CN102337154A - Method for catalytic conversion production of propylene and light aromatics - Google Patents
Method for catalytic conversion production of propylene and light aromatics Download PDFInfo
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- CN102337154A CN102337154A CN2010102336517A CN201010233651A CN102337154A CN 102337154 A CN102337154 A CN 102337154A CN 2010102336517 A CN2010102336517 A CN 2010102336517A CN 201010233651 A CN201010233651 A CN 201010233651A CN 102337154 A CN102337154 A CN 102337154A
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention provides a method for catalytic conversion production of propylene and light aromatics, which is characterized in that a hydrocarbon raw material and a catalytic cracking catalyst are contacted in a composite reactor for reacting under the catalytic cracking condition, the reaction products and the to-be-regenerated catalyst are separated, the separated to-be-regenerated catalyst is circularly used through stripping and performing coke burn-off regeneration, the separated reaction products is fractionated to obtain low carbon olefin, gasoline containing light aromatics and the like, and separated to obtain the light aromatics further; the composite reactor comprises a riser reactor and a fluidized bed reactor, an outlet of the riser reactor is communicated with a lower part of the fluidized bed reactor, a stripper is positioned at the lower part of the fluidized bed reactor, an upper part of the stripper is communicated with the bottom of the fluidized bed reactor, and the outlet of the fluidized bed reactor is communicated with the inlet of a gas solid separation device in a settler though a conveying pathway, a catalyst outlet of the settler is communicated with the lower part of the fluidized bed reactor. According to the invention, propylene and light aromatics enable high yield by using the method.
Description
Technical field
The present invention relates to a kind of catalysis conversion method of hydro carbons, more particularly, thereby relate to a kind of method that makes hydrocarbons raw oil catalytic cracking in combined reactor obtain propylene and light aromatic hydrocarbons with high productive rate.
Background technology
With ethene, propylene is that the low-carbon alkene of representative is basic raw material for chemical industry, many both at home and abroad with Sweet natural gas, low-density oil hydro carbons, adopts in the ethene machinery steam cracking process to produce low-carbon alkene.The second largest source of low-carbon alkene is catalytic cracking (FCC) device of refinery.Conventional catalytic cracking process also by-product low-carbon alkene when producing gasoline and solar oil, but its productive rate only accounts for below 15% of raw oil.It is predicted that in the period of 2010-2015, the propylene demand will be with annual rate 4.7% speed increment, nearly be doubled to demand in 2010.
Light aromatic hydrocarbons (benzene, toluene and YLENE) is widely used in synthon, synthetic resins, viton and various fine chemicals.It is predicted, in the period of 2010-2015, the average demand rate of increase of global benzene, toluene and YLENE with reach 4.4% respectively, 3-4% and 5.4%, and the same period, China will be up to 16%, 8.2% and 19.1% to the growth rate of demand of benzene, toluene and YLENE.At present, BTX is mainly derived from noble metal platinum reforming process and preparing ethylene by steam cracking technology.
Low-carbon alkene, light aromatic hydrocarbons production at present mainly with lighter hydrocarbons as raw material, but the shortage of raw material is serious day by day, so exploitation is raw material and the technological line of direct production low-carbon alkene and light aromatic hydrocarbons has become trend with heavy oil.
USP5, disclosed cracking hydrocarbon method adopts duo-lift tube reactor cracking hydrocarbon raw material of different nature in 009,769.Wax oil and residual oil inject first riser tube, cracking under agent-oil ratio 5～10, the condition of 1～4 second residence time; Straight-run spirit, straight run intermediate oil and catalysis heavy petrol inject second riser tube, cracking under agent-oil ratio 3～12, the condition of 1～5 second residence time.Two terminal entering in the same settling vessel of riser tube, and shared follow-up fractionating system.This method can be used for producing high aromatic hydrocarbons stop bracket gasoline and low-carbon (LC) hydro carbons.
Disclose a kind of among the CN1299403A by heavy hydrocarbon feedstocks selectivity production C
2～C
4The two-stage catalytic cracking process of alkene.This method comprises: in the presence of conventional large pore zeolite catalytic cracking catalyst, in first conversion zone of being made up of CCU, heavy feed stock is changed into than low-boiling products.Getting into by reaction zone, gas than the naphtha fraction in the low-boiling products of being generated carried in second conversion zone that district, catalyst regeneration zones and fractionation zone form; Under 500～600 ℃ of temperature, contact the formation crackate with containing the zeolite catalyst of about 10～50 heavy % mean pore sizes less than about 0.7 nanometer, wherein productivity of propylene is up to 16.8 heavy %.
Though above technology is obtaining apparent in view progress aspect the increase catalytic cracking productivity of propylene; But all mainly be to rely on the liquefied gas yield that improves catalytic cracking to improve propene yield; Owing to receive the restriction of drastic cracking, isomerizing, aromizing and hydrogen transfer reactions under the catalytic cracking reaction condition, its limitation that increases CCU propylene selectivity and productive rate is still very big.
Summary of the invention
The technical problem that the present invention solves provide a kind of with hydrocarbon raw material more the highly selective catalyzed conversion be the method for the light aromatic hydrocarbons of propylene coproduction simultaneously.
The catalysis conversion method of production propylene provided by the invention and light aromatic hydrocarbons comprises:
In the reactor drum of catalytic convention design; Hydrocarbon raw material contacts reaction under catalytic cracking condition with the catalyzer that contains modified beta zeolite; Reaction product isolated and reclaimable catalyst; Isolated reclaimable catalyst recycles behind stripping, coke burning regeneration, isolated reaction product through fractionation obtain low-carbon alkene, be rich in light aromatic type gasoline, diesel oil, heavy oil and other low molecule saturated hydrocarbons, be rich in light aromatic type gasoline through further obtaining light aromatic hydrocarbons behind unifining and the solvent extraction; Described catalytic convention design comprises compound reactor, settling vessel, stripper and catalyst regenerator; Wherein said compound reactor is made up of riser reactor and fluidized-bed reactor; The outlet of riser reactor and the bottom of fluidized-bed reactor are communicated with; Stripper is positioned at the below of fluidized-bed reactor; And stripper top directly is communicated with the bottom of fluidized-bed reactor, and the inlet of the settling vessel in the outlet of fluidized-bed reactor and the settling vessel is communicated with through carrying path, and the catalyst outlet of settling vessel is communicated with the catalyst transport path that passes through of fluidized-bed reactor bottom.
In context of the present invention, only if special explanation is arranged, term " low-carbon alkene " refers to that all C2～C4 alkene, " light aromatic hydrocarbons " all refer to benzene,toluene,xylene.
Production propylene provided by the invention with the beneficial effect of the catalysis conversion method of light aromatic hydrocarbons is:
Compare with existing hydro carbons catalyzed conversion; In the catalytic convention design that method provided by the invention is used; Owing to contain the segmentation cracking reaction of the compound reactor of riser reactor and fluidized-bed reactor, when under the situation that does not have hydrogen, raw oil being carried out catalytic cracking, can be with the low high productivity of low carbon olefin hydrocarbon of dry gas yied acquisition; Especially high productivity of propylene, the light aromatic hydrocarbons of coproduction simultaneously.Simultaneously, the technology flexibility ratio of catalytic convention design of the present invention, the catalyzer utilising efficiency is high, and the energy consumption reduction, and carrying capacity of environment also reduces.The present invention can use plurality of raw materials oil simultaneously, and the technology flexibility ratio of catalytic cracking is high, and raw oil is applied widely, but also can improve raw oil to the low-carbon alkene comprehensive transformation efficiency of propylene particularly, and the gasoline of light aromatic hydrocarbons is rich in coproduction simultaneously.
Description of drawings
Fig. 1 is the catalysis conversion method schematic flow sheet of production propylene provided by the invention and light aromatic hydrocarbons; Fig. 2 is the catalytic convention design schematic flow sheet that adopts in the Comparative Examples 1;
Wherein: 1-heavy oil cracking riser reactor; 2-service hoisting pipe reactor; The 3-fluidized-bed reactor; The 4-settling vessel; The 5-stripper; The 6-catalyst regenerator; 11,21-regenerated catalyst; 12,22-regenerated catalyst flowrate control valve; 13,23-raw oil feed nozzle; 14, the sparger of 24-riser reactor outlet; 31-fluidized-bed reactor outlet undergauge section; 32-fluidized-bed reactor outlet dilute phase pipe; The 41-primary cyclone; The 42-secondary cyclone; The catalyst transport path of 43-settling vessel to fluidized-bed reactor; 44-catalyst stream control valve; Baffle plate in the 51-stripper; 52-reclaimable catalyst transfer lime; 53-reclaimable catalyst flowrate control valve.
Embodiment
Method provided by the invention is to implement like this:
Catalytic convention design comprises compound reactor, settling vessel, stripper and catalyst regenerator; Wherein said compound reactor is made up of riser reactor and fluidized-bed reactor; The outlet of riser reactor and the bottom of fluidized-bed reactor are communicated with; Stripper is positioned at the below of fluidized-bed reactor; And stripper top directly is communicated with the bottom of fluidized-bed reactor, and the inlet of the outlet of fluidized-bed reactor through the interior separating device of dilute phase pipe and settling vessel be communicated with, and the catalyst outlet of settling vessel is communicated with the catalyst transport path that passes through of fluidized-bed reactor bottom.
In catalytic convention design; Heavier hydrocarbon feeds is through after being preheated to 200-400 ℃; Spray in the riser reactor of compound reactor with water vapour, with the regenerated catalyst contact reacts from the heat of revivifier, described catalyzer is the catalyzer that contains modified beta zeolite; Temperature of reaction is 480-620 ℃, preferred 500-600 ℃; Pressure is 0.15-0.3MPa, preferred 0.18-0.28MPa (absolute pressure), and the weight ratio of catalyzer and hydrocarbon raw material is 4-30, and the reaction times is 0.5-6s, preferred 1～4s.Reaction oil gas and catalyzer get into the fluidized-bed reactor bottom by the outlet of heavy oil cracking riser reactor; In fluidized-bed reactor, continue reaction; Reaction conditions is: temperature is 480-630 ℃, preferred 500-610 ℃, and the weight ratio of catalyzer and raw material is 4-30, and weight hourly space velocity is 0.2-30h
-1, preferred 0.5-20h
-1
In the catalysis conversion method provided by the invention, described compound reactor comprises fluidized-bed reactor and at least two riser reactors, and the outlet of riser reactor and the bottom of this fluidized-bed reactor are communicated with.
For effective controlling flow fluidized bed reactor interior reaction temperature; Improve catalyst activity; The preferred scheme of catalysis conversion method provided by the invention is that described compound reactor comprises at least two riser reactors; Wherein the heavy oil cracking riser reactor passes the inside of stripper and communicates with the fluidized-bed reactor bottom, and at least one service hoisting pipe reactor is positioned at the outside of said stripper.Regenerated catalyst is delivered to fluidized-bed reactor through regenerated catalyst line and service hoisting pipe reactor.In the service hoisting pipe reactor, reaction raw materials can be do not introduced, also the light oil reaction raw materials can be introduced.
The raw material nozzles that preferred scheme is light hydrocarbon feedstocks such as the C4 hydro carbons that is rich in alkene that later separation is obtained, petroleum naphtha component through the subsidiary riser reactor lower part sprays into the service hoisting pipe reactor; With contact, react by hot regenerated catalyst from the regenerated catalyst line, reaction oil gas and catalyzer get into the fluidized-bed reactor bottom by the outlet of service hoisting pipe reactor.The operational condition of service hoisting pipe reactor is: temperature is 520-680 ℃, preferred 540-650 ℃; Pressure is 0.15-0.3MPa, preferred 0.18-0.28MPa (absolute pressure); The weight ratio of catalyzer and light hydrocarbon feedstocks is 10-50, and the reaction times is 0.05-4s, preferred 0.1-3s.
Reaction product in heavy oil cracking riser reactor and the service hoisting pipe reactor and catalyzer get into fluidized-bed reactor; Wherein gasoline, diesel oil middle runnings continuation contact with catalyzer and carry out catalytic cracking reaction, and gasoline, diesel oil middle runnings highly selective are converted into low-carbon alkene particularly propylene, the light aromatic hydrocarbons of coproduction simultaneously.The dilute phase pipe of oil gas that is rich in low-carbon alkene, light aromatic hydrocarbons that generates and the catalyst fluidized bed outlet of carrying goes the gas-solid separation equipment of settling vessel to carry out gas solid separation; The settlement separate catalyzer that obtains returns the fluidized-bed reactor bottom by the catalyst transport pipeline, gets in the stripper then.
The reclaimable catalyst that stripper is carried through gas is introduced catalyst regenerator through the reclaimable catalyst pipeline and is carried out coke burning regeneration, and coke burning regeneration recovers active regenerated catalyst through the use of catalyst transport introducing riser reactor bottom cycle in the revivifier.
Isolated reaction oil gas leaves reactive system in the settling vessel, further separates, and obtains gas dry gas, liquefied gas, petroleum naphtha, is rich in light aromatic hydrocarbons heavy petrol, a small amount of diesel oil and heavy oil.The stripping technique that gas products is known by one of skill in the art obtains low-carbon alkenes such as propylene.Be rich in light aromatic type gasoline through further obtaining light aromatic hydrocarbons behind unifining and the solvent extraction.
In the catalysis conversion method provided by the invention, described settling vessel, fluidized-bed reactor and stripper are coaxial, described settling vessel be positioned at fluidized-bed reactor directly over, described stripper be positioned at fluidized-bed reactor under.
In the catalysis conversion method provided by the invention; The fluidized-bed reactor of the inlet of the gas-solid separation equipment in the outlet of described fluidized-bed reactor and the said settling vessel through undergauge exports the dilute phase pipe and is communicated with; Wherein, the diameter of the dilute phase pipe of undergauge is the 20-70% of the diameter of fluidized-bed reactor, preferred 30-50%.
In the catalysis conversion method provided by the invention, described hydrocarbon raw material is selected from C
4The mixture of one or more in hydro carbons, gasoline, diesel oil, hydrogenation tail oil, vacuum gas oil, crude oil, residual oil, liquefied coal coil, tar sand oil and the shale oil.
In the catalysis conversion method provided by the invention, the riser reactor in the described compound reactor be selected from the equal diameter riser reactor, etc. linear speed riser reactor and become in the diameter riser reactor one or more.Said fluidized-bed reactor is selected from one or more in particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor drum, fast bed reactor drum and the dense, fluidized bed bioreactor.
In the riser reactor of prior art; Carrying out along with cracking reaction; Carbon deposit on the catalyzer increases gradually, and its activity decreases, and catalyst concentration also reduces along with the increase of gas volume; Generally speaking, has only 30kg/m in the mass concentration of the second half section of riser reactor catalyzer
3About, simultaneously temperature of reaction also obviously descends, thereby middle runnings such as the gasoline that in riser tube, generates after the cracking of raw oil, diesel oil and uncracked raw oil are difficult to back segment at riser tube and further cracking take place and generate low-carbon alkene such as propylene.
In order to improve reaction later stage catalyst quality concentration; To improve the cracking heavy feedstocks productivity of low carbon olefin hydrocarbon; Method provided by the invention; After riser tube, be provided with fluidized-bed reactor, and the bottom of this fluidized-bed reactor is communicated with stripper, thereby the aperture of the reclaimable catalyst flowrate control valve that the reserve of fluidized-bed reactor inner catalyst can be through stripper is regulated.Gas superficial flow velocity in the riser reactor is generally at 6-30m/s; Gas superficial flow velocity in the fluidized-bed reactor is generally below 3m/s; Thereby for riser reactor, can keep higher catalyst concn in the fluidized-bed reactor, generally at 200kg/m
3More than.
In the catalysis conversion method provided by the invention; Catalytic cracking reaction takes place earlier in described heavy hydrocarbon oil raw material in the heavy oil cracking riser reactor; Device produces or in all the other service hoisting pipe reactors, catalytic cracking takes place from the outside C4-C8 lighter hydrocarbons that are rich in alkene of device simultaneously, and the catalyzer of simultaneously a small amount of carbon deposit is promoted to the bottom of fluidized-bed reactor.Through the operational throughput of control subsidiary riser catalyst reactor, can effectively regulate and control the temperature of reaction of fluidized-bed reactor, and activity of such catalysts.The intermediate product that is produced in two riser reactors gets into said fluidized-bed reactor and carries out further drastic cracking.Thus; Catalytic convention design of the present invention is through being provided with at least three relatively independent reaction zones; Make raw oil, be rich in the C4-C8 lighter hydrocarbons of alkene and the cracking of intermediates is carried out in different reaction zones, thereby be convenient to dissimilar reaction conditionss is carried out independent control and adjusting, further increase the technology flexibility ratio of catalytic cracking reaction; Can increase substantially the particularly productive rate of propylene of low-carbon alkene, the gasoline fraction of light aromatic hydrocarbons is rich in coproduction simultaneously.
In the method provided by the invention, the outlet of said fluidized-bed reactor is communicated with through the effected fluid of going into of the gas-solid separation equipment in dilute phase pipe and the said settling vessel.Preferred construction is that the dilute phase pipe of outlet through undergauge of fluidized-bed reactor is communicated with the inlet of the gas-solid separation equipment of settling vessel, and the exit end of said dilute phase pipe directly is communicated with the inlet of gas-solid separation equipment or be open near gas-solid separation equipment enters the mouth.Thereby adopt these preferred construction can make effusive material in the fluidized-bed reactor get into product and the sharp separation of reclaimable catalyst after the gas-solid separation equipment realization response fast; And shorten the residence time of oil gas in settling vessel; Thereby help suppressing to generate the again conversion reaction of propylene under hot environment; Suppress secondary reactions such as thermally splitting simultaneously, reach the purpose that reduces dry gas yied.
In the method provided by the invention, make stripper be positioned at the below of fluidized-bed reactor, and stripper is communicated with the bottom of fluidized-bed reactor.Thus, the water vapor of in stripper, supplying can be upwards obtains second stage employ through fluidized-bed reactor as the water filling steam of the catalytic cracking reaction that wherein takes place, and helps reducing the overall energy consumption of reaction.
In addition; Because stripper is communicated with the fluidized-bed reactor bottom; Therefore, through regulating the flowrate control valve of stripper to revivifier discharge reclaimable catalyst, the directly charge level of catalyzer in the controlling flow fluidized bed reactor; And then the weight hourly space velocity of controlling flow fluidized bed reactor internal reaction, can increase the technology flexibility ratio of catalytic cracking reaction thus.
In catalysis conversion method provided by the invention; For reducing oil gas dividing potential drop in the reactor drum; In the process of carrying out said catalytic cracking reaction, can in said reactor drum, inject the thinner that is selected from water vapour, nitrogen and C1～C4 alkane, carbonic acid gas, carbon monoxide etc.; Wherein, the preferably water steam, and the weight ratio of water vapour and hydrocarbon raw material is preferably 0.01～1: 1.
In the catalysis conversion method provided by the invention, be benchmark with the gross weight of catalyzer, the said catalyzer that contains modified beta molecular sieve contains 1～60% molecular sieve mixture, 5～99% heat-resistant inorganic oxide and 0～70% clay.Gross weight with said molecular sieve mixture is a benchmark, contain in the said molecular sieve mixture 1%～75% by the beta-molecular sieve of phosphorus and transition metal M modification, 25%～99% molecular sieve with MFI structure.
In the catalysis conversion method provided by the invention, be benchmark with the total catalyst weight, said catalyzer preferably contains 10%～50% zeolite mixture, 10%～70% heat-resistant inorganic oxide and 0～60% clay.
Described modified beta molecular sieve is the β zeolite by phosphorus and transition metal M modification; Can adopt the whole bag of tricks to prepare; Such as in the process of synthetic β zeolite, introducing phosphorus and said transition metal M, perhaps behind synthetic β zeolite, adopt steps such as ammonium exchange, phosphorus modification, said transition metal M modification and calcination process to introduce phosphorus and said transition metal M.Described transition metal M is selected from one or more among Fe, Co, Ni and the Cu, more preferably Fe and/or Cu.
The zeolite of the described MFI of having structure is the supersiliceous zeolite with pentasil structure, preferred ZSM-5 and/or ZRP series zeolite.The zeolite of the said MFI of having structure can adopt commercially available article, also can adopt the whole bag of tricks well known in the art to prepare, and does not give unnecessary details at this.
Described heat-resistant inorganic oxide is selected from SiO
2And/or Al
2O
3Said clay is selected from kaolin and/or halloysite.
In the catalysis conversion method provided by the invention, the gasoline fraction that is rich in light aromatic hydrocarbons obtains aromatic hydrocarbon products such as benzene,toluene,xylene through after the unifining through solvent extraction.Said gasoline selective unifining, extracting can be adopted prior art well known to those skilled in the art.
The full cut of gasoline that is rich in aromatic hydrocarbons can be cut into light gasoline fraction and the heavy naphtha that is rich in aromatic hydrocarbons, and cut point is 70～85 ℃.Light gasoline fraction that obtains after the cutting and/or C4 hydro carbons can return the further cracking of service hoisting pipe reactor.Heavy naphtha that will obtain after the full cut of gasoline that is rich in aromatic hydrocarbons maybe will cut and hydrogenation catalyst, contacted with hydrogen are at hydrogen dividing potential drop 2.0-15.0MPa, temperature of reaction 200-400 ℃, hydrogen to oil volume ratio 100-1000v/v, volume space velocity 0.5-5h
-1Condition under, wherein alkene is saturated, remove impurity such as sulphur, nitrogen simultaneously, obtain being rich in the refining heavy petrol of light aromatic hydrocarbons.
Wherein, said hydrogenation catalyst is VIB and/or the VIII family non-precious metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium, and said VIB base metal is selected from Mo or/and W, and VIII family base metal is selected from Co or/and Ni.Require this catalyzer to possess high-selective and hydrogenating saturated activity and denitrogenation, desulphurizing activated.Preferred hydrogenation catalyst is to be made up of one or more group vib metals of one or more group VIII metals of the heavy % additive of 0-10, the heavy % of 1-9, the heavy % of 12-39 and surplus aluminum oxide and/or amorphous silicon aluminium carrier, and wherein said additive is selected from non-metallic element and metallic elements such as fluorine, phosphorus, titanium.
Gasoline fraction after the unifining contacts with solvent, and at temperature 80-120 ℃, extracting under the condition of the volume ratio 2-6 between solvent and the treated gasoline obtains benzene,toluene,xylene.The solvent of solvent extraction is selected from tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, DMSO 99.8MIN. and the N-formyl morpholine ether one or more mixed solvent.Recycle after the solvent recuperation.
Below in conjunction with accompanying drawing method provided by the present invention is further explained, but therefore do not limited the present invention.
Fig. 1 is a preferred scheme of the production propylene provided by the invention and the catalysis conversion method of light aromatic hydrocarbons.As shown in Figure 1, described catalytic convention design comprises compound reactor, settling vessel 4, stripper 5 and catalyst regenerator 6.Described compound reactor is made up of heavy oil riser reactor 1, service hoisting pipe reactor 2 and fluidized-bed reactor 3.Wherein, settling vessel, fluidized-bed reactor, stripper arranged in co-axial alignment, settling vessel is on the top of fluidized-bed reactor, and stripper 5 is positioned at the below of fluidized-bed reactor 3, and said stripper 5 tops directly are communicated with the bottom of fluidized-bed reactor 3.The inlet of the settling vessel in the outlet of fluidized-bed reactor 3 and the settling vessel 4 is communicated with through carrying path 32, and the catalyst outlet of settling vessel is communicated with through catalyst transport path 43 with the bottom of fluidized-bed reactor 3.The optional position, bottom of the outlet of heavy oil riser reactor, service hoisting pipe reactor and fluidized-bed reactor is communicated with.
Following embodiment will further explain present method, but therefore not limit the present invention.
Effect when catalysis conversion method provided by the invention is adopted in embodiment 1-3 explanation.
Embodiment 1
The trade names of employed catalyzer are DMMC-1, are produced by Shandong catalyzer branch office of ltd of China Petrochemical Industry.The medium-sized tester of use shown in accompanying drawing 1, wherein the internal diameter of heavy oil riser reactor is 18 millimeters, highly is 6 meters, and the fluidized-bed reactor internal diameter is 64 millimeters, highly is 0.5 meter, and the internal diameter of service hoisting pipe reactor is 16 millimeters, highly is 5 meters.The undergauge ratio of fluidized-bed reactor outlet dilute phase pipe is 30%.Catalyzer is at 800 ℃, and with 100% steam aging 10 hours, the loading amount of catalyzer was 60 kilograms in the compound reactor.
The heavy hydrocarbon oil raw material is introduced the contact of heavy oil cracking riser reactor catalyst neutralisation carry out catalytic cracking reaction; Do not introduce hydrocarbon oil crude material in the service hoisting pipe reactor, be the catalyst transport passage.The heavy hydrocarbon oil raw material properties is seen table 1, and catalyzer is formed and character is seen table 3, and reaction conditions and productive rate are seen table 4.
Comparative Examples 1
Comparative Examples 1 is explained the effect when adopting riser tube to add fluidized-bed reactor carries out heavy hydrocarbon oil catalytic material method for transformation.The medium-sized tester that Comparative Examples adopts is seen shown in the accompanying drawing 2.Wherein the internal diameter of riser reactor is 18 millimeters, 6 meters of height, and 64 millimeters of fluidized-bed reactor internal diameters, 0.5 meter of height, the heavy hydrocarbon oil raw material properties is seen table 1, operation condition and result see table 4.
Table 1 raw material oil properties
Table 2
| Petroleum naphtha group composition (wt%) | ? |
| Alkane | 30 |
| Alkene | 63 |
| |
3 |
| |
2 |
| Diolefine and |
2 |
| C4 forms (wt%) | ? |
| Alkene | 65 |
| Alkane | 33 |
| Diolefine and |
2 |
Table 3 catalyzer is formed:
| Trade names | DMMC-1 |
| Form: | ? |
| Modified beta molecular sieve | 10％ |
| The ZSM-5 molecular sieve | 20％ |
| Aluminum oxide) | 20％ |
| Clay | 50％ |
[0064]Table 4
Visible by table 4; Compare with Comparative Examples; The productivity of propylene that method provided by the invention obtains improves 2.4-5.1 percentage point; Light aromatics yield improves 1.6-3 percentage point, at the catalysis conversion method that adopts production propylene of the present invention with light aromatic hydrocarbons, and can also the light aromatic hydrocarbons of coproduction when obtaining high productivity of propylene.
Claims (14)
1. catalysis conversion method of producing propylene and light aromatic hydrocarbons comprises:
In the reactor drum of catalytic convention design; Hydrocarbon raw material contacts reaction under catalytic cracking condition with the catalyzer that contains modified beta zeolite; Reaction product isolated and reclaimable catalyst; Isolated reclaimable catalyst recycles behind stripping, coke burning regeneration, and isolated reaction product obtains low-carbon alkene, is rich in gasoline, diesel oil, heavy oil and other low molecule saturated hydrocarbons of light aromatic hydrocarbons through fractionation, and the gasoline that is rich in light aromatic hydrocarbons is through further obtaining light aromatic hydrocarbons behind unifining and the solvent extraction; It is characterized in that described catalytic convention design comprises compound reactor, settling vessel, stripper and catalyst regenerator; Described compound reactor is made up of riser reactor and fluidized-bed reactor; Wherein, The outlet of riser reactor and the bottom of fluidized-bed reactor are communicated with, and stripper is positioned at the below of fluidized-bed reactor, and stripper top directly is communicated with the bottom of fluidized-bed reactor; The inlet of the gas-solid separation equipment in the outlet of fluidized-bed reactor and the settling vessel is communicated with through carrying path, and the catalyst outlet of settling vessel is communicated with the catalyst transport path that passes through of fluidized-bed reactor bottom.
2. according to the catalysis conversion method of claim 1, it is characterized in that in the catalytic convention design that described fluidized-bed reactor outlet is communicated with through the carrying path of undergauge and the inlet of the gas-solid separation equipment in the settling vessel.
3. according to the catalysis conversion method of claim 2, it is characterized in that the diameter of the undergauge carrying path of said fluidized-bed reactor outlet is the 20-70% of the diameter of fluidized-bed reactor.
4. according to the catalysis conversion method of claim 1; It is characterized in that in the catalytic convention design; Described settling vessel, fluidized-bed reactor and stripper are coaxial, described settling vessel be positioned at fluidized-bed reactor directly over, described stripper be positioned at fluidized-bed reactor under.
5. according to claim 1,2 or 3 catalysis conversion method; It is characterized in that in the catalytic convention design; Described compound reactor comprises at least two riser reactors; Wherein the heavy oil cracking riser reactor passes the inside of stripper and communicates with the fluidized-bed reactor bottom, and at least one auxiliary cracking riser reactor is positioned at the outside of said stripper.
6. according to the catalysis conversion method of claim, it is characterized in that at least one said transfer lime catalyst stream control valve being installed in the catalytic convention design.
7. according to the method for claim 1, it is characterized in that described hydrocarbon raw material is selected from C
4The mixture of one or more in hydro carbons, gasoline, diesel oil, hydrogenation tail oil, vacuum gas oil, crude oil, residual oil, liquefied coal coil, tar sand oil and the shale oil.
8. according to the method for claim 1, it is characterized in that in the operational condition of said heavy oil riser reactor being: temperature of reaction is 480-620 ℃, and the absolute pressure of reaction zone is 0.15-0.3MPa, and agent-oil ratio is 5-20, and the reaction times of said raw material is 0.1-6 second.
9. according to the method for claim 1, it is characterized in that the operational condition in the auxiliary cracking riser reactor is: temperature of reaction is 520-680 ℃, and the absolute pressure of reaction zone is 0.15-0.3MPa, and agent-oil ratio is 10-50, and the reaction times of said raw material is 0.05-4 second.
10. according to the method for claim 1, it is characterized in that the operational condition in the said fluidized-bed reactor is: temperature of reaction is 480-630 ℃, and the absolute pressure of reaction zone is 0.15-0.3MPa, and the weight hourly space velocity of said raw material is 0.2-30h
-1
11. method according to claim 1; It is characterized in that in the process of reaction, in said riser reactor, injecting thinner; Reducing the dividing potential drop of said raw material, wherein said thinner is selected from one or more the mixture in water vapor, low-carbon alkanes and the nitrogen.
12., it is characterized in that said thinner is a water vapor, and the weight ratio of said water vapor and said raw material is 0.01-2: 1 according to the method for claim 11.
13. according to the method for claim 1, it is characterized in that the gross weight with catalyzer is a benchmark, the said catalyzer that contains modified beta molecular sieve contains the molecular sieve mixture of 1-60%, the heat-resistant inorganic oxide of 5-99% and the clay of 0-70%; Gross weight with said molecular sieve mixture is a benchmark, contain in the said molecular sieve mixture 1-75% by the beta-molecular sieve of phosphorus and transition metal M modification, the molecular sieve of 25-99% with MFI structure.
14. according to the method for claim 13, the molecular sieve that it is characterized in that the said MFI of having structure is ZSM-5 and/or ZRP molecular sieve.
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