CN101760227B - Catalytic conversion method for preparing propylene and high octane gasoline - Google Patents
Catalytic conversion method for preparing propylene and high octane gasoline Download PDFInfo
- Publication number
- CN101760227B CN101760227B CN2008102465224A CN200810246522A CN101760227B CN 101760227 B CN101760227 B CN 101760227B CN 2008102465224 A CN2008102465224 A CN 2008102465224A CN 200810246522 A CN200810246522 A CN 200810246522A CN 101760227 B CN101760227 B CN 101760227B
- Authority
- CN
- China
- Prior art keywords
- oil
- catalyst
- cracking
- reaction
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a catalytic conversion method for preparing propylene and high octane gasoline. Raw oil of different cracking properties enters different reaction regions of a first riser reactor to contact with catalytic cracking catalysts for carrying out cracking reactions so as to separate a spent catalysts from reaction oil gas; the reaction oil gas is separated for obtaining a product comprising the propylene, gasoline and a re-cracking raw material, wherein the re-cracking raw material is transmitted into a second riser reactor to contact with hot regenerated catalysts for carrying out catalytic conversion; and after the spent catalysts in the two riser reactors are burned in a same regenerator, the spent catalysts are respectively returned to the two riser reactors. In the method, the yields of the propylene and the gasoline are obviously increased; the octane value of the gasoline is also obviously improved. Under the condition of largely increasing the yield of the propylene, the yield of dry gas is obviously reduced by more than 80% by weight.
Description
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 propylene and stop bracket gasoline.
Background technology
Propylene is important Organic Chemicals, 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 is mainly 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 is only that about 15 heavy %, FCC is take mink cell focuses such as decompressed wax oils (VGO) as 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 uses.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, 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.
Along with China's expanding economy, China's gasoline car recoverable amount increases year by year, therefore the demand of premium-type gasoline is improved day by day.China's motor spirit is mainly from catalytic cracking unit, catalytically cracked gasoline last running part octane value is on the low side, thereby affect the octane value of gasoline, in addition, catalytic cracking diesel oil is second-rate, but catalytic cracking diesel oil contains more mononuclear aromatics, and the mononuclear aromatics in diesel oil is converted into the increase that gasoline component both had been conducive to gasoline yield, can improve the octane value of gasoline again simultaneously.
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 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 is to provide a kind of catalysis conversion method heavy feed stock is converted into propylene and stop bracket gasoline.
Technical scheme of the present invention is the catalysis conversion method of a kind of preparing propone and stop bracket gasoline, and the method comprises the following steps:
(1) stock oil of difficult cracking enters bottom the first riser reactor, contacts with the catalytic cracking catalyst of heat regeneration, at 600 ℃-750 ℃ 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 500 ℃-670 ℃ 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 react 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 450 ℃-650 ℃ 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 enters revivifier after stripping, returns to the first riser tube after coke burning regeneration, and reaction oil gas goes separation system;
(5) the described reaction oil gas of step (4) enters separation system and separates that to obtain comprising propylene, C 4 olefin, gasoline, boiling range be the 180 ℃～cut of 250 ℃ and the product of catalytic wax oil;
(6) the described catalytic wax oil of step (5) or/and Aromatics Extractive Project is processed, obtains the hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil through hydrotreatment;
(7) the described C 4 olefin of step (5), the described boiling range of step (5) be a kind of during cut, the described hydrogenation catalyst wax oil of step (6), the described catalytic wax oil of step (6) of 180 ℃～250 ℃ raffinated oil or wherein more than one mixture send in the second riser reactor as cracking stock again, contact 500 ℃-750 ℃ 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, wherein reclaimable catalyst is through returning to the second riser reactor after coke burning regeneration in revivifier after stripping, and the separation of reaction oil gas is identical with step (5).
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), catalytic wax oil 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 a kind of of 2～8 hydro carbons, slurry oil, diesel oil, gasoline or more than one mixture wherein.Described difficult cracking stock both can install from this, also can be from outer device.
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 that selects in self cooled regenerated catalyst, cooling half regenerated catalyst, reclaimable catalyst and live catalyst, and wherein 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 that C 4 olefin, boiling range are a kind of during cut, hydrogenation catalyst wax oil, the catalytic wax oil of 180 ℃～250 ℃ raffinated oil or more than one mixture wherein, and wherein each raw material can be from this device and the outer raw material of this device.
Fractionation plant can be the fractionation plant of each reactor catalytic cracking unit separately, can be also the fractionation plant that two reactors share a cover catalytic cracking unit, can also be independent fractionation plant.
The method of separation of propylene is identical with the method that those of ordinary skills know from reaction oil gas.
The cut of described 180～250 ℃ 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, return to the first riser tube or/and the cracking again of the second riser tube.
The boiling range of described catalytic wax oil is preferably greater than 260 ℃ greater than 250 ℃.Catalytic wax oil or/and Aromatics Extractive Project is processed, obtains the hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil through hydrotreatment, returns to the first riser tube or/and the cracking again of the second riser tube.
The catalytic wax oil hydrotreatment is under there is situation in hydrogen, contacts with hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under to carry out hydrotreatment resulting.The hydrogenation catalyst wax oil is as the stock oil of cat-cracker.
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 it is non-aromatics as one of raw material of catalytic pyrolysis that catalytic wax oil is raffinated oil.
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 is selected from mesopore zeolite and optional large pore zeolite as active ingredient, and mesopore zeolite accounts for the 50 heavy % of heavy %-100 of zeolite gross weight, and the preferred 70 heavy % of heavy %-100, large pore zeolite account for the 0 heavy % of heavy %-50 of zeolite gross weight, the preferred 0 heavy % of 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 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 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 identical, and reclaimable catalyst shares same revivifier regeneration.
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.
Two riser reactors of the present invention can be identical, also can be different.Riser tube can be conventional isodiametric riser tube, can be also the riser tube of various forms reducing.The present invention preferably carries out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.The second riser tube can have a reaction zone, also plural reaction zone can be arranged, preferred two reaction zones.
This technical scheme organically combines the techniques such as catalytic pyrolysis and catalytic wax oil hydrogenation, heavy aromatic solvent extracting, produces to greatest extent low-carbon alkene especially propylene and stop bracket gasoline from the lower heavy feed stock of hydrogen richness.The optimum combination that this technical scheme provides different catalytic pyrolysis raw materials and dissimilar catalyzer to carry out cracking reaction.
The present invention compared with prior art has following unforeseeable technique effect:
1, productivity of propylene and the propylene selectivity in liquefied gas increases considerably, for paraffinic base VGO, and the heavy % of productivity of propylene nearly 30;
2, gasoline yield increases significantly, and gasoline octane rating improves significantly;
3, in the situation that productivity of propylene increases considerably, dry gas yied reduces significantly, can reduce to reach 80 heavily more than %.
Description of drawings
Fig. 1 is the method flow schematic diagram of one of embodiment.
Fig. 2 is two method flow schematic diagram of embodiment.
Embodiment
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 one of embodiment.
Its technical process is as follows:
Pre-lift steam is entered by riser reactor 2 bottoms through pipeline 1, mix with the regenerated catalyst from pipeline 7, under the castering action of steam along the riser tube accelerated motion that makes progress, difficult cracking stock oil is through pipeline 3 and injecting lift pipe together with the atomizing steam of pipeline 4 simultaneously, mix with the existing logistics of riser reactor, cracking reaction occurs in difficult cracking stock on the hotter catalyzer that contains a small amount of charcoal, and upwards accelerated motion.Easily cracking stock oil is through pipeline 5 and injecting lift pipe together with the atomizing steam of pipeline 6 (cracking stock can mix with difficult cracking stock through pipeline line 3 injecting lift pipes again), mix with the existing logistics of riser reactor, cracking reaction occurs on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in settling vessel 10 through pipeline 9, realize separating of reclaimable catalyst and oil gas, oil gas enters collection chamber 22, and catalyst fines returns to settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 11, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through standpipe 8, and 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.Catalyzer after regeneration enters riser tube through inclined tube 7.Oil gas in collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
Pre-lift steam is entered by riser reactor 12 bottoms through pipeline 11, mix with the regenerated catalyst from pipeline 17, regenerated catalyst is along the riser tube accelerated motion that makes progress under the castering action of steam, part or all of cracking stock oil again is through pipeline 13 and injecting lift pipe together with the atomizing steam of pipeline 14 simultaneously, mix with the existing logistics of riser reactor, cracking reaction occurs in cracking stock on the hotter catalyzer that contains a small amount of charcoal again, and upwards accelerated motion.Part again cracking stock oil (as the cut of 180～250 ℃) through pipeline 15 and injecting lift pipe 12 together with the atomizing steam of pipeline 16, mix with the existing logistics of riser reactor, this part again cracking stock cracking reaction occurs on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in settling vessel 10 through pipeline 19, realize separating of reclaimable catalyst and oil gas, oil gas enters collection chamber 22, and catalyst fines returns to settling vessel 10 by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 11, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through standpipe 8, and 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.Catalyzer after regeneration enters respectively riser tube 2 and riser tube 12 through pipeline 7 and pipeline 17.Oil gas in collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
Mixed oil and gas obtains splitting gas (consisting of hydrogen, C1-C2 alkane and ethene) through separation system 24 separation and goes out device through pipeline 33; Propylene goes out device as one of purpose product through pipeline 32; The propane that separation obtains and butane are drawn through pipeline 34 and are turned back to the first reactor; C4 alkene returns to riser tube 12 bottoms through pipeline 31,13 successively; Another kind of purpose product stop bracket gasoline goes out device through pipeline 29; Choose wantonly, part light gasoline fraction (forming the various hydro carbons of C5-C8) returns to riser tube; The cut of 180～250 ℃ is all or part of returns to riser tube 12 bottoms through pipeline 26; Catalytic wax oil (greater than the cut of 250 ℃) enters aromatic extraction unit 27 through pipeline 25, and catalytic wax oil is raffinated oil successively and to be returned to riser tube 2 middle parts through pipeline 28,5, and the aromatic hydrocarbons that extracts goes out device through pipeline 30.
Fig. 2 is two method flow schematic diagram of embodiment.
Its technical process is as follows:
Pre-lift steam is entered by riser reactor 2 bottoms through pipeline 1, mix with the regenerated catalyst from pipeline 7, under the castering action of steam along the riser tube accelerated motion that makes progress, difficult cracking stock oil is through pipeline 3 and injecting lift pipe together with the atomizing steam of pipeline 4 simultaneously, mix with the existing logistics of riser reactor, cracking reaction occurs in difficult cracking stock on the hotter catalyzer that contains a small amount of charcoal, and upwards accelerated motion.Easily cracking stock oil is through pipeline 5 and injecting lift pipe together with the atomizing steam of pipeline 6 (cracking stock can mix with easy cracking stock through pipeline line 3 injecting lift pipes again), mix with the existing logistics of riser reactor, cracking reaction occurs on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in settling vessel 10 through pipeline 9, realize separating of reclaimable catalyst and oil gas, oil gas enters collection chamber 22, and catalyst fines returns to settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 11, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through standpipe 8, and 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.Catalyzer after regeneration enters riser tube through inclined tube 7.Oil gas in collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
Pre-lift steam is entered by riser reactor 12 bottoms through pipeline 11, mix with the regenerated catalyst from pipeline 17, regenerated catalyst is along the riser tube accelerated motion that makes progress under the castering action of steam, part or all of cracking stock oil again is through pipeline 13 and injecting lift pipe together with the atomizing steam of pipeline 14 simultaneously, mix with the existing logistics of riser reactor, cracking reaction occurs in cracking stock (as the hydrogenation catalyst wax oil) on the hotter catalyzer that contains a small amount of charcoal again, and upwards accelerated motion.The part again cracking stock oil through pipeline 15 and injecting lift pipe together with the atomizing steam of pipeline 16, mix with the existing logistics of riser reactor, cracking reaction occurs in this part difficult cracking stock on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in settling vessel 10 through pipeline 19, realize separating of reclaimable catalyst and oil gas, oil gas enters collection chamber 22, and catalyst fines returns to settling vessel 10 by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 11, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 18 through standpipe 8, and 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.Catalyzer after regeneration enters respectively riser tube 2 and riser tube 12 through pipeline 7 and pipeline 17.Oil gas in collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
Mixed oil and gas obtains dry gas (consisting of hydrogen, C1-C2 alkane and ethene) through separation system 24 separation and goes out device through pipeline 33; Propylene goes out device as one of purpose product through pipeline 32; The propane that separation obtains and butane are drawn through pipeline 34 and are turned back to the first reactor; C4 alkene returns to riser tube 12 bottoms through pipeline 31,13 successively; Another kind of purpose product stop bracket gasoline goes out device through pipeline 29; Choose wantonly, part light gasoline fraction (forming the various hydro carbons of C5-C8) returns to riser tube; The cut of 180～250 ℃ is all or part of returns to riser tube 12 bottoms through pipeline 26,13 successively; Catalytic wax oil (greater than the cut of 250 ℃) enters hydrotreater 27 through pipeline 25, and the hydrogenation catalyst wax oil returns to riser tube 12 middle parts through pipeline 28,15 successively.
The following examples will be further described present method, but therefore not limit present method.
In embodiment, raw material used is AR, 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), with 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 get 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 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), with 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 63m%), with hydrochloric acid, its PH is transferred 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), with 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 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, 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.
Method provided by the invention is adopted in the present embodiment explanation, difficult cracking and easy cracking stock enter the first reactor, cracking stock enters the second reactor again, catalytic wax oil is raffinated oil into the second reactor, and two reactive systems use same fractionating system catalyzed conversion to generate the situation of propylene and stop bracket gasoline.
This embodiment tests on the middle-scale device of riser reactor according to the flow process of Fig. 1, and directly as the raw material of easy cracking, propane and butane are as the raw material of difficult cracking for stock oil A, and the character of stock oil A is listed in table 1, and operational condition and product distribute and list in table 2.
As can be seen from Table 2, productivity of propylene is up to 27.74 heavy %, and gasoline yield is up to 35.64 heavy %, RON up to 97.5, MON up to being 85.3.
Method provided by the invention is adopted in the present embodiment explanation, difficult cracking and easy cracking stock enter the first reactor, cracking stock enters the second reactor again, the hydrogenation catalyst wax oil advances the second reactor, and two reactive systems use same fractionating system catalyzed conversion to generate the situation of propylene and stop bracket gasoline.
This embodiment tests on the middle-scale device of riser reactor according to the flow process of Fig. 2, and directly as the raw material of easy cracking, propane and butane are as the raw material of difficult cracking for stock oil A, and the character of stock oil A is listed in table 1, and operational condition and product distribute and list in table 2.
As can be seen from Table 2, productivity of propylene is up to heavy by 28.88%, and gasoline yield is up to heavy by 38.28%, RON up to 98.5, MON up to being 84.3.
Table 1
| The stock oil numbering | A |
| Stock oil character | |
| Density (20 ℃), g/cm 3 | 0.8934 |
| Sulphur content, ppm | 5600 |
| Nitrogen content, ppm | 2800 |
| Aromatic hydrocarbons, m% | 32.6 |
| C，m％ | 86.23 |
| H，m％ | 12.93 |
| Boiling range (ASTM D-1160), ℃ | |
| IBP | 327 |
| 10％ | 363 |
| 30％ | 409 |
| 50％ | 450 |
| 70％ | 482 |
| 90％ | 504 |
| 95％ | 526 |
| EP | 542 |
Table 2
| Embodiment 1 | Embodiment 2 | |
| Operational condition | ||
| The catalytic pyrolysis unit | ||
| Riser tube 2 | ||
| Reaction zone I temperature out, ℃ | 520 | 520 |
| Agent-oil ratio, m/m | 8 | 8 |
| Weight hourly space velocity, h -1 | 40 | 40 |
| Water filling (accounting for raw material), m% | 10 | 10 |
| Reaction zone II temperature out, ℃ | 520 | 520 |
| Agent-oil ratio, m/m | ||
| Weight hourly space velocity, h -1 | 20 | 20 |
| Water filling (accounting for raw material), m% | 10 | 10 |
| Riser tube 12 | ||
| Reaction zone III temperature out, ℃ | 510 | 515 |
| Agent-oil ratio, m/m | 10 | 10 |
| Weight hourly space velocity, h -1 | 30 | 30 |
| Water filling (accounting for raw material), m% | 15 | 15 |
| Reaction zone IV outlet ℃ | 500 | 505 |
| Agent-oil ratio, m/m | 10 | 10 |
| Weight hourly space velocity, h -1 | ||
| Water filling (accounting for raw material), m% | 10 | 10 |
| Hydrotreating unit | ||
| Temperature of reaction, ℃ | / | 350 |
| The hydrogen dividing potential drop, MPa | / | 13 |
| Volume space velocity, h -1 | / | 1.5 |
| Hydrogen to oil volume ratio, v/v | / | 1200 |
| The solvent extraction unit | ||
| Temperature, ℃ | 100 | / |
| Solvent ratio, v/v | 3.0 | / |
| Product distributes, m% | ||
| Dry gas | 4.88 | 4.96 |
| Liquefied gas | 47.26 | 49.60 |
| Propylene | 27.74 | 28.88 |
| Gasoline | 35.64 | 38.28 |
| Heavy aromatics | 5.20 | / |
| Coke | 7.02 | 6.86 |
| Add up to | 100 | 100 |
| Gasoline octane rating | ||
| RON | 97.5 | 98.5 |
| MON | 85.3 | 84.3 |
Claims (5)
1. the catalysis conversion method of a preparing propone and stop bracket gasoline, is characterized in that the method comprises the following steps:
(1) stock oil of difficult cracking enters bottom the first riser reactor, contacts with the catalytic cracking catalyst of heat regeneration, at 600 ℃-750 ℃ of temperature of reaction, weight hourly space velocity 100h
-1-800h
-1, reaction absolute 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 a kind of of 2～8 hydro carbons, slurry oil, diesel oil, gasoline or more than one mixture wherein;
(2) reaction effluent separates without finish, mixes with the stock oil of easy cracking, and easily the stock oil of cracking is at 500 ℃-670 ℃ of temperature of reaction, weight hourly space velocity 0.1h
-1-100h
-1, reaction absolute 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 react 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, catalytic wax oil and raffinates oil, and 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, cold shock medium are mixed, stock oil is at 450 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 10h
-1-300h
-1, reaction absolute 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, described cold shock medium is one or more the mixture of arbitrary proportion that selects in self cooled regenerated catalyst, cooling half regenerated catalyst, reclaimable catalyst and live catalyst, and wherein cooling regenerated catalyst and half cooling regenerated catalyst are reclaimable catalyst cooling obtaining after two-stage regeneration and one section regeneration respectively;
(4) separate reclaimable catalyst and reaction oil gas, wherein reclaimable catalyst enters revivifier after stripping, returns to the first riser tube after coke burning regeneration, and reaction oil gas goes separation system;
(5) the described reaction oil gas of step (4) enters separation system and separates that to obtain comprising propylene, C 4 olefin, gasoline, boiling range be the 180 ℃～cut of 250 ℃ and the product of catalytic wax oil;
(6) the described catalytic wax oil of step (5) or/and Aromatics Extractive Project is processed, obtains the hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil through hydrotreatment;
(7) the described C 4 olefin of step (5), the described boiling range of step (5) be a kind of during cut, the described hydrogenation catalyst wax oil of step (6), the described catalytic wax oil of step (6) of 180 ℃～250 ℃ raffinated oil or wherein more than one mixture send in the second riser reactor as cracking stock again, contact 300 ℃-620 ℃ 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, wherein reclaimable catalyst is through returning to the second riser reactor after coke burning regeneration in revivifier after stripping, and the separation of reaction oil gas is identical with step (5).
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 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, be 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, 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 the boiling range of described catalytic wax oil is greater than 250 ℃.
4. according to the method for claim 1, it is characterized in that described hydrotreatment is under there is situation in hydrogen, contact with hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under carry out hydrotreatment, obtain the hydrogenation catalyst wax oil.
5. according to the method for claim 1, it is characterized in that the extraction solvent that described Aromatics Extractive Project is processed is selected from methyl-sulphoxide, furfural, dimethyl formamide, monoethanolamine, ethylene glycol, 1, the mixture of one or more in the 2-propylene glycol, extraction temperature is 40～120 ℃, and the volume ratio between solvent and raw material is 0.5～5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102465224A CN101760227B (en) | 2008-12-25 | 2008-12-25 | Catalytic conversion method for preparing propylene and high octane gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102465224A CN101760227B (en) | 2008-12-25 | 2008-12-25 | Catalytic conversion method for preparing propylene and high octane gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101760227A CN101760227A (en) | 2010-06-30 |
| CN101760227B true CN101760227B (en) | 2013-06-05 |
Family
ID=42491610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102465224A Active CN101760227B (en) | 2008-12-25 | 2008-12-25 | Catalytic conversion method for preparing propylene and high octane gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101760227B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8529754B2 (en) | 2009-09-28 | 2013-09-10 | China Petroleum & Chemical Corporation | Catalytic conversion process for producing more diesel and propylene |
| CN102899078B (en) * | 2011-07-29 | 2015-03-18 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
| CN103627426A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Method for improving gasoline yield of catalytic cracking technology and device thereof |
| SG11201502991RA (en) * | 2012-10-19 | 2015-06-29 | Saudi Arabian Oil Co | Process for high severity catalytic cracking of crude oil |
| CN104560149B (en) * | 2013-10-16 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of hydrocarbons catalytic conversion method of voluminous butylene |
| CN104560166B (en) * | 2013-10-28 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of petroleum hydrocarbon is produced the catalysis conversion method of high-knock rating gasoline |
| CN113735676B (en) * | 2020-05-29 | 2023-10-13 | 中国石油化工股份有限公司 | Method for high-selectivity catalytic pyrolysis of high-yield propylene and high-yield gasoline |
| CN114426854A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking method for increasing yield of ethylene and BTX |
| CN114605219B (en) * | 2020-12-09 | 2024-04-02 | 中国石油化工股份有限公司 | Method and system for producing light olefins and gasoline |
| WO2022174435A1 (en) * | 2021-02-22 | 2022-08-25 | 广州智京科技有限公司 | Double settlers – based catalytic cracking device and method |
| CN116355651A (en) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for lightening catalytic diesel oil and obtained product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4422925A (en) * | 1981-12-28 | 1983-12-27 | Texaco Inc. | Catalytic cracking |
| US4980053A (en) * | 1987-08-08 | 1990-12-25 | Research Institute Of Petroleum Processing, Sinopec | Production of gaseous olefins by catalytic conversion of hydrocarbons |
| CN1085885A (en) * | 1992-10-22 | 1994-04-27 | 中国石油化工总公司 | The catalysis conversion method of petroleum hydrocarbon |
| CN1215041A (en) * | 1997-10-20 | 1999-04-28 | 中国石油化工总公司 | Process for direct-conversion preparation olefines from multiple fed hydrocarbon |
-
2008
- 2008-12-25 CN CN2008102465224A patent/CN101760227B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4422925A (en) * | 1981-12-28 | 1983-12-27 | Texaco Inc. | Catalytic cracking |
| US4980053A (en) * | 1987-08-08 | 1990-12-25 | Research Institute Of Petroleum Processing, Sinopec | Production of gaseous olefins by catalytic conversion of hydrocarbons |
| CN1085885A (en) * | 1992-10-22 | 1994-04-27 | 中国石油化工总公司 | The catalysis conversion method of petroleum hydrocarbon |
| CN1215041A (en) * | 1997-10-20 | 1999-04-28 | 中国石油化工总公司 | Process for direct-conversion preparation olefines from multiple fed hydrocarbon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101760227A (en) | 2010-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101760227B (en) | Catalytic conversion method for preparing propylene and high octane gasoline | |
| CN101747928B (en) | Catalytic conversion method for preparing lower olefins and aromatics | |
| CN101932672B (en) | A process of catalytic conversion | |
| CN101531558B (en) | Catalytic conversion method for preparing propylene and aromatic hydrocarbons | |
| CN101531923B (en) | Catalytic conversion method for preparing propylene and high-octane gasoline | |
| CN101747929B (en) | Catalytic conversion method for preparing lower olefins and aromatics | |
| CN101362959B (en) | Catalytic conversion method for preparing propone and high-octane number gasoline | |
| CN101942340B (en) | Method for preparing light fuel oil and propylene from inferior raw material oil | |
| CN101362669B (en) | Catalytic conversion method of ethylene, propylene and aromatic hydrocarbon preparation | |
| CN100465250C (en) | Production of low-carbon olefine and arene | |
| CN101531924B (en) | Method for preparing light fuel oil and propylene from poor-quality raw oil | |
| CN101760228B (en) | Catalytic conversion method for preparing propylene and high octane gasoline | |
| CN101993726B (en) | Method for preparing high-quality fuel oil from inferior crude oil | |
| CN101724430B (en) | Method for preparing light-weight fuel oil and propylene from inferior raw oil | |
| CN102344831B (en) | Petroleum hydrocarbon catalytic conversion method | |
| CN101362670B (en) | Catalytic conversion method of propylene preparation | |
| CN102344832B (en) | Catalytic conversion method for petroleum hydrocarbon | |
| CN102021031B (en) | Method for preparing superior fuel oil from inferior crude oil | |
| CN101362961B (en) | Catalytic conversion method for preparing aromatic hydrocarbons and light olefins | |
| CN102344830B (en) | Catalytic conversion method for petroleum hydrocarbon | |
| CN101362963B (en) | Catalytic conversion method for preparing propylene and simultaneously preparing aromatic hydrocarbons | |
| CN102021030B (en) | Catalytic conversion method | |
| CN101935266B (en) | Catalytic conversion method for preparing propylene and high-octane value gasoline | |
| CN101724431A (en) | Catalytic conversion method for preparing light fuel oil and propylene | |
| CN101993328B (en) | Catalytic conversion combination method for producing propylene and high-quality fuel oil in high yield |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |