CN101161786A - 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
Fluid catalytic cracking is in contact with one another in fluidized-bed or riser reactor by 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 by 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 completely.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 mutually with the pyritous regenerated catalyst.US 3,821,103 and US 2,451,619 disclosed be exactly a kind of method in back.More complete stripping reclaimable catalyst both can improve the recovery of hydrocarbon product, can also improve the thermal equilibrium of fluidized catalytic cracker, thereby because the intact hydrocarbon of stripping does not burn in revivifier and can influence thermal equilibrium by a large amount of waste heat of generation.
Realize that by the equipment that changes existing apparatus stock 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 stock oil and catalyzer by the dispersion that improves stock oil.US 4,960, and 503 by increasing the mixing that a plurality of nozzles improve stock oil and catalyzer in riser reactor.Although these methods have been improved the distribution of stock oil in regenerated catalyst, when a small amount of stock 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 stock oil and catalyst mix, US 4,960, and 503 have adopted the method with stock 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 stock 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
2Further generate a large amount of waste heats, and the revivifier heat remove on the one hand discharging by stack gas, mainly still take away by regenerated catalyst, therefore this just will increase the temperature difference of revivifier and reactor, 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 by catalyzer (catalyzer is turned back to revivifier from the taking-up of revivifier again through cooling) reduces the interdependent property of catalyst recirculation amount between reactor 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 for many years with the catalytic cracking, 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, in same riser tube reaction, being difficult to take into account, 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 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 both can have been controlled first reaction zone, can make the stock oil of different performance carry out the segmentation cracking again, obtains required purpose product.Use during gasoline is formed behind this reactor olefin(e) centent can reduce to below the 30 heavy %.
CN1076751C discloses a kind of reactor and has comprised two reaction zones, first reaction zone of its middle and lower part is a pyrolysis reaction zone, temperature of reaction is higher, residence time of material is shorter, and second reaction zone on top is the secondary reaction district, and the temperature of reaction in this district is lower, and residence time of material is longer, material carries out alkylated reaction and hydrogen transfer reactions, has reduced the content of alkene during gasoline is formed.
CN1137959C discloses the mode of catalyst make-up to second reaction zone bottom, contact with raw material with the catalyzer of strengthening in the riser reactor, 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 by following proposal: the regenerated catalyst of heat is through cooling, turn back to reactor bottom, be transported to the bottom of reactor first reaction zone by pre-lift gas, contact with the stock oil of preheating and carry out cracking reaction, reaction product, hydrocarbon conversion reactions further takes place in second reaction zone that water vapor and mixture of catalysts enter hole enlargement, reaction product, water vapor and reclaimable catalyst carry out gas solid separation, gas-phase product obtains various products after separating, reclaimable catalyst is through being transported to the mixing tank that recycles after revivifier carries out coke burning regeneration or partly directly enter reactor bottom behind the stripping.
Concrete operations step of the present invention is as follows: 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 by pre-lift gas, contact with the stock oil of preheating and react, catalyzer and stock 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 by cyclonic separator, and gaseous product enters 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 enters 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 by 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 fully at the catalyst mix device with temperature, " mixed catalyst " of formation temperature homogeneous, hot regenerated catalyst with and 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 enters mixing tank is generally inert material, and its superficial gas velocity is 0.06～0.9m/s.Perhaps be that by water cooler hot regenerated catalyst to be cooled to temperature be 580 ℃～670 ℃ for 700 ℃ hot regenerated catalyst 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 enters 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, hydrocracking 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 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 catalytic cracking unit 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 catalytic cracking unit, coaxial with riser tube, place the bottom of riser tube, mixing tank and riser tube mode of connection have two kinds, a kind of mode is that the riser tube bottom is connected with mixer outlet, between the inlet of the stock 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 stock oil inlet catalyst distributor can be set.
Enter revivifier regeneration through steam stripped spent agent, catalyzer after the regeneration enters degassing vessel, remove the flue gas that regenerated catalyst is carried secretly, regenerated catalyst is gone into mixing tank through regenerator sloped tube then, with mix fully in the catalyst mix device from another strand of stripping stage reclaimable catalyst, the catalyzer of formation temperature homogeneous, deliver to the bottom of riser tube first reaction zone again by delivery conduit, with the raw material hybrid reaction that enters by nozzle, reaction oil gas and mixture of catalysts enter second reaction zone through first reaction zone hydrocarbon conversion reactions further take place, reaction product and spent agent carry out gas solid separation through cyclonic separator, oil gas enters fractionating system, reclaimable catalyst enters stripper, reclaimable catalyst is divided into two-way behind the stripping, one road reclaimable catalyst enters the revivifier reprocessing cycle through inclined tube to be generated and uses, and another road reclaimable catalyst enters the catalyst mix device through circulation inclined tube to be generated, to reduce the temperature of hot regenerated catalyst.
Two of embodiment:
Catalytic cracking unit for single riser reactor with two reaction zones, enter revivifier regeneration through steam stripped spent agent through inclined tube to be generated, catalyzer after the regeneration enters degassing vessel, remove the flue gas that regenerated catalyst is carried secretly, hot regenerated catalyst enters the water cooler cooling then, cooled regenerated catalyst enters the bottom of riser tube first reaction zone through regenerator sloped tube, with the raw material hybrid reaction that enters by nozzle, reaction oil gas and mixture of catalysts enter second reaction zone through first reaction zone hydrocarbon conversion reactions further take place, reaction product and spent agent carry out gas solid separation through cyclonic separator, oil gas enters fractionating system, reclaimable catalyst enters stripping stage, and stripping is after inclined tube to be generated enters the use of revivifier reprocessing cycle.
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction.
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 are not subjected to the restriction of accompanying drawing, but determine 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 is described as follows among the figure: 1,2,12,14,19,20,24 all represent pipeline; 3 is riser reactor first reaction zone, 23 is riser reactor second reaction zone, 4 is stripper, 5 is settling vessel, and 6 is inclined tube to be generated, and 7 is guiding valve to be generated, 8 and 9 are respectively first and second revivifier, 10 is inclined tube to be generated, and 11 is guiding valve to be generated, and 13 is degassing vessel, 15 is the regenerated catalyst guiding valve, 16 is the regenerated catalyst inclined tube, and 17 is half regenerated catalyst guiding valve, and 18 is half regenerated catalyst inclined tube, 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 as follows:
From the reclaimable catalyst of stripper 4 successively through spent agent inclined tube 10, guiding valve 11 to be generated, spent agent inclined tube 10, with from the regenerated catalyst of degassing vessel 13 successively through regenerated catalyst inclined tube 16, regenerated catalyst guiding valve 15, regenerated catalyst inclined tube 16 enters catalyst mix device 21 to be mixed, the pre-medium that promotes enters catalyst mix jar 21 through pipeline 1, promoting mixed catalyst can be distributed by catalyst distributor 22, or directly enter riser tube first reaction zone 3 bottoms, the conventional cracking stock oil of preheating enters riser tube first reaction zone 3 through pipeline 2, contact with the blended catalyzer and react, reaction oil gas and mixture of catalysts enter second reaction zone 23 through first reaction zone 3 hydrocarbon conversion reactions further take place, and reacted oil gas and spent agent enter settling vessel 5 and carry out gas solid separation.Oil gas enters fractionating system through pipeline 24, reclaimable catalyst enters stripper 4, reclaimable catalyst is divided into two-way behind the stripping, and one road reclaimable catalyst enters catalyst mix device 21 through circulation inclined tube 10 to be generated, guiding valve to be generated 11, circulation inclined tube 10 to be generated successively, to reduce the temperature of hot regenerated catalyst.Another road reclaimable catalyst is successively through spent agent inclined tube 6, guiding valve 7 to be generated, spent agent inclined tube 6 enters first revivifier 8 and carries out incomplete regen-eration, then successively through half regenerated catalyst inclined tube 18, half regenerated catalyst guiding valve 17, half regenerated catalyst inclined tube 18 enters second revivifier 9 and carries out holomorphosis, the regenerated catalyst of heat enters degassing vessel 13 through pipeline 12, the flue gas of carrying secretly between the regenerated catalyst stripping particle, regenerated catalyst behind the stripping is successively through regenerated catalyst inclined tube 16, regenerated catalyst guiding valve 15, regenerated catalyst inclined tube 16 enters mixing tank 21, form mixed catalyst and use with mixing from the reclaimable catalyst of stripper for reaction cycle through spent agent inclined tube 10, all the other catalyzer and fluidized gas are returned second revivifier 9 through pipeline 14, air enters 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 as follows:
The refrigerative regenerated catalyst enters the bottom of riser tube first reaction zone 3 through regenerator sloped tube 26, the pre-medium that promotes enters riser tube first reaction zone 3 bottoms through pipeline 1, promote catalyzer and enter riser tube first reaction zone 3, the conventional cracking stock oil of preheating enters riser tube first reaction zone 3 through pipeline 2, contact with the refrigerative catalyzer and react, reaction oil gas and mixture of catalysts enter second reaction zone 23 through first reaction zone 3 hydrocarbon conversion reactions further take place, and reacted oil gas and spent agent enter settling vessel 5 and carry out gas solid separation.Oil gas enters fractionating system through pipeline 24, reclaimable catalyst enters stripper 4, behind the stripping successively through spent agent inclined tube 6, guiding valve 7 to be generated, spent agent inclined tube 6 enters first revivifier 8 and carries out incomplete regen-eration, enter second revivifier 9 then and carry out holomorphosis, the regenerated catalyst of heat enters the flue gas of carrying secretly between the degassing vessel 13 regenerated catalyst stripping particles through pipeline 12, regenerated catalyst behind the stripping is successively through regenerated catalyst inclined tube 16, regenerated catalyst guiding valve 15, regenerated catalyst inclined tube 16 enters water cooler 25 coolings, cooled regenerated catalyst is used for reaction cycle, all the other catalyzer and fluidized gas are returned second revivifier 9 through pipeline 14, air enters 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, by reducing finish contact temperature, improves the contact condition of stock oil and catalyzer, thereby improves productive rate, the selectivity of 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 by control, regulate the temperature of regenerated catalyst, so just, can regulate and control temperature of reaction and needed agent-oil ratio independently, improve 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 enters 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 the use of other technology.
The following examples will be further specified the present invention, but not thereby limiting the 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 operational conditions on kitty cracker.
The kitty cracker schema as shown in Figure 1, listed stock oil M is a raw material with table 2, 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 enters stripper, go out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping, reclaimable catalyst is divided into two-way behind the stripping, one road reclaimable catalyst enters 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 enters 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 steps such as reclaimable catalyst mixes yet.Other situation is basic identical.
Adopt conventional kitty cracker, the pre-steam that promotes promotes the listed oily M of preheating material of 700 ℃ of regenerated catalyst A and table 2 and contacts, in the riser reactor first reaction zone temperature of reaction is 515 ℃, 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 enters 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, enters 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.
As can be seen 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.
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 as shown in Figure 2, listed stock oil N is a raw material with table 2, preheating material oil N is in pipeline 2 injecting lift pipe reactors, 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 ℃, reactor head pressure is 0.2 MPa, 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 enters 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 enters that second revivifier carries out holomorphosis after cooling recirculation 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, the pre-steam that promotes promotes 700 ℃ of regenerated catalysts and contacts with stock oil N with the listed preheating of table 2, in temperature of reaction is 500 ℃, reactor head pressure is 0.2 MPa, 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 enters 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, enters second revivifier after the combustion 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.
As can be seen from Table 4, embodiment 2 adopts the riser reactor with two reaction zones, and reduces the temperature of regenerated catalyst, and 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 |
| Ferric oxide | 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 stock 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, ℃ | ||
| Initial boiling point | 303 | 324 |
| 10％ | 365 | 322 |
| 30％ | 404 | 486 |
| 50％ | 427 | - |
| 70％ | 478 | - |
| 90％ | 492 | - |
Table 3
| Scheme | Embodiment 1 | Comparative Examples 1 |
| Reactor | 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 |
| Water-oil ratio | 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
| | Embodiment | 2 | Comparative Examples 2 |
| Reactor | 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 | |
| Water-oil ratio | 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 first reaction zone by pre-lift gas, contact with the stock oil of preheating and carry out cracking reaction, reaction product, hydrocarbon conversion reactions further takes place in second reaction zone that water vapor and mixture of catalysts enter hole enlargement, reaction product, water vapor and reclaimable catalyst carry out gas solid separation, gas-phase product obtains various products after separating, reclaimable catalyst is through being transported to the mixing tank that recycles after revivifier carries out coke burning regeneration or partly directly enter reactor bottom behind the stripping.
2. according to the method for claim 1, it is characterized in that described 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, hydrocracking 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 described 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, also can be the amorphous silicon aluminium catalyzer.
4. according to the method for claim 1, it is characterized in that described catalyzer is the amorphous silicon aluminium catalyzer.
5. according to the method for claim 1, it is characterized in that described reactor 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 stock 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 stock oil weight ratio are 5～40.
8. according to the method for claim 1, the regenerated catalyst that it is characterized in that heat and temperature are that 480 ℃～530 ℃ reclaimable catalyst 0.5～6.0 mixes by weight, and the temperature of mixed catalyst is 580 ℃～670 ℃.
9. according to the method for claim 1 or 8, the regenerated catalyst that it is characterized in that heat and temperature are that 480 ℃～530 ℃ reclaimable catalyst 1.0～4.0 mixes by weight, and the temperature of mixed catalyst is 600 ℃～650 ℃.
10. according to the method for claim 1, it is characterized in that the regenerated catalyst of heat is cooled to 580 ℃～670 ℃ by water cooler with hot regenerated catalyst.
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