CN101747929B

CN101747929B - Catalytic conversion method for preparing lower olefins and aromatics

Info

Publication number: CN101747929B
Application number: CN2008102276523A
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: 2013-01-09
Anticipated expiration: 2028-11-28
Also published as: CN101747929A

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 spent catalyst after stripping enters a first regenerator and returns to a first riser after scorching regeneration, 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 catalyst is burned and regenerated in a second regenerator and then returns to a second riser reactor. 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 to the catalysis conversion method of hydro carbons in the situation that does not have hydrogen, more particularly, is a kind of method that heavy feed stock is converted into 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 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 mainly is steam cracking and catalytic cracking (FCC), wherein steam cracking is produced ethene, propylene take lightweight oils such as petroleum naphthas as raw material by thermo-cracking, but the productive rate of propylene only is that FCC is then take mink cell focuses such as decompressed wax oils (VGO) as raw material about 15 heavy %.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, and a small amount of (about 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 owing to 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 behind coke burning regeneration uses.The overall yield of the method propylene and butylene can reach about 40%, 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, the catalyzer take a large amount of inert substances as matrix, and take VGO as raw material, 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 a plurality of reaction zones carries out cracking reaction, with voluminous low-molecular olefine.

Aromatic hydrocarbons also is 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 with through regeneration catalytic cracking catalyst, water vapor in the catalytic cracking reaction device, contact, under the condition of the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the stock oil of 500～700 ℃ of temperature, pressure 0.15～0.4MPa, catalytic cracking catalyst and 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 simultaneously aromatic hydrocarbons such as coproduction toluene and dimethylbenzene.

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 come catalytically cracked gasoline is carried out upgrading 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 the 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 satisfy 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 a large amount of propylene, ethene and aromatic hydrocarbons.

Summary of the invention

Technical problem to be solved by this invention provides a kind of catalysis conversion method heavy feed stock is converted into 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, contacts with the catalytic cracking catalyst of heat regeneration, 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, the 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 the first riser tube through entering the first revivifier behind the stripping behind 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 180 ℃～250 ℃ cut 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 180 ℃～250 ℃ the cut or wherein more than one mixture send in the second riser reactor as cracking stock again, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h with hot regenerated catalyst ^-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, in Second reactivator, return the second riser reactor behind the coke burning regeneration.

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 behind the 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, the 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, the 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 in half regenerated catalyst, reclaimable catalyst and the live catalyst of the regenerated catalyst that is selected from cold shock agent, cooling, cooling, 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, the water; The regenerated catalyst of cooling and half regenerated catalyst of cooling are that reclaimable catalyst cools off after two-stage regeneration and one section regeneration respectively and obtains.

Described again cracking stock is a kind of in the raffinating oil of cut, the light Aromatics Extractive Project of gasoline (being that boiling range is 70 ℃～180 ℃ cut) of boiling range＜70 ℃, cut, C4 alkene and the 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 the 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 zeolite 10 heavy %-50, the heavy % of inorganic oxide 5 heavy %-90, the heavy % of clay 0 heavy %-70.

Its mesolite is selected from mesopore zeolite and optional large pore zeolite as active ingredient, and mesopore zeolite accounts for the heavy % of 50 heavy %-100 of zeolite gross weight, and the heavy % of preferred 70 heavy %-100, large pore zeolite account for the heavy % of 0 heavy %-50 of zeolite gross weight, the heavy % of preferred 0 heavy %-30.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel 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 is selected from one or more the mixture in this group zeolite that the super steady Y that is obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods, high silicon Y consist of.

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

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

Catalytic cracking catalyst in each reactor is different, and large pore zeolite and mesopore zeolite shared ratio in zeolite is different in the catalyzer.

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.The regenerated catalyst of cooling and half regenerated catalyst of cooling are that reclaimable catalyst cools off after two-stage regeneration and one section regeneration respectively and obtains, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 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 the 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, perhaps ethene, propylene and butylene.

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

Described 180-250 ℃ cut is between the FCC of routine 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 seen patent of invention 200710120105.0, after separating unit separates, returns the cracking unit; Enter the heavy aromatics extraction plant greater than 250 ℃ cuts, raffinate oil and return the cracking unit, 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 the 25 heavy %, more than the preferred 40 heavy %, and the aromatic hydrocarbons such as while coproduction toluene and dimethylbenzene.

Description of drawings

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

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

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

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

Embodiment

The embodiment that the below enumerates 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 180 ℃～250 ℃ the cut or wherein more than one mixture send in the second riser reactor as cracking stock again, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h with hot regenerated catalyst ^-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, in Second reactivator, return the second riser reactor behind the coke burning regeneration;

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

Embodiment two

(7) catalytic wax oil is returned 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 180 ℃～250 ℃ cut 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° enter the steam cracking reaction device with water vapor, 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 ⁼Be 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, obtains aromatic hydrocarbons and raffinates oil through solvent extraction again, and wherein aromatic hydrocarbons is one of purpose product, raffinates oil and returns 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 180 ℃～250 ℃ cut 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 180 ℃～250 ℃ the cut or wherein more than one mixture send in the second riser reactor as cracking stock again, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h with hot regenerated catalyst ^-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, in Second reactivator, return the second riser reactor behind the coke burning regeneration;

(7) ethene and butylene enter the olefin metathesis reactions device, and ethene and butylene are converted into 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 respectively narration.

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, 180～250 ℃ cut 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 that comes from the cracking unit is sent into separation column with steam cracking reaction oil gas and is separated.

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

Extract the boiling range scope from the separation column middle and lower part out and be 250～360 ℃ cut, mainly contain double ring arene and polycyclic aromatic hydrocarbons in this cut, 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.

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

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

Stripping tower is actually a depentanizer, and thick light aromatic hydrocarbons material is divided into C6+ cut and C5-cut in stripping tower.Mainly containing mononuclear aromatics in the C6+ cut, 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 separating, discharge C4 and C 5 fraction at the bottom of the depropanizing tower, after cooling, enter debutanizing tower.The logistics of debutylize cat head enters the butylene rectifying tower, and the debutanizing tower bottoms stream is discharged C 5 fraction, and the reactor that this cut returns the cracking unit further reacts.The butylene of butylene rectifying tower top returns 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 the cracking unit further reacts.Cat head is discharged the C3-cut, sends into demethanizing tower after cooling.The demethanizing cat head 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 cat head, and the deethanizing column bottoms stream is sent into propylene rectification tower.Ethylene distillation cat head polymer grade ethylene goes out device, and ethane send the ethane cracking furnace cracking of cracking unit at the bottom of the ethylene rectification tower.Propylene rectification tower top polymerization-grade propylene goes out device, and propane send the ethane cracking furnace cracking of cracking unit at the bottom of the propylene rectification tower.

The steam cracking unit

In this unit, catalytic pyrolysis C ₂°-C ₃° contact under 700 ℃-1000 ℃ with water vapor, 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 ⁼Be one of purpose product;

In this unit, catalytic pyrolysis petroleum naphtha and steam cracking petroleum naphtha obtain first 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 obtaining purpose product propylene for contacting the generation metathesis reaction with metathesis catalyst under the 0.2-10 condition.

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 the steam cracking unit as one of raw material of steam cracking.

The solvent of light Aromatics Extractive Project is selected from one or more mixture of this group material of being made of tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether.Recycle after the solvent recuperation.The temperature of solvent extraction is 80-120 ℃, and the volume ratio between solvent and the 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 the 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, produce to greatest extent the low-carbon alkenes such as propylene, ethene from the heavy feed stock that hydrogen richness is lower, especially propylene, its productive rate can surpass 40 heavy %, the aromatic hydrocarbons such as simultaneously coproduction toluene, 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 synoptic 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 raffinate oil etc. the raw material of difficult cracking through pipeline 3 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of difficult cracking, and upwards accelerated motion.Easily the raw material of cracking through pipeline 5 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone II of pipeline 6, mix with the existing logistics of riser reactor, easily cracking reaction occurs at the hotter catalyzer that contains a small amount of charcoal in the raw material of cracking, and upwards accelerated motion; Cold shock medium or other raw materials (also can not establishing) through pipeline 13 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone III of pipeline 14, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of the lesser temps that contains certain charcoal in cold shock medium or other raw materials (also can not establishing), and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the 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 the first settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 12 in the first settling vessel, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 23 behind cyclonic separator.Reclaimable catalyst behind the stripping enters the first 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 pipeline 15 with the bottom from the atomizing steam injecting lift pipe 12 reaction zone IV of pipeline 16, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of cracking again, and upwards accelerated motion.180-250 ℃ of grade again the raw material of cracking through pipeline 50 with the bottom from the atomizing steam injecting lift pipe 12 reaction zone V of pipeline 51, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of the lesser temps that contains certain charcoal in the raw material of cracking again, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the second settling vessel 52 through pipeline 19, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 24, and catalyst fines returns the second settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 22 in the second settling vessel, contacts with steam from pipeline 20.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 24 behind cyclonic separator.Reclaimable catalyst behind the stripping enters Second reactivator 18 through regeneration standpipe 18.

The first main air enters the first 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 the regeneration enters the first riser tube through inclined tube 7.The second main air enters Second reactivator through pipeline 49, 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 the regeneration enters the second riser tube through inclined tube 17.Oil gas in the collection chamber 23 and 24 passes through respectively main oil gas piping 25 and 26, enter follow-up separation system 28 (oil gas in the collection chamber 23 and 24 also can enter respectively separately separation system) after in gas pipeline 27, mixing, separate the propylene that obtains 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 to tell aromatic hydrocarbons and draw through pipeline 45, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) is drawn through pipeline 46; 180～250 ℃ cut 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 synoptic 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 raffinate oil etc. the raw material of difficult cracking through pipeline 3 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of difficult cracking, and upwards accelerated motion.Easily the raw material of cracking through pipeline 5 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone II of pipeline 6, mix with the existing logistics of riser reactor, easily cracking reaction occurs at the hotter catalyzer that contains a small amount of charcoal in the raw material of cracking, and upwards accelerated motion; Cold shock medium or other raw material through pipeline (also can not establishing) 26 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone III of pipeline 27, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of the lesser temps that contains certain charcoal in cold shock medium or other raw materials (also can not establishing), and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the first settling vessel 8 through pipeline 9, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 22, and catalyst fines returns the first settling vessel by dipleg.Reclaimable catalyst flows to stripping stage in the first settling vessel, contacts with steam from pipeline.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 behind cyclonic separator.Reclaimable catalyst behind the stripping enters in the first revivifier 10 through regeneration standpipe.

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 pipeline 13 with the bottom from the atomizing steam injecting lift pipe 12 reaction zone IV of pipeline 14, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of cracking again, and upwards accelerated motion.180-250 ℃ of grade again the raw material of cracking through pipeline 15 with the bottom from the atomizing steam injecting lift pipe 12 reaction zone V of pipeline 16, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of the lesser temps that contains certain charcoal in the raw material of cracking again, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the second settling vessel 18 through pipeline 19, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 23, and catalyst fines returns the second settling vessel by dipleg.Reclaimable catalyst flows to stripping stage in the second settling vessel, contacts with steam from pipeline.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 23 behind cyclonic separator.Reclaimable catalyst behind the stripping enters in the Second reactivator 11 through regeneration standpipe.

The first 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 the regeneration enters in the first riser tube 2 through inclined tube 7.The second main air enters revivifier through pipeline 21, 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 the regeneration enters in the second riser tube 12 through inclined tube 17.Oil gas in the collection chamber 22 and 23 passes through respectively main oil gas piping 24 and 25, enters follow-up separation system 28, separates the propylene that obtains 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 to tell aromatic hydrocarbons and draw through pipeline 24, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) enters pipeline through pipeline 22 and returns riser reactor; 180～250 ℃ cut is drawn through pipeline 27 and is returned riser reactor; Cut more than 250 ℃ is drawn through pipeline 41 and is entered the exquisite device production diesel oil of hydrogenation or enter hydrogenation unit 44, and the hydrogenation after cut enters the first riser reaction zone II through pipeline 45.

Fig. 3 is the method flow synoptic 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 through pipeline 3 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of difficult cracking, and upwards accelerated motion.Easily the raw material of cracking through pipeline 5 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone II of pipeline 6, mix with the existing logistics of riser reactor, easily cracking reaction occurs at the hotter catalyzer that contains a small amount of charcoal in the raw material of cracking, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the first settling vessel 8 through pipeline 9, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 22, and catalyst fines returns the first settling vessel by dipleg.Reclaimable catalyst flows to stripping stage in the first settling vessel, contacts with steam from pipeline.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 behind cyclonic separator.Reclaimable catalyst behind the stripping enters the first revivifier 10 through regeneration standpipe.

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, again the raw material of cracking through pipeline 13 with the bottom from the atomizing steam injecting lift pipe 12 reaction zone III of pipeline 14, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of cracking again, and upwards accelerated motion.The raw material of cracking, mixes with the existing logistics of riser reactor with the bottom from the atomizing steam injecting lift pipe 12 reaction zone IV of pipeline 16 through pipeline 15 again, and the raw material of cracking at the catalyzer of heat cracking reaction occurs again, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the second settling vessel 18 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 the second settling vessel by dipleg.Reclaimable catalyst flows to stripping stage in the second settling vessel, contacts with steam from pipeline.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 23 behind cyclonic separator.Reclaimable catalyst behind the stripping enters Second reactivator 11 through regeneration standpipe 8.

The first 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 the regeneration enters in the first riser tube 2 through inclined tube 7.The second main air enters revivifier through pipeline 21, 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 the regeneration enters in the second riser tube 12 through inclined tube 17.Oil gas in the collection chamber 22 and 23 passes through respectively main oil gas piping 24 and 25, enter follow-up separation system 45, separating the propylene that obtains draws through pipeline 47, and C 4 olefin is drawn through pipeline 48, the part C 4 olefin enters pipeline 44 and returns riser reactor, the catalytic pyrolysis dry gas is drawn through pipeline 46, catalytic pyrolysis ethene is drawn through pipeline 41, catalytic pyrolysis C5 draws through pipeline 42 and returns riser reactor, light aroamtic hydrocarbon raw material is drawn through pipeline 24, enter selective hydrogenation device 49, and then enter light aromatic extraction unit 50, the light aromatic hydrocarbons of telling is drawn through pipeline 51, and non-aromatics (being that light aromatic hydrocarbons is extracted oil out) is returned steam cracking unit 35 through pipeline 45, or/and return riser reactor through pipeline 52,180～250 ℃ cut returns riser reactor through pipeline 29, catalytic wax oil raw material (namely〉250 ℃ cut) is drawn out to heavy aromatics extracting unit 31 through pipeline 30, isolates heavy aromatics and draws through pipeline 32, and heavy aromatics is raffinated oil and returned riser reactor through pipeline 33; The ethane of catalytic pyrolysis, propane and butane are drawn through pipeline 34 and are entered steam cracking unit 35, the purpose product ethene of telling and propylene are drawn through pipeline 36 and 43 respectively, the hydrogen of telling and methane are drawn through pipeline 37, the ethane of telling, propane, butane and pentane return steam cracking unit 35 through pipeline 38, the butylene of telling and amylene enter pipeline 5 through pipeline 39 and return riser tube, and the steam cracking petroleum naphtha of telling enters hydrogenation unit 25 through pipeline 40.

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

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, again the raw material of cracking through pipeline 13 with the bottom from the atomizing steam injecting lift pipe 12 reaction zone III of pipeline 14, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of cracking again, and upwards accelerated motion.The raw material of cracking, mixes with the existing logistics of riser reactor with the bottom from the atomizing steam injecting lift pipe 12 reaction zone IV of pipeline 16 through pipeline 15 again, and the raw material of cracking at the catalyzer of heat cracking reaction occurs again, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the second settling vessel 18 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 the second settling vessel by dipleg.Reclaimable catalyst flows to stripping stage in the second settling vessel, contacts with steam from pipeline.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 23 behind cyclonic separator.Reclaimable catalyst behind the stripping enters Second reactivator 11 through regeneration standpipe.

The first 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 the regeneration enters in the first riser tube 2 through inclined tube 7.The second main air enters revivifier through pipeline 21, 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 the regeneration enters in the second riser tube 12 through inclined tube 17.Oil gas in the collection chamber 22 and 23 passes through respectively main oil gas piping 24 and 25, enters follow-up separation system 41, separates the propylene that obtains 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 45, enters selective hydrogenation device 46; And then enter light aromatic extraction unit 47, and to tell aromatic hydrocarbons and draw through pipeline 49, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) is returned riser tube through pipeline 48; 180～250 ℃ cut is drawn through pipeline 29 and is returned riser tube; 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 riser tube 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.

Used raw material is VGO among the embodiment, and its character is as shown in table 1.Used extraction solvent is tetramethylene sulfone among the embodiment.

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

1), with 20gNH ₄Cl is dissolved in the 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 %), behind 90 ℃ of exchange 0.5h, filter to get filter cake; Add 4.0gH ₃PO ₄(concentration 85%) and 4.5gFe (NO ₃) ₃Be dissolved in the 90g water, dry with the filter cake hybrid infusion; Then process at 550 ℃ of roasting temperatures 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 with 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 63.0m%), with hydrochloric acid its PH is transferred to 2-4, stir, left standstill under 60-70 ℃ aging 1 hour, maintenance PH is 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), with step 1) MFI structural zeolite (butt is 18kg) and DASY zeolite (the Qilu Petrochemical Company catalyst plant Industrial products of the phosphorous and iron of preparation, 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, the flush away Na that dissociates ⁺, being drying to obtain catalytic cracking catalyst sample 1, consist of 15 heavy % MFI structural zeolite, 2 heavy %DASY zeolites, the 29 heavy % pseudo-boehmites, 8 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.

4), with step 1) MFI structural zeolite (butt is 42kg) and DASY zeolite (the Qilu Petrochemical Company catalyst plant Industrial products of the phosphorous and iron of preparation, 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, the flush away Na that dissociates ⁺, being drying to obtain catalytic cracking catalyst sample 2, consist of 30 heavy % MFI structural zeolite, 1 heavy %DASY zeolite, the 24 heavy % pseudo-boehmites, 6 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.

Embodiment 1

This embodiment tests according to the flow process of Fig. 1, stock oil A is directly as the raw material of catalytic pyrolysis, tested by the middle-scale device of riser reactor, the temperature of reaction of the first riser reaction zone I, II is followed successively by 610 ℃, 500 ℃, and the temperature of reaction of the second riser reaction zone IV, V is followed successively by 530 ℃, 470 ℃.The first riser tube catalyst system therefor is that catalyst sample 1, the second riser tube catalyst system therefor is catalyst sample 2.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.Oil gas is mixed in the subsequent separation system 28 in pipeline 27 through

pipeline

25 and 26 respectively in the collection chamber 23 and 24.Operation condition, product distribute as shown in table 2.

As can be seen from Table 2, propylene, yield of ethene are respectively up to 42.03 heavy %, 15.17 heavy %, and toluene and dimethylbenzene yield are respectively 7.17 heavy % and 10.44 heavy %.

Embodiment 2

This embodiment tests according to the flow process of Fig. 2, stock oil B is directly as the raw material of catalytic pyrolysis, in the middle scale riser reactor, test, the temperature of reaction of the first riser reaction zone I, II is followed successively by 590 ℃, 505 ℃, and the temperature of reaction of the second riser reaction zone IV, V is followed successively by 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.Oil gas enters in the subsequent separation system 28 through

pipeline

24 and 25 respectively in the collection chamber 22 and 23.Operation condition, product distribute as shown in table 2.

As can be seen from Table 2, propylene, yield of ethene are respectively up to 35.14 heavy %, 10.57 heavy %, and toluene and dimethylbenzene yield are respectively 4.39 heavy % and 7.12 heavy %.

Embodiment 3

This embodiment tests according to the flow process of Fig. 3, stock oil C is directly as the raw material of catalytic pyrolysis, in the middle scale riser reactor, test, the temperature of reaction of the first riser reaction zone I, II is followed successively by 620 ℃, 530 ℃, and the temperature of reaction of the second riser reaction zone IV, V is followed successively by 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.Oil gas enters in the subsequent separation system 45 through

pipeline

24 and 25 respectively in the collection chamber 22 and 23.Operation condition, product distribute as shown in table 3.

As can be seen from Table 3, propylene, yield of ethene are respectively up to 29.94 heavy %, 19.88 heavy %, and toluene and dimethylbenzene yield are respectively 3.45 heavy % and 8.53 heavy %.

Embodiment 4

This embodiment tests according to the flow process of Fig. 4, stock oil A is directly as the raw material of catalytic pyrolysis, in the middle scale riser reactor, test, the temperature of reaction of the first riser reaction zone I, II is followed successively by 630 ℃, 540 ℃, and the temperature of reaction of the second riser reaction zone IV, V is followed successively by 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.Oil gas enters in the subsequent separation system 41 through

pipeline

As can be seen from Table 3, propylene is up to 49.70 heavy %, and toluene and dimethylbenzene yield are respectively 3.59 heavy % and 9.61 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, ℃	610	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, ℃	530	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	4.98	4.82
			Ethene	15.17	18.5
Propylene	42.03	43.98
			Benzene	3.18	4.02
Toluene	7.15	7.86
			Dimethylbenzene	10.44	11.65
Polycyclic aromatic hydrocarbons	8.94	1.05
			Coke	8.11	8.12

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 IV, ℃
Temperature of reaction, ℃	520	530
			Agent-oil ratio, m/m	15	15
Water vapor/raw material weight ratio	0.1	0.1
			Reaction zone V, ℃
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	4.61	5.18
			Ethene	19.88	/
Propylene	29.94	49.70
			Benzene	3.45	3.59
Toluene	8.53	9.61
			Dimethylbenzene	12.61	14.73
Polycyclic aromatic hydrocarbons	13.07	9.18
			Coke	7.91	8.01

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, contacts with the catalytic cracking catalyst of heat regeneration, 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, 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;

(2) reaction effluent separates without finish, mixes with the stock oil of easy cracking, and mixed stock oil 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, 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 described other mineral oil is liquefied coal coil, tar sand oil, shale oil;

(3) reaction effluent separates without finish, and with the stock oil of optional difficult cracking, easily one or more in cracking stock oil, the cold shock medium are mixed, 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;

(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 180 ℃～250 ℃ the cut or wherein more than one mixture send in the second riser reactor as cracking stock again, contact 250 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 100h with hot regenerated catalyst ^-1-800h ^-1, reaction absolute pressure 0.10MPa-1.0MPa, 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, in Second reactivator, return the second riser reactor behind the coke burning regeneration.

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

3. 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 in half regenerated catalyst, reclaimable catalyst and the live catalyst of the regenerated catalyst that is selected from cold shock agent, cooling, cooling, wherein the cold shock agent is one or more that are selected from liquefied gas, propane, C4 hydrocarbon, raw gasline, stable gasoline, diesel oil, the water; The regenerated catalyst of cooling and half regenerated catalyst of cooling are that reclaimable catalyst cools off after two-stage regeneration and one section regeneration respectively and obtains.

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

The oil that acts as a fuel,

Through hydrofining as diesel component,

Returning reactor after hydrofining,

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

(7) catalytic pyrolysis carbon two to butane and water vapor enters the steam cracking reaction device, carries out cracking reaction under 700 ℃-1000 ℃ of temperature of reaction, and separating reaction oil gas obtains H ₂, CH ₄, steam cracking carbon two is to carbon alkatrienes, steam cracking carbon two to carbon three alkane, steam cracking carbon four to carbon five hydrocarbon, steam cracking petroleum naphtha, oil fuel, wherein steam cracking carbon two to carbon alkatrienes is one of purpose product, steam cracking carbon two loops back the steam cracking reaction device to carbon three alkane, and steam cracking carbon four to carbon five hydrocarbon loop back the catalytic cracking reaction device;

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