CN101456782A - Method for improving propone output during catalytic conversion process - Google Patents

Method for improving propone output during catalytic conversion process Download PDF

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Publication number
CN101456782A
CN101456782A CNA2007101794183A CN200710179418A CN101456782A CN 101456782 A CN101456782 A CN 101456782A CN A2007101794183 A CNA2007101794183 A CN A2007101794183A CN 200710179418 A CN200710179418 A CN 200710179418A CN 101456782 A CN101456782 A CN 101456782A
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reaction
reaction zone
fraction
rich
catalyzer
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Inventor
刘宪龙
许友好
马建国
崔守业
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CNA2007101794183A priority Critical patent/CN101456782A/en
Publication of CN101456782A publication Critical patent/CN101456782A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

The invention relates to a method for improving the yield of propylene during catalytic conversion, which comprises: preheated raw oil enters a reactor which comprises two reaction zones; gaseous hydrocarbon which is rich in C4 fractions is injected into the bottom of a first reaction zone or/and the bottom of a second reaction zone, and contacts a hot cracking catalyst and reacts with the hot cracking catalyst in the presence of water vapor; reaction products and a spent catalyst are separated; the reaction products are further separated by a fractionating system into gaseous products which are rich in the propylene and the C4 fractions and liquid products such as gasoline, diesel fuel and so on; and the spent catalyst is subjected to steam stripping, enters a regenerator, and is burnt and recycled. The method can treat hydrocarbon fractions which are rich in the C4 and processed and produced by different technical skills, and produce miacromolecular olefin and particularly the propylene on the premise of not influencing the prior product distribution of catalytic conversion technology.

Description

A kind of method that improves propone output during catalytic conversion process
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of catalysis conversion method of propone output.
Background technology
Small-numerator olefins such as ethene, propylene and butylene are the most basic organic synthesis raw materials.Steam cracking method is mainly adopted in the production of small-numerator olefin in the world at present, but the installation cost of steam cracking device is very high, is not easy to build; In addition because the easy coking of high-temperature cracking furnace, so steam cracking device can only be with Sweet natural gas, petroleum naphtha and solar oil etc. as raw material, and a certain amount of aromatic hydrocarbons of by-product.Because the crude oil of China is heavier, light oil yields such as petroleum naphtha are lower, and the raw material imbalance between supply and demand of steam cracking and catalytic reforming is serious day by day.Catalytic cracking is the main second complete processing of China's heavy oil lighting, because CN1078094C can reduce the olefin(e) centent in the catalytic cracking unit gasoline products significantly, thereby a lot of catalytic cracking unit has adopted this patented technology.The small-numerator olefin productive rate of this patented technology is lower, general propylene weight productive rate only 3~5%, and ethylene yield is then lower.Therefore, the productivity of low carbon olefin hydrocarbon that improves the catalytic convention design that adopts this patented technology will bring huge economic benefit.
Below two pieces of patent applications relate to the catalysis conversion method of producing low-carbon alkene.
CN1031834A discloses a kind of hydrocarbons catalytic conversion method of producing low-carbon alkene, with the petroleum hydrocarbon cut of different boiling ranges such as gasoline, kerosene, diesel oil, vacuum gas oil, or its mixed fraction and residual oil, crude oil are raw material, use solid catalyst to carry out catalytic conversion reaction in fluidized-bed or moving-burden bed reactor, can obtain butylene and productivity of propylene is 40 heavy %.
Disclose the method for a kind of voluminous liquefied gas and gasoline among the CN1085885A, the raw material of employing is selected from the time processing distillate: gasoline, diesel oil, decompressed wax oil, residual oil; Be mixed with time processing distillate or its mixture of part wax tailings, deasphalted oil or other secondary processing distillate; Crude oil.Contact with the solid acid catalyst that contains rare-earth five-membered ring supersiliceous zeolite, three kinds of zeolites of REY and high silicon Y in riser tube or fluidized-bed, reaction conditions is as follows: 480~550 ℃ of temperature of reaction, 130~350 kPas of pressure, weight hourly space velocity 1~150 hour -1, agent-oil ratio is 4~15, the weight ratio of water vapor and raw material hydrocarbon is 0.05~0.21:1, yield of liquefied gas is 30~40 heavy % in the reaction product.
In sum, still do not relate to the technological process of utilizing the C4 component to improve the catalytic convention design low-carbon alkene that adopts the CN1078094C technology in the prior art.
Summary of the invention
The objective of the invention is on the basis of prior art CN1078094C, a kind of method that improves propone output during catalytic conversion process is provided.
The reactor that characteristics of the present invention are to use comprises two reaction zones, first reaction zone of its middle and lower part is a pyrolysis reaction zone, temperature of reaction is higher, residence time of material is shorter, and second reaction zone on top is the secondary reaction district, and the temperature of reaction in this district is lower, and residence time of material is longer, material carries out alkylated reaction and hydrogen transfer reactions, improves the content of isoparaffin in the gasoline composition.
Technical scheme provided by the invention is as follows: the stock oil of preheating enters in the reactor that comprises two reaction zones, the hydrocarbon gas that is rich in C 4 fraction injects the bottom of first reaction zone or/and the bottom of second reaction zone, in the presence of water vapor, contact and react with the cracking catalyst of heat, reaction product isolated and reclaimable catalyst, reaction product further is separated into product liquids such as the gaseous product that is rich in propylene, C 4 fraction and gasoline, diesel oil through fractionating system, reclaimable catalyst enters revivifier through stripping, recycles after burning.
The reaction conditions of this method is as follows: first reaction zone temperature is 500~700 ℃, the reaction times of first reaction zone is 0.5~2.0 second, second reaction zone temperature is 450~550 ℃, the reaction times of second reaction zone is 2~30 seconds, the weight ratio of catalyzer and stock oil (hereinafter to be referred as agent-oil ratio) is 3~15:1, the weight ratio of water vapor and stock oil (hereinafter to be referred as water-oil ratio) is 0.03~0.3:1, and pressure is normal pressure~450 kPa.
A kind of optimized technical scheme is: the C 4 fraction freshening in the gaseous product is as the gaseous hydrocarbon feedstock that is rich in C 4 fraction.
Another kind of optimized technical scheme is: reclaimable catalyst is behind stripping, and a part enters second reaction zone through the catalyzer outer circulating tube, and another part enters revivifier regeneration.
The stock oil that this method is suitable for is selected from one or more in the petroleum fractions, residual oil, crude oil of different boiling ranges.Specifically, they are time processing distillates, comprise gasoline, diesel oil, decompressed wax oil, residual oil; The mixture of the arbitrary proportion of two or more above-mentioned time processing distillate; Be mixed with the following wax tailings of 30 heavy % and/or the time processing distillate of deasphalted oil; Crude oil.
The described hydrocarbon gas that is rich in C 4 fraction is meant with the C 4 fraction to be the low-molecular-weight hydrocarbon that exists with gas form under the normal temperature, normal pressure of main component, comprises C4 and following alkane, alkene and alkynes thereof.It can be the gaseous hydrocarbon products that is rich in C 4 fraction from this device, cat-cracker or normal top methane gas, also can be the hydrocarbon gas that is rich in C 4 fraction that other oil refining or chemical process are produced.In the described hydrocarbon gas that is rich in C 4 fraction,, also contain a certain amount of C3 composition mainly based on C4 alkane and/or alkene.
In method provided by the invention, being rich in the hydrocarbon gas of C 4 fraction and the weight ratio of stock oil is 0.03~0.1:1, preferred 0.05~0.08:1.
When the hydrocarbon gas that is rich in C 4 fraction injected the bottom of first reaction zone, catalyzer contacted with the hydrocarbon gas that is rich in C 4 fraction earlier, and temperature of reaction is 600~700 ℃, and preferred 620~680 ℃, 0.1~10 second reaction times, preferred 0.5~8 second; C 4 fraction reactant flow, catalyzer further contact, react at first reaction zone with stock oil again.
When the hydrocarbon gas that is rich in C 4 fraction injects the bottom of second reaction zone, be rich in the hydrocarbon gas of C 4 fraction and contact with catalyzer, reactant flow from first reaction zone, temperature of reaction is that 450~550 ℃, reaction times are 0.1~10 second; Reactant flow, catalyzer further contact, react at second reaction zone.
This method is suitable for all types of conventional catalysts, its active ingredient be selected from the Y that contains or do not contain rare earth or HY type zeolite, the ultrastable Y that contains or do not contain rare earth, ZSM-5 series zeolite or the supersiliceous zeolite that makes with other method with five-membered ring structure in a kind of, two or three catalyzer, and amorphous silicon aluminium catalyzer.
The reactor that this method is suitable for can be selected from the equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or the reducing riser tube, also can be the compound reactor that constitutes by equal diameter riser tube-fluidized-bed.
Method provided by the invention can the equal diameter riser tube, etc. carry out in linear speed riser tube or the fluidized-bed reactor, its intermediate diameters riser tube is identical with the catalyst cracker of refinery's routine, waits in the linear speed riser tube fluidic linear speed basic identical.The equal diameter riser tube, etc. linear speed riser tube or fluidized-bed reactor be followed successively by pre lift zone, first reaction zone, second reaction zone from bottom to up, the ratio of the height of first reaction zone, second reaction zone is 10~40:90~60, when use the equal diameter riser tube, etc. when linear speed riser tube or fluidized-bed reactor, inject the cold shock agent in second reaction zone bottom, and/or in second reaction zone, heat collector being set, the height of heat collector accounts for 50~90% of the second reaction zone height.Control the temperature and the reaction times of each reaction zone respectively.The cold shock agent is one or more the mixture of arbitrary proportion that is selected from raw gasline, gasoline, diesel oil, the separation column first stage casing turning oil or the water.
Method provided by the invention also can be carried out in the compound reactor that is made of equal diameter riser tube-fluidized-bed, the equal diameter riser tube of bottom is first reaction zone, the fluidized-bed on top is second reaction zone, controls the temperature and the reaction times of each reaction zone respectively.Can establish cold shock agent inlet in the bottom of fluidized-bed, and/or heat collector is set in fluidized-bed, the height of heat collector accounts for 50~90% of fluidized bed height.The cold shock agent is one or more the mixture of arbitrary proportion that is selected from raw gasline, gasoline, diesel oil, the separation column first stage casing turning oil or the water.
Optimum response device of the present invention is a kind of reducing riser reactor, and the constitutional features of this reactor is referring to the applicant's granted patent CN1078094C.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
1, the present invention adopts the reactor of CN1078094C to carry out successive reaction-reprocessing cycle operating method to carry out catalyzed conversion, is not influencing voluminous small-numerator olefin, particularly propylene under the prerequisite that original product distributes;
2, can use the catalytic cracking catalyst of any kind, as HY, USY, REY and REHY etc.;
3, the present invention can handle the hydrocarbon-fraction that is rich in C4 of different process technology processing output;
4, the present invention does not have particular requirement to foreign matter content in the raw material, does not therefore need stock oil is carried out pre-treatment;
When 5, employing was of the present invention, the change that device is done was minimum, and fixed investment reduces a lot;
6, C 4 fraction can partly or entirely replace promoting in advance steam, reduces plant energy consumption.
Embodiment
One of embodiment:
The hydrocarbon gas that is rich in C 4 fraction is injected the bottom of first reaction zone, contact, react with the acidic catalyst cracking catalyst of any type, temperature of reaction is 600~700 ℃, 0.1~10 second reaction times; Catalyzer, C4 hydrocarbon gas post reaction mixture with contact and react at first reaction zone through the catalytically cracked stock of preheating from the stock oil nozzle, first reaction zone temperature is 500~700 ℃, the reaction times of first reaction zone is 0.5~2.0 second, agent-oil ratio is 3~15:1, water-oil ratio is 0.03~0.3:1, pressure is normal pressure~450 kPa, reacted oil gas and reclaimable catalyst enter second reaction zone, second reaction zone temperature is 450~550 ℃, the reaction times of second reaction zone is 2~30 seconds, enters settling vessel at last.Reaction oil gas enters fractionating system through revolving sub-system, reaction product further is separated into product liquids such as the gaseous product that is rich in propylene, C 4 fraction and gasoline, diesel oil through fractionating system, wherein the C 4 fraction freshening in the gaseous product is as the gaseous hydrocarbon feedstock that is rich in C 4 fraction; The reclaimable catalyst of separating is behind stripping, and a part enters second reaction zone through the catalyzer outer circulating tube; A part enters revivifier, carry out coke burning regeneration after, Returning reactor recycles.
Two of embodiment:
Stock oil and regenerated catalyst enter first reaction zone and contact and react, first reaction zone temperature is 500~700 ℃, the reaction times of first reaction zone is 0.5~2.0 second, agent-oil ratio is 3~15:1, water-oil ratio is 0.03~0.3:1, pressure is normal pressure~450 kPa, reacted oil gas and reclaimable catalyst enter second reaction zone, the hydrocarbon gas that is rich in C 4 fraction is injected the bottom of second reaction zone, with catalyzer with certain carbon content from first reaction zone, reacted oil gas contact, reaction, temperature of reaction is 450~550 ℃, 0.1~10 second reaction times, reactant flow, catalyzer further contacts at second reaction zone, reaction, second reaction zone temperature is 450~550 ℃, the reaction times of second reaction zone is 2~30 seconds; Post reaction mixture enters fractionating system through revolving sub-system; The reclaimable catalyst of separating is behind stripping, and a part enters second reaction zone through the catalyzer outer circulating tube; A part enters revivifier, carry out coke burning regeneration after, Returning reactor recycles.
Three of embodiment:
The hydrocarbon gas that is rich in C 4 fraction is injected the bottom of first reaction zone, contact, react with the acidic catalyst cracking catalyst of any type, temperature of reaction is 600~700 ℃; Catalyzer, C4 hydrocarbon gas post reaction mixture with contact and react at first reaction zone through the catalytically cracked stock of preheating from the stock oil nozzle, first reaction zone temperature is 500~700 ℃, the reaction times of first reaction zone is 0.5~2.0 second, agent-oil ratio is 3~15:1, water-oil ratio is 0.03~0.3:1, pressure is normal pressure~450 kPa, reacted oil gas and reclaimable catalyst enter second reaction zone, the hydrocarbon gas that is rich in C 4 fraction is injected the bottom of second reaction zone, with catalyzer with certain carbon content from first reaction zone, reacted oil gas contact, reaction, temperature of reaction is 450~550 ℃, 0.1~10 second reaction times, reactant flow, catalyzer further contacts at second reaction zone, reaction, second reaction zone temperature is 450~550 ℃, the reaction times of second reaction zone is 2~30 seconds, reaction oil gas, reclaimable catalyst enters settling vessel at last.Reaction oil gas enters fractionating system through revolving sub-system; The reclaimable catalyst of separating is behind stripping, and a part enters second reaction zone through the catalyzer outer circulating tube; A part enters revivifier, carries out coke burning regeneration, and back Returning reactor recycles.
The following examples will be further specified the present invention, but not thereby limiting the invention.
Employed C 4 fraction, catalyzer and raw material properties are listed in table 1, table 2 and table 3 respectively among the embodiment.Catalyzer in the table 2 is by Qilu Petrochemical company of Sinopec Group catalyst plant industrial production, and trade names are CGP-2.
Embodiment 1
Present embodiment explanation: utilize method provided by the invention, can under different C4 charge proportions, implement.With hydrocarbon gas and the catalytically cracked material that is rich in C 4 fraction, use the CGP-2 catalyzer testing in the riser reactor continuously, hydrocarbon gas that is rich in C 4 fraction as shown in table 1 and the catalytically cracked stock shown in the table 3 enter riser reactor bottom and middle and lower part respectively, are that 510 ℃, reactor head pressure are to contact with catalyzer under the condition of 200 kPas, water to be 0.1:1, catalyzer to the catalytically cracked material weight ratio to the weight ratio of catalytically cracked stock be 8:1 to carry out catalyzed reaction in the first reactor outlet temperature.Oil gas and catalyzer rise to separator together, and oil gas enters the rear portion fractionating system through sedimentation with after filtering from the settling vessel top.Oil gas enters separation column, goes out reacted gas and liquid ingredient through the fractionation subzero fractionation.Reacted gas measures through gas meter, and it is formed by gas chromatographic analysis in sampling, and the above component of C5 counts in the gasoline fraction.Product liquid is by its gasoline of determination of simulated distillation, diesel oil, heavy oil content.Carbon deposited catalyst falls into stripper and enter revivifier after steam stripped.Carbon deposited catalyst is by the air coke burning regeneration in revivifier.The flue gas that comes out from revivifier measures through the dry gas table, and from thief hole sampling analysis CO 2, CO content.Composition and weight according to reacted gas, liquid, flue gas calculate material balance (weight with stock oil serves as to calculate benchmark, down together).Test conditions and main result see Table 4.
From the test-results of table 4 as can be seen, compare with 8.36 productivity of propylene that weigh % of conventional catalytic cracking, when the weight fraction that accounts for the catalytic cracking charging when the C 4 fraction of injecting lift pipe bottom is brought up to 10 heavy % by 5 heavy %, propylene is brought up to 9.89 heavy % to the productive rate of raw material by 9.20 heavy %, has improved 10.0%, 12.4% and 18.3% relatively.As seen, adopt method provided by the invention, can increase substantially the productivity of propylene of the catalytic cracking unit that adopts CN1078094C.Also adopt simultaneously method provided by the invention as can be seen, can inject scope at very big C 4 fraction and all have good effect.
Embodiment 2
Present embodiment explanation: utilize method provided by the invention, can under different C4 charge proportions and processing condition, implement.With hydrocarbon gas and the catalytically cracked material that is rich in C 4 fraction, use the CGP-2 catalyzer testing in the riser reactor continuously, hydrocarbon gas that is rich in C 4 fraction as shown in table 1 and the catalytically cracked stock shown in the table 3 enter riser reactor bottom and middle and lower part, contact with catalyzer under the condition of the first reactor outlet temperature to be 510 ℃, reactor head pressure to be 200 kPas, water to the weight ratio of catalytically cracked stock be 0.1:1, catalyzer to the weight ratio of catalytically cracked material be 8:1 and carry out catalyzed reaction.Oil gas and catalyzer rise to separator together, and oil gas enters the rear portion fractionating system through sedimentation with after filtering from the settling vessel top.Oil gas enters separation column, goes out reacted gas and liquid ingredient through the fractionation subzero fractionation.Reacted gas measures through gas meter, and it is formed by gas chromatographic analysis in sampling, and the above component of C5 counts in the gasoline fraction.Product liquid is by its gasoline of determination of simulated distillation, diesel oil, heavy oil content.Carbon deposited catalyst falls into stripper and enter revivifier after steam stripped.Carbon deposited catalyst is by the air coke burning regeneration in revivifier.The flue gas that comes out from revivifier measures through the dry gas table, and from thief hole sampling analysis CO 2, CO content.Composition and weight according to reacted gas, liquid, flue gas calculate material balance.Test conditions and main result see Table 5.
From the test-results of table 5 as can be seen, compare with 8.36 productivity of propylene that weigh % of conventional catalytic cracking, when the weight fraction that accounts for the catalytic cracking charging when the C 4 fraction that injects second reaction zone bottom is brought up to 10 heavy % by 5 heavy %, propylene is brought up to 10.07 heavy % to the productive rate of stock oil by 9.18 heavy %, has improved 9.8%, 13.9%, 14.5% and 20.5% respectively relatively.As seen, adopt method provided by the invention, can increase substantially the productivity of propylene of the catalytic cracking unit that adopts CN1078094C.Also adopt simultaneously method provided by the invention as can be seen, can inject scope at very big C 4 fraction and all have good effect.Have in addition in the table data as can be seen, when the C4 inlet amount is 7.5 weight % of catalytically cracked material charging, when water injection rate is brought up to 20 weight % by the 10 heavy % that account for raw material, productivity of propylene is brought up to 10.07 heavy % by 9.52 heavy %, as seen, increase the productive rate that water injection rate can improve propylene, illustrated that also the present invention can implement in the scope of the water injection rate of broad.
Table 1
C 4 fraction is formed, heavy %
Propane 13.11
Propylene 1.40
Trimethylmethane 14.35
Normal butane 7.64
Butene-1 11.91
Iso-butylene 26.88
Anti-butene-2 14.82
Maleic-2 9.89
Divinyl-1,3 0.00
Amount to 100.00
Table 2
Table 3
The cracking stock oil nature
Density (20 ℃), g/cm 3 0.9154
Condensation point, ℃ 35
Carbon residue, heavy % 0.18
Four components, heavy %
Stable hydrocarbon 64.0
Aromatic hydrocarbons 32.0
Colloid 4.0
Bituminous matter 0.0
Elementary composition, heavy %
C 85.38
H 12.03
S 2.00
N 0.16
Table 4
Test number Blank Test 1 Test 2 Test 3
C4/ stock oil, heavy % 0.0 5.0 7.5 10.0
The C4 temperature of reaction, ℃ / 675 675 675
One anti-temperature out, ℃ 510 510 510 510
Two anti-temperature, ℃ 490 490 490 490
Between two inverse time, second 4.3 4.1 3.9 3.8
Agent-oil ratio 8 8 8 8
Atomized water, heavy % 10 10 10 10
Regeneration temperature, ℃ 680 680 680 680
Material balance, heavy %
H 2~C 2 3.26 3.32 3.28 3.37
Liquefied gas 23.53 27.89 29.47 32.53
Propylene 8.36 9.20 9.40 9.89
Gasoline 43.52 40.82 41.48 41.03
Diesel oil 13.53 14.64 14.94 14.84
Heavy oil 8.07 10.02 10.15 9.99
Coke 8.09 8.31 8.18 8.24
Amount to 100.00 105.00 107.50 110.00
Table 5
Test number Blank Test 1 Test 2 Test 3 Test 4
C4/ stock oil, heavy % 0.0 5.0 7.5 10.0 7.5
One anti-temperature out, ℃ 510 510 510 510 510
The C4 temperature of reaction, ℃ 490 490 490 490 490
Two anti-temperature, ℃ 490 490 490 490 490
Between two inverse time, second 4.3 4.2 4.0 3.9 3.7
Agent-oil ratio 8 8 8 8 8
Atomized water, heavy % 10 10 10 10 20
Regeneration temperature, ℃ 680 680 680 680 680
Material balance, heavy %
H 2-C 2 3.26 3.34 3.25 3.27 3.10
Liquefied gas 23.53 27.48 29.56 31.33 29.70
Propylene 8.36 9.18 9.52 9.57 10.07
C5+ gasoline 43.52 41.10 41.47 42.31 41.57
Diesel oil 13.53 14.54 14.81 14.61 14.99
Heavy oil 8.07 10.00 9.88 9.98 10.95
Coke 8.09 8.54 8.53 8.50 7.19
Amount to 100.00 105.00 107.50 110.00 107.50

Claims (11)

1, a kind of method that improves propone output during catalytic conversion process, the stock oil of preheating enters in the reactor that comprises two reaction zones, in the presence of water vapor, contact and react with the cracking catalyst of heat, reaction product isolated and reclaimable catalyst, reaction product further is separated into the gaseous product that is rich in propylene, C 4 fraction through fractionating system, reclaimable catalyst enters revivifier through stripping, after burning, recycle, it is characterized in that the hydrocarbon gas that is rich in C 4 fraction injects the bottom of first reaction zone or/and the bottom of second reaction zone.
2, according to the method for claim 1, it is characterized in that described reaction conditions is as follows: first reaction zone temperature is 500~700 ℃, the reaction times of first reaction zone is 0.5~2.0 second, second reaction zone temperature is 450~550 ℃, the reaction times of second reaction zone is 2~30 seconds, the weight ratio of catalyzer and stock oil is 3~15:1, and the weight ratio of water vapor and stock oil is 0.03~0.3:1, and pressure is normal pressure~450 kPa.
3,, it is characterized in that C 4 fraction freshening in the gaseous product is as being rich in the gaseous hydrocarbon feedstock of C 4 fraction according to the method for claim 1.
4, according to the method for claim 1, it is characterized in that reclaimable catalyst behind stripping, a part enters second reaction zone through the catalyzer outer circulating tube, and another part enters revivifier regeneration.
5,, it is characterized in that described stock oil is selected from one or more in the petroleum fractions of different boiling ranges, residual oil, the crude oil according to the method for claim 1.
6, according to the method for claim 1, it is characterized in that it is the low-molecular-weight hydrocarbon that exists with gas form under the normal temperature, normal pressure of main component that the described hydrocarbon gas that is rich in C 4 fraction is meant with the C 4 fraction, comprises C4 and following alkane, alkene and alkynes thereof.
7,, it is characterized in that describedly being rich in the hydrocarbon gas of C 4 fraction and the weight ratio of stock oil is 0.03~0.1:1, preferred 0.05~0.08:1 according to the method for claim 1.
8, according to the method for claim 1, it is characterized in that when the hydrocarbon gas that is rich in C 4 fraction injects the bottom of first reaction zone catalyzer contacts with the hydrocarbon gas that is rich in C 4 fraction earlier, temperature of reaction is 600~700 ℃, 0.1~10 second reaction times; C 4 fraction reactant flow, catalyzer further contact, react at first reaction zone with stock oil again.
9, according to the method for claim 1, it is characterized in that when the hydrocarbon gas that is rich in C 4 fraction injects the bottom of second reaction zone, be rich in the hydrocarbon gas of C 4 fraction and contact with catalyzer, reactant flow from first reaction zone, temperature of reaction is 450~550 ℃, and the reaction times is 0.1~10 second; Reactant flow, catalyzer further contact, react at second reaction zone.
10, according to the method for claim 1, it is characterized in that described catalyzer is selected from all types of conventional catalysts, its active ingredient be selected from the Y that contains or do not contain rare earth or HY type zeolite, the ultrastable Y that contains or do not contain rare earth, ZSM-5 series zeolite or the supersiliceous zeolite that makes with other method with five-membered ring structure in a kind of, two or three catalyzer, and amorphous silicon aluminium catalyzer.
11, according to the method for claim 1, it is characterized in that described reactor be selected from the equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or the reducing riser tube, or the compound reactor that constitutes by equal diameter riser tube-fluidized-bed.
CNA2007101794183A 2007-12-13 2007-12-13 Method for improving propone output during catalytic conversion process Pending CN101456782A (en)

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CN102453507A (en) * 2010-10-19 2012-05-16 中国石油化工股份有限公司 Conversion method for hydrocarbon oil
CN102453506A (en) * 2010-10-19 2012-05-16 中国石油化工股份有限公司 Hydrocarbon oil conversion method
CN102453508A (en) * 2010-10-19 2012-05-16 中国石油化工股份有限公司 Hydrocarbon oil conversion method
CN102952577A (en) * 2011-08-30 2013-03-06 中国石油化工股份有限公司 Catalytic conversion method for increasing propylene yield
CN103571530A (en) * 2012-08-02 2014-02-12 中国石油天然气股份有限公司 Method for preparing low-carbon olefin through wax oil catalytic cracking

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102453507A (en) * 2010-10-19 2012-05-16 中国石油化工股份有限公司 Conversion method for hydrocarbon oil
CN102453506A (en) * 2010-10-19 2012-05-16 中国石油化工股份有限公司 Hydrocarbon oil conversion method
CN102453508A (en) * 2010-10-19 2012-05-16 中国石油化工股份有限公司 Hydrocarbon oil conversion method
CN102453508B (en) * 2010-10-19 2014-03-26 中国石油化工股份有限公司 Hydrocarbon oil conversion method
CN102453507B (en) * 2010-10-19 2014-03-26 中国石油化工股份有限公司 Conversion method for hydrocarbon oil
CN102952577A (en) * 2011-08-30 2013-03-06 中国石油化工股份有限公司 Catalytic conversion method for increasing propylene yield
CN102952577B (en) * 2011-08-30 2015-04-29 中国石油化工股份有限公司 Catalytic conversion method for increasing propylene yield
CN103571530A (en) * 2012-08-02 2014-02-12 中国石油天然气股份有限公司 Method for preparing low-carbon olefin through wax oil catalytic cracking
CN103571530B (en) * 2012-08-02 2015-11-18 中国石油天然气股份有限公司 Wax catalysis cracking is for the method for low-carbon alkene

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Application publication date: 20090617