CN105368493B - A kind of catalysis conversion method producing high-knock rating gasoline - Google Patents
A kind of catalysis conversion method producing high-knock rating gasoline Download PDFInfo
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Abstract
The present invention relates to a kind of catalysis conversion method producing high-knock rating gasoline, this method includes：By after preheating feedstock oil and the first catalytic converting catalyst carry out catalytic conversion reaction in the initial reaction area of riser reactor, and the oil agent mixture generated by the initial reaction area is made to enter the main reaction region of riser reactor, continue catalytic conversion reaction with the second catalytic converting catalyst of supplement injection, wherein, the reaction temperature of main reaction region is higher than the reaction temperature in initial reaction area, the temperature of second catalytic converting catalyst is higher than the temperature of the first catalytic converting catalyst, and the reaction time in initial reaction area is less than the reaction time of main reaction region.The catalysis conversion method of production high-knock rating gasoline provided by the invention can not only obtain the gasoline products of higher gasoline RON octane numbers, and the quality of the gasoline products obtained is preferable, has significant lower alkene and higher isoparaffin and arene content.
Description
Technical field
The present invention relates to a kind of catalysis conversion methods of hydrocarbon ils, and in particular, to a kind of to produce urging for high-knock rating gasoline
Change method for transformation.
Background technology
In recent years, as car ownership quickly increases, environmental regulation is increasingly stringent, and market needs petroleum chemical enterprise's offer to fill
The high-quality gasoline of foot, and current quality of gasoline escalation process, inevitably cause the loss of octane number of gasoline.Catalysis
Cracking (FCC) is to produce the main secondary processing process of gasoline, and 80% or more Chinese commodity gasoline comes from fluid catalytic cracking
(FCC) gasoline.However catalytically cracked gasoline, due to the limitation of technique itself, RON octane numbers are generally below 93, and gasoline forms
Middle olefin(e) centent is higher, and for volume content generally 35% or more, arene content is relatively low, and general volume content is in 10-25% (GB
17930-2011 provides that olefin(e) centent is no more than 30%, 40%) arene content is no more than.It reduces content of olefin in gasoline and improves vapour
There are certain contradiction between oily octane number, need to do deeper into work.Octane number is improved, it is pungent especially to improve gasoline
Alkane value bucket, it has also become the most important thing of catalytic cracking worker work.
US3784463A discloses a kind of method improving octane number using catalytic cracking process.This method uses two
The riser reactor of root or two or more, wherein a riser makes it higher dedicated for processing low-quality gasoline
At a temperature of catalytic cracking reaction occurs.This method at high temperature modifies gasoline, and some olefin cracking again leads to gasoline
Waste is larger.
Quantity flexibility method disclosed in CN1069054A is corresponding using two independent risers and two
Settler so that light petroleum hydrocarbon and heavy petroleum hydrocarbon is reacted under different reaction conditions using same catalyst.
In first riser reactor, thermocatalyst that light hydrocarbons and regenerator come 600-700 DEG C, oil ratio 10-40, stop
It stays and is reacted under conditions of time 2-20 second, coke on regenerated catalyst 0.1-0.4 weight %, with yield-increasing gas alkene, improve vapour
Oily octane number, the impurity such as removing sulphur nitrogen, improves gasoline stability, reducing atmosphere is provided, to the heavy metal contaminants on catalyst
It is passivated, the cracking reaction to carry out heavy hydrocarbon in catalyst circulation to second riser provides advantage.Heavy
Hydro carbons is reacted under the conditions of Conventional riser catalytic cracking reaction.
CN1160746A discloses a kind of catalysis conversion method improving gasoline octane number.This method is will be low pungent
Alkane value gasoline is by the upstream injecting lift pipe reactor of Conventional catalytic cracking feed(raw material)inlet, with the high-temperature catalytic from regenerator
Agent contact, reaction temperature be 600-730 DEG C, oil ratio 6-180, weight (hourly) space velocity (WHSV) 1-180h-1Under conditions of reacted.
Although the method for directly carrying out high temperature modification to catalytic gasoline in riser of above-mentioned use helps to improve institute
Octane number is produced, but increase rate is limited, and the waste of gasoline is larger, the yield of gasoline reduces.
CN1237477A discloses a kind of riser reactor, which vertically sequentially consists of each other
Coaxial pre lift zone, first reactor, expanding second reaction zone, undergauge outlet area, have a level in outlet area end
Pipe.The reactor not only can selectively control process conditions difference of first reaction zone with second reaction zone, but also can make not
Connatural feedstock oil carries out segmentation cracking, obtains required purpose product.It discloses in CN1232069A and is carried with above-mentioned new construction
Iso-butane and the catalysis conversion method rich in isoparaffin gasoline are produced based on riser reactors, this method is after preheating
Feedstock oil introduce a reducing reactor for including two reaction zones, contacted with hot Cracking catalyst, the first reaction zone temperature
530 DEG C -620 DEG C of degree, reaction time 0.5-2.0 second；460-530 DEG C of second reaction zone temperature, reaction time 2-30 second, separation are anti-
After answering product, reclaimable catalyst recycles after stripping is burnt into regenerator.It is different in the liquefied gas produced using this method
Butane content 20-40 weight %, the isoparaffin content 30-45 weight % in gasoline family's composition, olefin(e) centent is reduced to 30 weights
Measure % hereinafter, its research octane number (RON) be 90-93, motor octane number 80-84, to octane number improve it is limited.
US4268700A discloses a kind of method producing high-knock rating gasoline using polymerization of low-carbon olefin.C3 and C4 components
Oligomerisation, the wherein oligomerization of propene in C3 components, in C4 components 80% isobutene and the n-butene oligomerisation less than 40% generate vapour
Polymer in oily boiling range.The gasoline fraction that unreacted C4 alkylating hydrocarbons generate can be concocted with the polymer of C3, C4 component
Produce high-knock rating gasoline.But still contains compared with polyene in such method product, and contain more alkadienes, gasoline is stable
Property is poor.
In conclusion carrying out high temperature modification, the drop larger to the waste of gasoline that put forward high-octane method to catalytic gasoline
The low yield of gasoline, double-reaction area produce the method rich in isoparaffin gasoline and improve limited, and low-carbon to octane number
The quality of gasoline of the method production of alkene oligomerization is difficult to meet the requirements, and the olefin(e) centent of gasoline is high.
Invention content
The purpose of the invention is to overcome the octane number present in the existing method for improving octane number to carry
It is high limited, or the yield of gasoline can be reduced while improving octane number, and olefin(e) centent in gasoline is higher etc. scarce
It falls into, a kind of catalysis conversion method of new production high-knock rating gasoline is provided.
The present invention provides a kind of catalysis conversion method producing high-knock rating gasoline, this method includes：After preheating
Feedstock oil and the first catalytic converting catalyst carry out catalytic conversion reaction in the initial reaction area of riser reactor, and make by
The oil agent mixture that the initial reaction area generates enters the main reaction region of riser reactor, the second catalysis with supplement injection
Reforming catalyst continues catalytic conversion reaction, wherein the reaction temperature of the main reaction region is higher than the initial reaction area
Reaction temperature, the temperature of second catalytic converting catalyst is higher than the temperature of first catalytic converting catalyst, and institute
The reaction time for stating initial reaction area is less than the reaction time of the main reaction region.
The catalysis conversion method of the production high-knock rating gasoline provided by the invention is implemented in riser reactor, leads to
Cross reduce riser reactor initial reaction area reaction severity, control cracking level, and main reaction region by high temperature,
High agent-oil ratio and long residence time promote the aromatization of the alkene in the crackate in initial reaction area, reduce thermal cracking
Reaction ratio, to reduce olefin(e) centent in dry gas yied and gasoline, and raising gasoline is pungent while increasing gasoline production
Alkane value, improves product selectivity.
In addition, the method provided by the invention is easy to operate, letter is carried out on the basis of conventional catalytic cracking unit
Single transformation can operate.
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 to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is that a kind of flow of the catalysis conversion method of the production high-knock rating gasoline of embodiment according to the present invention is shown
It is intended to.
Reference sign
1- riser reactors；2- regenerators；3- settlers；
4- stripping sections；5- catalyst heat collectors；
6- (1 outlet end of riser reactor) cyclone separator；
7- (gas vent and main oil gas piping 20 of connection cyclone separator 6) collection chamber；
8- reclaimable catalyst inclined tube pipelines；
9- (is connected) regenerated catalyst inclined tube pipeline with main reaction region bottom；
10- (catalyst outlet and catalyst heat collector 5 that are connected to the regenerator 2) pipeline；
11- (the initial reaction area of connection catalyst heat collector 5 and riser reactor 1) pipeline；
14- is the pipeline that riser reactor 1 conveys pre-lift medium；
15- is the pipeline of 1 transferring raw material of riser reactor；
16- is the pipeline that riser reactor 1 conveys atomizing steam and transferring raw material；
The initial reaction area of 17- riser reactors；
The main reaction region of 18- riser reactors；
19- is the pipeline that stripping section 4 conveys atomizing steam；
20- main oil gas pipings；
21- (2 main wind entrance of regenerator) pipeline；
22- air distributors；
23- regenerator cyclone separators；
24- (is connected to) flue with 23 gas vent of cyclone separator.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
All ranges disclosed herein all includes endpoint and can independently combine.Range presently disclosed
Endpoint and any value are not limited to the accurate range or value, these ranges or value should be understood as comprising close to these ranges or
The value of value.
It is provided by the invention it is described production high-knock rating gasoline catalysis conversion method include：By after preheating feedstock oil with
First catalytic converting catalyst carries out catalytic conversion reaction in the initial reaction area of riser reactor, and makes by described initial
The oil agent mixture that reaction zone generates enters the main reaction region of riser reactor, is catalyzed with the second catalyzed conversion of supplement injection
Agent continues catalytic conversion reaction, wherein the reaction temperature of the main reaction region is higher than the reaction temperature in the initial reaction area
Degree, the temperature of second catalytic converting catalyst are higher than the temperature of first catalytic converting catalyst, and described initial anti-
The reaction time in area is answered to be less than the reaction time of the main reaction region.
In the method provided by the invention, it is preferable that the reaction temperature of the main reaction region is than the initial reaction
The reaction temperature in area is 5-100 DEG C high, more preferable 10-80 DEG C, further preferred 30-60 DEG C.
In the method provided by the invention, vapor, and the water injected can also be injected in the initial reaction area
The amount of steam and the weight ratio of feedstock oil can be 0.01-2：1, preferably 0.05-1：1.The vapor can be steamed with being atomized
The form of vapour is injected.
In the method provided by the invention, it is preferable that the reaction time in the initial reaction area is than the main reaction
The reaction time in area is 0.5-5 seconds short, 0.6-4 seconds more preferable, 0.7-3.8 seconds further preferred.
In the method provided by the invention, the reaction condition in the initial reaction area may include：Reaction temperature is
400-600 DEG C, preferably 450-550 DEG C；Oil ratio (i.e. the weight ratio of catalyst and feedstock oil) is 1-50: 1, preferably 1-30
∶1；Reaction time is 0.1-1.9 seconds, preferably 0.2-1.5 seconds.
In the method provided by the invention, the reaction condition of the main reaction region may include：Reaction temperature is
450-700 DEG C, preferably 500-600 DEG C；Reaction pressure is 130-450kPa, preferably 200-400kPa；Agent weight of oil ratio is
5-50: 1, preferably 10-40: 1；Reaction time is 1-8 seconds, preferably 1.5-6 seconds.The agent weight of oil ratio of the main reaction region is
Refer to the total amount of the first catalytic converting catalyst and the second catalytic converting catalyst and the weight ratio of feedstock oil.
In the present invention, the reaction temperature of riser reactor refers to certain of riser reactor or riser reactor
The outlet temperature of a reaction zone；Reaction pressure refers to gauge pressure.
In the method provided by the invention, the main reaction region in used riser reactor can be provided with one
It is a or multiple.In order to enable raw material fully to react, and according to different purpose product quality requirements, the promotion tube reaction
The quantity of main reaction region could be provided as 2-8, preferably 2-3 in device.
A kind of embodiment according to the present invention, as shown in Figure 1, the riser reactor includes just successively from bottom to top
Beginning reaction zone and main reaction region.In the riser reactor, the initial reaction area and the main reaction region can be according to normal
The mode of rule is distributed or is connected.Under preferable case, the initial reaction area is undergauge relative to the main reaction region, and described
The ratio between the riser diameter of main reaction region and the initial reaction area can be 1.2-1.5：1.The initial reaction area and described
The junction of main reaction region can be truncated cone-shaped, and the apex angle of the preferably vertical section isosceles trapezoid of the truncated cone-shaped can be 45-
75°.In this embodiment, first catalytic converting catalyst is preferably injected in the bottom in the initial reaction area, described
Second catalytic converting catalyst is preferably injected in the lower part of the main reaction region.Specifically, the first catalytic converting catalyst is being noted
It after entering, is flowed up in the initial reaction area under the action of pre-lift medium, the feedstock oil after preheating is initial anti-
Answer the lower part in area to inject, and the first catalytic converting catalyst haptoreaction, be formed by oil agent mixture continue on be advanced into master
Reaction zone continues to react with the second catalytic converting catalyst of supplement injection.
For the initial reaction area of riser reactor, structure may be conventional equal diameter riser reactor,
Its diameter can be 0.2-5 meters, and length can be 0.5-5 meters.For the main reaction region of riser reactor, structure can be
Conventional equal diameter riser reactor, length can be 10-50 meters.
In the present invention, the weight ratio of the pre-lift medium and feedstock oil can be 0.01-2：1, preferably 0.05-1：
1.The pre-lift medium can be selected from least one of vapor, dry gas and nitrogen.
In the method provided by the invention, the temperature of second catalytic converting catalyst is catalyzed higher than described first
The temperature of reforming catalyst.Under preferable case, the temperature of second catalytic converting catalyst is urged than first catalyzed conversion
The temperature of agent is 10-150 DEG C high, more preferable 15-100 DEG C.It is further preferred that the temperature of first catalytic converting catalyst
It is 450-650 DEG C, more preferably 500-620 DEG C；The temperature of second catalytic converting catalyst is 600-730 DEG C, more preferably
It is 620-700 DEG C.
In the present invention, the catalysis conversion method can also include：It will be discharged by the outlet of the riser reactor
Reaction mass carry out gas solid separation, the solid catalyst isolated is stripped, coke burning regeneration is urged with obtaining high temperature regeneration
Agent cools down a part of high-temperature regenerated catalyst, and cooling regenerated catalyst is recycled as first catalysis
Reforming catalyst, while another part high-temperature regenerated catalyst is recycled as second catalytic converting catalyst.The gas
Admittedly the process detached can carry out in cyclone separator.For the reaction oil gas isolated during gas solid separation, usually will
It injects subsequent separation system, and separation obtains the fractions such as dry gas, liquefied gas, gasoline and diesel oil.
The regenerated process can be implemented according to the catalyst recovery process of this field routine, for example, the regeneration side
Method may include：Oxygen-containing gas (such as air) is introduced from the bottom of regenerator, after oxygen-containing gas introduces regenerator, reclaimable catalyst
Coke burning regeneration is contacted with oxygen, for the flue gas generated after catalyst coke burning regeneration in regenerator top gas solid separation, flue gas can be into
Enter subsequent power recovery system.The regeneration condition of the reclaimable catalyst can be the operating condition of this field routine, such as can
To include：Temperature is 550-750 DEG C, preferably 600-730 DEG C, further preferably 650-700 DEG C；Gas superficial linear speed is
0.5-3 meter per seconds, preferably 0.8-2.5 meter per seconds, more preferably 1-2 meter per seconds；Reclaimable catalyst mean residence time is 0.6-3
Minute, preferably 0.8-2.5 minutes, more preferably 1-2 minutes.
The mode that high-temperature regenerated catalyst is cooled down can be that high-temperature regenerated catalyst is made to be mixed with low temperature reclaimable catalyst
It is cooled down, high-temperature regenerated catalyst can also be cooled to required temperature by cooler.
In the method provided by the invention, whole feedstock oil can be introduced into reactor in a feed entrance point
It is interior, feedstock oil can also be introduced according to identical or different ratio in reactor at least two different feed entrance points.So
And either one or more than two feed entrance points, all feed entrance points of preferred raw material oil are respectively positioned on the riser
The initial reaction area of reactor is more preferably located at the lower part in the initial reaction area.
In the method provided by the invention, before the feedstock oil is contacted with the first catalytic converting catalyst,
The feedstock oil is preheated, such as by fuel oil preheating to being re-introduced into the initial anti-of riser reactor after 150-400 DEG C
Area is answered, is preferably preheated to 250-360 DEG C.
In the method provided by the invention, the feedstock oil can be the catalytically cracked material of this field routine, example
Such as can be petroleum hydrocarbon and/or other mineral oil, wherein the petroleum hydrocarbon can be selected from vacuum gas oil (VGO), AGO (atmospheric gas oil), coke
Change at least one of gas oil, deasphalted oil, decompression residuum and reduced crude.
In the method provided by the invention, the catalytic converting catalyst can be the conventional selection of this field, needle
To the present invention, the catalytic converting catalyst is preferably solid acid catalyst.The solid acid catalyst contain active component and
Carrier.The active component can be selected from Y or HY types zeolite, the zeolite with MFI structure, faujasite with or without rare earth
At least one of with alumina silicate, it is preferably selected from the ultrastable with or without rare earth, the zeolite with MFI structure and dilute
At least one of the faujasite of native ion exchange.The carrier can be selected from inorganic oxide (such as artificial synthesized) and day
At least one of right clay.
In the present invention, each component accounts for total catalyst weight respectively in the catalytic converting catalyst：Zeolite 1-50 weights
Measure %, inorganic oxide 5-99 weight %, clay 0-70 weight %.Wherein zeolite as active component, selected from mesopore zeolite and/
Or optional large pore zeolite, mesopore zeolite account for the 0-100 weight % of zeolite total weight, preferably 0-50 weight %, more preferable 0-20
Weight %, large pore zeolite account for the 0-100 weight % of zeolite total weight, preferably 20-80 weight %.Mesopore zeolite is selected from ZSM series
Zeolite and/or ZRP zeolites, also can be to the nonmetalloids and/or iron, cobalt, nickel etc. such as above-mentioned mesopore zeolite phosphorus transition metal member
Element is modified, and related ZRP is more described in detail referring to US5,232,675, ZSM series zeolites be selected from ZSM-5, ZSM-11,
At least one of the zeolite of ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, related ZSM-
5 more detailed descriptions are referring to US3,702,886.Large pore zeolite is selected from by Rare Earth Y (REY), rare earth hydrogen Y (REHY), not Tongfang
At least one of this group of zeolite that super steady Y, the high silicon Y that method obtains are constituted.
In the present invention, the inorganic oxide is preferably selected from silica (SiO as bonding agent2) and/or three oxidations two
Aluminium (Al2O3)。
In the present invention, the clay is preferably selected from kaolin and/or halloysite as matrix (i.e. carrier).
The catalysis conversion method of a kind of specific implementation mode according to the present invention, the production high-knock rating gasoline includes such as
Lower step：
High-temperature regenerated catalyst from regenerator enters the bottom of riser reactor after supercooling, is situated between in pre-lift
The initial reaction area of riser reactor is flowed up under the action of matter, the feedstock oil after preheating is by under riser reactor
Portion enters in initial reaction area, is contacted with regenerated catalyst, reacts simultaneously uplink；Being formed by oil agent mixture, to enter riser anti-
The main reaction region for answering device, the high-temperature regenerated catalyst from regenerator with the lower part supplement injection in main reaction region is (without cold
But) continue to react, logistics, which enters, after reaction carries out gas solid separation in the cyclone separator in settler, the solid isolated
Catalyst obtains reclaimable catalyst through stripping, and the reclaimable catalyst is injected coke burning regeneration in regenerator, then by one
Divide high-temperature regenerated catalyst to cool down and then recycle the bottom of injecting lift pipe reactor, again by another part high temperature
The main reaction region of raw catalyst direct circulation injecting lift pipe reactor；The reaction oil pneumatic transmission isolated is to subsequent product segregative line
System isolates the fractions such as dry gas, liquefied gas, gasoline and diesel oil.
The specific implementation mode of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific implementation mode stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Fig. 1 is the flow diagram of the catalysis conversion method of the production high-knock rating gasoline provided by the invention.
The technological process of method provided by the invention is illustrated referring to Fig. 1：As shown in Figure 1, pre-lift medium passes through
Pipeline 14 is entered by 1 bottom of riser reactor, the regenerated catalyst from pipeline 11 and after the cooling of catalyst heat collector 5
It into 1 bottom of riser reactor, is accelerated upwards along riser under the castering action of pre-lift medium, the raw material of preheating
Initial reaction area 17 of the oil through 1 lower part of injecting lift pipe together with the atomizing steam from pipeline 16 of pipeline 15, it is anti-with riser
The existing logistics mixing of device is answered, on the catalyst of heat cracking reaction occurs for feedstock oil, and accelerates upwards, into riser
The main reaction region 18 of reactor.The reaction product oil gas of generation and the reclaimable catalyst of inactivation enter the whirlwind in settler 3 point
From device 6, realize the separation of reclaimable catalyst and reaction product oil gas, reaction product oil gas enters collection chamber 7, catalyst fines by
Dipleg returns to settler 3.Reclaimable catalyst flows to stripping section 4 in settler 3, is contacted with the steam from pipeline 19.From to be generated
The reaction product oil gas being stripped off in catalyst enters collection chamber 7 after cyclone separator.Reclaimable catalyst after stripping is through waiting for
Regenerator 2 is entered by pipeline 8 after raw guiding valve adjusting, the air from pipeline 21 enters regenerator after the distribution of air distributor 22
2, burning-off is located at the coke on reclaimable catalyst in the dense-phase bed of 2 bottom of regenerator, so that the reclaimable catalyst of inactivation is regenerated, cigarette
Upper gas flue 24 of the gas through cyclone separator 23 enters subsequent power recovery system.Wherein, the pre-lift medium
Can be dry gas, vapor or their mixture.
The pipeline 10 through being connected with regenerator 2 enters catalyst heat collector to the high-temperature regenerated catalyst obtained after regeneration all the way
5, through with pipeline 12 take thermal medium heat exchange cooling after by pipeline 11 regeneration guiding valve adjust after enter 1 bottom of riser reactor
Portion；The pipeline 9 through being connected with regenerator 2 enters the main reaction region 18 of riser reactor 1 under the adjusting of regeneration guiding valve all the way
Lower part.Reaction product oil gas in collection chamber 7 enters subsequent separation system by main oil gas piping 20.Wherein, described to take heat
Medium can be at least one of raw gasoline, gasoline, diesel oil, fractionating column the first stage casing recycle oil and water.
Below will by embodiment, the invention will be further described, but it is not thereby limiting the invention.
In the following Examples and Comparative Examples, conversion ratio is calculated according to following formula：
Conversion ratio=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield
The property of feedstock oil used in following embodiment and comparative example is as shown in table 1, catalytic converting catalyst used
Property it is as shown in table 2, the catalyst by Sinopec Group's catalyst branch Shandong catalyst plant give birth to
Production, trade names MLC-500.
Table 1
Table 2
| The catalyst trade mark | MLC-500 |
| Molecular sieve type | ZSM-5+Y |
| Chemical quality forms, weight % | |
| Al2O3 | 55.9 |
| Na2O | 0.29 |
| Re2O3 | 2.7 |
| Specific surface area, m2/g | 153 |
| Pore volume (water droplet method), ml/g | 0.174 |
| Apparent density, ml/g | 0.70 |
| * micro-activity after burin-in process, % | 65 |
Embodiment 1
The present embodiment is used to illustrate the catalysis conversion method of production high-knock rating gasoline provided by the invention.
It is tested, is tested on the middle- scale device of riser reactor, feedstock oil is pre- according to flow shown in FIG. 1
Heat to 300 DEG C of initial reaction areas through 15 injecting lift pipe reactor lower part of pipeline, with after the cooling that is promoted by vapor again
Raw catalyst (560 DEG C) is in the contact of initial reaction area, reaction.The weight ratio of catalyst and feedstock oil is 10, and feedstock oil is initial
Residence time in reaction zone is 0.8 second, and reaction temperature is 480 DEG C.Oil agent mixture is advanced into main reaction region on continuing, in master
Reaction zone bottom contacts that the reaction was continued with the high-temperature regenerated catalyst (630 DEG C) from pipeline 9, and reaction temperature is 530 DEG C, reaction
Time is 1.6 seconds, and the weight ratio of catalyst and feedstock oil is 15.Oil gas from outlet area come out after in settler dilute phase through whirlwind point
Enter the fractionating system at rear portion after being detached from device.Reclaimable catalyst with charcoal enters stripping section, and the reclaimable catalyst after stripping is gone
Regenerator regenerates, and the catalyst part after regeneration returns to the initial reaction area of riser reactor lower part after cooling exchanges heat,
A part is directly transported to riser main reaction region bottom cycle through inclined tube and uses, and operating condition and test result are shown in Table 3.
Comparative example 1
Using Conventional catalytic cracking riser reactor, fuel oil preheating to 215 DEG C of injecting lift pipe reactor lower parts, with
(680 DEG C) contacts of high-temperature regenerated catalyst, the reaction promoted by vapor.The weight ratio of catalyst and feedstock oil is in reaction zone
8, the reaction time is 2.5 seconds, and reaction temperature is 500 DEG C.Oil gas from outlet area come out after in settler dilute phase through cyclone separator
Enter the fractionating system at rear portion after separation.Reclaimable catalyst with charcoal enters stripping section, and the reclaimable catalyst after stripping goes to regenerate
Device regenerates, and the catalyst after regeneration returns to riser reactor and recycles, and operating condition and test result are shown in Table 3.
Comparative example 2
Catalytic cracking is carried out to feedstock oil according to the method for embodiment 1, the difference is that riser reactor is initial anti-
It is high-temperature regenerated catalyst (650 DEG C), the reaction temperature in the initial reaction area of riser reactor to answer the catalyst injected in area
It it is 540 DEG C, operating condition and test result are shown in Table 3.
Embodiment 2
The present embodiment is used to illustrate the catalysis conversion method of production high-knock rating gasoline provided by the invention.
It is tested, is tested on the middle- scale device of riser reactor, feedstock oil is pre- according to flow shown in FIG. 1
Heat to 300 DEG C of initial reaction areas through 15 injecting lift pipe reactor lower part of pipeline, with after the cooling that is promoted by vapor again
Raw catalyst (580 DEG C) is in the contact of initial reaction area, reaction.The weight ratio of catalyst and feedstock oil is 16, and feedstock oil is initial
Residence time in reaction zone is 1 second, and reaction temperature is 510 DEG C.Oil agent mixture is advanced into main reaction region on continuing, main anti-
The bottoms Ying Qu contact that the reaction was continued with the high-temperature regenerated catalyst (670 DEG C) from pipeline 9, and reaction temperature is 550 DEG C, when reaction
Between be 2 seconds, the weight ratio of catalyst and feedstock oil is 20.Oil gas from outlet area come out after in settler dilute phase through cyclone separator
Enter the fractionating system at rear portion after separation.Reclaimable catalyst with charcoal enters stripping section, and the reclaimable catalyst after stripping goes to regenerate
Device regenerates, and the catalyst part after regeneration returns to the initial reaction area of riser reactor after cooling exchanges heat, and a part is straight
It connects and is transported to the bottom cycle use of riser main reaction region through inclined tube, operating condition and test result are shown in Table 3.
Comparative example 3
Catalytic cracking is carried out to feedstock oil according to the method for embodiment 2, the difference is that extending the first of riser reaction zone
The promotion length of tube of beginning reaction zone so that the reaction time in initial reaction area is 2 seconds, and operating condition and test result are shown in Table 3.
Embodiment 3
The present embodiment is used to illustrate the catalysis conversion method of production high-knock rating gasoline provided by the invention.
It is tested, is tested on the middle- scale device of riser reactor, feedstock oil is pre- according to flow shown in FIG. 1
Heat to 300 DEG C of initial reaction areas through 15 injecting lift pipe reactor lower part of pipeline, with after the cooling that is promoted by vapor again
Raw catalyst (610 DEG C) is in the contact of initial reaction area, reaction.The weight ratio of catalyst and feedstock oil is 20, and feedstock oil is initial
Residence time in reaction zone is 0.4 second, and reaction temperature is 520 DEG C.Oil agent mixture is advanced into main reaction region on continuing, in master
Reaction zone bottom contacts that the reaction was continued with the high-temperature regenerated catalyst (680 DEG C) from pipeline 9, and reaction temperature is 570 DEG C, reaction
Time is 2.5 seconds, and the weight ratio of catalyst and feedstock oil is 23.Oil gas from outlet area come out after in settler dilute phase through whirlwind point
Enter the fractionating system at rear portion after being detached from device.Reclaimable catalyst with charcoal enters stripping section, and the reclaimable catalyst after stripping is gone
Regenerator regenerates, the initial reaction area of the return riser reactor after cooling exchanges heat of the catalyst part after regeneration, one
Divide and be directly transported to the bottom cycle use of riser main reaction region through inclined tube, operating condition and test result are shown in Table 3.
Table 3
Note：NP indicates that normal paraffin content, IP indicate isoparaffin content in table；O indicates olefin(e) centent；N indicates cycloalkanes
Hydrocarbon content；A indicates arene content.
As can be seen from the above-described embodiment, according to the catalyzed conversion side of the production high-knock rating gasoline provided by the invention
Method can not only obtain the gasoline products of higher gasoline RON octane numbers, and the quality of the gasoline products obtained is preferable, tool
There are significant lower alkene and higher isoparaffin and arene content.Specifically, by by embodiment 1 and comparative example 1 into
For row relatively as can be seen that the gasoline yield of embodiment 1 increases 3.28%, gasoline RON octane numbers reach 98, improve 8 lists
Position；In quality of gasoline composition, olefin(e) centent falls below 23.61% by 56.49%, and isoparaffin content is increased to by 11.83%
19.0%, arene content increases 44.18% by 21.20%.It can be with by the way that embodiment 2 and comparative example 1 to be compared
Find out, the gasoline yield of embodiment 1 increases 1.73%, and gasoline RON octane numbers reach 101, improve 11 units；Gasoline matter
In amount composition, olefin(e) centent falls below 27.04% by 56.49%, and isoparaffin content increases 13.03% by 11.83%,
Arene content increases 48.73% by 21.20%.
Claims (13)
1. a kind of catalysis conversion method producing high-knock rating gasoline, this method include：Feedstock oil after preheating is urged with first
Change reforming catalyst and carry out catalytic conversion reaction in the initial reaction area of riser reactor, and makes by the initial reaction area
The oil agent mixture of generation enters the main reaction region of riser reactor, continues with the second catalytic converting catalyst of supplement injection
Carry out catalytic conversion reaction, wherein the reaction temperature of the main reaction region is higher than the reaction temperature in the initial reaction area, described
The temperature of second catalytic converting catalyst is higher than the temperature of first catalytic converting catalyst, and the initial reaction area is anti-
It is less than the reaction time of the main reaction region between seasonable, the temperature of second catalytic converting catalyst turns than first catalysis
Change high 10 DEG C of the temperature of catalyst less than 100 DEG C, the reaction condition in the initial reaction area includes：Reaction temperature is
450-550 DEG C, agent weight of oil ratio is 1-30: 1, and the reaction time is 0.2-1.5 seconds；The reaction time of the main reaction region is 1-
2.5 the second；
In the riser reactor, the ratio between the main reaction region and the riser diameter in the initial reaction area are 1.2：1
To less than 1.5：1.
2. according to the method described in claim 1, wherein, the reaction temperature of the main reaction region is more anti-than the initial reaction area
Answer temperature 5-100 DEG C high.
3. according to the method described in claim 2, wherein, the reaction temperature of the main reaction region is more anti-than the initial reaction area
Answer temperature 10-80 DEG C high.
4. according to the method described in claim 1, wherein, the reaction time in the initial reaction area is more anti-than the main reaction region
It is 0.5-5 seconds short between seasonable.
5. according to the method described in any one of claim 1-4, wherein the reaction condition of the main reaction region includes：Instead
It is 450-700 DEG C, reaction pressure 130-450kPa to answer temperature, and agent weight of oil ratio is 5-50: 1.
6. according to the method described in claim 5, wherein, the reaction condition of the main reaction region includes：Reaction temperature is 500-
600 DEG C, reaction pressure 200-400kPa, agent weight of oil ratio is 10-40: 1, and the reaction time is 1.5-2.5 seconds.
7. according to the method described in claim 1, wherein, the temperature of first catalytic converting catalyst is 450-650 DEG C, institute
The temperature for stating the second catalytic converting catalyst is 600-730 DEG C.
8. according to the method described in claim 7, wherein, the temperature of first catalytic converting catalyst is 500-620 DEG C, institute
The temperature for stating the second catalytic converting catalyst is 620-700 DEG C.
9. according to the method described in any one of claim 1,7 and 8, wherein the method further includes：It will be by the promotion
The reaction mass of the outlet discharge of pipe reactor carries out gas solid separation, and the solid catalyst isolated is stripped, is burnt again
Life is cooled down a part of high-temperature regenerated catalyst, and cooling regenerated catalyst is followed with obtaining high-temperature regenerated catalyst
Ring is used as first catalytic converting catalyst, while another part high-temperature regenerated catalyst is recycled as second catalysis
Reforming catalyst.
10. according to the method described in any one of claim 1,7 and 8, wherein catalytic converting catalyst is to contain activearm
Point and carrier solid acid catalyst, the active component is selected from Y or HY types zeolite with or without rare earth, has MFI structure
At least one of zeolite, faujasite and alumina silicate, the carrier in inorganic oxide and natural clay at least
It is a kind of.
11. according to the method described in claim 1, wherein, the temperature after the fuel oil preheating is 150-400 DEG C.
12. according to the method for claim 11, wherein the temperature after the fuel oil preheating is 250-360 DEG C.
13. according to the method described in any one of claim 1,11 and 12, wherein the feedstock oil is petroleum hydrocarbon, described
Petroleum hydrocarbon in vacuum gas oil (VGO), AGO (atmospheric gas oil), coker gas oil, deasphalted oil, decompression residuum and reduced crude extremely
Few one kind.
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| CN108246342B (en) * | 2018-01-16 | 2020-03-27 | 西南化工研究设计院有限公司 | In-situ synthesis method of nickel-based propylene oligomerization molecular sieve catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784463A (en) * | 1970-10-02 | 1974-01-08 | Texaco Inc | Catalytic cracking of naphtha and gas oil |
| CN1237477A (en) * | 1999-04-23 | 1999-12-08 | 中国石油化工集团公司 | Lift pipe reactor for fluidized catalytic conversion |
| CN103031147A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784463A (en) * | 1970-10-02 | 1974-01-08 | Texaco Inc | Catalytic cracking of naphtha and gas oil |
| CN1237477A (en) * | 1999-04-23 | 1999-12-08 | 中国石油化工集团公司 | Lift pipe reactor for fluidized catalytic conversion |
| CN103031147A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
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