CN105349171B - Catalytic conversion method for producing propylene and fuel oil - Google Patents
Catalytic conversion method for producing propylene and fuel oil Download PDFInfo
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- CN105349171B CN105349171B CN201410407448.5A CN201410407448A CN105349171B CN 105349171 B CN105349171 B CN 105349171B CN 201410407448 A CN201410407448 A CN 201410407448A CN 105349171 B CN105349171 B CN 105349171B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
The invention relates to a catalytic conversion method for producing propylene and fuel oil. The method comprises the following steps: carrying out a catalytic conversion reaction on preheated a light hydrocarbon oil raw material and carbon dioxide in the first reaction zone of a reactor in the presence of a catalytic conversion catalyst, injecting a reaction material in the first reaction zone of the reactor to the second reaction zone of the reactor, and carrying out a catalytic conversion reaction on the injected reaction material and injected carbon dioxide. High propylene yield and high yield of gasoline with high octane number can be obtained through the catalytic conversion method for producing propylene and fuel oil.
Description
Technical field
The present invention relates to a kind of catalysis conversion method producing propylene and fuel oil, more particularly, it relates to one kind is by light
The method that matter hydrocarbon oil crude material catalyzed conversion produces propylene and fuel oil.
Background technology
Propylene is important Organic Chemicals, according to analysis, global propylene demand growth amount about 4.0% in 2012, about
83Mt, propylene supply and demand ratio is about 1.0.Over nearly 10 years, the rate of increase of World Propylene demand is always above ethylene it is contemplated that from now on 20
Year, the rate of increase of World Propylene demand will exceed the rate of increase of ethylene requirements.At present, 61% propylene is derived from steam in the world
The side-product of producing ethylene by cracking, 34% is derived from refinery catalytic cracking unit produces gasoline, the side-product of diesel oil, wherein, steams
Vapour cracking produces ethylene and propylene for raw material by thermal cracking with light oils such as Petroleums, but the yield of propylene is only 15 weight %
Left and right, in Conventional catalytic cracking technology, productivity of propylene is about 3-5%, and in mink cell focus catalytic conversion technique, productivity of propylene is about 15-
20%.Heaviness with crude oil and in poor quality aggravation, produce the technical advantage of propylene from mink cell focus and economy will be subject to
Obtain and greatly challenge.
By increasingly strict the promoting that environmental regulation requires and automobile industry requires to fuel mass, global in recent years automobile-used
Quality of gasoline lifting is very rapid, and oil quality upgrading paces are also substantially accelerated.At present, FCC gasoline accounts for motor petrol total amount
More than 70%, Reformed Gasoline and other high-quality high octane gasoline component contents too low, less than 9%, and low-octane straight
Evaporate gasoline proportion higher, reach about 13%.Therefore, FCC gasoline quality plays very important work to gasoline aggregate level
With.FCC gasoline octane RON is up to 90-92, minimum 87-88, average out to 89-90；MON is up to 80.6, minimum
78, average out to 79, there is larger gap compared with the quality of gasoline of some other developed country, therefore, improve gasoline octane
Value, realizing gasoline upgrading is trend of the times.In addition, during gasoline cleaning, some measures such as control gasoline olefin
Content, desulfurization, result in octane number and lose to some extent, and the contradiction of octane number shortage will be more prominent.In sum, develop
Produce propylene and produce the high-grade fuel oil such as catalytic cracking technology of high-knock rating gasoline simultaneously, to meet prescription continuous improvement
Industrial chemicals and high-grade fuel oil Production requirement, undoubtedly have important practical significance.
By boiling range, the feedstock for 160-260 DEG C is contacted with Conventional catalytic cracking catalyst for CN101362960A proposition,
Carry out cracking reaction in fluidized-bed reactor, reaction oil gas are isolated to purpose product high-knock rating gasoline.The method carries
The high octane number of gasoline and yield, by-product part small-numerator olefin such as ethylene and propylene simultaneously.
CN101362959A proposes first to contact the raw material of difficult cracking with hot regenerated catalyst, then the raw oil with easy cracking
Carry out cracking reaction after mixing, obtain the raw material of purpose product propylene and high-knock rating gasoline and recracking, the raw material of recracking
Comprise fraction, heavy aromatics that boiling range is 180-260 DEG C to raffinate oil.The yield of the method propylene and selectivity are significantly increased, gasoline
Yield and octane number significantly improve, and dry gas yied reduces amplitude up to 80 weight more than %.
CN101531923A proposes first to contact the raw material of difficult cracking with hot recycling catalytic converting catalyst, and reaction stream is again
With the raw oil hybrid reaction of easy cracking, obtain propylene and gasoline, will>260 DEG C of the hydrogenated hydrogenation weight processing gained of fraction
Oil is as raw oil.The method increase productivity of propylene and selectivity, and high-knock rating gasoline yield increases, dry gas yied drops
Low, liquid yield increases considerably.
CN101724430A proposes inferior feedstock oil is implanted sequentially first reaction zone and second of catalytic conversion reactor
Reaction zone and catalytic converting catalyst haptoreaction, obtain propylene, gasoline, catalytic wax oil and other products, wherein, catalytic wax oil
Enter aromatic extraction unit, separate and obtain tapped oil and raffinate oil；Raffinate oil be recycled to the first reaction zone of reactor or/and its
Its catalytic convention design is reacted further and is obtained purpose product propylene and gasoline.
CN101760227A proposes the differential responses area of raw oil entrance first riser reactor of different cracking performances
Contact with catalytic converting catalyst and carry out cracking reaction, obtain comprising propylene, gasoline, the product of recracking raw material, wherein, then split
Change raw material to send in the second riser reactor, the reclaimable catalyst of two riser reactors burns in same regenerator
Two riser reactors are returned respectively after regeneration.The method propylene and gasoline yield significantly increase, and octane number is obvious
Ground improves, and in the case that productivity of propylene increases considerably, dry gas yied significantly reduces, it is possible to decrease reach more than 80 weight %.
CN102453540A proposition quality raw materials oil is relatively low with average activity and the relatively uniform hot recycling of activity distribution is urged
There is cracking reaction in the lower contacts of reactor in agent, the diesel oil distillate in product is cut into light diesel fuel fraction and weight
Diesel oil distillate, heavy diesel fuel fraction is individually or/and freshening oil distillate, slurry oil fraction carry out hydrotreating and obtain being hydrogenated with heavy diesel fuel evaporating
Point, hydrogenation heavy diesel fuel fraction individually or/and light diesel fuel fraction return this reactor or/and other reactors carry out anti-further
Should.The method not only improves gasoline yield, and improves octane number, reduces dry gas and coke yield simultaneously.
Technology disclosed in from above-mentioned patent application can be seen that existing hydrocarbons catalytic conversion and produces low-carbon alkene and combustion
The exploitation of material oil tech focuses primarily upon mink cell focus catalytic cracking technology aspect, and due to mink cell focus boiling range wider range, hydro carbons divides
Sub larger, product structure numerous and complicated, in order to improve propene yield, using higher reaction temperature, causes increasing propylene product
In the case of rate, dry gas yied especially methane production increases considerably.In order to meet growing propylene and high-grade fuel oil
And the demand of raw material multiformity and motility is it is necessary to exploitation one kind is converted into light petroleum hydrocarbon to greatest extent for raw material
Propylene and the catalysis conversion method of high-grade fuel oil, to improve process choosing, efficiently to utilize petroleum resources.
Content of the invention
The invention aims to overcoming the production method of existing propylene and fuel oil to focus primarily upon mink cell focus and urge
Change cracking technology, and dry gas yied is higher, relatively low the lacking of octane number of productivity of propylene and fuel oil (mainly gasoline)
Fall into, a kind of method converting production propylene and fuel oil by light hydrocarbon oil catalytic material is provided.
In order to overcome drawbacks described above, the present inventor is found after research, draws during catalytic conversion reaction
Enter carbon dioxide, carbon dioxide can occur chemical reaction with the skeleton oxygen of zeolite molecular sieve in catalytic converting catalyst, in catalysis
Agent surface forms carbonate and proton, and these protons can provide active center for catalytic conversion reaction, reduces cracking reaction and lives
Change and such that it is able to improve the cracking reaction speed of light hydrocarbon oil raw material, and then ethylene and propene yield, particularly propylene can be improved
Yield, can also improve the yield of fuel oil (particularly gasoline) and the quality such as octane number of fuel oil simultaneously, thus
Complete the present invention.
The invention provides a kind of catalysis conversion method producing propylene and fuel oil, the method includes：In catalyzed conversion
In the presence of catalyst, the light hydrocarbon oil raw material after preheating and carbon dioxide are carried out catalysis in the first reaction zone of reactor and turns
Change reaction, then the reaction mass of the first reaction zone of described reactor is injected the second reaction zone of described reactor, and with
The carbon dioxide of injection carries out catalytic conversion reaction.
According to the present invention provide described production propylene and fuel oil catalysis conversion method can effectively improve propylene and
The yield of fuel oil, reduces dry gas yied, and improves the quality such as octane number of fuel oil.
And, the method that the present invention provides is so that petroleum chemical enterprise can substitute hot-working method using catalysis processing method
Produce industrial chemicals and vehicle fuel oil to greatest extent from fraction oil of petroleum, make petroleum chemical enterprise successfully realize low-carbon (LC) transition, delay
Solved the immense pressure of carbon emission, both solved the problems, such as petrochemical material shortage, improve again petrochemical industry economic benefit and
Social benefit.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of stream of the catalysis conversion method producing propylene and fuel oil of the preferred implementation according to the present invention
Journey schematic diagram.
Description of reference numerals
1- riser reactor first reaction zone；2- regenerator；3- settler；
4- stripping section；5- degassing tank；
6- (riser reactor 1 port of export) cyclone separator；
7- (gas outlet of connection cyclone separator 6 and main oil gas piping 20) collection chamber；
8- reclaimable catalyst inclined tube pipeline；9- guiding valve to be generated；
10- (catalyst outlet of connection regenerator 2 and degassing tank 5) pipeline；
11- (connection degassing tank 5 gas outlet and regenerator 2) pipeline；
12- (connection regenerator 2 and riser reactor 1) pipeline (regenerated catalyst inclined tube)；
13- regenerates guiding valve；
14- is the pipeline that riser reactor 1 conveys pre-lift medium；
15- is the pipeline of riser reactor 1 transferring raw material；
16- is the pipeline that riser reactor 1 conveys atomizing steam transferring raw material；
17- is the pipeline of riser reactor 1 conveying mixing C4 component；
18- is that riser reactor 1 conveys atomizing steam and conveys the pipeline of mixing C4 component；
19- is the pipeline that stripping section 4 conveys atomizing steam；
20- main oil gas piping；
The pipeline of 21- (regenerator 2) main air entrance；
22- air distributor；
23- is the pipeline that degassing tank 5 conveys atomizing steam；
24- regenerator cyclone separator；
25- (gas outlet connects with cyclone separator 24) flue；
26- riser reactor second reaction zone；
27- conveys CO for riser reactor second reaction zone2Pipeline.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
All ranges disclosed herein all comprises end points and can independently combine.Scope presently disclosed
End points and any value are not limited to this accurate scope or value, these scopes or value should be understood to comprise close to these scopes or
The value of value.
The invention provides a kind of catalysis conversion method producing propylene and fuel oil, the method includes：In catalyzed conversion
In the presence of catalyst, the light hydrocarbon oil raw material after preheating and carbon dioxide are carried out catalysis in the first reaction zone of reactor and turns
Change reaction, then the reaction mass of the first reaction zone of described reactor is injected the second reaction zone of described reactor, and with
The carbon dioxide of injection carries out catalytic conversion reaction.
In the methods described that the present invention provides, the carbon dioxide of injection and institute in the first reaction zone of described reactor
The weight ratio stating lightweight material oil is for 0.0025-10：100, the carbon dioxide of injection in the second reaction zone of described reactor
With the weight ratio of described lightweight material oil for 0.0025-10：100, and the first reaction zone in described reactor and the second reaction
The weight of the total amount of the carbon dioxide and described lightweight material oil of area's injection ratio is for 0.005-20：100；Under preferable case, in institute
State in the first reaction zone of reactor the carbon dioxide of injection and the weight of described lightweight material oil ratio for 0.005-5：100,
The weight of the carbon dioxide and described lightweight material oil of injection in the second reaction zone of described reactor ratio is for 0.005-5：100,
And the total amount of carbon dioxide of the first reaction zone in described reactor and second reaction zone injection and described lightweight material oil
Weight is than for 0.01-10：100.
The described catalysis conversion method that the present invention provides can be carried out in the conventional reactor in this area, for example, described
Reactor can selected from riser reactor, etc. the fluidized-bed reactor of linear speed, isodiametric fluidized-bed reactor, upstriker defeated
One of line sending, downstriker pipeline or two or more combinations, described combination includes series connection and/or parallel connection.According to this
A kind of preferred implementation of invention, described catalysis conversion method is implemented in riser reactor, namely of the present invention
Reactor is preferably riser reactor.
When described reactor selects riser reactor, described riser reactor has the first reaction zone and second anti-
Answer area.Preferably, in described riser reactor, the first reaction zone is 0.1-1 with the ratio of the height of second reaction zone：1, more
It is preferably 0.2-0.8：1.It is further preferred that described riser reactor is reducing riser reactor, for example, can be special
Reducing riser reactor described in profit application CN1237477A, described reducing riser reactor includes direct tube section and expanding
Section.Specifically, when reducing riser reactor selected by described riser reactor, described direct tube section constitutes described first reaction
Area, described extension diameter section constitutes described second reaction zone.For described reducing riser reactor, it is highly preferred that described extension diameter section
Diameter ratio with described direct tube section is 1.2-3：1, preferably 1.5-2：1.
In the methods described that the present invention provides, in the first reaction zone of reactor, carbon dioxide can be with light hydrocarbon
Add it is also possible to be individually added into together after oily raw material mixing.And, the coal addition position of carbon dioxide can be with light hydrocarbon oil raw material
Coal addition position identical or after light hydrocarbon oil feedstock position (namely under light hydrocarbon oil feedstock position
Trip).In the second reaction zone of reactor, the coal addition position of carbon dioxide is preferably in the upstream of second reaction zone.In the present invention
In, for " upstream " and " downstream " of reactor is all based on the flow direction of reaction mass, the upstream of riser reactor
Namely the bottom of reactor or bottom.
A preferred embodiment of the invention, when described reactor selects riser reactor, described anti-
Answer in the first reaction zone of device, carbon dioxide with described light hydrocarbon oil raw material identical position and/or in described light hydrocarbon oil
Raw material enters the position charging after riser；In the second reaction zone of described reactor, carbon dioxide is anti-described second
Answer the bottom feed in area.
According in the embodiment of present invention further optimization, when described reactor selects aforementioned reducing to lift tube reaction
During device, in the first reaction zone of described reactor, carbon dioxide with described light hydrocarbon oil raw material identical position and/or
Described light hydrocarbon oil raw material enters the position charging after riser；In the second reaction zone of described reactor, carbon dioxide
Bottom feed in extension diameter section.
In the methods described that the present invention provides, in a feed entrance point, whole light hydrocarbon oil raw materials can be introduced anti-
Answer in device it is also possible to introduce light hydrocarbon oil raw material according to identical or different ratio at least two different feed entrance points anti-
Answer in device.No matter however, being one or plural feed entrance point, all feed entrance points of preferably light hydrocarbon oil raw material are equal
Positioned at the first reaction zone of described reactor, it is more preferably located at the upstream of the first reaction zone of described reactor.
In the present invention, described catalysis conversion method can also include：Reaction by the second reaction zone of described reactor
Material carries out gas solid separation, the reaction oil gas isolated separately is obtained further ethylene, propylene, mixing C4 component (also referred to as
C4 hydrocarbon-fraction, refers to C4 alkane and the mixture of C4 alkene) and other products, the reclaimable catalyst isolated is carried out again
Raw, and will recycle in regenerated catalyst Returning reactor.The process of described gas solid separation can be entered in cyclone separator
OK, specifically, described gas solid separation process is usually：First reclaimable catalyst is separated with reaction oil gas and obtain reclaimable catalyst
And reaction oil gas, then the reaction oil gas obtaining are separated dry gas, liquefaction through follow-up piece-rate system (such as cyclone separator)
The fractions such as gas, gasoline and diesel oil, then by dry gas and liquefied gas through gas separation equipment separately obtain further methane, ethylene,
Propylene, C2-C3 alkane, mixing C4 group are graded, and the method such as propylene and gasoline that separates from product can be normal using this area
Rule technical method, the present invention is not limited in this respect, and is not described here in detail.
The process of described regeneration can be implemented according to the conventional catalyst recovery process in this area, for example, described regeneration side
Method can include：Introduce oxygen-containing gas (as air) from the bottom of regenerator, after oxygen-containing gas introduces regenerator, reclaimable catalyst
Contact coke burning regeneration with oxygen, in regenerator top gas solid separation, flue gas can enter the flue gas generating after catalyst coke burning regeneration
Enter subsequent power recovery system.The regeneration condition of described reclaimable catalyst can be the conventional operating condition in this area, for example may be used
To include：Temperature is 550-750 DEG C, preferably 600-730 DEG C, more preferably 650-700 DEG C；Gas superficial linear speed is
0.5-3 meter per second, preferably 0.8-2.5 meter per second, more preferably 1-2 meter per second；Reclaimable catalyst mean residence time is 0.6-3
Minute, preferably 0.8-2.5 minute, more preferably 1-2 minute.
In the present invention, described catalysis conversion method can also include：Regenerated catalyst is stripped, to slough gas
Deng impurity.Described steam stripped process can be stripped using vapor.
In the present invention, described catalysis conversion method can also include：The mixing isolated C4 component is returned to described
First reaction zone of reactor is reacted.Preferably, by described mixing C4 component described light hydrocarbon oil raw material feed position
Reactor is introduced after putting.
In the methods described that the present invention provides, the reaction condition of the first reaction zone of described reactor can include：Instead
Temperature is answered to be 460-650 DEG C, preferably 480-630 DEG C, more preferably 510-600 DEG C；Response time is the 1-2.4 second, preferably
The 1-2 second；Reaction pressure is 1.05-5MPa；Oil ratio is 1-50：1, preferably 5-30：1.The second reaction zone of described reactor
Reaction condition can include：Reaction temperature is 450-630 DEG C, preferably 480-580 DEG C；Response time is the 2.5-10 second, excellent
Elect the 2.5-6 second as；Reaction pressure is 1.05-5MPa；Oil ratio is 1-50：1, preferably 5-30：1.In the present invention, when described
When reactor is riser reactor, reaction temperature refers to certain reaction zone of riser reactor or riser reactor
Outlet temperature；Reaction pressure refers to gauge pressure.
In the methods described that the present invention provides, vapor can also be injected in the first reaction zone of described reactor.Institute
State vapor to inject preferably in the form of atomizing steam.Injection vapor with the weight ratio of light hydrocarbon oil raw material can be
0.01-1：1, preferably 0.05-0.5：1.
In the methods described that the present invention provides, the hydrocarbon that described light hydrocarbon oil raw material can be 25-204 DEG C for boiling range evaporates
Part, for example can be selected from catalyzed conversion gasoline, catalytically cracked gasoline, straight-run naphtha, coker gasoline, pyrolysis gasoline, hot tearing
Change at least one in gasoline and hydrogasoline.
In the methods described that the present invention provides, described light hydrocarbon oil raw material is being contacted it with catalytic converting catalyst
Before, described light hydrocarbon oil raw material is preheated, is preferably preheated as gaseous state, such as by light hydrocarbon oil raw material preheating to 350-420
Introduce reactor after DEG C to contact with catalytic converting catalyst, be preferably preheated to 380-400 DEG C.
In the methods described that the present invention provides, described catalytic converting catalyst can be the conventional selection of this area, pin
To the present invention, preferably with the gross weight meter of catalyst, described catalytic converting catalyst contains the zeolite of 1-60 weight %, 5-99 weight
The amount inorganic oxide of % and the clay of 0-70 weight %.
In described catalytic converting catalyst, described zeolite is selected from mesopore zeolite as active component, preferably described zeolite
And/or large pore zeolite, and preferred mesopore zeolite accounts for 50-100 weight % of zeolite gross weight, preferably mesopore zeolite accounts for zeolite gross weight
70-100 weight % of amount, large pore zeolite accounts for 0-50 weight % of zeolite gross weight, and preferably large pore zeolite accounts for zeolite gross weight
0-30 weight %.
In the present invention, described mesopore zeolite and large pore zeolite continue to use the conventional definition in this area, and that is, mesopore zeolite is average
Aperture 0.5-0.6nm, average pore size 0.7-1.0nm of large pore zeolite.For example, described large pore zeolite can be selected from Rare Earth Y
(REY) this of super steady Y, the high silicon Y composition that, rare earth hydrogen Y (REHY), distinct methods obtain organizes the mixed of one or more of zeolite
Compound.
Described mesopore zeolite can be selected from the zeolite with MFI structure, such as ZSM series zeolite and/or ZRP zeolite,
The transition metal such as nonmetalloid and/or ferrum, cobalt, nickel such as above-mentioned mesopore zeolite phosphorus can be modified, relevant ZRP is more
For detailed description referring to US5,232,675, ZSM series zeolite be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35,
The zeolite of ZSM-38, ZSM-48 and other similar structures one or more of mixture, relevant ZSM-5 is more detailed
Description is referring to US3,702,886.
In the present invention, described inorganic oxide, as bonding agent, is preferably selected from silicon dioxide (SiO2) and/or three oxidations two
Aluminum (Al2O3).
In the present invention, described clay, as substrate (i.e. carrier), is preferably selected from Kaolin and/or halloysite.
A preferred embodiment of the invention, when described catalysis conversion method is carried out in riser reactor
When, the method comprises the steps：
Regenerated catalyst (catalytic converting catalyst) rich in mesopore zeolite enters the pre-lift of riser reactor bottom
Section, flows up in the presence of pre-lift medium (as dry gas, vapor etc.), the light hydrocarbon oil raw material after preheating and titanium dioxide
Carbon mixes, and the bottom of mixing logistics first reaction zone of injecting lift pipe reactor together with atomizing steam, with regenerated catalyst
Contact carries out catalytic conversion reaction and flows up simultaneously；Reaction oil gas and the outlet entrance of reclaimable catalyst boosted pipe reactor carry
There is secondary response, the boosted pipe of reacted logistics behind riser reactors second reaction zone, with the carbon dioxide exposure of injection
Reactor outlet enters in cyclone separator, the reaction oil gas ejector isolated, and separately obtains dry gas, liquefaction further
The fractions such as gas, drippolene；The reclaimable catalyst isolated enters coke burning regeneration in regenerator, the regenerated catalyst of activity recovery
Return in riser reactor and recycle.
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
A kind of flow process of the preferred implementation of the catalysis conversion method producing ethylene and propylene that Fig. 1 provides for the present invention
Schematic diagram.
The technological process of the method for present invention offer is provided referring to Fig. 1：As shown in figure 1, pre-lift medium warp
Pipeline 14 is entered by riser reactor the first reaction zone 1 bottom, and the regenerated catalyst from pipeline 12 is adjusted through regeneration guiding valve 13
Enter the bottom of riser reactor the first reaction zone 1 after section, add upwards in the castering action lower edge riser of pre-lift medium
Speed motion, light hydrocarbon oil raw material after pipeline 15 mixes, is injected together with the atomizing steam from pipeline 16 and carries with carbon dioxide
The bottom of riser reactors the first reaction zone 1, is mixed with the existing logistics in riser reactor the first reaction zone 1, light hydrocarbon oil
There is cracking reaction in raw material on hot catalyst, and accelerate upwards.The product oil gas generating is to be generated with inactivation
The outlet of the boosted pipe reactor of catalyst the first reaction zone enters second reaction zone 26, with the carbon dioxide exposure from pipeline 27
Secondary response more afterwards, logistics after reaction enters the cyclone separator 6 in settler 3, realizes reclaimable catalyst and product oil gas
Separation, product oil gas enter collection chamber 7, catalyst fines return settler by dipleg.Reclaimable catalyst in settler
Flow to stripping section 4, contact with the steam from pipeline 19.The product oil gas being stripped off from reclaimable catalyst divides through whirlwind
Collection chamber 7 is entered after device.Reclaimable catalyst after stripping enters regenerator 2 by pipeline 8 after adjusting through guiding valve 9 to be generated, comes
Enter regenerator 2 from the air of pipeline 21 after air distributor 22 distribution, burning-off is located in the dense-phase bed of regenerator 2 bottom
Coke on reclaimable catalyst, makes the reclaimable catalyst of inactivation regenerate, the upper gas fume pipe through cyclone separator 24 for the flue gas
Road 25 enters subsequent power recovery system.Wherein, described pre-lift medium can be dry gas, vapor or their mixture.
Catalyst after the regeneration pipeline 10 entrance degassing tank 5 through connect with regenerator 2 catalyst outlet, and from degassing
The stripping fluid contact of the pipeline 23 of tank 5 bottom, the flue gas that removing regenerated catalyst is carried secretly, the regenerated catalyst after degassing is through pipe
Line 12 is recycled to the bottom of riser reactor 1, can control catalyst circulating load by regenerating guiding valve 13, gas is through pipeline 11
Return in regenerator 2, the product oil gas in collection chamber 7 enters subsequent separation system through main oil gas piping 20.Reaction oil
After the mixing C4 component that gas system is isolated can be mixed with light hydrocarbon oil raw material, return riser reactor through pipeline 15,
Riser reactor can be returned through pipeline 17 with the atomizing steam from pipeline 18；After carbon dioxide can be mixed with raw oil
Return riser reactor through pipeline 15 it is also possible to steam with the atomization from pipeline 18 through pipeline 17 after the mixing of C4 component with mixing
Vapour returns riser reactor.
Below will by embodiment, the invention will be further described, but not thereby limiting the invention.
In embodiment 1-4 and comparative example, raw oil used is straight-run naphtha, and its property is as shown in table 1.
Table 1
| Raw material oil nature | |
| Density (20 DEG C), g/cm3 | 0.7358 |
| Vapour pressure/kPa | 50.0 |
| Race forms/weigh % | |
| Alkane | 58.52 |
| Cycloalkane | 38.24 |
| Alkene | 0.12 |
| Aromatic hydrocarbons | 10.52 |
| Boiling range, DEG C | |
| IBP | 46 |
| 10% | 87 |
| 30% | 107 |
| 50% | 120 |
| 70% | 133 |
| 90% | 149 |
| 95% | 155 |
Preparation example
In embodiment and comparative example, the preparation method of catalytic converting catalyst used is as follows：
(1) by 20g NH4Cl is dissolved in 1000g water, adds 100g (butt) crystallization product ZRP-1 zeolite in this solution
(Si/Al (mol ratio)=30, content of rare earth RE2O3=2.0 weight %), after exchanging 0.5h at 90 DEG C, filter to obtain filter cake；Add
4.0g H3PO4(concentration is 85 weight %) and 4.5g Fe (NO3)3It is dissolved in 90g water, dry with filter cake hybrid infusion；Then exist
At 550 DEG C, calcination process obtains phosphorous and ferrum MFI structure mesopore zeolite for 2 hours, and elementary analytical chemistry consists of 0.1Na2O·
5.1Al2O3·2.4P2O5·1.5Fe2O3·3.8RE2O3·88.1SiO2.
(2) use 250kg decationized Y sieve water that 75.4kg halloysite (solid content 71.6 weight %) is pulled an oar, add
Its pH is adjusted to 3 with hydrochloric acid, stirs, stands aging 1 at 65 DEG C by 54.8kg boehmite (solid content 63 weight %)
Hour, keep pH to be 3, cool the temperature to less than 60 DEG C, add 41.5kg Alumina gel (Al2O3Content is 21.7 weight %), stirring
40 minutes, obtain mixed serum.
(3) the MFI structure mesopore zeolite (butt is 22.5kg) of phosphorous and ferrum prepared by step (1) and DASY zeolite
(lattice constant is 2.445-2.448nm, and butt is 2.0kg) is added in the mixed serum that step (2) obtains, and stirs,
Spray drying forming, is washed with ammonium dihydrogen phosphate (phosphorus content is 1 weight %), washes away free Na+, it is drying to obtain catalysis and turn
Change catalyst sample, this catalyst consist of that 18 weight % are phosphorous and the MFI structure mesopore zeolite of ferrum, 2 weight %DASY boilings
Stone, 28 weight % boehmites, 7 weight % Alumina gel and balance kaolin.
Embodiment 1
The present embodiment is used for the catalysis conversion method producing propylene and fuel oil of the present invention is described.
Tested according to the flow process shown in Fig. 1, the middle- scale device of reducing riser reactor is tested, raw material
Oil is straight-run naphtha, enters the straight tube of reducing riser reactor after the raw oil (350 DEG C) of preheating and carbon dioxide mix
Bottom (the CO of section (i.e. the first reaction zone)2Mass ratio with raw oil is 0.5：100), when reaction temperature is 575 DEG C, reacts
Between for 1.5 seconds, reaction pressure be the weight ratio of 2.17MPa, catalytic converting catalyst and raw oil for 30, vapor and raw oil
Weight than for 0.25：Reacted under conditions of 1, reaction oil gas and vapor and reclaimable catalyst enter from reactor outlet
(i.e. second reaction zone, the ratio of direct tube section and the height of extension diameter section is 0.6 to enter the extension diameter section of reducing riser reactor：1, expanding
Section is 1.5 with the diameter ratio of direct tube section：1), reaction temperature be 565 DEG C, the response time be 3.75 seconds, reaction pressure be
The weight of 2.1MPa, catalytic converting catalyst and raw oil ratio is for the carbon dioxide exposure (CO with injection under conditions of 302With former
The mass ratio of material oil is 1.0：100) continue reaction, logistics after reaction enters closed cyclone separator, reaction oil gas and to be generated
Catalyst sharp separation, reaction oil gas are cut by boiling range in piece-rate system, thus obtaining methane, ethylene, propylene, mixing C4
The fraction such as component and drippolene.
Reclaimable catalyst enters stripping section under gravity, is stripped off the hydro carbons of absorption on reclaimable catalyst by vapor
Product, the reclaimable catalyst after stripping enters into regenerator, is regenerated with air contact；Catalyst after regeneration enters degassing
Tank, to remove regenerated catalyst absorption and the non-hydrocarbon gas impurity carrying；Regenerated catalyst after degassing again returns to riser
Recycle in reaction；Operating condition and product slates are listed in table 2；
From table 2 it can be seen that productivity of propylene is up to 8.70 weight %, gasoline yield is 76.72 weight %, octane number
It is about 93.7.
Comparative example 1
Tested according to the method for embodiment 1, except that, in first reaction zone and second of riser reactor
All it is not injected into carbon dioxide, operating condition and product slates are listed in table 2 in reaction zone.
From the results shown in Table 2, up to 7.33 weight %, gasoline yield is 77.50 weight % to productivity of propylene, gasoline
Octane number is about 89.1.
Comparative example 2
Tested according to the method for embodiment 1, except that, do not note in the second reaction zone of riser reactor
Enter carbon dioxide, operating condition and product slates are listed in table 2.
From the results shown in Table 2, up to 8.23 weight %, gasoline yield is 76.11 weight % to productivity of propylene, gasoline
Octane number is about 91.5.
Comparative example 3
Tested according to the method for embodiment 1, except that, riser reactor does not have described in embodiment 1
Second reaction zone, namely described in through embodiment 1 first reaction zone reaction after material directly carry out gas solid separation and
Subsequent step, operating condition and product slates are listed in table 2.
From the results shown in Table 2, up to 8.11 weight %, gasoline yield is 77.05 weight % to productivity of propylene, gasoline
Octane number is about 90.
Embodiment 2
The present embodiment is used for the catalysis conversion method producing propylene and fuel oil of the present invention is described.
Tested according to the method for embodiment 1, except that, the riser reactor of use is isodiametric lifting
Pipe reactor, does not have extension diameter section, and operating condition and product slates are listed in table 2.
From the results shown in Table 2, up to 8.52 weight %, gasoline yield is 77.70 weight % to productivity of propylene, gasoline
Octane number is about 91.2.
Embodiment 3
The present embodiment is used for the catalysis conversion method producing propylene and fuel oil of the present invention is described.
Tested according to the flow process shown in Fig. 1, the middle- scale device of reducing riser reactor is tested, raw material
Oil is straight-run naphtha, the raw oil (350 DEG C) of preheating and CO2The direct tube section of reducing riser reactor is entered (i.e. after mixing
First reaction zone) bottom (CO2Mass ratio with raw oil is 5：100), reaction temperature be 510 DEG C, the response time be 2
Second, reaction pressure be 2.17MPa, catalyst and raw oil weight than the weight ratio for 5, vapor and raw oil for 0.25：1
Under conditions of reacted, reaction oil gas and vapor and reclaimable catalyst enter reducing lifting tube reaction from reactor outlet
(i.e. second reaction zone, direct tube section is 0.6 with the ratio of the height of extension diameter section to the extension diameter section of device：1, the diameter of extension diameter section and direct tube section
Ratio be 1.5：1), reaction temperature be 480 DEG C, the response time be 5 seconds, reaction pressure be 2.1MPa, catalytic converting catalyst
With the weight of raw oil ratio for the carbon dioxide exposure (CO with injection under conditions of 52Mass ratio with raw oil is 10：100)
Continue reaction, logistics after reaction enters closed cyclone separator, reaction oil gas and reclaimable catalyst sharp separation, reaction oil gas
Cut by boiling range in piece-rate system, thus obtaining methane, ethylene, propylene, the mixing fraction such as C4 component and drippolene, its
The further cracking in the first reaction zone that middle mixing C4 component backs into reactor is ethylene and propylene.
Reclaimable catalyst enters stripping section under gravity, is stripped off the hydro carbons of absorption on reclaimable catalyst by vapor
Product, the reclaimable catalyst after stripping enters into regenerator, is regenerated with air contact；Catalyst after regeneration enters degassing
Tank, to remove regenerated catalyst absorption and the non-hydrocarbon gas impurity carrying；Regenerated catalyst after degassing again returns to riser
Recycle in reaction；Operating condition and product slates are listed in table 2；
From table 2 it can be seen that productivity of propylene is up to 10.49 weight %, gasoline yield is 71.65 weight %, gasoline octane
Value is about 94.2.
Embodiment 4
The present embodiment is used for the catalysis conversion method producing propylene and fuel oil of the present invention is described.
Tested according to the flow process shown in Fig. 1, the middle- scale device of reducing riser reactor is tested, raw material
Oil is straight-run naphtha, enters the straight tube of reducing riser reactor after the raw oil (350 DEG C) of preheating and carbon dioxide mix
Bottom (the CO of section (i.e. the first reaction zone)2Mass ratio with raw oil is 1：100), reaction temperature be 600 DEG C, response time
For 1 second, reaction pressure be 2.17MPa, catalyst and raw oil weight than the weight ratio for 20, vapor and raw oil be
0.25：Reacted under conditions of 1, reaction oil gas and vapor and reclaimable catalyst enter reducing lifting from reactor outlet
(i.e. second reaction zone, direct tube section is 0.6 with the ratio of the height of extension diameter section to the extension diameter section of pipe reactor：1, extension diameter section and direct tube section
Diameter ratio be 1.5：1), reaction temperature be 580 DEG C, the response time be 2.5 seconds, reaction pressure be 2.1MPa, catalysis turn
Change the weight of catalyst and raw oil ratio for the carbon dioxide exposure (CO with injection under the conditions of 202Mass ratio with raw oil is
2：100) continue reaction, logistics after reaction enters cyclone separator, reaction oil gas and reclaimable catalyst sharp separation, reaction oil gas
Being cut by boiling range in piece-rate system, thus obtaining methane, propylene, the mixing fraction such as C4 component and drippolene, wherein, being mixed
Close C4 component and a small amount of CO2The further cracking in the first reaction zone backing into reactor after mixing is ethylene and propylene.
Reclaimable catalyst enters stripping section under gravity, is stripped off the hydro carbons of absorption on reclaimable catalyst by vapor
Product, the reclaimable catalyst after stripping enters into regenerator, is regenerated with air contact；Catalyst after regeneration enters degassing
Tank, to remove regenerated catalyst absorption and the non-hydrocarbon gas impurity carrying；Regenerated catalyst after degassing again returns to riser
Recycle in reaction；Operating condition and product slates are listed in table 2；
From table 2 it can be seen that productivity of propylene is up to 10.86 weight %, gasoline yield is 70.76 weight %, gasoline octane
Value is about 94.3.
Be can be seen that according to propylene and the fuel oil of producing of the present invention by the result of above-described embodiment and comparative example
Catalysis conversion method can obtain higher productivity of propylene and higher high-knock rating gasoline yield.
Claims (16)
1. a kind of catalysis conversion method producing propylene and fuel oil, the method includes：In the presence of catalytic converting catalyst,
Light hydrocarbon oil raw material after preheating and carbon dioxide are carried out catalytic conversion reaction in the first reaction zone of reactor, then by institute
The reaction mass stating the first reaction zone of reactor injects the second reaction zone of described reactor, and enters with the carbon dioxide of injection
Row catalytic conversion reaction, wherein, with the gross weight meter of catalyst, described catalytic converting catalyst contains the boiling of 1-60 weight %
The clay of stone, the inorganic oxide of 5-99 weight % and 0-70 weight %.
2. method according to claim 1, wherein, in the first reaction zone of described reactor injection carbon dioxide with
The weight of described lightweight material oil ratio is for 0.0025-10：100, the titanium dioxide of injection in the second reaction zone of described reactor
The weight of carbon and described lightweight material oil ratio is for 0.0025-10：100, and the first reaction zone in described reactor and second anti-
The weight ratio of the total amount of carbon dioxide and described lightweight material oil answering area's injection is for 0.005-20：100.
3. method according to claim 2, wherein, in the first reaction zone of described reactor injection carbon dioxide with
The weight of described lightweight material oil ratio is for 0.005-5：100, the carbon dioxide of injection in the second reaction zone of described reactor
With the weight ratio of described lightweight material oil for 0.005-5：100, and the first reaction zone in described reactor and second reaction zone
The weight of the total amount of the carbon dioxide and described lightweight material oil of injection ratio is for 0.01-10：100.
4. the method according to any one in claim 1-3, wherein, described reactor is riser reactor.
5. method according to claim 4, wherein, in described riser reactor, the first reaction zone and described second
The ratio of the height of reaction zone is 0.1-1：1.
6. method according to claim 4, wherein, described riser reactor is reducing riser reactor, described change
Footpath riser reactor includes direct tube section and extension diameter section, and described direct tube section constitutes described first reaction zone, and described extension diameter section is constituted
Described second reaction zone.
7. method according to claim 6, wherein, described extension diameter section is 1.2-3 with the diameter ratio of described direct tube section：1.
8. method according to claim 4, wherein, in the first reaction zone of described reactor, carbon dioxide with institute
State light hydrocarbon oil raw material identical position and/or the charging of the position after described light hydrocarbon oil raw material enters riser；Institute
State in the second reaction zone of reactor, carbon dioxide is in the bottom feed of described second reaction zone.
9. method according to claim 1, wherein, methods described also includes：By the second reaction zone of described reactor
Reaction mass carries out gas solid separation, the reaction oil gas isolated separately are obtained further ethylene, propylene, mixing C4 component and its
His product, the reclaimable catalyst isolated is regenerated, and will recycle in regenerated catalyst Returning reactor.
10. method according to claim 9, wherein, methods described also includes：The mixing isolated C4 component is returned to
First reaction zone of described reactor is reacted.
11. methods according to any one in claim 1-3 and 9-10, wherein, the first reaction zone of described reactor
Reaction condition include：Reaction temperature is 460-650 DEG C, and the response time is the 1-2.4 second, and reaction pressure is 1.05-5MPa, agent oil
Than for 1-50：1；
The reaction condition of the second reaction zone of described reactor includes：Reaction temperature is 450-600 DEG C, and the response time is 2.5-10
Second, reaction pressure is 1.05-5MPa, and oil ratio is 1-50：1.
12. methods according to claim 1, wherein, described light hydrocarbon oil raw material is 25-204 DEG C of hydrocarbon-fraction for boiling range.
13. methods according to claim 12, wherein, described light hydrocarbon oil raw material is selected from catalytically cracked gasoline, straight run stone
At least one in cerebrol, coker gasoline, pyrolysis gasoline, pressure gasoline and hydrogasoline.
14. methods according to claim 12, wherein, described light hydrocarbon oil raw material is selected from catalyzed conversion gasoline.
15. methods according to claim 1, wherein, described zeolite is selected from mesopore zeolite and optional large pore zeolite, mesopore
Zeolite accounts for 50-100 weight % of zeolite gross weight, and large pore zeolite accounts for 0-50 weight % of zeolite gross weight.
16. methods according to claim 15, wherein, described mesopore zeolite accounts for 70-100 weight % of zeolite gross weight,
Large pore zeolite accounts for 0-30 weight % of zeolite gross weight.
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| CN114405418B (en) * | 2022-02-25 | 2023-04-14 | 北京石油化工工程有限公司 | System and method for producing methyl methacrylate by using methanol and methyl propionate as raw materials |
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