CN101161786B - Conversion method for petroleum hydrocarbons - Google Patents
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Abstract
A transformation method for petroleum hydrocarbons includes the following steps: hot regenerated catalyst is returned to the bottom of a reactor after cooling down and is conveyed to the bottom of the first reaction zone of the reactor by pre-lifting gas so as to contact preheated base oil for cracking reaction; the mixture of reaction products, water vapor and catalyst enters into a diameter-expanded second reaction zone for further hydrocarbon transformation reaction with the reaction products, water vapor and spent catalyst undergoing gal-solid separation; gas phase products are separated to obtain various products; in addition, the spent catalyst is conveyed to a regenerator after steam stripping for recycling use after singeing regeneration or part of the spent catalyst directly enters into the mixer arranged at the bottom of the reactor. The method which adopts a reactor riser with two reaction zones improves the contact state of base oil and catalyst through lowering oil contact temperature so as to increase the yield and the selectivity of object reactant and to improve the properties of object product.
Description
Technical field
The invention belongs to the catalyst cracking method of hydrocarbon ils under the situation that does not have hydrogen, more particularly, is to belong to the method that petroleum hydrocarbon contacts and transforms with catalyzer.
Background technology
FCC is in contact with one another in fluidized-bed or riser reactor through petroleum hydrocarbon and catalyzer and realizes.Along with the carrying out of cracking reaction, generate a large amount of sedimentation of coke and on catalyzer, form reclaimable catalyst, reclaimable catalyst is circulated to revivifier; At high temperature with the air catalytic combustion; Burn the back and form regenerated catalyst, regenerated catalyst is Returning reactor again, continues to react with fresh feed oil again.The fluidized circulation of catalyzer can be realized through all gases medium.
Although fluid catalytic cracking process is comparatively ripe, people still endeavour to seek new technology with improve the quality of products, yield and selectivity.At present rather noticeable mainly is two aspects: the one, and the recovery of adsorption production on the reclaimable catalyst; The 2nd, the mixing of catalytically cracked stock and regenerated catalyst.Reclaim the yield that product can directly improve product from reclaimable catalyst, the optimization of catalytically cracked stock and catalyzer mixes the yield and the selectivity that then can improve product.
The method that reclaims the adsorption production on the reclaimable catalyst is exactly the lighter hydrocarbons product on the stripping reclaimable catalyst more fully.Complete steam stripped ordinary method is exactly to improve the temperature of the reclaimable catalyst in the stripper.And the temperature of reclaimable catalyst improves the method that can adopt indirect heat exchange, also can in stripper, reclaimable catalyst be mixed with the pyritous regenerated catalyst mutually.US 3,821,103 disclosed with US 2,451,619 be exactly back a kind of method.The stripping reclaimable catalyst recovery that both can improve hydrocarbon product more fully can also improve the thermal equilibrium of fluidized catalystic cracker, thereby because the intact hydrocarbon of stripping burn in revivifier and can influence thermal equilibrium by a large amount of waste heat of generation.
Realize that through the equipment that changes existing apparatus raw oil and the well-mixed method of catalyzer are a lot.US 5,017, and 343 is exactly an exemplary device, and it mainly improves the mixing of raw oil and catalyzer through the dispersion that improves raw oil.US 4,960, and 503 through increasing the mixing that a plurality of nozzles improve raw oil and catalyzer in riser reactor.Although these methods have been improved the distribution of raw oil in regenerated catalyst, when small number of materials oil contacts with a large amount of catalyzer, will cause the skewness of moment, thereby cause non-selective cracking to increase the weight of, dry gas yied generates too much.Local temperature distributing disproportionation when reducing raw oil and catalyst mix, US 4,960, and 503 have adopted the method with raw oil and thermocatalyst indirect heat exchange, but this method causes the interchanger green coke again easily.
At present, because catalytically cracked stock becomes heavy day by day, thereby coke yield also increases considerably, and this just makes the temperature control of revivifier become complicated more.On the one hand; The heavy % in coke content on the raw oil cracking general requirement preferably catalyzer＜0.1; Be preferably＜0.05 heavy %, this just requires to provide excessive air and higher regeneration temperature, generates CO but air excess and too high regeneration temperature can make the CO of generation continue reaction again
2, further generate a large amount of waste heats, and the revivifier heat remove on the one hand discharging through stack gas; Mainly still take away through regenerated catalyst; Therefore this just will increase the temperature difference of revivifier and reactor drum, and in order to keep the internal circulating load that temperature of reactor just is necessary to reduce catalyzer, and the catalyst recirculation amount reduces the transformation efficiency that can reduce hydrocarbon; And just must improve temperature of reactor, thereby cause product distribution and quality to change to some extent in order to keep transformation efficiency.Certainly, water cooler that can be through catalyzer (catalyzer is turned back to revivifier from the taking-up of revivifier through cooling again) reduces the interdependent property of catalyst recirculation amount between reactor drum and revivifier, but this method is limited by regeneration temperature and thermal equilibrium also.
Countries in the world improve constantly the requirement to motor spirit fuel oil meter lattice for strengthen environmental protection, the production of clean fuel has become the theme of current petroleum refining industry.It is the cooked mode of core that China petroleum refining industry has progressively formed with the catalytic cracking for many years, and FCC gasoline is the main blending component of China's gasoline pool, causes olefin(e) centent to be higher than the clean gasoline standard thus.How reducing content of olefin in gasoline and keeping gasoline octane rating is one of severe challenge of facing of current FCC technology.But, because the ideal conditions of the lighting reaction of heavy fcc raw material and gasoline upgrading reaction is inequality,, same riser tube is difficult to take into account in reacting, this has just proposed demand that conventional catalyst cracking technology is carried out technological innovation.
CN1078094C adopts a kind of riser reactor of fluidized catalytic conversion, and being provides a kind of can suitably increase the secondary reaction time on the basis of existing catalytic cracking technology, can be used for the novel riser reactor of two section feedings again.This reactor drum vertically be followed successively by co-axial each other pre lift zone, first reaction zone, enlarged-diameter from bottom to up second reaction zone, reduced outlet area, at the outlet area end one level pipe is arranged.It is different with the processing condition of second reaction zone that this reactor drum both can have been controlled first reaction zone, can make the raw oil of different performance carry out the segmentation cracking again, obtains required purpose product.Use during gasoline is formed behind this reactor drum olefin(e) centent can reduce to below the 30 heavy %.
CN1076751C discloses a kind of reactor drum and has comprised two reaction zones, and first reaction zone of its middle and lower part is a pyrolysis reaction zone, and 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, has reduced the content of alkene during gasoline is formed.
CN1137959C discloses the mode of catalyst make-up to second reaction zone bottom; Catalyzer to strengthen in the riser reactor contacts with raw material; Thereby improve the character of purpose product; The catalyzer that is replenished can be a reclaimable catalyst, and fresh catalyzer is or/and refrigerative regenerated catalyst or half regenerated catalyst.
In above-mentioned prior art, also can not accomplish both to have improved products distribution, reduce the content of alkene in the gasoline composition simultaneously again.
Summary of the invention
The objective of the invention is on existing technical foundation, to provide a kind of method for transformation of petroleum hydrocarbon, with productive rate, selectivity that improves the purpose product and the character of improving the purpose product.
The objective of the invention is to reach through following proposal: the regenerated catalyst of heat is through cooling; Turn back to reactor bottom; Be transported to the bottom of reactor drum first reaction zone by preparatory lift gas; Contact with the raw oil of preheating and carry out cracking reaction, hydrocarbon conversion reactions further takes place in second reaction zone that reaction product, water vapor and mixture of catalysts get into hole enlargement, and reaction product, water vapor and reclaimable catalyst carry out gas solid separation; Gas-phase product obtains various products after separating, reclaimable catalyst recycles after revivifier carries out coke burning regeneration or the direct mixing tank that gets into reactor bottom of part through being transported to behind the stripping.
Concrete operations step of the present invention is following: with temperature is that hot regenerated catalyst about 700 ℃ is cooled to 580 ℃～670 ℃; Be preferably 600 ℃～650 ℃, be transported to the riser reactor first reaction zone bottom, contact with the raw oil of preheating and react by preparatory lift gas; Catalyzer and raw oil weight ratio (hereinafter to be referred as agent-oil ratio) are 5～40; Be preferably 6～30,0.2～2.5 second reaction times, 530 ℃～600 ℃ of temperature of reaction.The mixture of the reclaimable catalyst of band coke is delivered directly to riser reactor second reaction zone of hole enlargement after reaction product, water vapor and the reaction; Hydrocarbon conversion reactions will further take place in reaction oil gas on the catalyzer of band coke; Agent-oil ratio is 5～40; Be preferably 6～30,2.0～20 seconds reaction times, 460 ℃～530 ℃ of temperature of reaction.Reaction product, water vapor, reclaimable catalyst carry out gas solid separation through cyclonic separator, and gaseous product gets into separation column separates heavy component such as slurry oil, recycle stock and light component gasoline, diesel oil etc.And reclaimable catalyst is introduced into stripper, and the water steam stripped goes out the hydrocarbon product that adsorbs on the catalyzer, returns revivifier through the reclaimable catalyst inclined tube again, carries out in the presence of oxygen-containing gas that coke burning regeneration recycles or part directly gets into mixing tank.
The type of cooling of regenerated catalyst of heat can be that hot regenerated catalyst mixes with the low temperature reclaimable catalyst and cools off, and also can hot regenerated catalyst be cooled to required temperature through water cooler.
The type of cooling of the hot regenerated catalyst that the present invention is used is to be that 700 ℃ hot regenerated catalyst and temperature is that 480 ℃～530 ℃ reclaimable catalyst mixes at the catalyst mix device fully with temperature; " mixed catalyst " of formation temperature homogeneous; Hot regenerated catalyst with the ratio of reclaimable catalyst be 0.5～6.0, be preferably 1.0～4.0, the mixture temperature is 580 ℃～670 ℃; Be preferably 600 ℃～650 ℃; In order to make hot regenerated catalyst and to treat coldly living catalyzer contact heat transfer better, mixing tank is kept close operation mutually, and density requirements is greater than 160kg/m
3, be preferably 320～600kg/m
3The fluidized gas that gets into mixing tank is generally inert material, and its superficial gas velocity is 0.06～0.9m/s.Be that through water cooler hot regenerated catalyst to be cooled to temperature be 580 ℃～670 ℃ for 700 ℃ hot regenerated catalyst perhaps with temperature; Be preferably 600 ℃～650 ℃; In order to make hot regenerated catalyst and heat-obtaining medium contact heat transfer better; Catalyzer in the water cooler is kept close operation mutually, and density requirements is greater than 160kg/m
3, be preferably 320～600kg/m
3The superficial gas velocity that gets into the fluidized gas of water cooler is 0.06～0.9m/s.
The used raw material of the present invention is selected from conventional catalytically cracked material or/and gasoline stocks, and conventional catalytically cracked material is selected from the mixture of one or more (comprising two kinds) in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum, the long residuum; Gasoline stocks is selected from straight-run spirit, coker gasoline, visbreaking gasoline, hydrofined gasoline, hydrogen cracking gasoline, reforming raffinate oil, be rich in the mixture of one or more (comprising two kinds) in the catalytically cracked gasoline of alkene.
The catalyzer that the present invention is suitable for can be that active ingredient is selected from a kind of, two or three the catalyzer in Y or HY type zeolite, the ultrastable Y that contains or do not contain rare earth, the ZSM-5 series zeolite that contains or do not contain rare earth or the supersiliceous zeolite with five-membered ring structure, β zeolite, the ferrierite, also can be the amorphous silicon aluminium catalyzer.
The used reactor drum of the present invention is riser tube or the fluidized-bed reactor with two reaction zones.The detailed description of relevant two reaction zones is consulted CN1078094C.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for transformation embodiment one of petroleum hydrocarbon provided by the invention.
Fig. 2 is the schematic flow sheet of the method for transformation embodiment two of petroleum hydrocarbon provided by the invention.
Embodiment
Specify method provided by the invention with two kinds of embodiments below, but method provided by the invention is not limited to following two kinds of embodiments.
One of embodiment:
For the CCU of single riser reactor, need newly-built mixing tank, a riser reactor to be provided with two spent agent outlets with two reaction zones.The stripping stage of mixing tank sizableness in CCU; Coaxial with riser tube; Place the bottom of riser tube; Mixing tank and riser tube mode of connection have two kinds, and a kind of mode is that the riser tube bottom is connected with mixer outlet, between the inlet of the raw oil on mixing tank middle and upper part and the riser tube, catalyst distributor can be set; Another kind of mode is that insert in the mixing tank dense-phase catalyst riser tube bottom, between riser tube bottom and the raw oil inlet catalyst distributor can be set.
Get into revivifier regeneration through steam stripped spent agent, the catalyzer after the regeneration gets into degassing vessel, removes the flue gas that regenerated catalyst is carried secretly; Regenerated catalyst is gone into mixing tank through regenerator sloped tube then, and in the catalyst mix device, mixes the catalyzer of formation temperature homogeneous fully from another strand of stripping stage reclaimable catalyst; Deliver to the bottom of riser tube first reaction zone again by delivery conduit; With the raw materials mix reaction that is got into by nozzle, reaction oil gas and mixture of catalysts get into second reaction zone through first reaction zone hydrocarbon conversion reactions further take place, and reaction product and spent agent carry out gas solid separation through cyclonic separator; Oil gas gets into fractionating system; Reclaimable catalyst gets into stripper, and reclaimable catalyst is divided into two-way behind the stripping, and one road reclaimable catalyst gets into the revivifier reprocessing cycle through inclined tube to be generated and uses; Another road reclaimable catalyst gets into the catalyst mix device through circulation inclined tube to be generated, to reduce the temperature of hot regenerated catalyst.
Two of embodiment:
CCU for single riser reactor with two reaction zones; Get into revivifier regeneration through steam stripped spent agent through inclined tube to be generated, the catalyzer after the regeneration gets into degassing vessel, removes the flue gas that regenerated catalyst is carried secretly; Hot regenerated catalyst gets into the water cooler cooling then; Cooled regenerated catalyst gets into the bottom of riser tube first reaction zone and the raw materials mix reaction that is got into by nozzle through regenerator sloped tube, and reaction oil gas and mixture of catalysts get into second reaction zone through first reaction zone hydrocarbon conversion reactions further takes place; Reaction product and spent agent carry out gas solid separation through cyclonic separator; Oil gas gets into fractionating system, and reclaimable catalyst gets into stripping stage, and stripping is after inclined tube to be generated gets into the use of revivifier reprocessing cycle.
Below in conjunction with accompanying drawing method provided by the present invention is further explained.
Fig. 1～2 illustrate the flow process of first to two kind of embodiment of the contact method of petroleum hydrocarbon and catalyzer respectively, and the shape and size of equipment and pipeline do not receive the restriction of accompanying drawing, but confirm as the case may be.
Fig. 1～2 are respectively the schematic flow sheet of first kind, second kind embodiment of the contact method of petroleum hydrocarbon and catalyzer, and each numbering explanation as follows among the figure: 1,2,12,14,19,20,24 all represent pipeline; 3 is riser reactor first reaction zone, and 23 is riser reactor second reaction zone, and 4 is stripper, and 5 is settling vessel; 6 is inclined tube to be generated, and 7 is guiding valve to be generated, and 8 and 9 are respectively first and second revivifier, and 10 is inclined tube to be generated; 11 is guiding valve to be generated, and 13 is degassing vessel, and 15 is the regenerated catalyst guiding valve, and 16 is the regenerated catalyst inclined tube; 17 is half regenerated catalyst guiding valve, and 18 is half regenerated catalyst inclined tube, and 21 is the catalyst mix jar; 22 is catalyst distributor, and 25 is water cooler, and 26 is the cooled catalyst inclined tube.
As shown in Figure 1, the flow process of first kind of embodiment is following:
From the reclaimable catalyst of stripper 4 successively through spent agent inclined tube 10, guiding valve to be generated 11, spent agent inclined tube 10; Get into 21 mixing of catalyst mix device through regenerated catalyst inclined tube 16, regenerated catalyst guiding valve 15, regenerated catalyst inclined tube 16 successively with regenerated catalyst from degassing vessel 13; Promote medium in advance and get into catalyst mix jar 21 through pipeline 1; Promoting mixed catalyst can be distributed by catalyst distributor 22; Or directly getting into riser tube first reaction zone 3 bottoms, the conventional cracking stock oil of preheating gets into riser tubes first reaction zone 3 through pipeline 2, contacts with the blended catalyzer and reacts; Reaction oil gas and mixture of catalysts get into second reaction zone 23 through first reaction zone 3 hydrocarbon conversion reactions further take place, and reacted oil gas and spent agent get into settling vessel 5 and carry out gas solid separation.Oil gas gets into fractionating system through pipeline 24; Reclaimable catalyst gets into stripper 4; Reclaimable catalyst is divided into two-way behind the stripping, and one road reclaimable catalyst gets into catalyst mix devices 21 through circulation inclined tube to be generated 10, guiding valve to be generated 11, circulation inclined tube to be generated 10 successively, to reduce the temperature of hot regenerated catalyst.Another road reclaimable catalyst gets into first revivifier 8 through spent agent inclined tube 6, guiding valve to be generated 7, spent agent inclined tube 6 successively and carries out incomplete regen-eration; Get into second revivifier 9 and carry out holomorphosis through half regenerated catalyst inclined tube 18, half regenerated catalyst guiding valve 17, half regenerated catalyst inclined tube 18 successively then; The regenerated catalyst of heat gets into degassing vessel 13 through pipeline 12; The flue gas of carrying secretly between the regenerated catalyst stripping particle; Regenerated catalyst behind the stripping gets into mixing tank 21 through regenerated catalyst inclined tube 16, regenerated catalyst guiding valve 15, regenerated catalyst inclined tube 16 successively; Form mixed catalyst and supply reaction cycle to use with mixing from the reclaimable catalyst of stripper through spent agent inclined tube 10; All the other catalyzer and fluidized gas are returned second revivifier 9 through pipeline 14, and air gets into first revivifier 8 and second revivifier 9 through pipeline 19, and flue gas goes out first revivifier 8 and second revivifier 9 through pipeline 20.
As shown in Figure 2, the flow process of second kind of embodiment is following:
The refrigerative regenerated catalyst gets into the bottom of riser tube first reaction zone 3 through regenerator sloped tube 26; Promote medium in advance and get into riser tube first reaction zone 3 bottoms through pipeline 1; Promote catalyzer and get into riser tube first reaction zone 3; The conventional cracking stock oil of preheating gets into riser tube first reaction zone 3 through pipeline 2; Contact with the refrigerative catalyzer and react, reaction oil gas and mixture of catalysts get into second reaction zone 23 through first reaction zone 3 hydrocarbon conversion reactions further take place, and reacted oil gas carries out gas solid separation with spent agent entering settling vessel 5.Oil gas gets into fractionating system through pipeline 24; Reclaimable catalyst gets into stripper 4; Get into first revivifier 8 through spent agent inclined tube 6, guiding valve to be generated 7, spent agent inclined tube 6 successively behind the stripping and carry out incomplete regen-eration; Get into second revivifier 9 then and carry out holomorphosis, the regenerated catalyst of heat gets into the flue gas of carrying secretly between the degassing vessel 13 regenerated catalyst stripping particles through pipeline 12, and the regenerated catalyst behind the stripping gets into water cooler 25 coolings through regenerated catalyst inclined tube 16, regenerated catalyst guiding valve 15, regenerated catalyst inclined tube 16 successively; Cooled regenerated catalyst supplies reaction cycle to use; All the other catalyzer and fluidized gas are returned second revivifier 9 through pipeline 14, and air gets into first revivifier and second revivifier through pipeline 19, and flue gas goes out revivifier 9 through pipeline 20.
The invention has the advantages that:
1, the present invention adopts the riser reactor with two reaction zones, through reducing finish contact temperature, improves the contact condition of raw oil and catalyzer, thus productive rate, the selectivity of raising purpose reactant and improve the character of purpose product.
2, the present invention is provided with heat collector on the regenerator transfer line; Reduced regenerated catalyst temperature; Can take what of heat away through control; Regulate the temperature of regenerated catalyst, so just can regulate and control temperature of reaction and needed agent-oil ratio independently, improved the concentration of riser reactor inner catalyst.
3, the present invention is provided with a catalyst mix device in the riser tube bottom, regulates regenerator and the ratio of spent agent in mixture, can regulate the activity of such catalysts that gets into riser reactor.
4, the present invention can guarantee that regeneration temperature is constant and be in ideal value, regenerated catalyst has under the prerequisite of good regeneration effect, regulates the temperature of regenerated catalyst.
5, use the present invention, do not influence other technological use.
Following embodiment will further specify the present invention, but therefore not limit the present invention.Employed catalyzer of embodiment and raw material oil properties are listed in table 1 and table 2 respectively.Catalyzer in the table 1 is produced by China PetroChemical Corporation's Shandong catalyst plant.
Embodiment 1
Method provided by the invention is adopted in the present embodiment explanation, and straight-run gas oil adopts the resulting product distribution situation of different operating conditions on kitty cracker.
The kitty cracker schema is as shown in Figure 1, and listed raw oil M is a raw material with table 2, and preheating material oil M is in pipeline 2 injecting lift pipe reactors; Contact with the mixed catalyst of the listed catalyst A of table 1; Mixture is by 490 ℃ of reclaimable catalysts and 700 ℃ of regenerated catalysts, forms by 0.1: 1 mixed, and be 515 ℃ in the riser reactor first reaction zone temperature of reaction; Reactor head pressure is 0.2 MPa, and the reaction times is 1.2 seconds; The second reaction zone temperature of reaction is 500 ℃, and the reaction times is 4 seconds.The device agent-oil ratio is 9.6: 1.Reaction product, steam and reclaimable catalyst separate in settling vessel; Reaction product isolated obtains gaseous product and product liquid; And reclaimable catalyst gets into stripper, goes out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping, and reclaimable catalyst is divided into two-way behind the stripping; One road reclaimable catalyst gets into the catalyst mix device through circulation inclined tube to be generated, to reduce the temperature of hot regenerated catalyst; Another road reclaimable catalyst enters into first revivifier through inclined tube to be generated; Contact with the warm air that heated and to carry out incomplete regen-eration; Obtaining carbon content is half regenerated catalyst of 0.3 heavy %; This half regenerated catalyst gets into second revivifier and carries out holomorphosis, turns back to the catalyst mix device then and mixes with reclaimable catalyst.The character of test conditions, test-results and gasoline is listed in table 3.
Comparative Examples 1
Compare with embodiment 1, this Comparative Examples does not have the catalyst mix device in riser reactor first reaction zone bottom, does not have regenerated catalyst cooling or regenerated catalyst and reclaimable catalyst mixing and other steps yet.Other situation is basic identical.
Adopt conventional kitty cracker; Promoting 700 ℃ of regenerated catalyst A of steam lifting in advance and contact with the listed preheating material oil M of table 2, is 515 ℃ in the riser reactor first reaction zone temperature of reaction, and reactor head pressure is 0.2 MPa; Reaction times is 1.2 seconds; The second reaction zone temperature of reaction is 500 ℃, and in 4 seconds reaction times, agent-oil ratio is to carry out catalytic cracking reaction under 6: 1 the condition.Reaction product, steam and reclaimable catalyst separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst gets into stripper, is gone out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping.Catalyzer behind the stripping enters into first revivifier, contacts with the warm air that heated and carries out incomplete regen-eration, gets into second revivifier then and carries out holomorphosis, and the catalyzer after the regeneration turns back to the riser tube bottom.The character of test conditions, test-results and gasoline is listed in table 3.
Can find out from table 3; Embodiment 1 is not after riser reactor first reaction zone bottom has the catalyst mix device; Regenerated catalyst is mixed with reclaimable catalyst, and after reducing the temperature of regenerated catalyst, dry gas and coke yield reduce; The productive rate of gasoline and liquefied gas obviously improves, and olefin content in gasoline significantly reduces.
Embodiment 2
Method provided by the invention is adopted in the present embodiment explanation, and long residuum is response situation on kitty cracker.
The kitty cracker schema is as shown in Figure 2; Listed raw oil N is a raw material with table 2, and preheating material oil N is in pipeline 2 injecting lift pipe reactors, and the catalyst B listed with table 1 contacts; Catalyst B after the regeneration is 650 ℃ a cooling regenerated catalyst; In the riser reactor first reaction zone temperature of reaction is 515 ℃, and reactor head pressure is 0.2 MPa, and the reaction times is 1.2 seconds; The second reaction zone temperature of reaction is 500 ℃, and the reaction times is to carry out catalytic conversion reaction under 4 seconds the condition.Reaction product, steam and reclaimable catalyst separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst gets into stripper, is gone out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping.Catalyzer behind the stripping enters into first revivifier; Contact with the warm air that heated and to carry out incomplete regen-eration; Obtaining carbon content is half regenerated catalyst of 0.3 heavy %; This half regenerated catalyst gets into that second revivifier carries out holomorphosis after cooling recycling is used, and the character of test conditions, test-results and gasoline is listed in table 4.
Comparative Examples 2
Compare with embodiment 2, the riser reactor of this Comparative Examples is conventional riser tube, has only the single reaction district, does not also have steps such as regenerated catalyst cooling.Other situation is basic identical.
Adopt conventional kitty cracker; Promoting in advance steam promotes 700 ℃ of regenerated catalysts and contacts with raw oil N with the listed preheating of table 2; In temperature of reaction is 500 ℃; Reactor head pressure is 0.2 MPa, and the reaction times is 2 seconds, and agent-oil ratio is to carry out catalytic conversion reaction under 6: 1 the condition.Reaction product, steam and reclaimable catalyst separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst gets into stripper, is gone out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping.Catalyzer behind the stripping enters into first revivifier, contacts with the warm air that heated and carries out incomplete regen-eration, and the combustion back gets into second revivifier and carries out holomorphosis, and the catalyzer after the regeneration turns back to the riser tube bottom.The character of test conditions, test-results and gasoline is listed in table 4.
Can find out that from table 4 embodiment 2 adopts the riser reactor with two reaction zones, and reduce the temperature of regenerated catalyst, dry gas and coke yield reduce, and the productive rate of gasoline and liquefied gas obviously improves, and olefin content in gasoline significantly reduces.
Table 1
| The catalyzer numbering | A | B |
| Trade names | CGP-1 | ZCM-7 |
| Zeolite type | Y+MFI | USY |
| Chemical constitution, heavy % | ||
| Aluminum oxide | 56.3 | 46.4 |
| Sodium oxide | 0.19 | 0.22 |
| Red stone | 0.32 | |
| Apparent density, kilogram/rice 3 | 0.62 | 690 |
| Pore volume, milliliter/gram | 0.151 | 0.38 |
| Specific surface area, rice 2/ gram | 145 | 164 |
| Abrasion index is when weighing % -1 | 1.5 | - |
| Size composition, heavy % | ||
| 0～40 micron | 13.1 | 4.8 |
| 40～80 microns | 54.9 | 47.9 |
| ＞80 microns | 32.0 | 47.3 |
Table 2
| The raw oil numbering | M | N |
| Density (20 ℃), kilogram/rice 3 | 874.6 | 897.4 |
| Kinematic viscosity, millimeter 2/ second | ||
| 80℃ | 8.88 | 54.20 |
| 100℃ | 30.02 | |
| Carbon residue, heavy % | 0.07 | 4.5 |
| Sulphur, ppm | 4400 | 1400 |
| Nitrogen, ppm | 1200 | 2700 |
| Carbon, heavy % | 86.28 | 86.26 |
| Hydrogen, heavy % | 12.97 | 12.91 |
| Boiling range, ℃ | ||
| Over point | 303 | 324 |
| 10％ | 365 | 322 |
| 30％ | 404 | 486 |
| 50％ | 427 | - |
| 70％ | 478 | - |
| 90％ | 492 | - |
Table 3
| Scheme | Embodiment 1 | Comparative Examples 1 |
| Reactor drum | Double-reaction area | Double-reaction area |
| Preheating temperature, ℃ | 190 | 190 |
| Temperature of reaction, ℃ first reaction zone, second reaction zone | 515 500 | 515 500 |
| Reaction times, second first reaction zone, second reaction zone | 1.2 4 | 1.2 4 |
| Regeneration temperature, ℃ | 700 | 700 |
| Mixed regeneration agent temperature, ℃ | 630 | |
| Agent-oil ratio | 9.6 | 6 |
| WOR | 0.03 | 0.03 |
| Product distributes, heavy % | ||
| Dry gas | 0.72 | 1.33 |
| Liquefied gas | 17.43 | 16.61 |
| Gasoline | 50.86 | 46.86 |
| Solar oil | 23.06 | 23.44 |
| Heavy gas oil | 6.18 | 8.88 |
| Coke | 1.75 | 2.88 |
| Gasoline property | ||
| RON | 91.4 | 90.2 |
| MON | 80.8 | 79.7 |
| Sulphur, ppm | 250 | 400 |
| Nitrogen, ppm | 0.4 | 0.8 |
| Aromatic hydrocarbons, heavy % | 26.0 | 23.68 |
| Alkene, heavy % | 11.9 | 28.11 |
| Alkane, heavy % | 54.9 | 41.01 |
| Normal paraffin | 5.2 | 5.01 |
| Isoparaffin | 49.7 | 36.00 |
| Naphthenic hydrocarbon, heavy % | 7.2 | 7.2 |
Table 4
| Scheme | Embodiment 2 | Comparative Examples 2 |
| Reactor drum | Double-reaction area | Conventional riser tube |
| Preheating temperature, ℃ | 200 | 200 |
| Temperature of reaction, ℃ first reaction zone, second reaction zone | 515 500 | 500 |
| Reaction times, second first reaction zone, second reaction zone | 1.0 4 | 3.5 |
| Regeneration temperature, ℃ | 700/650 | 700 |
| Agent-oil ratio | 7.0 | 4 |
| WOR | 0.03 | 0.03 |
| Product distributes, heavy % | ||
| Dry gas | 0.94 | 1.62 |
| Liquefied gas | 17.59 | 12.88 |
| Gasoline | 48.08 | 40.07 |
| Solar oil | 20.97 | 20.81 |
| Heavy gas oil | 6.44 | 17.76 |
| Coke | 5.98 | 6.86 |
| Gasoline property | ||
| RON | 90.9 | 90.0 |
| MON | 80.0 | 79.9 |
| Sulphur, ppm | 80 | 132 |
| Nitrogen, ppm | 0.7 | 1.0 |
| Aromatic hydrocarbons, heavy % | 26.4 | 21.2 |
| Alkene, heavy % | 13.4 | 46.49 |
| Alkane, heavy % | 52.9 | 25.81 |
| Normal paraffin | 5.1 | 4.98 |
| Isoparaffin | 47.8 | 20.83 |
| Naphthenic hydrocarbon, heavy % | 7.3 | 6.50 |
Claims (10)
1. the method for transformation of a petroleum hydrocarbon; The regenerated catalyst that it is characterized in that heat turns back to reactor bottom through cooling; Be transported to the bottom of reactor drum first reaction zone by preparatory lift gas; Contact with the raw oil of preheating and carry out cracking reaction; Hydrocarbon conversion reactions further takes place in second reaction zone that reaction product, water vapor and mixture of catalysts get into hole enlargement, and reaction product, water vapor and reclaimable catalyst carry out gas solid separation, and gas-phase product obtains various products after separating; Reclaimable catalyst recycles after revivifier carries out coke burning regeneration or the direct mixing tank that gets into reactor bottom of part through being transported to behind the stripping; Regenerated catalyst and the temperature of heat is that 480 ℃～530 ℃ reclaimable catalyst mixes in this mixing tank by weight 0.5～6.0, and the temperature of mixed catalyst is 580 ℃～670 ℃, and the interior density of mixing tank is 160～600kg/m
3, superficial gas velocity is 0.06～0.9m/s.
2. according to the method for claim 1; It is characterized in that said raw material is selected from conventional catalytically cracked material or/and gasoline stocks, conventional catalytically cracked material is selected from one or more the mixture in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum, the long residuum; Gasoline stocks is selected from straight-run spirit, coker gasoline, visbreaking gasoline, hydrofined gasoline, hydrogen cracking gasoline, reforming raffinate oil, be rich in one or more the mixture in the catalytically cracked gasoline of alkene.
3. according to the method for claim 1; It is characterized in that said catalyzer is that active ingredient is selected from a kind of, two or three the catalyzer in Y or HY type zeolite, the ultrastable Y that contains or do not contain rare earth, the ZSM-5 series zeolite that contains or do not contain rare earth or the supersiliceous zeolite with five-membered ring structure, β zeolite, the ferrierite, or the amorphous silicon aluminium catalyzer.
4. according to the method for claim 1, it is characterized in that said catalyzer is the amorphous silicon aluminium catalyzer.
5. according to the method for claim 1, it is characterized in that said reactor drum is riser tube or the fluidized-bed reactor with two reaction zones.
6. according to the method for claim 1, it is characterized in that the condition of first reaction zone is: 530 ℃～600 ℃ of temperature of reaction, in 0.2～2.5 second reaction times, catalyzer and raw oil weight ratio are 5～40.
7. according to the method for claim 1, it is characterized in that the condition of second reaction zone is: 460 ℃～530 ℃ of temperature of reaction, in 2.0～20 seconds reaction times, catalyzer and raw oil weight ratio are 5～40.
8. according to the method for claim 1, it is characterized in that the regenerated catalyst of heat and reclaimable catalyst that temperature is 480 ℃～530 ℃ mix by weight 1.0～4.0, the temperature of mixed catalyst is 600 ℃～650 ℃.
9. according to the method for claim 1, it is characterized in that the regenerated catalyst of heat will through water cooler
Hot regenerated catalyst is cooled to 580 ℃～670 ℃.
10. according to the method for claim 1, it is characterized in that density is 320～600kg/m in the mixing tank
3
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