CN101747928B

CN101747928B - Catalytic conversion method for preparing lower olefins and aromatics

Info

Publication number: CN101747928B
Application number: CN2008102276519A
Authority: CN
Inventors: 崔守业; 许友好; 龚剑洪; 张执刚; 马建国; 程从礼; 刘守军; 杨轶男
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2008-11-28
Filing date: 2008-11-28
Publication date: 2013-11-27
Anticipated expiration: 2028-11-28
Also published as: CN101747928A

Abstract

The invention relates to a catalytic conversion method for preparing lower olefins and aromatics. Raw oil with different cracking performances enters different reaction zones of a first riser reactor to contact with a catalytic cracking catalyst for cracking reaction to separate a spent catalyst from reaction oil gas, wherein the reaction oil gas is separated to obtain a product containing lower olefins, gasoline, distillates with distillation range of 180-250 DEG C and catalytic wax oil, wherein the gasoline is extracted by light aromatics to obtain light aromatics and gasoline raffinate; the raw materials are cracked to be sent into a second riser reactor to contract with a hot regenerated catalyst for catalytic conversion; and the spent catalysts of the two riser reactors are burned and regenerated in the same one regenerator and then returns to the two riser reactors. The method uses heavy raw materials to furthest produce the lower olefins, such as propylene, ethylene, and the like, particularly the propylene, the production rate can exceed 40 wt%, and at the same time the method can coproduce the aromatics, such as toluene, xylene, and the like.

Description

The catalysis conversion method of a kind of preparing low-carbon olefins and aromatic hydrocarbons

Technical field

The invention belongs in the situation that there is not the catalysis conversion method of hydrogen hydro carbons, more particularly, is a kind of method that heavy feed stock is converted into to low-carbon alkenes such as being rich in propylene and ethene and is rich in the aromatic hydrocarbons such as toluene and dimethylbenzene.

Background technology

Low-carbon alkene such as ethene, propylene etc. are important Organic Chemicals, and wherein propylene is the synthon of the products such as polypropylene, vinyl cyanide.Along with increasing rapidly of the derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in World Propylene market is from 1,520 ten thousand tons of 5,120 ten thousand tons of being increased to 2000 before 20 years, and average growth rate per annum reaches 6.3%.The demand that expects propylene in 2010 will reach 8,600 ten thousand tons, and average growth rate per annum is about 5.6% therebetween.

The method of producing propylene is mainly steam cracking and catalytic cracking (FCC), wherein steam cracking be take the lightweight oils such as petroleum naphtha and by thermo-cracking, is produced ethene, propylene as raw material, but the productive rate of propylene is only 15 heavy % left and right, FCC be take the mink cell focus such as decompressed wax oil (VGO) and is raw material.At present, 66% propylene is produced the byproduct of ethene from steam cracking in the world, and 32% produces the byproduct of vapour, diesel oil from refinery FCC, a small amount of (approximately 2%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.

If petrochemical complex is walked traditional preparing ethylene by steam cracking, propylene route, will face several large restraining factors such as the shortage of lightweight material oil, inefficiency of production and high cost.

FCC is because the advantages such as its adaptability to raw material is wide, flexible operation come into one's own day by day.In the U.S., almost 50% of the propylene market demand all derive from FCC apparatus.It is very fast that the catalytic cracking of propylene enhancing improves technical development.

US4,980,053 disclose a kind of hydrocarbon conversion processes of preparing low-carbon olefins, and raw material is petroleum fractions, residual oil or the crude oil of different boiling ranges, uses solid acid catalyst in fluidized-bed or moving-burden bed reactor, temperature 500-650 ℃, pressure 1.5-3 * 10 ⁵Pa, weight hourly space velocity 0.2-2.0h ^-1, agent-oil ratio 2-12 condition under carry out catalytic conversion reaction, reacted catalyzer Returning reactor internal recycle after coke burning regeneration is used.The overall yield of the method propylene and butylene can reach 40% left and right, and wherein productivity of propylene is up to 26.34%.

WO00/31215A1 discloses a kind of catalyst cracking method of producing alkene, and the method adopts ZSM-5 and/or ZSM-11 zeolite to do active component, and a large amount of inert substances of take are the catalyzer of matrix, and the VGO of take is raw material, and the productive rate of propylene also is no more than 20 heavy %.

US4,422,925 disclose the method that multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, the described hydro carbons of the method contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material at least, the method has different cracking performances according to different hydrocarbon molecules, reaction zone is divided into to a plurality of reaction zones and carries out cracking reaction, with voluminous low-molecular olefine.

Aromatic hydrocarbons is also a kind of important industrial chemicals, and especially light aromatic hydrocarbons BTX (benzene,toluene,xylene) is mainly for the production of synthetic materialss such as chemical fibre, plastics.The main method of producing at present aromatic hydrocarbons is catalytic reforming, because the active ingredient of reforming catalyst is precious metal, therefore must carry out strict pre-treatment to raw material.In addition, the movement of reforming catalyst, regeneration flow process be more complicated also.

CN1667089A discloses a kind of chemical industry type oil refining method of producing low-carbon alkene and aromatic hydrocarbons, stock oil contacts in the catalytic cracking reaction device with catalytic cracking catalyst, water vapor through regeneration, under the condition of the weight ratio 5～50 of 500～700 ℃ of temperature, pressure 0.15～0.4MPa, catalytic cracking catalyst and stock oil, water vapor and the weight ratio 0.05～0.6 of stock oil, react, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regeneration; Separating reaction oil gas obtains purpose product low-carbon alkene and aromatic hydrocarbons.The method is produced the low-carbon alkenes such as propylene, ethene to greatest extent from heavy feed stock, wherein the productive rate of propylene surpasses 30 heavy %, the aromatic hydrocarbons such as coproduction toluene and dimethylbenzene simultaneously.

CN1208431C discloses the method and apparatus that a kind of easy modifying catalytically cracked gasoline reduces alkene, this device is to set up auxiliary fluidizing reactor to carry out upgrading to catalytically cracked gasoline in conventional catalytic cracking unit, this technique has reached the purpose that reduces gasoline olefin in the sacrificial section light oil yield, productivity of propylene increases to some extent.

Cracking reaction designs still Shortcomings to above-mentioned prior art to alkane molecule, simultaneously, the product of prior art distributes and is that routinely FCC fractionating system is cut, and the arene underwater content in gasoline or diesel oil and low-carbon alkene potential content are underused, and cause the productive rate of propylene and aromatic hydrocarbons on the low side.In order to meet the demand of the industrial chemicals such as growing propylene, ethene and aromatic hydrocarbons, be necessary to develop a kind of catalysis conversion method that heavy feed stock is converted into to a large amount of propylene, ethene and aromatic hydrocarbons.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of catalysis conversion method heavy feed stock is converted into to low-carbon alkene and aromatic hydrocarbons.

Technical scheme of the present invention is the catalysis conversion method of a kind of preparing low-carbon olefins and aromatic hydrocarbons, and the method comprises the following steps:

(1) stock oil of difficult cracking enters the first riser reactor bottom, with the catalytic cracking catalyst of heat regeneration, contacts, at 550 ℃-800 ℃ of temperature of reaction, weight hourly space velocity 100h ^-1-800h ^-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;

(2) reaction effluent separates without finish, mixes with the stock oil of easy cracking, and easily the stock oil of cracking is at 450 ℃-620 ℃ of temperature of reaction, weight hourly space velocity 0.1h ^-1-100h ^-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 2-30, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;

(3) reaction effluent separates without finish, and with the stock oil of optional difficult cracking, easily one or more in cracking stock oil, cold shock medium are mixed, stock oil is at 400 ℃-550 ℃ of temperature of reaction, weight hourly space velocity 10h ^-1-300h ^-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;

(4) separate reclaimable catalyst and reaction oil gas, wherein reclaimable catalyst returns to the first riser tube through after stripping, entering revivifier after coke burning regeneration, and reaction oil gas goes separation system;

(5) the described reaction oil gas of step (4) enters separation system to separate cut, gasoline, the boiling range obtain comprising low-carbon alkene, C4 alkene and C5 hydrocarbon, boiling range<70 ℃ is the 180 ℃～cut of 250 ℃ and the product of catalytic wax oil, and wherein gasoline obtains light aromatic hydrocarbons and gasoline is raffinated oil through light Aromatics Extractive Project;

(6) cut, the gasoline of the described C4 alkene of step (5) and C5 hydrocarbon, boiling range<70 ℃ are raffinated oil, boiling range is a kind of in the cut of 180 ℃～250 ℃ or wherein more than one mixture as cracking stock again, send in the second riser reactor, with hot regenerated catalyst, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h ^-1-800h ^-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 2-100, the weight ratio of water vapor and raw material is to carry out catalyzed conversion under the condition of 0.05-1.0, reclaimable catalyst separates by cyclonic separator with reaction oil gas, reclaimable catalyst enters stripper, through stripping or not stripping, after coke burning regeneration in described revivifier, return to the second riser reactor.

Described easy cracking stock is petroleum hydrocarbon and/or other mineral oil, and its Petroleum Hydrocarbon is selected from decompressed wax oil (VGO), normal pressure wax oil (AGO), wax tailings (CGO), deasphalted oil (DAO), vacuum residuum (VR), long residuum (AR), heavy aromatics and raffinates oil.Other mineral oil is liquefied coal coil, tar sand oil, shale oil.Preferred raw material is selected from that decompressed wax oil, normal pressure wax oil, wax tailings, deasphalted oil, vacuum residuum, long residuum, heavy aromatics raffinate oil a kind of or more than one mixture wherein.Wherein VGO, AGO, CGO, DAO, VR, AR are full cut or the part cut of not hydrogenation, or are full cut or part cut after hydrogenation.

Described difficult cracking stock is the low-carbon (LC) molecule, is selected from carbonatoms and is 2～8 hydro carbons, slurry oil, diesel oil, gasoline, light aromatic hydrocarbons raffinates oil a kind of or more than one mixture wherein.

Described gasoline is selected from a kind of in present method gained catalytic cracking gasoline, catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, hydrogenated gasoline or more than one mixture wherein, and wherein catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, hydrogenated gasoline are from the outer gasoline of this device.

Described diesel oil is to be selected from a kind of in present method gained catalytic pyrolysis diesel oil, catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, hydrogenated diesel oil or more than one mixture wherein, and wherein catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, hydrogenated diesel oil are from the outer diesel oil of this device.

Carbonatoms is that 2～8 hydrocarbon can be from catalytic cracking method of the present invention, also can be from techniques such as conventional catalytic cracking, coking, thermally splitting, hydrogenation.

Described cold shock medium is one or more the mixture of arbitrary proportion be selected from cold shock agent, cooling regenerated catalyst, cooling half regenerated catalyst, reclaimable catalyst and live catalyst, and wherein the cold shock agent is one or more that are selected from liquefied gas, propane, C4 hydrocarbon, raw gasline, stable gasoline, diesel oil, water; Cooling regenerated catalyst and half cooling regenerated catalyst are reclaimable catalyst cooling obtaining after two-stage regeneration and one section regeneration respectively.

Described cracking stock again is a kind of in the raffinating oil of cut, the light Aromatics Extractive Project of gasoline (being that boiling range is the cut of 70 ℃～180 ℃) of boiling range<70 ℃, cut, C4 alkene and C5 hydrocarbon that boiling range is 180 ℃～250 ℃ or more than one mixture wherein, and wherein each raw material can be from this device and this device raw material outward.

The boiling range of described catalytic wax oil is greater than 250 ℃, and the outlet of catalytic wax oil has one or more in following items:

The oil that acts as a fuel,

Through hydrofining as diesel component,

Returning reactor after hydrofining,

The Returning reactor of raffinating oil after solvent extraction goes out heavy aromatics.

Described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight: the heavy % of the heavy %-50 of zeolite 10, the heavy % of the heavy %-90 of inorganic oxide 5, the heavy % of the heavy %-70 of clay 0.

Its mesolite, as active ingredient, is selected from mesopore zeolite and optional large pore zeolite, and mesopore zeolite accounts for the heavy % of 50 heavy %-100 of zeolite gross weight, preferably 70 weighs the heavy % of %-100, and large pore zeolite accounts for the heavy % of 0 heavy %-50 of zeolite gross weight, and preferably 0 heavy %-30 weighs %.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can with transition metals such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel, carry out modification to above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.Large pore zeolite selects one or more the mixture in this group zeolite that super steady Y, high silicon Y that free Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods obtain form.

Inorganic oxide, as caking agent, is selected from silicon-dioxide (SiO ₂) and/or aluminium sesquioxide (Al ₂O ₃).

Clay, as matrix (being carrier), is selected from kaolin and/or halloysite.

Catalytic cracking catalyst in each reactor is identical, and reclaimable catalyst shares same revivifier.

In order to increase the agent-oil ratio of reaction catchment, improve the lytic activity of catalyzer, can be by supplemental heat or cold regenerated catalyst, half regenerated catalyst, catalyzer, live catalyst to be generated.Cooling regenerated catalyst and half cooling regenerated catalyst are reclaimable catalyst cooling obtaining after two-stage regeneration and one section regeneration respectively, the regenerated catalyst carbon content is below 0.1 heavy %, be preferably below 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7; The reclaimable catalyst carbon content is more than 0.9 heavy %, and preferably carbon content is the heavy % in 0.9 heavy %～1.2.

Described low-carbon alkene is ethene, propylene and butylene, and namely low-carbon alkene is ethene, propylene, or ethene, propylene and butylene.

Identical with the method that those of ordinary skills know from the method for separating ethene reaction oil gas, identical with the method that those of ordinary skills know with the method for the butylene of choosing wantonly from separation of propylene reaction oil gas.From the method for aromatics separation the pyrolysis gasoline cut fraction of reaction oil gas, be that the solvent extracting is identical with the method that those of ordinary skills know, before present method gained catalytic cracking gasoline aromatics separation, can be by the C in this gasoline ₅-C ₈First separate as recycle stock.

The cut of described 180-250 ℃ is between conventional FCC gasoline last running and diesel oil lighting end, its separation method is different from the separation method of existing FCC separation column, its separation method is shown in patent of invention 200710120105.0, after separating unit separates, returns the cracking unit; The cut that is greater than 250 ℃ enters the heavy aromatics extraction plant, raffinates oil and returns the cracking unit, and heavy aromatics is as industrial chemicals or as combustion oil.

The method is produced the low-carbon alkenes such as propylene, ethene to greatest extent from heavy feed stock, wherein the productive rate of propylene is more than 25 heavy %, preferably more than 40 heavy %, and aromatic hydrocarbons such as coproduction toluene and dimethylbenzene simultaneously.

The accompanying drawing explanation

Fig. 1 is the method flow schematic diagram of embodiment one.

Fig. 2 is the method flow schematic diagram of embodiment two.

Fig. 3 is the method flow schematic diagram of embodiment three.

Fig. 4 is the method flow schematic diagram of embodiment four.

Embodiment

The embodiment of below enumerating is that technical scheme of the present invention is further detailed, but not thereby limiting the invention.

Embodiment one

The preferred technical scheme of present embodiment comprises the following steps:

(6) cut, the gasoline of the described C4 alkene of step (5) and C5 hydrocarbon, boiling range<70 ℃ are raffinated oil, boiling range is a kind of in the cut of 180 ℃～250 ℃ or wherein more than one mixture as cracking stock again, send in the second riser reactor, with hot regenerated catalyst, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h ^-1-800h ^-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 2-100, the weight ratio of water vapor and raw material is to carry out catalyzed conversion under the condition of 0.05-1.0, reclaimable catalyst separates by cyclonic separator with reaction oil gas, reclaimable catalyst enters stripper, through stripping or not stripping, after coke burning regeneration in described revivifier, return to the second riser reactor;

(7) catalytic wax oil raffinating oil after heavy aromatics extracts heavy aromatics returned to the first riser reactor or/and the second riser reactor.

Embodiment two

(7) catalytic wax oil is returned to the first riser reactor or/and the second riser reactor after hydrofining.

Embodiment three

(5) the described reaction oil gas of step (4) enters the separation system separation and obtains comprising low-carbon alkene, C ₂°-C ₄°, cut, gasoline, the boiling range of C4 alkene and C5 hydrocarbon, boiling range<70 ℃ be the 180 ℃～cut of 250 ℃ and the product of catalytic wax oil, wherein gasoline obtains light aromatic hydrocarbons and gasoline is raffinated oil through light Aromatics Extractive Project;

(7) catalytic pyrolysis C ₂°-C ₄° with water vapor, enter the steam cracking reaction device, carry out cracking reaction under 700 ℃-1000 ℃ of temperature of reaction, separating reaction oil gas obtains H ₂, CH ₄, steam cracking C ₂ ⁼-C ₃ ⁼, steam cracking C ₂-° C ₃°, steam cracking C ₄-C ₅, steam cracking petroleum naphtha, oil fuel, wherein steam cracking C ₂ ⁼-C ₃ ⁼For one of purpose product, steam cracking C ₂°-C ₃° loop back steam cracking reaction device, steam cracking C ₄-C ₅Loop back the catalytic cracking reaction device;

(8) the steam cracking petroleum naphtha of step (7) is first after selective hydrogenation, then obtains aromatic hydrocarbons and raffinate oil through solvent extraction, and wherein aromatic hydrocarbons is one of purpose product, raffinates oil and returns to step (7) as one of raw material of steam cracking.

Embodiment four

(5) the described reaction oil gas of step (4) enters separation system and separates that to obtain comprising low-carbon alkene be ethene and propylene, C ₂°-C ₄°, cut, gasoline, the boiling range of butylene and C5 hydrocarbon, boiling range<70 ℃ be the 180 ℃～cut of 250 ℃ and the product of catalytic wax oil, wherein gasoline obtains light aromatic hydrocarbons and gasoline is raffinated oil through light Aromatics Extractive Project;

(6) cut, the gasoline of the described C5 hydrocarbon of step (5), boiling range<70 ℃ are raffinated oil, boiling range is a kind of in the cut of 180 ℃～250 ℃ or wherein more than one mixture as cracking stock again, send in the second riser reactor, with hot regenerated catalyst, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h ^-1-800h ^-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 2-100, the weight ratio of water vapor and raw material is to carry out catalyzed conversion under the condition of 0.05-1.0, reclaimable catalyst separates by cyclonic separator with reaction oil gas, reclaimable catalyst enters stripper, through stripping or not stripping, after coke burning regeneration in described revivifier, return to the second riser reactor;

(7) ethene and butylene enter the olefin metathesis reactions device, and ethene and butylene are converted into to propylene by metathesis reaction.

The device that method provided by the invention relates to comprises: catalytic pyrolysis unit, fractionation unit, light/heavy aromatics extracting unit, gas separation unit, steam cracking unit, transposable element.Below narration respectively.

The catalytic pyrolysis unit:

The cracking unit comprises catalytic pyrolysis and steam cracking two portions.The catalytic pyrolysis part is comprised of reactor and revivifier, and stock oil contacts in reactor with catalyst for cracking, at temperature 400-800 ℃, weight hourly space velocity 0.1-750h ^-1Condition under react, reacted oil gas and catalyst separating, reclaimable catalyst is Returning reactor after stripping, regeneration, isolated oil gas send fractionation unit, gas separation unit and extracting unit, the cut of 180～250 ℃ of fractionation unit returns the cracking unit, lytic unit is returned in raffinating oil of extracting unit, and the ethane of gas separation unit, propane and butane send the steam cracking unit or returns the catalytic pyrolysis unit.The C 4 olefin of gas separation unit returns the catalytic pyrolysis unit or advances transposable element or go out device as product.The C5-C6 hydro carbons returns the cracking unit.

Fractionation unit:

Fractionation unit is comprised of separation column, vapor-liquid separation tank and stripping tower, is divided into rich gas, light aromatic hydrocarbons material, freshening material, heavy aromatics material and oil fuel at the fractionation unit reaction oil gas.

The catalytic cracking reaction oil gas come from the cracking unit is sent into separation column with steam cracking reaction oil gas and is separated.

Through fractionation, from the cut of Fractionator Bottom extraction boiling range scope higher than 360 ℃, in this cut, mainly contain polycyclic aromatic hydrocarbons, after filtering out a small amount of catalyst fines wherein carried, can be used as the component of Blended fuel oil or the raw material that carbon black is produced in conduct.

It from separation column middle and lower part extraction boiling range scope, is the cut of 250～360 ℃, in this cut, mainly contain double ring arene and polycyclic aromatic hydrocarbons, and contain a small amount of mononuclear aromatics, naphthenic hydrocarbon and paraffinic hydrocarbons, these raw materials are the low-carbon olefines high-output of high-quality and the raw material of aromatic hydrocarbons, deliver to heavy aromatics extracting cell processing, mononuclear aromatics, naphthenic hydrocarbon and paraffinic hydrocarbons and double ring arene and polycyclic aromatic hydrocarbons are separated, mononuclear aromatics, naphthenic hydrocarbon and paraffinic hydrocarbons are as the raw material of cracking unit, and double ring arene and polycyclic aromatic hydrocarbons are as industrial chemicals.

It from separation column middle and upper part extraction boiling range scope, is the cut of 180～250 ℃, in this cut, mainly contain paraffinic hydrocarbons, naphthenic hydrocarbon and part mononuclear aromatics, the low-carbon olefines high-output of high-quality and the raw material of aromatic hydrocarbons, returning to the cracking unit further reacts, make the side chain fracture on paraffinic hydrocarbons and mononuclear aromatics, produce to greatest extent low-carbon alkene and aromatic hydrocarbons.

The oil gas of discharging from the fractionation tower top enters vapor-liquid separation tank through condensation, after cooling to be separated, the rich gas the separated body separating unit of supplying gas, and the thick light aromatic hydrocarbons material separated gives the processing of the stripping tower this unit in, recycles after the water treatment separated.

Stripping tower is actually a depentanizer, and thick light aromatic hydrocarbons material is divided into C6+ cut and C5-cut in stripping tower.In the C6+ cut, mainly containing mononuclear aromatics, is the light aromatics extraction raw material of high-quality, delivers to light Aromatics Extractive Project cell processing, and aromatic hydrocarbons and stable hydrocarbon are separated, and stable hydrocarbon is as the raw material of cracking unit, and aromatic hydrocarbons is as industrial chemicals.The C5-cut is delivered to gas separation unit and is processed.

Gas separation unit:

Gas separation unit is comprised of rich gas compressor, depropanizing tower, demethanizing tower, deethanizing column, ethylene rectification tower and propylene rectification tower.

Rich gas is sent into depropanizing tower after rich gas compressor improves pressure, the C5-cut of fractionation unit is also sent into depropanizing tower.Through separation, at the bottom of depropanizing tower, discharge C4 and C 5 fraction, after cooling, enter debutanizing tower.The logistics of debutylize tower top enters the butylene rectifying tower, and the debutanizing tower bottoms stream is discharged C 5 fraction, and the reactor that this cut returns to the cracking unit further reacts.The butylene of butylene rectifying tower top returns to the catalytic pyrolysis unit or enters transposable element or go out device, and the reactor that the butane cut at the bottom of the butylene rectifying tower returns to the cracking unit further reacts.Tower top is discharged the C3-cut, after cooling, sends into demethanizing tower.The demethanizing tower top is discharged the fuel gas that mainly contains methane and hydrogen, and the demethanizing tower bottoms stream is sent into deethanizing column.Ethylene rectification tower is sent in the logistics of deethanizing tower top, and the deethanizing column bottoms stream is sent into propylene rectification tower.Ethylene distillation tower top polymer grade ethylene goes out device, and at the bottom of ethylene rectification tower, ethane send the ethane cracking furnace cracking of cracking unit.Propylene rectification tower top polymerization-grade propylene goes out device, and at the bottom of propylene rectification tower, propane send the ethane cracking furnace cracking of cracking unit.

The steam cracking unit

In this unit, catalytic pyrolysis C ₂°-C ₃° with water vapor, contact under 700 ℃-1000 ℃, separating reaction oil gas obtains H ₂, CH ₄, steam cracking C ₂ ⁼-C ₃ ⁼, steam cracking C ₂°-C ₃°, steam cracking C ₄-C ₅, steam cracking petroleum naphtha, oil fuel, wherein steam cracking C ₂ ⁼-C ₃ ⁼For one of purpose product;

In this unit, catalytic pyrolysis petroleum naphtha and steam cracking petroleum naphtha first obtain the selective hydrogenation petroleum naphtha after selective hydrogenation;

Transposable element

In this unit, the ethene of catalytic pyrolysis and butylene be at temperature 10-450 ℃, pressure 0.1-3.0MPa, butylene weight space velocity 0.01-3h ^-1, ethylene/butylene is than under the 0.2-10 condition, contact the generation metathesis reaction with metathesis catalyst, obtaining purpose product propylene.

The selective hydrogenation unit

The extracting unit:

The extracting unit comprises light Aromatics Extractive Project and heavy aromatics extracting two portions.Light Aromatics Extractive Project comprises solvent tower, extractive distillation solvent recovery tower, liquid liquid extraction tower, stripping tower, liquid liquid extracting and reclaiming tower etc.The heavy aromatics extracting comprises liquid liquid extraction tower, stripping tower, liquid liquid extracting and reclaiming tower etc.

In this unit, the selective hydrogenation petroleum naphtha obtains aromatic hydrocarbons and raffinating oil through solvent extraction, and wherein aromatic hydrocarbons is one of purpose product, raffinates oil and returns to the steam cracking unit as one of raw material of steam cracking.

The solvent of light Aromatics Extractive Project selects one or more mixture of this group material that free tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether forms.After solvent recuperation, recycle.The temperature of solvent extraction is 80-120 ℃, and the volume ratio between solvent and solvent extraction raw material is 2-6.The extraction oil of solvent extraction is one of purpose product aromatic hydrocarbons, and raffinating oil is non-aromatics as one of raw material of catalytic pyrolysis.

The heavy aromatics extraction solvent is selected from one or more the mixture in the materials such as methyl-sulphoxide, furfural, dimethyl formamide, monoethanolamine, ethylene glycol, 1,2-PD.The extractive process solvent recovery cycle is used.Extraction temperature is 40～120 ℃, and the volume ratio between solvent and raw material is 0.5～5.0.Extract is one of purpose product heavy aromatics, and raffinating oil is non-aromatics as one of raw material of step (3) catalytic pyrolysis.

The catalyzer of metathesis reaction is selected from Mo, W and Re is compound loaded on molecular sieve carrier, and molecular sieve comprises Y, β, SAPO series, ZSM is serial and MCM is serial.Temperature of reaction 10-450 ℃, pressure 0.1-3.0MPa, butylene weight space velocity 0.01-3h ^-1, ethylene/butylene is than being 0.2-10.The purpose product of metathesis reaction is propylene.

This technical scheme organically combines the techniques such as catalytic pyrolysis, steam cracking, oil gas fractionation, gas delivery, metathesis reaction, light aromatic solvent extracting and heavy aromatic solvent extracting, from the heavy feed stock that hydrogen richness is lower, produce to greatest extent the low-carbon alkenes such as propylene, ethene, especially propylene, its productive rate can surpass 40 heavy %, the aromatic hydrocarbons such as the toluene of coproduction simultaneously, dimethylbenzene.

Below in conjunction with accompanying drawing, method provided by the present invention is further detailed, but does not therefore limit the present invention.

Fig. 1 is the method flow schematic diagram of embodiment one.

Its technical process is as follows:

The pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 7 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, ethane, propane, butane and light aromatic hydrocarbons the raw material of difficult cracking such as raffinate oil through the bottom of pipeline 3 injecting lift pipe 2 reaction zone I together with atomizing steam from pipeline 4, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of difficult cracking on hot catalyzer, and upwards accelerated motion.Easily the raw material of cracking is through the bottom of pipeline 5 injecting lift pipe 2 reaction zone II together with atomizing steam from pipeline 6, with the existing logistics of riser reactor, mix, easily cracking reaction occurs in the raw material of cracking on the hotter catalyzer that contains a small amount of charcoal, and upwards accelerated motion; Chilling agent or other raw materials (also can not establishing) are through the bottom of pipeline 13 injecting lift pipe 2 reaction zone III together with atomizing steam from pipeline 14, with the existing logistics of riser reactor, mix, cracking reaction occurs in chilling agent or other raw materials (also can not establishing) on the catalyzer of the lesser temps that contains certain charcoal, and upwards accelerated motion.The oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 10 through pipeline 9, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 23, and catalyst fines returns to the first settling vessel by dipleg.In the first settling vessel, reclaimable catalyst flows to stripping stage 12, contacts with the steam from pipeline 21.The oil gas gone out from stripping reclaimable catalyst enters collection chamber 23 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 47 through regeneration standpipe 8.

The pre-lift medium is entered by riser reactor 12 bottoms through pipeline 11, from the regenerated catalyst of pipeline 17 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, C4 alkene and C5 hydrocarbon etc. again the raw material of cracking through the bottom of pipeline 15 injecting lift pipe 12 reaction zone IV together with atomizing steam from pipeline 16, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of cracking on hot catalyzer again, and upwards accelerated motion.180-250 ℃ of grade again the raw material of cracking through the bottom of pipeline 50 injecting lift pipe 12 reaction zone V together with atomizing steam from pipeline 51, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of cracking on the catalyzer of the lesser temps that contains certain charcoal again, and upwards accelerated motion.The oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator in the second settling vessel 20 through pipeline 19, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 24, and catalyst fines returns to the second settling vessel by dipleg.In the second settling vessel, reclaimable catalyst flows to stripping stage 22, contacts with the steam from pipeline 49.The oil gas gone out from stripping reclaimable catalyst enters collection chamber 24 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 47 through regeneration standpipe 18.

Main air enters revivifier through pipeline 48, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline.Catalyzer after regeneration enters riser tube through inclined tube 7 and 17.Oil gas in collection chamber 23 and 24 passes through respectively main oil gas piping 25 and 26, after in gas pipeline 27, mixing, enter follow-up separation system 28 (oil gas in collection chamber 23 and 24 also can enter respectively separation system separately), separate the propylene obtained and draw through pipeline 35; And C 4 olefin is drawn through pipeline 37; The catalytic pyrolysis dry gas is drawn through pipeline 32; Catalytic pyrolysis ethene is drawn through pipeline 33; Catalytic pyrolysis ethane is drawn through pipeline 34; Catalytic pyrolysis propane is drawn through pipeline 36; The catalytic pyrolysis butane is drawn through pipeline 38; Catalytic pyrolysis C5 draws through pipeline 39; Light aroamtic hydrocarbon raw material is drawn through pipeline 40, enters selective hydrogenation device 30; And then enter light aromatic extraction unit 31, and separating aromatic hydrocarbons and draw through pipeline 45, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) is drawn through pipeline 46; The cut of 180～250 ℃ is drawn through pipeline 41; The catalytic wax oil raw material is drawn out to heavy aromatics extracting unit 29 through pipeline 42, and isolated heavy aromatics is drawn through pipeline 43.

Fig. 2 is the method flow schematic diagram of embodiment two.

Its technical process is as follows:

The pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 7 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, ethane, propane, butane and light aromatic hydrocarbons the raw material of difficult cracking such as raffinate oil through the bottom of pipeline 3 injecting lift pipe 2 reaction zone I together with atomizing steam from pipeline 4, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of difficult cracking on hot catalyzer, and upwards accelerated motion.Easily the raw material of cracking is through the bottom of pipeline 5 injecting lift pipe 2 reaction zone II together with atomizing steam from pipeline 6, with the existing logistics of riser reactor, mix, easily cracking reaction occurs in the raw material of cracking on the hotter catalyzer that contains a small amount of charcoal, and upwards accelerated motion; Chilling agent or other raw material are through the bottom of pipeline (also can not establishing) 13 injecting lift pipe 2 reaction zone III together with atomizing steam from pipeline 14, with the existing logistics of riser reactor, mix, cracking reaction occurs in chilling agent or other raw materials (also can not establishing) on the catalyzer of the lesser temps that contains certain charcoal, and upwards accelerated motion.The oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 10 through pipeline 9, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 23, and catalyst fines returns to settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 12, contacts with the steam from pipeline 21.The oil gas gone out from stripping reclaimable catalyst enters collection chamber 23 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through regeneration standpipe 8.

The pre-lift medium is entered by riser reactor 12 bottoms through pipeline 11, from the regenerated catalyst of pipeline 17 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, C4 alkene and C5 hydrocarbon etc. again the raw material of cracking through the bottom of pipeline 13 injecting lift pipe 12 reaction zone IV together with atomizing steam from pipeline 14, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of cracking on hot catalyzer again, and upwards accelerated motion.180-250 ℃ of grade again the raw material of cracking through the bottom of pipeline 15 injecting lift pipe 12 reaction zone V together with atomizing steam from pipeline 16, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of cracking on the catalyzer of the lesser temps that contains certain charcoal again, and upwards accelerated motion.The oil gas generated and the reclaimable catalyst of inactivation enter through pipeline 19 cyclonic separator fallen in device 10, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 23, and catalyst fines returns to settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 12, contacts with the steam from pipeline 21.The oil gas gone out from stripping reclaimable catalyst enters collection chamber 23 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through regeneration standpipe 8.

Main air enters revivifier through pipeline 20, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline.Catalyzer after regeneration enters riser tube through inclined tube 7 and 17.Oil gas in collection chamber 23, through main oil gas piping 25, enters follow-up separation system 28, separates the propylene obtained and draws through pipeline 35; And C 4 olefin is drawn through pipeline 37; The catalytic pyrolysis dry gas is drawn through pipeline 32; Catalytic pyrolysis ethene is drawn through pipeline 33; Catalytic pyrolysis ethane is drawn through pipeline 34; Catalytic pyrolysis propane is drawn through pipeline 36; The catalytic pyrolysis butane is drawn through pipeline 38; Catalytic pyrolysis C5 draws through pipeline 39; Light aroamtic hydrocarbon raw material is drawn through pipeline 29, enters selective hydrogenation device 30; And then enter light aromatic extraction unit 31, and separating aromatic hydrocarbons and draw through pipeline 24, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) enters pipeline through pipeline 22 and returns to riser reactor; The cut of 180～250 ℃ is drawn and is returned to riser reactor through pipeline 27; Cut more than 250 ℃ is drawn through pipeline 26.

Fig. 3 is the method flow schematic diagram of embodiment three.

The pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 7 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, the raw material of difficult cracking is through the bottom of pipeline 3 injecting lift pipe 2 reaction zone I together with atomizing steam from pipeline 4, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of difficult cracking on hot catalyzer, and upwards accelerated motion.Easily the raw material of cracking is through the bottom of pipeline 5 injecting lift pipe 2 reaction zone II together with atomizing steam from pipeline 6, with the existing logistics of riser reactor, mix, easily cracking reaction occurs in the raw material of cracking on the hotter catalyzer that contains a small amount of charcoal, and upwards accelerated motion.The oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 10 through pipeline 9, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 23, and catalyst fines returns to settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 12, contacts with the steam from pipeline 21.The oil gas gone out from stripping reclaimable catalyst enters collection chamber 23 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through regeneration standpipe 8.

The pre-lift medium is entered by riser reactor 12 bottoms through pipeline 11, from the regenerated catalyst of pipeline 17 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, the raw material of cracking is through the bottom of pipeline 13 injecting lift pipe 12 reaction zone III together with atomizing steam from pipeline 14 again, with the existing logistics of riser reactor, mix, cracking reaction occurs in the raw material of cracking on hot catalyzer again, and upwards accelerated motion.The raw material of cracking, through the bottom of pipeline 15 injecting lift pipe 12 reaction zone IV together with atomizing steam from pipeline 16, mixes with the existing logistics of riser reactor again, then the raw material of cracking, on hot catalyzer, cracking reaction occurs, and upwards accelerated motion.The oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 10 through reaction zone IV and pipeline 19, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 23, and catalyst fines returns to settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 12, contacts with the steam from pipeline 21.The oil gas gone out from stripping reclaimable catalyst enters collection chamber 23 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through regeneration standpipe 8.

Main air enters revivifier through pipeline 20, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline.Catalyzer after regeneration enters riser tube through inclined tube 7 and 17.Oil gas in collection chamber 23 is through main oil gas piping 22, enter follow-up separation system 45, separating the propylene obtained draws through pipeline 47, and carbon four hydro carbons are drawn through pipeline 48, the part C 4 olefin enters pipeline 44 and returns to riser reactor, the catalytic pyrolysis dry gas is drawn through pipeline 46, catalytic pyrolysis ethene is drawn through pipeline 41, catalytic pyrolysis C5 draws and returns to riser reactor 12 through pipeline 42, light aroamtic hydrocarbon raw material is drawn through pipeline 24, enter selective hydrogenation device 25, and then enter light aromatic extraction unit 26, the light aromatic hydrocarbons separated is drawn through pipeline 27, non-aromatics (being that light aromatic hydrocarbons is extracted oil out) is returned to steam cracking unit 35 through pipeline 45, or/and return to riser reactor 2 through pipeline 28, the cut of 180～250 ℃ returns to riser reactor 12 through pipeline 29, the catalytic wax oil raw material cut of 250 ℃ (namely >) is drawn out to heavy aromatics extracting unit 31 through pipeline 30, isolating heavy aromatics draws through pipeline 32, heavy aromatics is raffinated oil and is returned to riser reactor 2 through pipeline 33, the ethane of catalytic pyrolysis, propane and butane are drawn and are entered steam cracking unit 35 through pipeline 34, the purpose product ethene separated and propylene are drawn through pipeline 36 and 43 respectively, the hydrogen separated and methane are drawn through pipeline 37, the ethane separated, propane, butane and pentane return to steam cracking unit 35 through pipeline 38, the butylene separated and amylene enter pipeline 5 through pipeline 39 and return to riser tube 2, and the steam cracking petroleum naphtha separated enters hydrogenation unit 25 through pipeline 40.

Fig. 4 is the method flow schematic diagram of embodiment four.

Main air enters revivifier through pipeline 20, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline.Catalyzer after regeneration enters riser tube through inclined tube 7 and 17.Oil gas in collection chamber 23, through main oil gas piping 22, enters follow-up separation system 41, separates the propylene obtained and draws through pipeline 43; And butylene is drawn through pipeline 44 and is entered transposable element 35; Catalytic pyrolysis ethene enters transposable element 35 through pipeline 34; Catalytic pyrolysis hydrogen and methane are drawn through pipeline 42; Catalytic pyrolysis ethane is drawn through pipeline 37; Propane is drawn through pipeline 38; Butane is drawn through pipeline 39; C5 draws through pipeline 40; Light aroamtic hydrocarbon raw material is drawn through pipeline 24, enters selective hydrogenation device 25; And then enter light aromatic extraction unit 26, and separating aromatic hydrocarbons and draw through pipeline 27, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) is returned to riser tube 12 through pipeline 28; The cut of 180～250 ℃ is drawn and is returned to riser tube 12 through pipeline 29; The catalytic wax oil raw material is drawn out to heavy aromatics extracting unit 31 through pipeline 30, and isolated heavy aromatics is drawn through pipeline 32, and heavy aromatics is raffinated oil and returned to riser tube 2 through pipeline 33; Transposable element purpose product propylene is drawn through pipeline 36.

The following examples will be further described present method, but therefore not limit present method.

In embodiment, raw material used is VGO, and its character is as shown in table 1.In embodiment, extraction solvent used is tetramethylene sulfone.

Catalytic cracking catalyst preparation method used in embodiment is summarized as follows:

1), by 20gNH ₄Cl is dissolved in 1000g water, adds 100g (butt) crystallization product ZRP-1 zeolite (production of Qilu Petrochemical Company catalyst plant, SiO in this solution ₂/ Al ₂O ₃=30, content of rare earth RE ₂O ₃=2.0 heavy %), after 90 ℃ of exchange 0.5h, filter to obtain filter cake; Add 4.0gH ₃PO ₄(concentration 85%) and 4.5gFe (NO ₃) ₃Be dissolved in 90g water, dry with the filter cake hybrid infusion; Then at 550 ℃ of roasting temperatures, process and obtained phosphorous and MFI structure mesopore zeolite iron in 2 hours, its elementary analytical chemistry consists of

0.1Na ₂O·5.1Al ₂O ₃·2.4P ₂O ₅·1.5Fe ₂O ₃·3.8RE ₂O ₃·88.1SiO ₂。

2), use 250kg decationized Y sieve water by 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add again 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%), with hydrochloric acid, its PH is adjusted to 2-4, stir, under 60-70 ℃ standing aging 1 hour, maintenance PH was 2-4, cools the temperature to below 60 ℃, add 41.5Kg aluminium colloidal sol (Qilu Petrochemical Company catalyst plant product, Al ₂O ₃Content is 21.7m%), stirred 40 minutes, obtain mixed serum.

3), by step 1) MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (the Qilu Petrochemical Company catalyst plant Industrial products of the phosphorous and iron for preparing, lattice constant is 2.445-2.448nm, butt is 2.0kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, wash away free Na ⁺, being drying to obtain the catalytic cracking catalyst sample, phosphorous MFI structure mesopore zeolite, 3 heavy %DASY zeolites, the 32 heavy % pseudo-boehmites, 6 with iron of 15 heavy % that consist of of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.

Embodiment 1

This embodiment tests according to the flow process of Fig. 1, and stock oil A directly, as the raw material of catalytic pyrolysis, tests on the middle-scale device by riser reactor, and the temperature of reaction of reaction zone I, II, IV, V is followed successively by 600 ℃, 500 ℃, 540 ℃, 470 ℃.Feeding line 3 chargings are that ethane, propane, butane and light aromatic hydrocarbons are raffinated oil; Feeding line 5 chargings are that heavy aromatics is raffinated oil and raw material A; Feeding line 15 chargings are C4 alkene and C5 hydro carbons; Feeding line 50 chargings are 180-250 ℃ of

cut.In collection chamber

23 and 24, oil gas is mixed in subsequent separation system 28 in pipeline 27 through

pipeline

25 and 26 respectively.Operation condition, product distribute as shown in table 2.

As can be seen from Table 2, propylene, yield of ethene are respectively up to 40.60 heavy %, 16.65 heavy %, and toluene and dimethylbenzene yield are respectively 7.09 heavy % and 10.43 heavy %.

Embodiment 2

This embodiment tests according to the flow process of Fig. 2, and stock oil B directly, as the raw material of catalytic pyrolysis, tests in the middle scale riser reactor, and the temperature of reaction of reaction zone I, II, IV, V is followed successively by 590 ℃, 505 ℃, 530 ℃, 470 ℃.Feeding line 3 chargings are that ethane, propane, butane and light aromatic hydrocarbons are raffinated oil; Feeding line 5 chargings are that heavy aromatics is raffinated oil and raw material B; Feeding line 13 chargings are C4 alkene and C5 hydro carbons; Feeding line 15 chargings are 180-250 ℃ of cut.In collection chamber 23, oil gas enters in subsequent separation system 28 through pipeline 25.Operation condition, product distribute as shown in table 2.

As can be seen from Table 2, propylene, yield of ethene are respectively up to 32.97 heavy %, 11.43 heavy %, and toluene and dimethylbenzene yield are respectively 4.38 heavy % and 7.10 heavy %.

Embodiment 3

This embodiment tests according to the flow process of Fig. 3, and stock oil C directly, as the raw material of catalytic pyrolysis, tests in the middle scale riser reactor, and the temperature of reaction of reaction zone I, II, III, IV is followed successively by 620 ℃, 530 ℃, 520 ℃, 470 ℃.Feeding line 3 chargings are that light aromatic hydrocarbons is raffinated oil; Feeding line 5 chargings are that heavy aromatics is raffinated oil and raw material C; Feeding line 13 chargings are C4 alkene and C5 hydro carbons; Feeding line 15 chargings are 180-250 ℃ of cut.In collection chamber 23, oil gas enters in subsequent separation system 45 through pipeline 22.Operation condition, product distribute as shown in table 4.

As can be seen from Table 4, propylene, yield of ethene are respectively up to 29.13 heavy %, 19.87 heavy %, and toluene and dimethylbenzene yield are respectively 8.54 heavy % and 12.89 heavy %.

Embodiment 4

This embodiment tests according to the flow process of Fig. 4, and stock oil A directly, as the raw material of catalytic pyrolysis, tests in the middle scale riser reactor, and the temperature of reaction of reaction zone I, II, III, IV is followed successively by 630 ℃, 540 ℃, 530 ℃, 500 ℃.Feeding line 3 chargings are that ethane, propane, the light aromatic hydrocarbons of butane are raffinated oil; Feeding line 5 chargings are that heavy aromatics is raffinated oil and raw material B; Feeding line 13 chargings are C4 alkene and C5 hydro carbons; Feeding line 15 chargings are 180-250 ℃ of cut.In collection chamber 23, oil gas enters in subsequent separation system 41 through pipeline 22.Operation condition, product distribute as shown in table 4.

As can be seen from Table 4, propylene is up to 46.38 heavy %, and toluene and dimethylbenzene yield are respectively 3.67 heavy % and 9.72 heavy %.

Table 1

	Embodiment 1,4	Embodiment 2	Embodiment 3
				The stock oil numbering	A	B	C
Stock oil character
				Density (20 ℃), g/cm ³	0.8976	0.9148	0.9015
Sulphur content, ppm	3700	5600	3200
				Nitrogen content, ppm	2600	2100	2800
Aromatic hydrocarbons, m%	24.9	30.6	33.1
				C，m％	86.44	86.25	86.45
H，m％	12.87	12.71	12.51
				Boiling range (ASTM D-1160), ℃
IBP	302	329	304
				10％	360	361	365
30％	417	408	410
				50％	457	450	443
70％	475	483	480
				90％	505	506	504
95％	537	528	530
				EP	540	542	541

Table 2

	Embodiment 1	Embodiment 2
			The stock oil numbering	A	B
The catalytic pyrolysis unit
			Operational condition
Riser reactor
			Reaction zone I
Temperature of reaction, ℃	600	590
			Agent-oil ratio, m/m	60	60
Water vapor/raw material weight ratio	0.25	0.25
			Reaction zone II
Temperature of reaction, ℃	500	505
			Agent-oil ratio, m/m	20	20
Water vapor/raw material weight ratio	0.15	0.15
			Reaction zone IV, ℃
Temperature of reaction, ℃	540	530
			Agent-oil ratio, m/m	15	15
Water vapor/raw material weight ratio	0.10	0.1
			Reaction zone V, ℃
Temperature of reaction, ℃	470	470
			Agent-oil ratio, m/m	8	8
Water vapor/raw material weight ratio	0.08	0.08
			Product distributes, m%
H ₂+CH ₄	5.01	4.98
			Ethene	16.65	18.79
Propylene	40.6	43.68
			Benzene	3.12	4
Toluene	7.09	7.83
			Dimethylbenzene	10.43	11.54
Polycyclic aromatic hydrocarbons	8.92	1.03
			Coke	8.18	8.15

Table 3

	Embodiment 3	Embodiment 4
			The stock oil numbering	C	A
The catalytic pyrolysis unit
			Operational condition
Riser reactor
			Reaction zone I
Temperature of reaction, ℃	620	630
			Agent-oil ratio, m/m	60	60
Water vapor/raw material weight ratio	0.25	0.25
			Reaction zone II
Temperature of reaction, ℃	530	540
			Agent-oil ratio, m/m	20	20
Water vapor/raw material weight ratio	0.15	0.15
			Reaction zone III, ℃
Temperature of reaction, ℃	520	530
			Agent-oil ratio, m/m	15	15
Water vapor/raw material weight ratio	0.1	0.1
			Reaction zone IV, ℃
Temperature of reaction, ℃	470	500
			Agent-oil ratio, m/m	8	8
Water vapor/raw material weight ratio	0.08	0.08
			Product distributes, m%
H ₂+CH ₄	4.62	5.35
			Ethene	19.87	/
Propylene	29.13	46.38
			Benzene	3.45	3.67
Toluene	8.54	9.72
			Dimethylbenzene	12.89	15.11
Polycyclic aromatic hydrocarbons	13.52	11.65
			Coke	7.98	8.12

Claims

1. the catalysis conversion method of a preparing low-carbon olefins and aromatic hydrocarbons, is characterized in that the method comprises the following steps:

(1) stock oil of difficult cracking enters the first riser reactor bottom, with the catalytic cracking catalyst of heat regeneration, contacts, at 550 ℃-800 ℃ of temperature of reaction, weight hourly space velocity 100h ^-1-800h ^-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;

(2) reaction effluent separates without finish, mixes with the stock oil of easy cracking, and easily the stock oil of cracking is at 450 ℃-620 ℃ of temperature of reaction, weight hourly space velocity 0.1h ^-1-100h ^-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 2-30, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;

(3) reaction effluent separates without finish, and with the stock oil of optional difficult cracking, easily one or more in cracking stock oil, cold shock medium are mixed, stock oil is at 400 ℃-550 ℃ of temperature of reaction, weight hourly space velocity 10h ^-1-300h ^-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;

(5) the described reaction oil gas of step (4) enter separation system separate obtain comprising ethene, propylene, C4 alkene, C2-C4 alkane and C5 hydrocarbon, gasoline, boiling range is the 180 ℃～cut of 250 ℃ and the product of catalytic wax oil, wherein gasoline obtains light aromatic hydrocarbons and gasoline is raffinated oil through light Aromatics Extractive Project;

(6) the described C4 alkene of step (5) and C5 hydrocarbon, gasoline are raffinated oil, boiling range is a kind of in the cut of 180 ℃～250 ℃ or wherein more than one mixture as cracking stock again, send in the second riser reactor, with hot regenerated catalyst, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h ^-1-800h ^-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 2-100, the weight ratio of water vapor and raw material is to carry out catalyzed conversion under the condition of 0.05-1.0, reclaimable catalyst separates by cyclonic separator with reaction oil gas, reclaimable catalyst enters stripper, through stripping or not stripping, after coke burning regeneration in described revivifier, return to the second riser reactor.

2. according to the method for claim 1, it is characterized in that described easy cracking stock is petroleum hydrocarbon and/or other mineral oil, its Petroleum Hydrocarbon is selected from decompressed wax oil, normal pressure wax oil, wax tailings, deasphalted oil, vacuum residuum, long residuum, heavy aromatics and raffinates oil, and other mineral oil is liquefied coal coil, tar sand oil, shale oil.

3. according to the method for claim 2, it is characterized in that described easy cracking stock is selected from one or more that decompressed wax oil, normal pressure wax oil, wax tailings, deasphalted oil, vacuum residuum, long residuum, heavy aromatics are raffinated oil.

4. according to the method for claim 1, it is characterized in that described difficult cracking stock is the low-carbon (LC) molecule, be selected from carbonatoms and be 2～8 hydro carbons, slurry oil, diesel oil, gasoline, light aromatic hydrocarbons are raffinated oil one or more.

5. according to the method for claim 1, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % of the heavy %-50 of zeolite 10, the heavy % of the heavy %-90 of inorganic oxide 5, the heavy % of the heavy %-70 of clay 0, its mesolite is as active ingredient, for mesopore zeolite and/or optional large pore zeolite, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, large pore zeolite selects free Rare Earth Y, rare earth hydrogen Y, the super steady Y that different methods obtains, one or more in this group zeolite that high silicon Y forms.

6. according to the method for claim 1, it is characterized in that described cold shock medium is one or more the mixture of arbitrary proportion be selected from cold shock agent, cooling regenerated catalyst, cooling half regenerated catalyst, reclaimable catalyst and live catalyst, wherein the cold shock agent is one or more that are selected from liquefied gas, propane, C4 hydrocarbon, raw gasline, stable gasoline, diesel oil, water; Cooling regenerated catalyst and half cooling regenerated catalyst are reclaimable catalyst cooling obtaining after two-stage regeneration and one section regeneration respectively.

7. according to the method for claim 1, it is characterized in that the boiling range of described catalytic wax oil is greater than 250 ℃, the outlet of catalytic wax oil has one or more in following items:

The oil that acts as a fuel,

Through hydrofining as diesel component,

Returning reactor after hydrofining,

8. according to the method for claim 1, it is characterized in that the method also comprises the following steps:

(7) catalytic pyrolysis C2-C4 alkane and water vapor enter the steam cracking reaction device, carry out cracking reaction under 700 ℃-1000 ℃ of temperature of reaction, and separating reaction oil gas obtains H ₂, CH ₄, steam cracking C2-C3 alkene, steam cracking C2-C3 alkane, steam cracking C ₄-C ₅, steam cracking petroleum naphtha, oil fuel, wherein steam cracking C2-C3 alkene is one of purpose product, steam cracking C2-C3 alkane loops back the steam cracking reaction device, steam cracking C ₄-C ₅Loop back the catalytic cracking reaction device;

9. according to the method for claim 1, it is characterized in that the method also comprises the following steps: