone (II) is in fluid communication, the settling section
(8) above second conversion zone (II), the stripping section (10) is positioned at the described second reaction
Below section (II), the settler is set in outside the middle and upper part of the riser reactor (2), and
The top exit of the outlet section (7) is located in second conversion zone (II)；By gained in step b
Second reaction product sends out the settler after the settling section (8) carries out gas solid separation and is sent into production
Thing separative element (18) carries out product separation described in step c, by gained reclaimable catalyst in step b
The settler, which is sent out, after the stripping section (10) stripping and is sent into the regenerator (13) carries out again
It is raw.
3. catalysis conversion method according to claim 1, this method also include：By lightweight material
Oil and/or cold shock medium are sent into the riser reactor (2) from the middle and lower part of the outlet section (7)
Carry out first catalytic conversion reaction；Wherein, lightweight material oil include selected from liquefied gas, gasoline,
Diesel oil and hydrogenation at least one of are raffinated oil, and the cold shock medium is selected from liquefied gas, raw gasoline, steady
Determine gasoline, diesel oil, hydrogenation raffinate oil, at least one of heavy diesel fuel and water.
4. catalysis conversion method according to claim 1, wherein, the condition of the Aromatics Extractive Project
Including：The solvent of Aromatics Extractive Project be selected from furfural, dimethyl sulfoxide, dimethylformamide, MEA,
At least one of ethylene glycol and 1,2-PD, the solvent separate institute with product separative element (18)
The volume ratio for obtaining diesel oil is (0.5-5.0)：1, the temperature of the Aromatics Extractive Project is 40-120 DEG C；It is described to add
The condition of hydrogen processing includes：Hydrogen dividing potential drop is 3.0-20.0 MPas, and temperature is 300-450 DEG C, hydrogen oil volume
Than for (300-2000)：1, raffinate diesel fuel volume air speed is 0.1-3.0 hours-1；The hydrotreating is urged
Agent includes the group vib metal and/or VIII base metal of carrier and load on the carrier,
The carrier is alumina support and/or silica-alumina supports.
5. catalysis conversion method according to claim 1, wherein, first urges described in step a
Changing the condition of conversion reaction includes：Temperature is 510-650 DEG C, and the time is the 0.05-1.5 seconds, and oil ratio is
(3-20)：1, water-oil factor is (0.03-0.8)：1, pressure is 130-450 kPas；Described in step b
The condition of second catalytic conversion reaction includes：Temperature is 420-550 DEG C, and the time is the 1.5-20 seconds.
6. catalysis conversion method according to claim 1, in terms of the weight of catalyst, carried accounting for
The 1-20 weight % of catalyst internal circulating load catalyst is from the extension diameter section (III) in riser reactors
Bottom is taken out, and will account for the 1-20 weight % of catalyst internal circulating load in riser reactor second regeneration
Catalyst is sent into second conversion zone (II).
7. catalysis conversion method according to claim 1, wherein, the inferior feedstock oil is choosing
From decompression residuum, reduced crude inferior, hydrogenated residue inferior, coker gas oil, deasphalted oil,
At least one of crude oil with high acid value, high metal crude oil, liquefied coal coil, tar sand oil and shale oil.
8. the catalysis conversion method according to claim 1 or 7, wherein, the inferior feedstock oil
Density be 900-1000 kgs/m3, carbon residue is 4-15 weight %, tenor 15-600ppm,
Acid number is 0.5-20.0mgKOH/g.
9. catalysis conversion method according to claim 1, wherein, carry out first catalysis and turn
Changing the catalyst of reaction and/or the second catalytic conversion reaction includes zeolite, inorganic oxide and optionally glues
Soil；Counted by butt and on the basis of the weight of the catalyst, the content of the zeolite weighs %, nothing for 1-50
The content of machine oxide is 5-99 weight %, and the content of clay is 0-70 weights %.
10. catalysis conversion method according to claim 9, wherein, the zeolite be selected from ZSM-5,
ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZRP, Rare Earth Y,
At least one of rare earth hydrogen Y, super steady Y and high silicon Y, the inorganic oxide be silica and/
Or aluminum oxide, the clay are kaolin and/or halloysite.
11. a kind of catalytic conversion system of inferior feedstock oil, the catalytic conversion system include：From the bottom to top
It is provided with the riser of pre lift zone, the first conversion zone (I), extension diameter section (III) and outlet section (7)
Reactor (2), from top to bottom it is provided with settling section (8), the second conversion zone (II) and stripping section (10)
Settler, and product separative element (18), Aromatics Extractive Project unit (24) and hydrotreating unit
(29)；Wherein, the second conversion zone (II) of the settler at the top of the outlet section (7) with going out
Mouth is in fluid communication.
12. catalytic conversion system according to claim 11, wherein, the pre lift zone is set
There is the first regenerated catalyst inlet, the first conversion zone (I) bottom is provided with the first inferior feedstock oil
Entrance, the middle and lower part of the extension diameter section (III) are provided with catalyst outlet, second conversion zone (II)
The second regenerated catalyst inlet is provided with, reacting product outlet is provided with the top of the settling section (8),
The stripping section (10) is provided with reclaimable catalyst outlet, the raw material of the product separative element (18)
Entrance is in fluid communication with the reacting product outlet at the top of the settling section (8), the product separative element
(18) diesel product outlet and the feed(raw material)inlet of Aromatics Extractive Project unit (24) is in fluid communication, the virtue
The raffinate diesel product outlet of hydrocarbon extraction unit (24) and the raw material of the hydrotreating unit (29) enter
Mouth is in fluid communication.
13. catalytic conversion system according to claim 11, wherein, the settler is set in
Outside the middle and upper part of the riser reactor (2), the top exit of the outlet section (7) is arranged on
In second conversion zone (II).
14. catalytic conversion system according to claim 11, wherein, the outlet section (7)
Middle and lower part is provided with lightweight material oil and/or cold shock medium inlet.
15. catalytic conversion system according to claim 11, the catalytic conversion system also includes again
Raw device (13), the catalyst inlet of the regenerator (13) and the catalyst of the extension diameter section (III)
Outlet and the reclaimable catalyst outlet of the stripping section (10), regenerator (13) are urged
Agent exports the with the first regenerated catalyst inlet of the pre lift zone and the second conversion zone (II)
Two regenerated catalyst inlets connect.
16. catalytic conversion system according to claim 11, wherein, the riser reactor
(2) height is 10-60 rice, and the internal diameter of the pre lift zone is 0.2-5 rice, the pre lift zone
Highly account for the 5-10% of riser reactor height, first conversion zone (I) and the internal diameter of pre lift zone
The ratio between be (0.5-1.5)：1, the height of first conversion zone (I) accounts for riser reactor (2) height
The ratio between internal diameter of the 50-70% of degree, the extension diameter section (III) and the first conversion zone (I) is (1.2-5.0)：
1, the height of the extension diameter section (III) accounts for the 5-10% of riser reactor height, the outlet section (7)
It is (0.8-1.5) with the ratio between the internal diameter of the first conversion zone (I)：1, the height of the outlet section (7) accounts for
The 10-30% of riser reactor height.
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| CN111040812A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Production method and system of low-carbon olefin and light aromatic hydrocarbon |
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