CN106590735B - A kind of catalyst cracking method and device - Google Patents
A kind of catalyst cracking method and device Download PDFInfo
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- CN106590735B CN106590735B CN201510672014.2A CN201510672014A CN106590735B CN 106590735 B CN106590735 B CN 106590735B CN 201510672014 A CN201510672014 A CN 201510672014A CN 106590735 B CN106590735 B CN 106590735B
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Abstract
The invention discloses a kind of catalyst cracking method and device, this method includes that the resulting reclaimable catalyst of conventional catalyst cracking reaction and feedstock oil are carried out adsorption reaction, and feedstock oil carries out catalytic cracking reaction after then adsorbing.The content that can reduce aniline in catalytically cracked gasoline using this method in the device of the invention, improves quality of gasoline, reduces NOx emission, and can reduce the sulfur content in catalytic cracking product simultaneously.
Description
Technical field
The present invention relates to a kind of catalyst cracking method and devices.
Background technique
With the heaviness and in poor quality of crude oil, sulphur, nitrogen and beavy metal impurity content are higher and higher in crude oil.Nitrogenous chemical combination
Object can generate greatly adverse effect to catalyzed cracking processing process, lead to catalyst poisoning, influence product distribution and conversion ratio,
And decline FCC gasoline quality.The presence of nitrogenous compound will lead to that gasoline color deepens, induction period shortens in gasoline, meanwhile,
Nitrogenous compound burning in gasoline generates oxynitrides (NOx), causes acid rain, photochemical fog, city fine particles pollution
Deng serious harm environment.Nitrogenous compound in gasoline is mainly phenyl amines, and the presence of aniline category matter will lead to gasoline face
Discoloration is deep, is also easy to produce colloid.When the gum level in gasoline is excessively high, can in combustion generate colloid, carbon deposit, cause into
Gas system generates deposit and bonds intake valve, and then damages engine, causes a series of failures.Benzene In Gasoline amine
The presence of substance can also shorten breakdown time, reduce the oxidation stability of gasoline, gumming tendency when making gasoline storage
Increase.Simultaneously it is also possible to which plastics and rubber material in automobile parts is made to generate swelling, cause oil leak, vehicle exhaust after burning
Middle NOx content increases, and pollutes environment.So reducing gasoline under the increasingly stringent situation of environmental requirement and gasoline quality standard
Middle aniline content is imperative.
US5051163 discloses a kind of high-nitrogen stock catalyst cracking method, and main contents are that the regeneration that regenerator comes is urged
Agent a part enters pre-contact area, after contacting a period of time at a certain temperature with high-nitrogen raw oil, enters reaction zone together,
It is contacted with another part regenerated catalyst, carries out catalytic cracking reaction.After reaction oil gas is separated with reclaimable catalyst, catalysis to be generated
Agent goes regenerator to regenerate, and reaction oil gas enters following process process.The nitrogen that this method can be lowered into the raw material of reactor contains
Amount, so that product nitrogen content is reduced, but high-nitrogen raw oil is contacted with a small amount of regenerated catalyst, since oil ratio is too small, denitrogenation
Effect is bad, and sacrifices the activity of this partial regeneration agent, reduces the oil ratio of reaction process also, is unfavorable for cracking reaction.
CN1100115C discloses a kind of catalysis conversion method for reducing content of olefin in gasoline and sulphur, nitrogen content, main
Content is that gasoline to be modified enters Conventional catalytic cracking stripping section, is contacted with reclaimable catalyst, reduces and contain in gasoline
The content of nitrogen compound.Although this method can be by reducing containing for Benzene In Gasoline amine to the independent modification of catalytically cracked gasoline
Amount, but it is complicated for operation, and energy consumption is high, and will lead to gasoline yield reduction.
CN1100121C discloses a kind of catalysis conversion method for reducing content of olefin in gasoline and sulphur, nitrogen content.It is main
Content is, using conventional FCC apparatus, using gasoline to be modified as feedstock oil, with the catalyst reaction for containing a small amount of coke, separation
Product and spent agent；Spent agent by stripping, into regenerator in be recycled after incomplete regen-eration.This method can reduce gasoline
Middle aniline content, but the independent upgrading operation of gasoline is complicated, energy consumption is high, economy is unreasonable.
Summary of the invention
The object of the present invention is to provide a kind of catalyst cracking method and devices, and this method energy is used in the device of the invention
The content for enough reducing aniline in catalytically cracked gasoline, improves quality of gasoline, reduces NOx emission, and can reduce catalysis simultaneously and split
Change the sulfur content in product.
To achieve the goals above, first aspect present invention: providing a kind of catalyst cracking method, this method comprises: a, general
Feedstock oil contacts with catalytic cracking catalyst and carries out fluid catalytic cracking reaction, obtains reaction product and reclaimable catalyst；b,
Gained reaction product in step a is isolated to dry gas, liquefied gas, gasoline, diesel oil and heavy oil；Gained in step a is to be generated
Catalyst is regenerated, and obtained regenerated catalyst is returned in step a and used as the catalytic cracking catalyst；Its feature
It is, the feedstock oil is first contacted in fluidised bed adsorption reactor with gained reclaimable catalyst in step a and adsorb instead
It answers, and feedstock oil and absorption rear catalyst to be generated after being adsorbed after gas solid separation, then feedstock oil carries out after gained is adsorbed
The reaction of fluid catalytic cracking described in step a, and gained absorption rear catalyst to be generated regenerate described in step b, it obtains described
Regenerated catalyst.
Preferably, the feedstock oil is selected from gasoline, diesel oil, decompressed wax oil, residual oil, extract oil, recycle oil, coking inferior
At least one of wax oil, deasphalted oil, crude oil, shale oil and oil-sand.
Preferably, the condition of the adsorption reaction are as follows: temperature is 200-500 DEG C, oil ratio 2-30, pressure 0.1-
0.5 megapascal, time of contact are 2-30 seconds, and catalyst bed density is 100-700 kilograms per cubic meter.
Preferably, this method further include: by the fuel oil preheating to carrying out the adsorption reaction again after 100-400 DEG C.
Preferably, the catalyst contains REY molecular sieve, Y type molecular sieve, HY molecular sieve, USY molecular sieve, RE-USY point
At least one of son, ZSM-5 molecular sieve and silica-rich zeolite of five-membered ring structure.
Preferably, the condition of the catalytic cracking reaction are as follows: temperature is 450-600 DEG C, oil ratio 2-30, and pressure is
0.1-0.5 megapascal, time of contact are 0.5-5 seconds.
Second aspect of the present invention: a kind of catalytic cracking unit is provided, which is characterized in that the device includes that fluidised bed adsorption is anti-
Answer device, catalyst cracker and catalytic cracking regenerator；The fluidised bed adsorption reactor is provided with raw material oil-in, to be generated
Material oil outlet and absorption rear catalyst to be generated outlet after catalyst inlet, absorption, the interior setting of the fluidised bed adsorption reactor
There is gas-solid separator；The catalyst cracker is provided with raw material oil-in, regenerated catalyst inlet, catalysis to be generated after absorption
Agent outlet and reacting product outlet；The catalytic cracking regenerator is provided with absorption rear catalyst entrance to be generated and regenerated catalyst
Outlet；The reclaimable catalyst entrance of the reclaimable catalyst outlet and the fluidised bed adsorption reactor of the catalyst cracker
Connection, feedstock oil after the absorption of material oil outlet and the catalyst cracker after the absorption of the fluidised bed adsorption reactor
Entrance connection, the absorption rear catalyst to be generated of the fluidised bed adsorption reactor export to be generated with the catalytic cracking regenerator
Adsorb the connection of rear catalyst entrance, the regenerated catalyst outlet of the catalytic cracking regenerator and the catalyst cracker
Regenerated catalyst inlet connection.
Preferably, the catalyst cracker and the fluidised bed adsorption reactor are upper and lower integrally connected, and described
Catalyst cracker is located above the fluidised bed adsorption reactor.
Preferably, the fluidised bed adsorption reactor, the catalyst cracker and the catalytic cracking regenerator are
Block form distribution.
Preferably, the catalyst cracker is riser reactor and/or fluidized-bed reactor.
Compared with prior art, methods and apparatus of the present invention has the advantages that
1, at a lower temperature, contact reclaimable catalyst with feedstock oil, to make nitrogenous/sulphur compound in feedstock oil
It is acted on the coke on spent agent, with nitrogenous/sulphur compound in coke absorption feedstock oil, meanwhile, exist on reclaimable catalyst
The non-deactivated acid centre in part can also adsorb nitrogenous/sulphur compound in feedstock oil, lower temperature is conducive to feedstock oil
In absorption of the nitrogenous/sulphur compound in catalyst coke and acid centre, so that nitrogenous/vulcanization in feedstock oil be made to close
Object is consumed substantially in fluidised bed adsorption reactor, that is, achieve the purpose that reduce even removing FCC gasoline in aniline content with
Reduce the purpose of sulfur content in catalytic cracking product.
2, the reclaimable catalyst that nitrogenous/sulphur compound has been adsorbed in fluidised bed adsorption reactor is directly entered regenerator burning
Coke regeneration can avoid urging caused by the mixing of spent agent and regenerative agent, circulation without entering cracker with reaction raw materials oil
The problem of agent equilibrium activity reduces and device load increases.
3, the present invention, can be in catalytic cracking by increasing fluidised bed adsorption reactor outside Conventional catalytic cracking reactor
Sulfur content in the removing (content reduces by 80% or more) and product of Benzene In Gasoline amine is completed at the same time in journey to be reduced, without list
Only reformulated gasoline, it is easy to operate, it is easy to accomplish, Conventional catalytic cracking device, which is simply transformed, to be operated by the present invention,
Greatly reduce energy consumption and installation cost.
4, the components such as heavy metal and the asphalitine in feedstock oil can be adsorbed due to spent agent, can increase catalytic cracking production
The liquid yield of product reduces coke and heavy oil yield, and further increases the yield of gasoline.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, 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 a kind of specific embodiment of apparatus of the present invention；
Fig. 2 is another specific embodiment of apparatus of the present invention.
Description of symbols
1 catalyst cracker, 2 catalytic cracking regenerator, 3 fluidised bed adsorption reactor
Material oil outlet after the absorption of 4 raw material oil-in, 5 reclaimable catalyst entrance 6
Raw material oil-in after 78 absorption of absorption rear catalyst outlet to be generated
9 regenerated catalyst inlet, 10 reclaimable catalyst exports 11 reacting product outlets
12 13 regenerated catalyst outlets of absorption rear catalyst entrance to be generated
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
First aspect present invention: providing a kind of catalyst cracking method, this method comprises: a, urging feedstock oil and catalytic cracking
Agent contacts and carries out fluid catalytic cracking reaction, obtains reaction product and reclaimable catalyst；B, gained reaction in step a is produced
Object is isolated to dry gas, liquefied gas, gasoline, diesel oil and heavy oil；Gained reclaimable catalyst in step a is regenerated, is obtained
Regenerated catalyst used back in step a as the catalytic cracking catalyst；It is characterized in that, the feedstock oil is first
It is contacted in fluidised bed adsorption reactor with gained reclaimable catalyst in step a and carries out adsorption reaction, and after gas solid separation
Feedstock oil and absorption rear catalyst to be generated after to absorption, then feedstock oil carries out fluidized catalytic cracking described in step a after gained is adsorbed
Change reaction, and gained absorption rear catalyst to be generated regenerate described in step b, obtains the regenerated catalyst.
According to the first aspect of the invention, the function of the fluidised bed adsorption reactor is to make feedstock oil and reclaimable catalyst
It is come into full contact with, and fully absorbs sulphur, nitrogen, heavy metal and asphalitine etc. in feedstock oil using the coke on reclaimable catalyst
Component, to make feedstock oil more suitable catalyst cracking after absorption.In the fluidised bed adsorption reactor, feedstock oil with it is to be generated
The way of contact of catalyst can be counter current contacting, be also possible to parallel flow contact；When counter current contacting, reclaimable catalyst can be from reaction
Enter at the top of device, feedstock oil enters from reactor bottom；When parallel flow contact, reclaimable catalyst and feedstock oil can be all from reactor bottoms
Portion's charging.
According to the first aspect of the invention, the feedstock oil is well-known to those skilled in the art, for example, can be choosing
From gasoline, diesel oil, decompressed wax oil, residual oil, extract oil, recycle oil, wax tailings, deasphalted oil, crude oil, shale oil and oil inferior
At least one of sand.
According to the first aspect of the invention, the condition of the adsorption reaction according to the difference of reclaimable catalyst and feedstock oil and
Difference can be obtained by experience, for example, the condition of the adsorption reaction can be with are as follows: temperature is 200-500 DEG C, preferably 300-
460 DEG C, oil ratio 2-30, preferably 5-20, pressure is 0.1-0.5 megapascal, and preferably 0.2-0.43 megapascal, time of contact be
2-30 seconds, preferably 5-25 seconds, catalyst bed density was 100-700 kilograms per cubic meter, preferably 200-600 kilograms/cube
Rice.
According to the first aspect of the invention, in order to promote feedstock oil to come into full contact with reclaimable catalyst, this method can be with
Include: by the fuel oil preheating to 100-400 DEG C, carries out the adsorption reaction after preferably 250-360 DEG C again.
According to the first aspect of the invention, the reclaimable catalyst, absorption rear catalyst to be generated, in regenerated catalyst
Catalyst refers both to catalytic cracking catalyst, and the stage for being only at reaction is different, and the catalyst can contain REY molecule
Sieve, Y type molecular sieve, HY molecular sieve, USY molecular sieve, RE-USY molecule, ZSM-5 molecular sieve and five-membered ring structure silica-rich zeolite
At least one of, other components can also be contained, the present invention is not restricted.
According to the first aspect of the invention, the condition of the catalytic cracking reaction can use normal condition, such as can be with
Are as follows: temperature is 450-600 DEG C, and preferably 460-560 DEG C, oil ratio 2-30, preferably 5-20, pressure is 0.1-0.5 megapascal,
Preferably 0.2-0.43 megapascal, time of contact are 0.5-5 seconds, preferably 0.8-4.5 seconds.
Second aspect of the present invention: a kind of catalytic cracking unit is provided, which is characterized in that the device includes that fluidised bed adsorption is anti-
Answer device 3, catalyst cracker 1 and catalytic cracking regenerator 2；The fluidised bed adsorption reactor 3 is provided with raw material oil-in
4, material oil outlet 6 and absorption rear catalyst to be generated outlet 7 after reclaimable catalyst entrance 5, absorption, the fluidised bed adsorption reaction
Gas-solid separator is provided in device 3；Raw material oil-in 8, regenerated catalyst enter after the catalyst cracker 1 is provided with absorption
Mouth 9, reclaimable catalyst outlet 10 and reacting product outlet 11；The catalytic cracking regenerator 2 is catalyzed after being provided with absorption to be generated
Agent entrance 12 and regenerated catalyst outlet 13；Reclaimable catalyst outlet 10 and the fluidized bed of the catalyst cracker 1
The reclaimable catalyst entrance 5 of adsorptive reactor 3 is connected to, material oil outlet 6 and institute after the absorption of the fluidised bed adsorption reactor 3
Raw material oil-in 8 is connected to after stating the absorption of catalyst cracker 1, is urged after the absorption to be generated of the fluidised bed adsorption reactor 3
Agent outlet 7 is connected to the absorption rear catalyst entrance 12 to be generated of the catalytic cracking regenerator 2, the catalytic cracking regenerator
2 regenerated catalyst outlet 13 is connected to the regenerated catalyst inlet 9 of the catalyst cracker 1.
According to the second aspect of the invention, feedstock oil carries out catalytic cracking reaction after adsorbing for convenience, as shown in Figure 1,
The catalyst cracker 1 and the fluidised bed adsorption reactor 3 can be upper and lower integrally connected, and the Catalytic Cracking Unit of Measure
Answer device 1 that can be located at 3 top of fluidised bed adsorption reactor, i.e., material oil outlet 6 and original after the absorption after the described absorption
Expect that oil-in 8 is overlapped (not marking in Fig. 1).
According to the second aspect of the invention, the fluidised bed adsorption reactor, the fluidised bed adsorption are set for convenience
Reactor 3, the catalyst cracker 1 and the catalytic cracking regenerator 2 can be distributed for block form, i.e., in catalysis to be generated
Fluidised bed adsorption reactor is set on the feed-line of agent.
According to the second aspect of the invention, the catalyst cracker 1 is well-known to those skilled in the art, such as
It can be riser reactor and/or fluidized-bed reactor.The riser reactor can be variable diameter riser reactor,
It can be isometrical riser reactor；The catalyst cracker can be upstriker reactor, and it is anti-to be also possible to downstriker
Answer device.
A specific embodiment of the invention is provided below in conjunction with attached drawing.
As shown in Figure 1, the reaction-regeneration system includes riser reactor 1, fluidised bed adsorption reactor 3 and catalytic cracking
Regenerator 2.The feedstock oil of preheating enters fluidised bed adsorption reactor from the bottom raw material oil-in 4 of fluidised bed adsorption reactor 3,
It is controlled from riser reactor 1 by inclined tube, by slide valve by fluidized bed by the reclaimable catalyst that settler carries out gas solid separation
The top of adsorptive reactor 3 enters fluidised bed adsorption reactor, feedstock oil and reclaimable catalyst counter current contacting, absorption.
Feedstock oil and absorption rear catalyst to be generated after absorption carry out gas solid separation at the top of adsorptive reactor.Absorption
The absorption rear catalyst to be generated of nitrogenous/sulphur compound etc. is controlled by inclined tube, by slide valve, from absorption rear catalyst entrance to be generated
12, which enter regenerator 2, carries out coke burning regeneration, and to be recycled, regenerated flue gas passes through the flue gas discharge opening discharge at the top of regenerator 2
To subsequent gas cleaning and energy recycling system.It is separated at the top of adsorptive reactor with reclaimable catalyst by the feedstock oil of absorption
Afterwards, directly enter riser reactor 1 from promotion bottom of the tube, contacted with the regenerated catalyst of regenerator 2, carry out catalytic cracking
Reaction.It reacts stripping section and settler of the oil agent mixture Jing Guo riser reactor top and carries out gas solid separation, separate
Reaction oil gas by reactor head reacting product outlet 11 come out send to subsequent product separation system, reclaimable catalyst enters stream
Change bed adsorptive reactor 3.
As shown in Fig. 2, the reaction-regeneration system includes riser reactor 1, fluidised bed adsorption reactor 3 and regenerator 2.
The feedstock oil of preheating enters fluidised bed adsorption reactor from the bottom raw material oil-in 4 of fluidised bed adsorption reactor 3, by sedimentation
The reclaimable catalyst that device carries out gas solid separation passes through inclined tube, is controlled by slide valve from riser reactor 1 and reacted by fluidised bed adsorption
The top of device 3 enters fluidised bed adsorption reactor, feedstock oil and reclaimable catalyst counter current contacting, absorption.
Feedstock oil and reclaimable catalyst after absorption carry out gas solid separation at the top of adsorptive reactor.It has adsorbed and has contained
The reclaimable catalyst of nitrogen/sulphur compound etc. is controlled by inclined tube, by slide valve, is entered from absorption rear catalyst entrance 12 to be generated and is regenerated
Device 2 carries out coke burning regeneration, and to be recycled, regenerated flue gas is expelled to subsequent flue gas by the flue gas discharge opening at 2 top of regenerator
Purification and energy recycling system.Material oil outlet 6 goes out after the feedstock oil of absorption is by 3 apex suction of fluidised bed adsorption reactor
Come, enters riser reactor 1 from feedstock oil feed inlet 8 after the absorption of the bottom of riser reactor 1, again with regenerator 2
Raw catalyst contact, carries out catalytic cracking reaction.Oil agent mixture is reacted by the stripping section on riser reactor top and is sunk
It drops device and carries out gas solid separation, the reaction oil gas separated is come out by reactor head reacting product outlet 11 and sent to subsequent product
Separation system, reclaimable catalyst enter fluidised bed adsorption reactor 3.
The present invention is further illustrated by embodiment below in conjunction with attached drawing, but therefore the present invention is not taken office
What is limited.
In the embodiment of the present invention and comparative example, gaseous product is carried out using petrochemical analysis method RIPP 77-90 method
Test measures coke content using petrochemical analysis method RIPP 107-90 method, and organic liquid product composition uses SH/T
The fraction cut point of the measurement of 0558-1993 method, gasoline and diesel oil is respectively 221 DEG C and 343 DEG C, and the measurement of gasoline nitrogen content is adopted
It is measured with gas-chromatography, for details, reference can be made to " the luminous detection method of gas-chromatography-nitrogen chemical analyzes nitrogenous chemical combination in catalytic gasoline
Species type ", Yang Yongtan etc., " chromatography ", 2010,4.
RIPP petrochemical analysis method of the present invention is selected from " petrochemical egineering analysis method (RIPP test methods) ",
Yang Cui is surely equal to be compiled, Science Press, and 1990.
The property of catalyst used in embodiment and comparative example is listed in table 1, and feedstock oil is decompressed wax oil (including triumph
First vacuum side stream and Liaohe River second line of distillation oil), property is listed in table 2.1 catalyst of table is by Sinopec Group's Shandong stone
Change company catalyst plant industrial production.
Embodiment 1
This example demonstrates that reducing aniline content in FCC gasoline using method provided by the invention, improving liquid receipts and gasoline
The case where yield and reduction coke and heavy oil yield.
Catalytic cracking unit flow chart is as shown in Fig. 1, using fluidised bed adsorption reactor, feedstock oil (triumph vacuum 1st side cut
Oil or Liaohe River second line of distillation oil) 350 DEG C are preheated to through the injection of raw material oil-in 4 fluidised bed adsorption reactor bottom, by settler
The reclaimable catalyst for carrying out gas solid separation enters reactor, feedstock oil and reclaimable catalyst from the top of fluidised bed adsorption reactor
Counter current contacting, absorption.Needing to maintain bed density in fluidised bed adsorption reactor in adsorption process is 420kg/m3.Adsorptive reactor
Interior reaction temperature is 400 DEG C, oil ratio 12, pressure 0.3MPa, time of contact 15s.
Feedstock oil and reclaimable catalyst after absorption carry out gas solid separation in fluidised bed adsorption reactor head.Absorption
The reclaimable catalyst of nitrogenous compound etc. enters regenerator and carries out coke burning regeneration, to be recycled.By the feedstock oil of absorption
After fluidised bed adsorption reactor head is separated with reclaimable catalyst, it is directly entered riser reactor from bottom of the tube is promoted, with
The regenerated catalyst contact that regenerator comes, carries out catalytic cracking reaction.Reaction temperature in riser reactor is 500 DEG C, agent
Oil is than being 8, pressure 0.3MPa, reaction time 1.5s.React the stripping that oil agent mixture passes through riser reactor top
Section and settler carry out gas solid separation, the reaction oil pneumatic transmission separated to subsequent product separation system, and reclaimable catalyst enters
Fluidised bed adsorption reactor.
Experiment condition is listed in table 3, and experimental result is listed in table 4.
Embodiment 2
This example demonstrates that reducing aniline content in FCC gasoline using method provided by the invention, improving liquid receipts and gasoline
The case where yield and reduction coke and heavy oil yield.
Catalytic cracking unit flow chart is as shown in Fig. 2, using fluidised bed adsorption reactor, feedstock oil (triumph vacuum 1st side cut
Oil or Liaohe River second line of distillation oil) 350 DEG C are preheated to through the injection of raw material oil-in 4 fluidised bed adsorption reactor bottom, by settler
The reclaimable catalyst for carrying out gas solid separation enters reactor, feedstock oil and reclaimable catalyst from the top of fluidised bed adsorption reactor
Counter current contacting, absorption.Needing to maintain bed density in fluidised bed adsorption reactor in adsorption process is 420kg/m3.Fluidised bed adsorption
Reactor interior reaction temperature is 400 DEG C, oil ratio 12, pressure 0.3MPa, time of contact 15s.
Feedstock oil and reclaimable catalyst after denitrogenation carry out gas solid separation in fluidised bed adsorption reactor head.Absorption
The reclaimable catalyst of the substances such as nitrogenous compound enters regenerator and carries out coke burning regeneration, to be recycled.By the original of absorption
Material oil raw material oil-in 8 after absorption enters riser reactor, and the regenerated catalyst come with regenerator contacts, and carries out catalysis and splits
Change reaction.Reaction temperature in riser reactor is 500 DEG C, oil ratio 8, pressure 0.3MPa, reaction time 1.5s.
It reacts stripping section and settler of the oil agent mixture Jing Guo riser reactor top and carries out gas solid separation, the reaction separated
Oil gas is sent to subsequent product separation system, and reclaimable catalyst enters fluidised bed adsorption reactor.
Experiment condition is listed in table 3, and experimental result is listed in table 5.
Comparative example
Comparative example is operated according to Conventional catalytic cracking reaction process, using riser reactor identical with embodiment.It is real
It is identical as the experiment condition that embodiment uses to test condition, is listed in table 3, and experimental result is listed in table 4 and table 5.
From table 4, it can be seen that operating result of the invention is much better than Conventional catalytic cracking operating result.For nitrogen
The lower triumph first vacuum side stream of object content is closed, after method of the invention, liquid product yield improves 5.24%, yield of gasoline
9.92% is improved, and the content of Benzene In Gasoline amine reduces 82.23%, is lower than 5ppm.It is higher for nitrogenous compound content
Liaohe River second line of distillation oil, after method of the invention, liquid product yield improves 7.35%, and yield of gasoline improves
15.56%, and the content of Benzene In Gasoline amine reduces 83.16%, also below 5ppm.
As can be seen from Table 5, operating result of the invention is also much better than Conventional catalytic cracking operating result.For nitrogenous
The lower triumph first vacuum side stream of compounds content, after method of the invention, liquid product yield improves 5.39%, and gasoline is received
Rate improves 10.44%, and the content of Benzene In Gasoline amine reduces 81.34%, is lower than 5ppm.For nitrogenous compound content compared with
High Liaohe River second line of distillation oil, after method of the invention, liquid product yield improves 7.33%, and yield of gasoline improves
14.58%, and the content of Benzene In Gasoline amine reduces 82.05%, also below 5ppm.
Compare the drop of improvement and gasoline aniline content that two kinds of feedstock oils are distributed using product after method of the invention
Inefficient fruit, the higher Liaohe River second line of distillation oil of nitrogenous compound content are more preferable compared with triumph first vacuum side stream effect, illustrate this method not only
It can handle the lower feedstock oil of nitrogenous compound, its catalytically cracked gasoline aniline content be greatly lowered, for nitrogen
The higher feedstock oil of object is closed, catalytically cracked gasoline aniline content is reduced and also achieves quite apparent effect, illustrate the present invention
Method also be suitble to processing the higher feedstock oil of nitrogenous compound content, reduce the content of aniline in its catalytically cracked gasoline.
1 catalyst property of table
| Catalyst | A |
| Chemical composition, weight % | |
| Aluminium oxide | 49.5 |
| Sodium oxide molybdena | 0.05 |
| Apparent density, kg/m3 | 865 |
| Pore volume, ml/g | 0.2 |
| Specific surface area, m2/g | 145 |
| Abrasion index, weight %h-1 | 1.6 |
| Screening composition, weight % | |
| 0-40μm | 15.8 |
| 40-80μm | 65.9 |
| >80μm | 18.3 |
| Micro-activity MA | 69 |
2 raw material oil nature of table
| Property | Triumph vacuum 1st side cut | Liaohe River second line of distillation |
| Alkali nitrogen, ppm | 411 | 794 |
| Total nitrogen, ppm | 989 | 1979 |
| Alkali nitrogen accounts for the ratio of total nitrogen | 0.42 | 0.40 |
| Condensation point, DEG C | 15 | -8 |
| 70 DEG C of refractive index | 1.475 | 1.51 |
| 70 DEG C of density, g/cm3 | 0.859 | 0.925 |
| Relative molecular mass | 282 | 380 |
| 10% recovered (distilled) temperature, DEG C | 296 | 390 |
| 50% recovered (distilled) temperature, DEG C | 345 | 418 |
| 95% recovered (distilled) temperature, DEG C | 439 | 448 |
3 reaction condition of table
| Project | Condition |
| Fuel oil preheating temperature, DEG C | 350 |
| Adsorptive reactor | |
| Bed density, kg/m3 | 420 |
| Temperature, DEG C | 400 |
| Oil ratio | 12 |
| Pressure, Mpa | 0.3 |
| Time of contact, s | 15 |
| Riser reactor | |
| Temperature, DEG C | 500 |
| Oil ratio | 8 |
| Pressure, Mpa | 0.3 |
| Time of contact, s | 1.5 |
4 experimental result of table
5 experimental result of table
Claims (10)
1. a kind of catalyst cracking method, this method comprises:
A, feedstock oil is contacted to catalytic cracking catalyst and carried out fluid catalytic cracking reaction, obtain reaction product and to be generated is urged
Agent；
B, gained reaction product in step a is isolated to dry gas, liquefied gas, gasoline, diesel oil and heavy oil；By institute in step a
It obtains reclaimable catalyst to be regenerated, obtained regenerated catalyst is returned in step a and used as the catalytic cracking catalyst；
It is characterized in that, the feedstock oil is first contacted in fluidised bed adsorption reactor with gained reclaimable catalyst in step a
Adsorption reaction is carried out, and feedstock oil and absorption rear catalyst to be generated after being adsorbed after gas solid separation, then after gained is adsorbed
Feedstock oil carries out the reaction of fluid catalytic cracking described in step a, and gained absorption rear catalyst to be generated is carried out described in step b again
It is raw, obtain the regenerated catalyst；
The fluidised bed adsorption catalyst reactor bed density is 100-700 kilograms per cubic meter.
2. the method according to claim 1, wherein the feedstock oil is selected from gasoline, diesel oil, decompressed wax oil, residual oil, extracting
At least one of oil, recycle oil, wax tailings, deasphalted oil, crude oil and shale oil inferior.
3. the method according to claim 1, wherein the condition of the adsorption reaction are as follows: temperature is 200-500 DEG C, and oil ratio is
2-30, pressure are 0.1-0.5 megapascal, and time of contact is 2-30 seconds, and catalyst bed density is 200-600 kilograms per cubic meter.
4. the method according to claim 1, wherein this method further include: by the fuel oil preheating to after 100-400 DEG C again into
The row adsorption reaction.
5. the method according to claim 1, wherein the catalyst contains REY molecular sieve, Y type molecular sieve, HY molecular sieve, USY
At least one of molecular sieve, RE-USY molecule, ZSM-5 molecular sieve and silica-rich zeolite of five-membered ring structure.
6. the method according to claim 1, wherein the condition of the fluid catalytic cracking reaction are as follows: temperature is 450-600 DEG C,
Oil ratio is 2-30, and pressure is 0.1-0.5 megapascal, and time of contact is 0.5-5 seconds.
7. a kind of catalytic cracking unit, which is characterized in that the device includes fluidised bed adsorption reactor (3), catalytic cracking reaction
Device (1) and catalytic cracking regenerator (2)；
The fluidised bed adsorption reactor (3) is provided with feedstock oil after raw material oil-in (4), reclaimable catalyst entrance (5), absorption
(6) and absorption rear catalyst to be generated outlet (7) are exported, are provided with gas-solid separator in the fluidised bed adsorption reactor (3)；Institute
It states catalyst cracker (1) and is provided with raw material oil-in (8), regenerated catalyst inlet (9), reclaimable catalyst outlet after absorption
(10) and reacting product outlet (11)；The catalytic cracking regenerator (2) be provided with absorption rear catalyst entrance (12) to be generated and
Regenerated catalyst outlet (13)；
The reclaimable catalyst outlet (10) of the catalyst cracker (1) is to be generated with the fluidised bed adsorption reactor (3)
Catalyst inlet (5) connection, material oil outlet (6) and the catalytic cracking after the absorption of the fluidised bed adsorption reactor (3)
Raw material oil-in (8) are connected to after the absorption of reactor (1), the absorption rear catalyst to be generated of the fluidised bed adsorption reactor (3)
Outlet (7) is connected to the absorption rear catalyst entrance (12) to be generated of the catalytic cracking regenerator (2), described catalytic cracked regenerated
The regenerated catalyst outlet (13) of device (2) is connected to the regenerated catalyst inlet (9) of the catalyst cracker (1).
8. device according to claim 7, which is characterized in that the catalyst cracker (1) and the fluidised bed adsorption are anti-
Answering device (3) is upper and lower integrally connected, and the catalyst cracker (1) is located above the fluidised bed adsorption reactor (3).
9. device according to claim 7, which is characterized in that the fluidised bed adsorption reactor (3), the catalytic cracking reaction
Device (1) and the catalytic cracking regenerator (2) are block form distribution.
10. device according to claim 7, which is characterized in that the catalyst cracker (1) be riser reactor and/
Or fluidized-bed reactor.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4090948A (en) * | 1977-01-17 | 1978-05-23 | Schwarzenbek Eugene F | Catalytic cracking process |
| US4436613A (en) * | 1982-12-03 | 1984-03-13 | Texaco Inc. | Two stage catalytic cracking process |
| CN1088246A (en) * | 1992-12-17 | 1994-06-22 | 中国石油化工总公司石油化工科学研究院 | A kind of catalytic cracking process of high-nitrogen raw oil |
| CN103031148A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2214222Y (en) * | 1994-08-02 | 1995-12-06 | 石油大学(华东) | Two-section catalytic cracking reactor with uper and lower action reaction tube |
-
2015
- 2015-10-15 CN CN201510672014.2A patent/CN106590735B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4090948A (en) * | 1977-01-17 | 1978-05-23 | Schwarzenbek Eugene F | Catalytic cracking process |
| US4436613A (en) * | 1982-12-03 | 1984-03-13 | Texaco Inc. | Two stage catalytic cracking process |
| CN1088246A (en) * | 1992-12-17 | 1994-06-22 | 中国石油化工总公司石油化工科学研究院 | A kind of catalytic cracking process of high-nitrogen raw oil |
| CN103031148A (en) * | 2011-09-30 | 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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