CN102337154B - Method for catalytic conversion production of propylene and light aromatics - Google Patents
Method for catalytic conversion production of propylene and light aromatics Download PDFInfo
- Publication number
- CN102337154B CN102337154B CN201010233651.7A CN201010233651A CN102337154B CN 102337154 B CN102337154 B CN 102337154B CN 201010233651 A CN201010233651 A CN 201010233651A CN 102337154 B CN102337154 B CN 102337154B
- Authority
- CN
- China
- Prior art keywords
- bed reactor
- fluidized
- reactor
- oil
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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
Taking ethene, propylene as the low-carbon alkene of representative is the most basic industrial chemicals, both at home and abroad mainly with Sweet natural gas, low-density oil hydro carbons, adopt steam cracking process in Ethylene Complex unit 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 in producing gasoline and solar oil, but its productive rate only accounts for below 15% of stock oil.It is predicted, between 2010-2015, propylene demand will be with annual rate 4.7% speed increment, is nearly doubled to demand in 2010.
Light aromatic hydrocarbons (benzene, toluene and dimethylbenzene) is widely used in synthon, synthetic resins, synthetic rubber and various fine chemicals.It is predicted, between 2010-2015, the average demand rate of increase of global benzene, toluene and dimethylbenzene by reaching respectively 4.4%, 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 dimethylbenzene.At present, BTX is mainly derived from noble metal platinum reforming process and preparing ethylene by steam cracking technique.
Low-carbon alkene, light aromatic hydrocarbons are produced mainly using lighter hydrocarbons as raw material at present, but the shortage of raw material is day by day serious, so exploitation has become trend taking heavy oil as raw material direct production low-carbon alkene with the technological line of light aromatic hydrocarbons.
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 riser tube ends enter in same settling vessel, and share follow-up fractionating system.The method can be used for producing high aromatic hydrocarbons stop bracket gasoline and low-carbon (LC) hydro carbons.
In CN1299403A, disclose a kind of by heavy hydrocarbon feedstocks selectivity production C
2～C
4the two-stage catalytic cracking process of alkene.The method comprises: under conventional large pore zeolite catalytic cracking catalyst exists, in the first conversion zone being made up of catalytic cracking unit, heavy feed stock is changed into compared with low-boiling products.The generated naphtha fraction compared with in low-boiling products is entered in the second conversion zone being formed by reaction zone, air lift district, catalyst regeneration zones and fractionation zone, at 500～600 DEG C of temperature, contact and form crackate with the zeolite catalyst that is less than approximately 0.7 nanometer containing approximately 10～50 heavy % mean pore sizes, wherein productivity of propylene is up to 16.8 heavy %.
Although above technology has obtained obvious progress in increase catalytic cracking propylene yield aspects, but be mainly all to rely on the liquefied gas yield that improves catalytic cracking to improve propene yield, owing to being subject to the restriction of drastic cracking, isomerization, aromizing and hydrogen transfer reactions under catalytic cracking reaction condition, its limitation that increases catalytic cracking unit Propylene Selectivity and productive rate is still very large.
Summary of the invention
The technical problem that the present invention solves be to provide a kind of by hydrocarbon raw material more highly selective be catalytically conveted to the simultaneously method of the light aromatic hydrocarbons of coproduction of propylene.
The catalysis conversion method of production propylene provided by the invention and light aromatic hydrocarbons, comprising:
In the reactor of catalytic convention design, hydrocarbon raw material contacts under catalytic cracking condition and reacts with the catalyzer that contains modified beta zeolite, reaction product isolated and reclaimable catalyst, isolated reclaimable catalyst recycles after 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 after hydrofining and 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 is directly communicated with the bottom of fluidized-bed reactor, and the outlet of fluidized-bed reactor is communicated with by carrying path with the entrance of the settling vessel in settling vessel, the catalyst outlet of settling vessel is communicated with the catalyst transport path that passes through of fluidized-bed reactor bottom.
In the context of the invention, unless there is special explanation, term " low-carbon alkene " all refers to that C2～C4 alkene, " light aromatic hydrocarbons " all refer to benzene,toluene,xylene.
The beneficial effect of the catalysis conversion method of production propylene provided by the invention and light aromatic hydrocarbons is:
Compared with existing hydrocarbons catalytic conversion, in the catalytic convention design that method provided by the invention is used, due to the segmentation cracking reaction of the compound reactor that contains riser reactor and fluidized-bed reactor, while stock oil being carried out to catalytic cracking in the situation that not there is not hydrogen, can obtain high productivity of low carbon olefin hydrocarbon with low dry gas yied, especially high productivity of propylene, the light aromatic hydrocarbons of coproduction simultaneously.Meanwhile, the technique flexibility ratio of catalytic convention design of the present invention, catalyzer utilising efficiency is high, and Energy Intensity Reduction, and carrying capacity of environment also reduces.The present invention can use plurality of raw materials oil simultaneously, and the technique flexibility ratio of catalytic cracking is high, and stock oil is applied widely, but also can improve stock oil to the particularly comprehensive transformation efficiency of propylene of low-carbon alkene, and the gasoline of light aromatic hydrocarbons is rich in coproduction simultaneously.
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 adopting in comparative example 1;
Wherein: 1-heavy oil cracking riser reactor; 2-auxiliary riser line reactor; 3-fluidized-bed reactor; 4-settling vessel; 5-stripper; 6-catalyst regenerator; 11,21-regenerated catalyst; 12,22-regenerated catalyst flowrate control valve; 13,23-stock 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; 41-primary cyclone; 42-secondary cyclone; 43-settling vessel is to the catalyst transport path of fluidized-bed reactor; 44-catalyst stream control valve; Baffle plate in 51-stripper; 52-reclaimable catalyst transfer lime; 53-reclaimable catalyst flowrate control valve.
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 is directly communicated with the bottom of fluidized-bed reactor, and the outlet of fluidized-bed reactor is communicated with the entrance of the separating device in settling vessel by dilute phase pipe, 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 being preheated to after 200-400 DEG C, spray into together with water vapour in the riser reactor of compound reactor, with the hot regenerated catalyst contact reacts from revivifier, described catalyzer is the catalyzer containing modified beta zeolite, temperature of reaction is 480-620 DEG C, preferred 500-600 DEG C, pressure is 0.15-0.3MPa, preferred 0.18-0.28MPa (absolute pressure), 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 enter 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 DEG C, preferred 500-610 DEG C, 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 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.
In order effectively to control 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 heavy oil cracking riser reactor communicates with fluidized-bed reactor bottom through the inside of stripper, and at least one auxiliary riser line reactor is positioned at the outside of described stripper.Regenerated catalyst is delivered to fluidized-bed reactor by regenerated catalyst line and auxiliary riser line reactor.In auxiliary riser line reactor, can not introduce reaction raw materials, also can introduce light oil reaction raw materials.
Preferred scheme is that the light hydrocarbon feedstocks such as C4 hydro carbons, petroleum naphtha component that is rich in alkene that later separation is obtained sprays into auxiliary riser line reactor by the raw material nozzles of auxiliary riser line reactor bottom, with by contacting, react from the hot regenerated catalyst of regenerated catalyst line, reaction oil gas and catalyzer enter fluidized-bed reactor bottom by the outlet of auxiliary riser line reactor.The operational condition of auxiliary riser line reactor is: temperature is 520-680 DEG C, preferred 540-650 DEG C, 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 and catalyzer in heavy oil cracking riser reactor and auxiliary riser line reactor enter 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 particularly propylene, the light aromatic hydrocarbons of coproduction simultaneously of low-carbon alkene.The dilute phase pipe of the oil gas that is rich in low-carbon alkene, light aromatic hydrocarbons generating 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 obtaining returns to fluidized-bed reactor bottom by catalyst transport pipeline, then enters in stripper.
Stripper is introduced catalyst regenerator through the reclaimable catalyst of air lift through reclaimable catalyst pipeline and is carried out coke burning regeneration, and in revivifier, the regenerated catalyst of coke burning regeneration activity recovery is introduced the use of riser reactor bottom cycle through catalyst transport.
In settling vessel, isolated reaction oil gas leaves reactive system, 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.Gas products, by isolation technique well known to those skilled in the art, obtains the low-carbon alkenes such as propylene.Be rich in light aromatic type gasoline through further obtaining light aromatic hydrocarbons after hydrofining and solvent extraction.
In 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 catalysis conversion method provided by the invention, the outlet of described fluidized-bed reactor is communicated with by the fluidized-bed reactor outlet dilute phase pipe of undergauge with the entrance of the gas-solid separation equipment in described settling vessel, the 20-70% of the diameter that wherein, the diameter of the dilute phase pipe of undergauge is fluidized-bed reactor, preferred 30-50%.
In 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 shale oil.
In catalysis conversion method provided by the invention, the riser reactor in described compound reactor be selected from equal diameter riser reactor, etc. linear speed riser reactor and straighten one or more in the riser reactor of footpath.Described fluidized-bed reactor is selected from one or more in particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor, fast bed reactor and dense fluidized bed bioreactor.
In the riser reactor of prior art, along with the carrying out of cracking reaction, carbon deposit on catalyzer increases gradually, its activity decreases, and the concentration of catalyzer also reduces along with the increase of gas volume, generally speaking, only has 30kg/m in the mass concentration of the second half section of riser reactor catalyzer
3left and right, simultaneous reactions temperature also obviously declines, thereby the middle runnings such as gasoline, diesel oil and uncracked stock oil that stock oil generates after cracking in riser tube are difficult to further cracking occur and generate the low-carbon alkenes such as propylene at the back segment of riser tube.
In order to improve reaction later stage catalyst quality concentration, to improve 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 reserve of fluidized-bed reactor inner catalyst can regulate by the aperture of the reclaimable catalyst flowrate control valve of stripper.Gas superficial flow velocity in riser reactor is generally at 6-30m/s, gas superficial flow velocity in fluidized-bed reactor is generally below 3m/s, thereby for riser reactor, in fluidized-bed reactor, can keep higher catalyst concn, generally at 200kg/m
3above.
In catalysis conversion method provided by the invention, first in heavy oil cracking riser reactor, there is catalytic cracking reaction in described heavy hydrocarbon oil raw material, produce or in all the other auxiliary riser line reactors, catalytic cracking occur from the outside C4-C8 lighter hydrocarbons that are rich in alkene of device with timer, the catalyzer of simultaneously a small amount of carbon deposit is promoted to the bottom of fluidized-bed reactor.By controlling the operational throughput of catalyzer in auxiliary riser line reactor, temperature of reaction that can Effective Regulation fluidized-bed reactor, and the activity of catalyzer.The intermediate product producing in two riser reactors enters described fluidized-bed reactor and carries out further drastic cracking.Thus, catalytic convention design of the present invention is by arranging at least three relatively independent reaction zones, make stock 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 conditions to carry out independent control and adjusting, further increase the technique 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 method provided by the invention, the outlet of described fluidized-bed reactor realizes fluid by dilute phase pipe with the entrance of the gas-solid separation equipment in described settling vessel and is communicated with.The outlet that preferred structure is fluidized-bed reactor is communicated with the entrance of the gas-solid separation equipment of settling vessel by the dilute phase pipe of undergauge, and the exit end of described dilute phase pipe and the entrance of gas-solid separation equipment are directly communicated with or are open near gas-solid separation equipment entrance.Thereby adopt material that these preferred structures can make to flow out in fluidized-bed reactor to enter fast product after gas-solid separation equipment realization response and the sharp separation of reclaimable catalyst, and shorten the residence time of oil gas in settling vessel, thereby be conducive to suppress to generate the again conversion reaction of propylene under hot environment, suppress the secondary reactions such as thermally splitting simultaneously, reach the object that reduces dry gas yied.
In 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, can upwards obtain second stage employ by fluidized-bed reactor as the water filling steam of the catalytic cracking reaction wherein occurring to the water vapor of supplying in stripper, be conducive to reduce the overall energy consumption of reaction.
In addition, because stripper is communicated with fluidized-bed reactor bottom, therefore, discharge the flowrate control valve of reclaimable catalyst to revivifier by regulating stripper, can directly control the charge level of catalyzer in fluidized-bed reactor, and then the weight hourly space velocity of reaction in control fluidized-bed reactor, can increase thus the technique flexibility ratio of catalytic cracking reaction.
In catalysis conversion method provided by the invention, for reducing oil gas dividing potential drop in reactor, in the process of carrying out described catalytic cracking reaction, can in described reactor, inject the thinner that is selected from water vapour, nitrogen and C1～C4 alkane, carbonic acid gas, carbon monoxide etc., wherein, preferably water steam, and the weight ratio of water vapour and hydrocarbon raw material is preferably 0.01～1: 1.
In catalysis conversion method provided by the invention, taking the gross weight of catalyzer as benchmark, the described catalyzer containing modified beta molecular sieve contains 1～60% molecular sieve mixture, 5～99% heat-resistant inorganic oxide and 0～70% clay.Taking the gross weight of described molecular sieve mixture as benchmark, in described molecular sieve mixture, contain 1%～75% by the beta-molecular sieve of phosphorus and transition metal M modification, 25%～99% the molecular sieve with MFI structure.
In catalysis conversion method provided by the invention, taking total catalyst weight as benchmark, described 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 be prepared, such as introduce phosphorus and described transition metal M in the process of synthetic β zeolite, or after synthetic β zeolite, adopt the steps such as ammonium exchange, phosphorus modification, described transition metal M modification and calcination process to introduce phosphorus and described transition metal M.Described transition metal M is selected from one or more in Fe, Co, Ni and Cu, more preferably Fe and/or Cu.
The described zeolite with MFI structure is the supersiliceous zeolite with pentasil structure, preferably ZSM-5 and/or ZRP series zeolite.The zeolite of the described MFI of having structure can adopt commercially available product, also can adopt the whole bag of tricks well known in the art to be prepared, and is not repeated herein.
Described heat-resistant inorganic oxide is selected from SiO
2and/or Al
2o
3; Described clay is selected from kaolin and/or halloysite.
In catalysis conversion method provided by the invention, be rich in the gasoline fraction of light aromatic hydrocarbons after hydrofining, obtain the aromatic hydrocarbon products such as benzene,toluene,xylene by solvent extraction.Described gasoline selective hydrofining, extracting can adopt 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 DEG C.The light gasoline fraction obtaining after cutting and/or C4 hydro carbons can return to the further cracking of auxiliary riser line reactor.The full cut of gasoline that is rich in aromatic hydrocarbons maybe contacts the heavy naphtha obtaining after cutting with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 2.0-15.0MPa, temperature of reaction 200-400 DEG C, hydrogen to oil volume ratio 100-1000v/v, volume space velocity 0.5-5h
-1condition under, by olefin saturated wherein, remove the impurity such as sulphur, nitrogen simultaneously, obtain being rich in the refining heavy petrol of light aromatic hydrocarbons.
Wherein, described hydrogenation catalyst is VIB and/or the VIII family non-precious metal catalyst loading on aluminum oxide and/or amorphous silicon aluminium, and described 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 the metallic elements such as fluorine, phosphorus, titanium.
Gasoline fraction after hydrofining contacts with solvent, and at temperature 80-120 DEG C, extracting under the condition of the volume ratio 2-6 between solvent and 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, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether one or more mixed solvent.After solvent recuperation, recycle.
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed, but not thereby limiting the invention.
Fig. 1 is a preferred scheme of the catalysis conversion method of production propylene provided by the invention and 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, auxiliary riser line 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 described stripper 5 tops are directly communicated with the bottom of fluidized-bed reactor 3.The outlet of fluidized-bed reactor 3 is communicated with by carrying path 32 with the entrance of the settling vessel in settling vessel 4, and the catalyst outlet of settling vessel is communicated with by catalyst transport path 43 with the bottom of fluidized-bed reactor 3.The optional position, bottom of the outlet of heavy oil riser reactor, auxiliary riser line reactor and fluidized-bed reactor is communicated with.
The following examples will be further described present method, but not thereby limiting the invention.
Effect when embodiment 1-3 explanation adopts catalysis conversion method provided by the invention.
Embodiment 1
The trade names of the catalyzer using are DMMC-1, are produced by Shandong catalyzer branch office of company limited of China Petrochemical Industry.Use medium-sized tester as shown in Figure 1, wherein the internal diameter of heavy oil riser reactor is 18 millimeters, is highly 6 meters, and fluidized-bed reactor internal diameter is 64 millimeters, is highly 0.5 meter, and the internal diameter of auxiliary riser line reactor is 16 millimeters, is highly 5 meters.The undergauge ratio of fluidized-bed reactor outlet dilute phase pipe is 30%.Catalyzer is at 800 DEG C, and with 100% steam aging 10 hours, in compound reactor, the loading amount of catalyzer was 60 kilograms.
Heavy hydrocarbon oil raw material is introduced to the contact of heavy oil cracking riser reactor catalyst neutralisation and carry out catalytic cracking reaction; In auxiliary riser line reactor, not introducing hydrocarbon oil crude material, is catalyst transport passage.The character of heavy hydrocarbon oil raw material is in table 1, and catalyzer composition and character are in table 3, and reaction conditions and productive rate are in table 4.
Embodiment 2
The catalyzer that embodiment 2 uses and reaction unit, with embodiment 1, are introduced the contact of heavy oil cracking riser reactor catalyst neutralisation by heavy hydrocarbon oil raw material and are carried out catalytic cracking reaction, and freshening C4 component is introduced in auxiliary riser line reactor and reacted.The character of heavy oil feedstock is in table 1, and freshening C4 forms in table 2, and reaction conditions and productive rate are in table 4.
Embodiment 3
The catalyzer that embodiment 3 uses and reaction unit are with embodiment 1, heavy hydrocarbon oil raw material is introduced to the contact of heavy oil cracking riser reactor catalyst neutralisation and carry out catalytic cracking reaction, will in freshening C4 component and petroleum naphtha component introducing auxiliary riser line reactor, react.In embodiment, agent-oil ratio refers to the weight ratio of catalyzer and fresh feed.The character of heavy hydrocarbon oil raw material is in table 1, and petroleum naphtha forms in table 2, operation condition and the results are shown in Table 4.
Comparative example 1
Comparative example 1 illustrates effect when adopting riser tube to add fluidized-bed reactor carries out heavy hydrocarbon oil raw material catalysis conversion method.The medium-sized tester that comparative example adopts is shown in shown in 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 character of heavy hydrocarbon oil raw material is in table 1, operation condition and the results are shown in Table 4.
Table 1 raw material oil properties
Table 2
| Petroleum naphtha group composition (wt%) | |
| Alkane | 30 |
| Alkene | 63 |
| Naphthenic hydrocarbon | 3 |
| Aromatic hydrocarbons | 2 |
| Diolefine and alkynes content | 2 |
| C4 forms (wt%) | |
| Alkene | 65 |
| Alkane | 33 |
| Diolefine and alkynes content | 2 |
Table 3 catalyzer composition:
| Trade names | DMMC-1 |
| Composition: | |
| Modified beta molecular sieve | 10％ |
| ZSM-5 molecular sieve | 20％ |
| Aluminum oxide) | 20％ |
| Clay | 50％ |
Table 4
From table 4, compare with comparative example, 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 and light aromatic hydrocarbons, can also the light aromatic hydrocarbons of coproduction in obtaining high productivity of propylene.
Claims (10)
1. a catalysis conversion method of producing propylene and light aromatic hydrocarbons, comprising:
In the reactor of catalytic convention design, hydrocarbon raw material contacts under catalytic cracking condition and reacts with the catalyzer that contains modified beta zeolite, reaction product isolated and reclaimable catalyst, isolated reclaimable catalyst recycles after stripping, coke burning regeneration, 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, is rich in the gasoline of light aromatic hydrocarbons through further obtaining light aromatic hydrocarbons after hydrofining and 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, stripper is positioned at the below of fluidized-bed reactor, and stripper top is directly communicated with the bottom of fluidized-bed reactor, the outlet of fluidized-bed reactor is communicated with by carrying path with the entrance of the gas-solid separation equipment in settling vessel, the catalyst outlet of settling vessel is communicated with the catalyst transport path that passes through of fluidized-bed reactor bottom, the 30-50% of the diameter that the diameter of the carrying path of described fluidized-bed reactor outlet is fluidized-bed reactor.
2. according to the catalysis conversion method of claim 1, it is characterized in that in 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.
3. according to the catalysis conversion method of claim 1 or 2, it is characterized in that described at least one, on transfer lime, being provided with in catalytic convention design catalyst stream control valve.
4. 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 shale oil.
5. according to the method for claim 1, it is characterized in that in the operational condition of described heavy oil riser reactor being: temperature of reaction is 480-620 DEG C, the absolute pressure of reaction zone is 0.15-0.3MPa, and agent-oil ratio is 5-20, and the reaction times of described raw material is 0.1-6 second.
6. according to the method for claim 1, it is characterized in that the operational condition in described fluidized-bed reactor is: temperature of reaction is 480-630 DEG C, the absolute pressure of reaction zone is 0.15-0.3MPa, and the weight hourly space velocity of described raw material is 0.2-30h
-1.
7. according to the method for claim 1, it is characterized in that in described riser reactor, injecting thinner in the process of reaction, to reduce the dividing potential drop of described raw material, wherein said thinner is selected from one or more the mixture in water vapor, low-carbon alkanes and nitrogen.
8. according to the method for claim 7, it is characterized in that described thinner is water vapor, and the weight ratio of described water vapor and described raw material is 0.01-2: 1.
9. according to the method for claim 1, it is characterized in that gross weight taking catalyzer is as benchmark, described molecular sieve mixture, the heat-resistant inorganic oxide of 5-99% and the clay of 0-70% that contains 1-60% containing the catalyzer of modified beta molecular sieve; Taking the gross weight of described molecular sieve mixture as benchmark, in described molecular sieve mixture, contain 1-75% by the beta-molecular sieve of phosphorus and transition metal M modification, the molecular sieve with MFI structure of 25-99%.
10. according to the method for claim 9, the molecular sieve described in it is characterized in that with MFI structure is ZSM-5 and/or ZRP molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010233651.7A CN102337154B (en) | 2010-07-22 | 2010-07-22 | Method for catalytic conversion production of propylene and light aromatics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010233651.7A CN102337154B (en) | 2010-07-22 | 2010-07-22 | Method for catalytic conversion production of propylene and light aromatics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102337154A CN102337154A (en) | 2012-02-01 |
| CN102337154B true CN102337154B (en) | 2014-12-03 |
Family
ID=45513109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010233651.7A Active CN102337154B (en) | 2010-07-22 | 2010-07-22 | Method for catalytic conversion production of propylene and light aromatics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102337154B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11891578B2 (en) | 2018-07-16 | 2024-02-06 | China Petroleum & Chemical Corporation | Process and system for catalytic cracking of hydrocarbon oils |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349178B (en) * | 2014-08-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalytic conversion method for producing low carbon olefins and light aromatic hydrocarbons |
| CN104549073B (en) * | 2015-01-05 | 2017-01-04 | 中国石油大学(华东) | A kind of dehydrating alkanes olefin recycle fluidized bed reaction |
| CN107974281B (en) * | 2016-10-21 | 2021-08-06 | 中国石油化工股份有限公司 | Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon |
| CN107971012B (en) * | 2016-10-21 | 2020-09-22 | 中国石油化工股份有限公司 | Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon |
| CN107974282B (en) * | 2016-10-21 | 2020-09-22 | 中国石油化工股份有限公司 | Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon |
| CN109705915B (en) * | 2017-10-26 | 2020-05-19 | 中国石油化工股份有限公司 | Catalytic cracking method for increasing yield of isobutane and light aromatic hydrocarbons |
| CN109722305B (en) * | 2017-10-27 | 2021-01-08 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN112745901B (en) * | 2019-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Catalytic conversion method and catalytic conversion device for producing low-carbon olefin |
| CN112745903B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Process and apparatus for catalytic conversion of heavy petroleum hydrocarbon feedstocks |
| CN113926390B (en) * | 2020-07-13 | 2022-12-13 | 中国石油化工股份有限公司 | Catalytic conversion reactor, catalytic conversion device and method for preparing propylene by catalytic cracking of heavy oil |
| CN113926396B (en) * | 2020-07-13 | 2022-12-13 | 中国石油化工股份有限公司 | Heavy oil catalytic conversion reactor and method for preparing propylene by heavy oil catalytic cracking |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045881A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Catalytic converter |
| CN101134913A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
| CN101724431A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing light fuel oil and propylene |
-
2010
- 2010-07-22 CN CN201010233651.7A patent/CN102337154B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045881A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Catalytic converter |
| CN101134913A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
| CN101724431A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing light fuel oil and propylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11891578B2 (en) | 2018-07-16 | 2024-02-06 | China Petroleum & Chemical Corporation | Process and system for catalytic cracking of hydrocarbon oils |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102337154A (en) | 2012-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102337154B (en) | Method for catalytic conversion production of propylene and light aromatics | |
| CN102286294B (en) | Method for producing propylene and light arenes by catalytic conversion of hydrocarbons | |
| CN102051213B (en) | Catalytic cracking method | |
| CN101531558B (en) | Catalytic conversion method for preparing propylene and aromatic hydrocarbons | |
| CN101747928B (en) | Catalytic conversion method for preparing lower olefins and aromatics | |
| CN101747929B (en) | Catalytic conversion method for preparing lower olefins and aromatics | |
| CN102206509B (en) | Hydrocarbon catalytic conversion method for producing propylene and light aromatic hydrocarbon | |
| CN101293806B (en) | Catalytic conversion method for improving productivity of low carbon olefin hydrocarbon | |
| CN102071054B (en) | Catalytic cracking method | |
| CN103131464B (en) | A kind of hydrocarbons catalytic conversion method producing low-carbon alkene and light aromatic hydrocarbons | |
| CN101362669A (en) | Catalytic conversion method of ethylene, propylene and aromatic hydrocarbon preparation | |
| CN103131463B (en) | Hydrocarbon catalytic conversion method for increasing propylene yield | |
| CN101029248B (en) | Method for increasing light olefin yield | |
| CN104560154A (en) | Hydrocarbon catalytic conversion method of productive low-carbon olefin and light aromatic hydrocarbon | |
| RU2009144146A (en) | INSTALLATION AND METHOD FOR PRODUCING MIDDLE DISTILLATES AND LOW OLEFINS FROM HYDROCARBON RAW MATERIALS | |
| CN103627434B (en) | A kind of catalyst cracking method with hydrotreatment combinations produce propylene | |
| CN105308008A (en) | Dual riser fluid bed process and reactor | |
| CN102086402B (en) | Catalytic cracking method and device capable of increasing propylene yield and improving properties of gasoline | |
| CN106609152A (en) | Hydrocarbon catalytic converting method with high butene and light arene yields | |
| CN101362963B (en) | Catalytic conversion method for preparing propylene and simultaneously preparing aromatic hydrocarbons | |
| CN103664454B (en) | A kind of Fischer-Tropsch synthesis oil catalytic reforming of less energy-consumption produces the method for propylene | |
| CN102399579B (en) | Catalytic cracking method | |
| CN103666551B (en) | Catalytic processing method and catalytic processing device of high-temperature Fischer-Tropsch synthetic oil | |
| CN112745945A (en) | Method and system for treating catalytic pyrolysis gasoline, catalytic pyrolysis process and device for producing more dimethylbenzene | |
| CN112745924A (en) | Method and system for treating catalytic cracking gasoline, and catalytic cracking process and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |