CN106590735A - Method and an apparatus of catalytic cracking - Google Patents
Method and an apparatus of catalytic cracking Download PDFInfo
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- CN106590735A CN106590735A CN201510672014.2A CN201510672014A CN106590735A CN 106590735 A CN106590735 A CN 106590735A CN 201510672014 A CN201510672014 A CN 201510672014A CN 106590735 A CN106590735 A CN 106590735A
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Abstract
The invention discloses a method and an apparatus of catalytic cracking. The method comprises the following steps: adsorption reaction is carried out for a spent catalyst obtained in traditional catalytic cracking reactions and raw oil; and a catalytic cracking reaction is carried out for adsorbed raw oil. The apparatus and the method are used, in order to reduce content of aniline in catalytic cracking gasoline, improve gasoline quality, reduce NOx discharge, and at the same time reduce sulfur content in the catalytic cracking products.
Description
Technical field
The present invention relates to a kind of catalyst cracking method and device.
Background technology
With the heaviness and in poor quality of crude oil, sulfur, nitrogen and beavy metal impurity content more and more higher in crude oil.Nitrogenous chemical combination
Thing can produce great adverse effect to catalyzed cracking processing process, cause catalyst poisoning, affect products distribution and conversion ratio,
And make FCC gasoline Quality Down.The presence of nitrogen-containing compound in gasoline can cause that gasoline color is deepened, induction period shortens, meanwhile,
Nitrogen-containing compound burning in gasoline produces oxynitride (NOx), causes acid rain, photochemical fog, city fine particles pollution
Deng serious harm environment.Nitrogen-containing compound in gasoline is mainly phenyl aminess, and the presence of aniline category matter can cause gasoline face
Complexion changed depth, is also easy to produce colloid.When the gum level in gasoline is too high, can in combustion produce colloid, carbon deposit, cause into
Gas system produces deposit and makes intake valve bond, and then damages electromotor, causes a series of failures.Benzene In Gasoline amine
The presence of material can also shorten breakdown time, reduce the oxidation stability of gasoline, gumming tendency when making gasoline storage
Increase.Simultaneously it is also possible to it is swelling to produce plastics and elastomeric material in auto parts machinery, cause oil leak, vehicle exhaust after burning
Middle NOx content increase, pollutes environment.So, under the increasingly strict situation of environmental requirement and gasoline quality standard, reduce gasoline
Middle aniline content is imperative.
US5051163 discloses a kind of high-nitrogen stock catalyst cracking method, and its main contents is that the regeneration that regenerator comes is urged
Agent is partly into pre-contact area, after contacting a period of time at a certain temperature with high-nitrogen raw oil, together into reaction zone,
Contact with another part regenerated catalyst, carry out catalytic cracking reaction.After reaction oil gas are separated with reclaimable catalyst, catalysis to be generated
Agent goes regenerator to regenerate, and reaction oil gas enter following process process.The method can be lowered into the nitrogen of the raw material of reactor and contain
Amount, so as to reduce product nitrogen content, but high-nitrogen raw oil is contacted with a small amount of regenerated catalyst, due to oil ratio it is too small, denitrogenation
Effect is bad, and sacrifices the activity of this partial regeneration agent, and making the oil ratio of course of reaction also reduces, and is unfavorable for cracking reaction.
CN1100115C discloses a kind of reduction content of olefin in gasoline and sulfur, the catalysis conversion method of nitrogen content, and its is main
Content is that gasoline to be modified enters Conventional catalytic cracking stripping section, is contacted with reclaimable catalyst, reduces containing in gasoline
The content of nitrogen compound.Although the method can be by reducing containing for Benzene In Gasoline amine to the independent modification of catalytically cracked gasoline
Amount, but complex operation, high energy consumption, and gasoline yield can be caused to reduce.
CN1100121C discloses a kind of reduction content of olefin in gasoline and sulfur, the catalysis conversion method of nitrogen content.Its is main
Content is, using conventional FCC apparatus, with gasoline to be modified as raw oil, with the catalyst reaction containing a small amount of coke, separates
Product and spent agent；Through stripping, incomplete regen-eration Posterior circle is used spent agent in regenerator.The method can reduce gasoline
Middle aniline content, but the independent upgrading operation complexity of gasoline, high energy consumption, economy are unreasonable.
The content of the invention
It is an object of the invention to provide a kind of catalyst cracking method and device, adopt the method energy on the device of the present invention
The content of aniline in catalytically cracked gasoline is enough reduced, quality of gasoline is improved, NOx emission is reduced, and is split while catalysis can be reduced
Change the sulfur content in product.
To achieve these goals, first aspect present invention：A kind of catalyst cracking method is provided, the method includes：A, general
Raw oil contacts and carries out fluid catalytic cracking reaction with catalytic cracking catalyst, obtains product and reclaimable catalyst；b、
Gained product in step a is isolated to into dry gas, liquefied gas, gasoline, diesel oil and heavy oil；Gained in step a is to be generated
Catalyst is regenerated, and the regenerated catalyst for obtaining is returned in step a and used as the catalytic cracking catalyst；Its feature
It is that first contacting the raw oil in fluidised bed adsorption reactor with gained reclaimable catalyst in step a carries out adsorbing anti-
Should, and raw oil and absorption rear catalyst to be generated after being adsorbed Jing after gas solid separation, then raw oil is carried out after gained is adsorbed
Fluid catalytic cracking reaction described in step a, and gained absorption rear catalyst to be generated is carried out being regenerated described in step b, obtain described
Regenerated catalyst.
Preferably, the raw oil is selected from gasoline, diesel oil, decompressed wax oil, residual oil, extract oil, recycle oil inferior, coking
At least one in wax oil, deasphalted oil, crude oil, shale oil and oil-sand.
Preferably, the condition of the adsorption reaction is：Temperature is 200-500 DEG C, and oil ratio is 2-30, and pressure is 0.1-
0.5 MPa, time of contact is the 2-30 seconds, and beds density is 100-700 kilograms per cubic meter.
Preferably, the method also includes：The fuel oil preheating is carried out again to after 100-400 DEG C the adsorption reaction.
Preferably, the catalyst contains REY molecular sieves, Y type molecular sieve, HY molecular sieves, USY molecular sieve, RE-USY point
At least one in the silica-rich zeolite of son, ZSM-5 molecular sieve and five-membered ring structure.
Preferably, the condition of the catalytic cracking reaction is：Temperature is 450-600 DEG C, and oil ratio is 2-30, and pressure is
0.1-0.5 MPa, time of contact is the 0.5-5 seconds.
Second aspect present invention：There is provided a kind of catalytic cracking unit, it is characterised 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, are arranged in the fluidised bed adsorption reactor after catalyst inlet, absorption
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 of the catalyst cracker exports the reclaimable catalyst entrance with the fluidised bed adsorption reactor
Connection, raw oil after material oil outlet and the absorption of the catalyst cracker after the absorption of the fluidised bed adsorption reactor
Entrance is connected, and the absorption rear catalyst to be generated outlet of the fluidised bed adsorption reactor is to be generated with the catalytic cracking regenerator
The entrance connection of absorption rear catalyst, the regenerated catalyst outlet of the catalytic cracking regenerator and the catalyst cracker
Regenerated catalyst inlet is connected.
Preferably, the catalyst cracker and the fluidised bed adsorption reactor are upper and lower integrally connected, and described
Catalyst cracker is located at fluidised bed adsorption reactor top.
Preferably, the fluidised bed adsorption reactor, the catalyst cracker are with the catalytic cracking regenerator
Block form is distributed.
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 advantage that：
1st, at a lower temperature, reclaimable catalyst is made to contact with raw oil, so that the nitrogenous/sulphur compound in raw oil
Act on the coke on spent agent, the nitrogenous/sulphur compound in raw oil is adsorbed with coke, meanwhile, exist on reclaimable catalyst
The non-deactivated acid centre in part can also adsorb nitrogenous/sulphur compound in raw oil, lower temperature is conducive to raw oil
In absorption of the nitrogenous/sulphur compound in catalyst coke and acid centre so that the nitrogenous/sulfuration in raw oil is closed
Thing is consumed substantially in fluidised bed adsorption reactor, that is, reduce in even removing FCC gasoline the purpose of aniline content with
Reduce the purpose of sulfur content in catalytic cracking product.
2nd, the reclaimable catalyst for having adsorbed nitrogenous/sulphur compound in fluidised bed adsorption reactor is directly entered regenerator burning
Jiao's regeneration, and cracker is not entered with reaction raw materials oil, can avoid being urged caused by spent agent and mixing, the circulation of regenerative agent
The problem that agent equilibrium activity is reduced and device load increases.
3rd, the present invention, can be in catalytic cracking by increasing fluidised bed adsorption reactor outside Conventional catalytic cracking reactor
Complete simultaneously in journey Benzene In Gasoline amine removing (content reduces by more than 80%) and product in sulfur content reduce, without list
Solely reformulated gasoline, simple to operate, it is easy to accomplish, the simply transformation of Conventional catalytic cracking device can be operated by the present invention,
Greatly reduce energy consumption and installation cost.
4th, the components such as heavy metal and asphalitine in raw oil can be adsorbed due to spent agent, catalytic cracking product can be increased
The liquid yield of product, reduces coke and heavy oil yield, and further improves the yield of gasoline.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, 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 kind of specific embodiment of apparatus of the present invention.
Description of reference numerals
The fluidised bed adsorption reactor of 1 catalyst cracker, 2 catalytic cracking regenerator 3
Material oil outlet after the absorption of 4 raw material oil-in, 5 reclaimable catalyst entrance 6
Raw material oil-in after the absorption of 7 absorption rear catalyst to be generated outlet 8
The reclaimable catalyst of 9 regenerated catalyst inlet 10 exports 11 reacting product outlets
12 regenerated catalyst outlets of absorption rear catalyst entrance 13 to be generated
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.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.
First aspect present invention：A kind of catalyst cracking method is provided, the method includes：A, raw oil and catalytic cracking are urged
Agent contacts and carries out fluid catalytic cracking reaction, obtains product and reclaimable catalyst；B, by step a gained reaction produce
Thing 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 return in step a and used as the catalytic cracking catalyst；Characterized in that, by the raw oil elder generation
Contacting in fluidised bed adsorption reactor with gained reclaimable catalyst in step a carries out adsorption reaction, and Jing after gas solid separation
Raw oil and absorption rear catalyst to be generated to after absorption, then raw oil carries out fluidized catalytic cracking described in step a after gained is adsorbed
Change reaction, and gained absorption rear catalyst to be generated is carried out being regenerated described in step b, obtain the regenerated catalyst.
According to the first aspect of the invention, the function of the fluidised bed adsorption reactor is to make raw oil and reclaimable catalyst
It is fully contacted, and the sulfur in raw oil, nitrogen, heavy metal and asphalitine etc. is fully absorbed using the coke on reclaimable catalyst
Component, so that raw oil more suitable catalyst cracking after absorption.In the fluidised bed adsorption reactor, raw oil with it is to be generated
The way of contact of catalyst can be counter current contacting, or current contacting；During counter current contacting, reclaimable catalyst can be from reaction
Device top enters, and raw oil is entered from reactor bottom；During current contacting, reclaimable catalyst and raw oil can all from reactor bottom
Portion feeds.
According to the first aspect of the invention, the raw oil is well-known to those skilled in the art, can be choosing for example
From gasoline, diesel oil, decompressed wax oil, residual oil, extract oil, recycle oil inferior, wax tailings, deasphalted oil, crude oil, shale oil and oil
At least one in sand.
According to the first aspect of the invention, the condition of the adsorption reaction according to reclaimable catalyst it is different from raw oil and
Difference, can be obtained by experience, and for example, the condition of the adsorption reaction can be：Temperature is 200-500 DEG C, preferably 300-
460 DEG C, oil ratio is 2-30, preferably 5-20, and pressure is 0.1-0.5 MPa, and preferably 0.2-0.43 MPa, time of contact is
2-30 seconds, preferably 5-25 seconds, beds density is 100-700 kilograms per cubic meter, preferably 200-600 kilogram/cube
Rice.
According to the first aspect of the invention, in order to promote raw oil to be fully contacted with reclaimable catalyst, the method can be with
Including：By the fuel oil preheating to 100-400 DEG C, the adsorption reaction is carried out after preferably 250-360 DEG C again.
According to the first aspect of the invention, in described reclaimable catalyst, absorption rear catalyst to be generated, 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 molecules
The silica-rich zeolite of sieve, Y type molecular sieve, HY molecular sieves, USY molecular sieve, RE-USY molecules, ZSM-5 molecular sieve and five-membered ring structure
In at least one, it is also possible to containing other components, the present invention is not restricted.
According to the first aspect of the invention, the condition of the catalytic cracking reaction can adopt normal condition, for example can be with
For：Temperature is 450-600 DEG C, and preferably 460-560 DEG C, oil ratio is 2-30, preferably 5-20, and pressure is 0.1-0.5 MPa,
Preferably 0.2-0.43 MPa, time of contact is 0.5-5 seconds, preferably 0.8-4.5 seconds.
Second aspect present invention：There is provided a kind of catalytic cracking unit, it is characterised 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
4th, material oil outlet 6 and absorption rear catalyst to be generated outlet 7, the fluidised bed adsorption reaction after reclaimable catalyst entrance 5, absorption
Gas-solid separator is provided with device 3；The catalyst cracker 1 is provided with raw material oil-in 8, regenerated catalyst after absorption and enters
Mouth 9, reclaimable catalyst outlet 10 and reacting product outlet 11；The catalytic cracking regenerator 2 is provided with after absorption to be generated and is catalyzed
Agent entrance 12 and regenerated catalyst outlet 13；Reclaimable catalyst outlet 10 and the fluid bed of the catalyst cracker 1
The reclaimable catalyst entrance 5 of adsorptive reactor 3 is connected, material oil outlet 6 and institute after the absorption of the fluidised bed adsorption reactor 3
State raw material oil-in 8 after the absorption of catalyst cracker 1 to connect, urge after the absorption to be generated of the fluidised bed adsorption reactor 3
Agent outlet 7 is connected with 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 with the regenerated catalyst inlet 9 of the catalyst cracker 1.
According to the second aspect of the invention, raw 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 to may be located at the top of the fluidised bed adsorption reactor 3, i.e., it is former after material oil outlet 6 and the absorption after described absorption
Material oil-in 8 overlaps (do not mark 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 can be distributed with the catalytic cracking regenerator 2 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 be it is well-known to those skilled in the art, for example
Can be riser reactor and/or fluidized-bed reactor.The riser reactor can be reducing riser reactor,
It can be isometrical riser reactor；The catalyst cracker can be that upstriker reactor, or downstriker are anti-
Answer device.
The specific embodiment of the present invention is provided below in conjunction with accompanying 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 raw oil of preheating enters fluidised bed adsorption reactor from the bottom raw material oil-in 4 of fluidised bed adsorption reactor 3,
The reclaimable catalyst for carrying out gas solid separation through settler is controlled from riser reactor 1 by fluid bed through inclined tube, by guiding valve
The top of adsorptive reactor 3 enters fluidised bed adsorption reactor, raw oil and reclaimable catalyst counter current contacting, absorption.
Raw oil after absorption carries out gas solid separation with absorption rear catalyst to be generated at the top of adsorptive reactor.Absorption
The absorption rear catalyst to be generated of nitrogenous/sulphur compound etc. is controlled through inclined tube, by guiding valve, from absorption rear catalyst entrance to be generated
12 carry out coke burning regeneration into regenerator 2, and to recycle, regenerated flue gas are discharged by the flue gas discharge opening at the top of regenerator 2
To follow-up gas cleaning and energy-recuperation system.Raw oil through adsorbing is separated at the top of adsorptive reactor with reclaimable catalyst
Afterwards, directly contact with the regenerated catalyst of regenerator 2 from bottom of the tube is lifted into riser reactor 1, carry out catalytic cracking
Reaction.Stripping section and settler of the reaction oil agent mixture through riser reactor top carries out gas solid separation, separates
Reaction oil gas subsequent product piece-rate system is out delivered to by reactor head reacting product outlet 11, reclaimable catalyst enters to become a mandarin
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 raw oil of preheating enters fluidised bed adsorption reactor from the bottom raw material oil-in 4 of fluidised bed adsorption reactor 3, through sedimentation
Device carries out the reclaimable catalyst of gas solid separation and is reacted by fluidised bed adsorption from riser reactor 1 through inclined tube, by guiding valve control
The top of device 3 enters fluidised bed adsorption reactor, raw oil and reclaimable catalyst counter current contacting, absorption.
Raw oil after absorption carries out gas solid separation with reclaimable catalyst at the top of adsorptive reactor.Adsorb and contained
The reclaimable catalyst of nitrogen/sulphur compound etc. is controlled through inclined tube, by guiding valve, and from absorption rear catalyst entrance 12 to be generated regeneration is entered
Device 2 carries out coke burning regeneration, and to recycle, regenerated flue gas are expelled to follow-up flue gas by the flue gas discharge opening at the top of regenerator 2
Purification and energy-recuperation system.Material oil outlet 6 goes out after the raw oil of absorption is by the apex suction of fluidised bed adsorption reactor 3
Come, enter riser reactor 1 from raw oil charging aperture 8 after the bottom absorption of riser reactor 1, with regenerator 2 again
Raw catalyst contact, carries out catalytic cracking reaction.Oil agent mixture is reacted through the stripping section on riser reactor top and sink
Drop device carries out gas solid separation, and the reaction oil gas separated out deliver to subsequent product by reactor head reacting product outlet 11
Piece-rate system, reclaimable catalyst enters fluidised bed adsorption reactor 3.
The present invention is further illustrated by embodiment below in conjunction with accompanying 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 Engineering Analysis method RIPP 77-90 methods
Test, using Petrochemical Engineering Analysis method RIPP 107-90 methods coke content is determined, and organic liquid product composition adopts SH/T
0558-1993 methods are determined, and the fraction cut point of gasoline and diesel oil is respectively 221 DEG C and 343 DEG C, and the measure of gasoline nitrogen content is adopted
It is measured with gas chromatogram, specifically can be found in " nitrogenous chemical combination in gas chromatogram-nitrogen chemical luminous detection method analysis catalytic gasoline
Species type ", Yang Yongtan etc.,《Chromatograph》, 2010,4.
RIPP Petrochemical Engineering Analysis method of the present invention is selected from《Petrochemical Engineering Analysis method (RIPP test methods)》,
Yang Cui is waited and compiled surely, Science Press, and 1990.
The property of the catalyst that embodiment and comparative example are used is listed in table 1, and raw 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.The catalyst of table 1 is by Sinopec Group's Shandong stone
Change company catalyst plant commercial production.
Embodiment 1
This example demonstrates that the method provided using the present invention is reduced aniline content in FCC gasoline, improves liquid receipts and gasoline
The situation of yield and reduction coke and heavy oil yield.
Catalytic cracking unit flow chart as shown in Figure 1, using fluidised bed adsorption reactor, raw oil (triumph vacuum 1st side cut
Oil or Liaohe River second line of distillation oil) the 350 DEG C of injection of Jing raw materials oil-in 4 fluidised bed adsorption reactor bottoms are preheated to, through settler
The reclaimable catalyst for carrying out gas solid separation enters reactor, raw oil and reclaimable catalyst from the top of fluidised bed adsorption reactor
Counter current contacting, absorption.Need to maintain bed density in fluidised bed adsorption reactor to be 420kg/m in adsorption process3.Adsorptive reactor
Interior reaction temperature is 400 DEG C, and oil ratio is 12, and pressure 0.3MPa, time of contact is 15s.
Raw oil after absorption carries out gas solid separation with reclaimable catalyst in fluidised bed adsorption reactor head.Absorption
The reclaimable catalyst of nitrogen-containing compound etc. into regenerator carries out coke burning regeneration, to recycle.Through the raw oil for adsorbing
After fluidised bed adsorption reactor head is separated with reclaimable catalyst, riser reactor is directly entered from bottom of the tube is lifted, with
The regenerated catalyst contact that regenerator comes, carries out catalytic cracking reaction.Reaction temperature in riser reactor is 500 DEG C, agent
Than being 8, pressure is 0.3MPa to oil, and the response time is 1.5s.Stripping of the reaction oil agent mixture through riser reactor top
Section and settler carry out gas solid separation, and the reaction oil gas separated deliver to subsequent product piece-rate system, and reclaimable catalyst is entered
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 the method provided using the present invention is reduced aniline content in FCC gasoline, improves liquid receipts and gasoline
The situation of yield and reduction coke and heavy oil yield.
Catalytic cracking unit flow chart as shown in Figure 2, using fluidised bed adsorption reactor, raw oil (triumph vacuum 1st side cut
Oil or Liaohe River second line of distillation oil) the 350 DEG C of injection of Jing raw materials oil-in 4 fluidised bed adsorption reactor bottoms are preheated to, through settler
The reclaimable catalyst for carrying out gas solid separation enters reactor, raw oil and reclaimable catalyst from the top of fluidised bed adsorption reactor
Counter current contacting, absorption.Need to maintain bed density in fluidised bed adsorption reactor to be 420kg/m in adsorption process3.Fluidised bed adsorption
Reactor interior reaction temperature is 400 DEG C, and oil ratio is 12, and pressure 0.3MPa, time of contact is 15s.
Raw oil after denitrogenation carries out gas solid separation with reclaimable catalyst in fluidised bed adsorption reactor head.Absorption
The reclaimable catalyst of the materials such as nitrogen-containing compound into regenerator carries out coke burning regeneration, to recycle.Through the original adsorbed
Material oil raw material oil-in 8 from after absorption enters riser reactor, and the regenerated catalyst come with regenerator is contacted, and is carried out catalysis and is split
Change reaction.Reaction temperature in riser reactor is 500 DEG C, and oil ratio is 8, and pressure is 0.3MPa, and the response time is 1.5s.
Stripping section and settler of the reaction oil agent mixture through riser reactor top carries out gas solid separation, the reaction separated
Oil gas delivers to subsequent product piece-rate 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 course of reaction, is adopted and embodiment identical riser reactor.It is real
It is identical with the experiment condition that embodiment is adopted 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 the operating result of the present invention is much better than Conventional catalytic cracking operating result.For nitrogen
The relatively low triumph first vacuum side stream of compound content, after the method for the present invention, liquid product yield improves 5.24%, yield of gasoline
9.92% is improve, and the content of Benzene In Gasoline amine reduces 82.23%, less than 5ppm.It is higher for nitrogen-containing compound content
Liaohe River second line of distillation oil, after the method for the present 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 relatively low triumph first vacuum side stream of compounds content, after the method for the present 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%, less than 5ppm.For nitrogen-containing compound content compared with
High Liaohe River second line of distillation oil, after the method for the present 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.
Relatively two kinds raw oils adopt the improvement and the drop of gasoline aniline content of products distribution after the method for the present invention
Poorly efficient fruit, the higher Liaohe River second line of distillation oil of nitrogen-containing compound content relatively wins first vacuum side stream effect more preferably, illustrates this method not only
The relatively low raw oil of nitrogen-containing compound can be processed so as to which catalytically cracked gasoline aniline content is greatly lowered, for nitrogen
The higher raw oil of compound, it reduces catalytically cracked gasoline aniline content and also achieves quite obvious effect, illustrates the present invention
Method also be adapted for processing the higher raw oil of nitrogen-containing compound content, reduce the content of aniline in its catalytically cracked gasoline.
The catalyst property of table 1
| Catalyst | A |
| Chemical composition, weight % | |
| Aluminium oxide | 49.5 |
| Sodium oxide | 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 |
The raw material oil nature of table 2
| 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 indexs | 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 |
The reaction condition of table 3
| 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 |
The experimental result of table 4
The experimental result of table 5
Claims (10)
1. a kind of catalyst cracking method, the method includes：
A, raw oil is contacted and carried out fluid catalytic cracking reaction with catalytic cracking catalyst, obtain product and to be generated urge
Agent；
B, by step a gained product be isolated to dry gas, liquefied gas, gasoline, diesel oil and heavy oil；By institute in step a
Obtain reclaimable catalyst to be regenerated, the regenerated catalyst for obtaining is returned in step a and used as the catalytic cracking catalyst；
Characterized in that, the raw oil is first contacted with gained reclaimable catalyst in step a in fluidised bed adsorption reactor
Adsorption reaction, and raw oil and absorption rear catalyst to be generated after being adsorbed Jing after gas solid separation are carried out, then after gained is adsorbed
Raw oil carries out fluid catalytic cracking reaction 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.
2. method according to claim 1, wherein, the raw oil is selected from gasoline, diesel oil, decompressed wax oil, residual oil, extracting
At least one in oil, recycle oil inferior, wax tailings, deasphalted oil, crude oil, shale oil and oil-sand.
3. method according to claim 1, wherein, the condition of the adsorption reaction is：Temperature is 200-500 DEG C, and oil ratio is
2-30, pressure is 0.1-0.5 MPa, and time of contact is the 2-30 seconds, and beds density is 100-700 kilograms per cubic meter.
4. method according to claim 1, wherein, the method also includes：The fuel oil preheating is entered again to after 100-400 DEG C
The row adsorption reaction.
5. method according to claim 1, wherein, the catalyst contains REY molecular sieves, Y type molecular sieve, HY molecular sieves, USY
At least one in the silica-rich zeolite of molecular sieve, RE-USY molecules, ZSM-5 molecular sieve and five-membered ring structure.
6. method according to claim 1, wherein, the condition of the fluid catalytic cracking reaction is：Temperature is 450-600 DEG C,
Oil ratio is 2-30, and pressure is 0.1-0.5 MPa, and time of contact is the 0.5-5 seconds.
7. a kind of catalytic cracking unit, it is characterised 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 raw oil after raw material oil-in (4), reclaimable catalyst entrance (5), absorption
Outlet (6) and absorption rear catalyst outlet (7) to be generated, in the fluidised bed adsorption reactor (3) gas-solid separator is provided with；Institute
State catalyst cracker (1) and be provided with raw material oil-in (8) after absorption, regenerated catalyst inlet (9), reclaimable catalyst outlet
And reacting product outlet (11) (10)；The catalytic cracking regenerator (2) be provided with it is to be generated absorption rear catalyst entrance (12) and
Regenerated catalyst outlet (13)；
Reclaimable catalyst outlet (10) of the catalyst cracker (1) is to be generated with the fluidised bed adsorption reactor (3)
Catalyst inlet (5) is connected, material oil outlet (6) and the catalytic cracking after the absorption of the fluidised bed adsorption reactor (3)
Raw material oil-in (8) connection, the absorption rear catalyst to be generated of the fluidised bed adsorption reactor (3) after the absorption of reactor (1)
Outlet (7) is connected with 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 with the regenerated catalyst inlet (9) of the catalyst cracker (1).
8. device according to claim 7, it is characterised in that the catalyst cracker (1) is anti-with the fluidised bed adsorption
Device (3) is answered for upper and lower integrally connected, and the catalyst cracker (1) is positioned at the fluidised bed adsorption reactor (3) top.
9. device according to claim 7, it is characterised in that the fluidised bed adsorption reactor (3), the catalytic cracking reaction
Device (1) is block form distribution with the catalytic cracking regenerator (2).
10. device according to claim 7, it is characterised in that the catalyst cracker (1) for riser reactor and/
Or fluidized-bed reactor.
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Citations (5)
| 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 |
| 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 |
| 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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- 2015-10-15 CN CN201510672014.2A patent/CN106590735B/en active Active
Patent Citations (5)
| 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 |
| 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 |
| 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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