CN101935266B - Catalytic conversion method for preparing propylene and high-octane value gasoline - Google Patents
Catalytic conversion method for preparing propylene and high-octane value gasoline Download PDFInfo
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Abstract
The invention discloses a catalytic conversion method for preparing propylene and high-octane value gasoline. Crude oil contacts a catalyst rich in mesoporous zeolite and with coarse particle size distribution for reaction; and reaction temperature, weight hourly space velocity and the weight ratio of the catalyst to the crude oil are sufficiently proper for preparing a reaction product comprising 12 to 60 percent of catalytic wax oil based on the weight of the crude oil in the reaction, wherein the weight hourly space velocity is 25 to 100 h<-1>; the reaction temperature is 450 to 600 DEG C; and the weight ratio of the catalyst to the crude oil is 1 to 30. The invention provides the catalytic conversion method based on the prior art, which particularly has the advantages of greatly reducing dry gas yield and coke yield at the same time of converting the heavy crude oil into the high-octane value gasoline and the propylene so as to realize the high-efficiency utilization of oil resources.
Description
Technical field
The present invention relates to a kind of catalysis conversion method, particularly when heavy feed stock is converted into stop bracket gasoline and propylene, thereby make dry gas and coke yield reduce the method for the efficient utilization that realizes petroleum resources significantly.
Background technology
Low-carbon alkenes such as propylene are important Organic Chemicals, and propylene is the synthon of products such as polypropylene, vinyl cyanide.Along with increasing rapidly of derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in propylene market, the world 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 that raw material is produced ethene, propylene by thermo-cracking with lightweight oils such as petroleum naphthas, but the productive rate of propylene only is that FCC is a raw material with vacuum gas oil mink cell focuses such as (VGO) then about 15 heavy %.At present, 61% propylene is produced the byproduct of ethene from steam cracking in the world, and 34% produces the byproduct of vapour, diesel oil from refinery FCC, and a small amount of (about 5%) 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 the shortage of lightweight material oil, inefficiency of production and cost and cross high several big restraining factors.
FCC is owing to 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 producing low-carbon alkene, 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 this 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 this method adopts ZSM-5 and/or ZSM-11 zeolite to do active component, is the catalyzer of matrix with a large amount of inert substances, is raw material with VGO, and the productive rate of propylene also is no more than 20 heavy %.
US4,422,925 disclose the method that multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, the described hydro carbons of this method contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material at least, this 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 expanding economy, global gasoline car recoverable amount increases year by year, and therefore the demand to premium-type gasoline improves day by day.The technology that improves gasoline octane rating at present mainly contains catalytic reforming technology, alkylation techniques, isomerization technique and interpolation gasoline octane rating improving agent etc.The great advantage of catalytic reforming gasoline is that its heavy constituent octane value is higher, and the light constituent octane value is lower.But reformation technology catalyzer cost height and ingredient requirement height.Alkylation techniques and isomerization technique obtain reformulated gasoline oil and have octane value height, characteristics that susceptibility is good, are ideal high-octane rating clean gasoline components, but the catalyzer that uses all exists corrosion and environmental issue.The interpolation of gasoline octane rating such as MTBE and ETBE improving agent can improve really gasoline octane value, improve automotive performance, but cost is generally higher.Catalytically cracked gasoline is one of motor spirit main source, catalytically cracked gasoline last running part octane value is on the low side, thereby influence 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 the diesel oil is converted into the increase that gasoline component had both helped gasoline yield, can improve the octane value and the energy propylene enhancing of gasoline simultaneously again.
Above-mentioned prior art still exists not enough to alkane molecule cracking reaction design, causing is increasing under the productivity of propylene situation, dry gas yied increases considerably, simultaneously, prior art is underused the gasoline potential content in gasoline octane rating and the diesel oil, cause productivity of propylene on the low side, there are room for improvement in gasoline yield and quality simultaneously.In order to satisfy the growing low-carbon alkene industrial chemicals and the demand of motor spirit, CN101362959A discloses a kind of catalysis conversion method of producing propylene and stop bracket gasoline, difficult cracked raw material contacts with hot regenerated catalyst earlier, at temperature 600-750 ℃, weight hourly space velocity 100-800h
-1, pressure 0.10-1.0MPa, catalyzer 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, reactant flow is mixed with easy cracked stock oil, at temperature 450-620 ℃, weight hourly space velocity 0.1-100h
-1, pressure 0.10-1.0MPa, catalyzer and raw material weight ratio 1.0-30, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0; Reclaimable catalyst is with after reaction oil gas separates, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration, reaction oil gas obtains purpose product propylene and stop bracket gasoline and cracked raw material again through separation, and it is that 180～260 ℃ cut, heavy aromatics raffinated oil that the described raw material of cracked again comprises boiling range.The productive rate and the selectivity of this method propylene significantly increase, and the productive rate and the octane value of gasoline improve significantly, and dry gas yied reduces amplitude up to more than the 80 heavy %.The size composition of the catalyzer that this method adopted is suitable with the size composition of conventional catalytic cracking catalyst, promptly is about 20% (volume) less than 40 microns fine particle.The contriver finds after deliberation, and is relatively poor to the selectivity of dry gas and coke though these fine grain catalyzer have higher cracking ability, and the size composition of optimizing catalyzer can improve the selectivity of dry gas and coke.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of catalysis conversion method, particularly when heavy feed stock is converted into stop bracket gasoline and propylene, thereby make dry gas and coke yield reduce the efficient utilization that realizes petroleum resources significantly.
In one embodiment of the present invention, a kind of catalysis conversion method is provided, wherein the catalyzer that directly distributes with the coarse grain that is rich in mesopore zeolite in reactor of stock oil contacts and reacts, the size composition of the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios less than 40 microns particle, temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil, and wherein said weight hourly space velocity is 25～100h
-1, described temperature of reaction is 450～600 ℃, described catalyzer and stock oil weight ratio are 1～30.
In a more preferred embodiment, temperature of reaction is 450～600 ℃, preferably, and 460～580 ℃, more preferably, 480～540 ℃.
In a more preferred embodiment, weight hourly space velocity is 30～80h
-1, preferably, 40～60h
-1
In a more preferred embodiment, catalyzer and stock oil weight ratio are 1～30, preferably, and 2～25, more preferably, 3～14.
In a more preferred embodiment, reaction pressure is 0.10MPa～1.0MPa.
In a more preferred embodiment, described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, the long residuum, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
In a more preferred embodiment, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, the heavy % of preferred 70 heavy %-100.Large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, the heavy % of preferred 0 heavy %-30.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y series zeolite.
The size composition of the catalyzer that described coarse grain directly distributes is lower than 10% and is preferably lower than 5% for account for all particulate volume ratios less than 40 microns particle.
In a more preferred embodiment, the more excellent size composition of the catalyzer that described coarse grain directly distributes should be lower than 10% for accounting for all particulate volume ratios less than 40 microns particle, is preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and should be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
In a more preferred embodiment, described stock oil is introduced in the reactor, or described stock oil is introduced in the reactor in the position of identical or different height more than a position.
In a more preferred embodiment, described method also comprises separates reaction product with catalyzer, and catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises propylene, stop bracket gasoline and catalytic wax oil.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than 260 ℃ cut, and hydrogen richness is not less than 10.5 heavy %.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, and hydrogen richness is not less than 10.8 heavy %.
In another embodiment of the invention, a kind of catalysis conversion method is provided, wherein the catalyzer that directly distributes with the coarse grain that is rich in mesopore zeolite in reactor of stock oil contacts and reacts, the size composition of the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios less than 40 microns particle, and this method comprises:
(1) stock oil comprises difficult cracking stock oil and easy cracking stock oil, a position described stock oil is introduced in the reactor, or in the position of identical or different height more than described stock oil is introduced in the reactor;
(2) difficult cracking stock oil is not later than easy cracking stock oil and reacts in reactor;
(3) temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil;
(4) easily the described weight hourly space velocity of cracking stock oil is 5～100h
-1
In a more preferred embodiment, described difficult cracking stock grease separation from or comprise that slurry oil, diesel oil, gasoline, carbonatoms are one or more the mixture in the hydrocarbon of 4-8.
In a more preferred embodiment, described easy cracking stock grease separation from or comprise petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, the long residuum, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
In a more preferred embodiment, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, the heavy % of preferred 70 heavy %-100.Large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, and mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y series zeolite.
The size composition of the catalyzer that described coarse grain directly distributes is lower than 10% and is preferably lower than 5% for account for all particulate volume ratios less than 40 microns particle.
In a more preferred embodiment, the more excellent size composition of the catalyzer that described coarse grain directly distributes should be lower than 10% for accounting for all particulate volume ratios less than 40 microns particle, is preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and should be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
In a more preferred embodiment, the reaction conditions of difficult cracking stock oil is: 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10～1.0MPa, catalyzer and difficult cracking stock oil weight ratio 30～150, the weight ratio of water vapor and difficult cracking stock oil is 0.05～1.0.
In a more preferred embodiment, easily the reaction conditions of cracking stock oil is: 450～600 ℃ of temperature of reaction, weight hourly space velocity 5～100h
-1, reaction pressure 0.10～1.0MPa, catalyzer and the easy weight ratio 1.0～30 of cracking stock oil, water vapor is 0.05～1.0 with the easy weight ratio of cracking stock oil.
In a more preferred embodiment, easily the temperature of reaction of cracking stock oil is 460-580 ℃, and weight hourly space velocity is 10～90h
-1, be preferably 20～60h
-1, 30～50h more preferably
-1, catalyzer and stock oil weight ratio are 3～14.
In a more preferred embodiment, described method also comprises separates reaction product with catalyzer, and catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises propylene, stop bracket gasoline and catalytic wax oil.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than 260 ℃ cut, and hydrogen richness is not less than 10.5 heavy %.
In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, and hydrogen richness is not less than 10.8 heavy %.
In another embodiment of the invention, provide a kind of catalysis conversion method of producing propylene and stop bracket gasoline, it is characterized in that this method comprises the following steps:
(1) raw material that contains difficult cracking stock oil earlier and the catalyzer that the coarse grain that is rich in mesopore zeolite directly distributes contact, the size composition of the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios less than 40 microns particle, at 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10～1.0MPa, catalyzer and difficult cracking stock oil weight ratio 30～150, the weight ratio of water vapor and difficult cracking stock oil is to carry out cracking reaction under 0.05～1.0 the condition;
(2) reactant flow that contains difficult cracking stock oil again with easy cracking stock oil at 450～600 ℃ of temperature of reaction, weight hourly space velocity 5～100h
-1, reaction pressure 0.10～1.0MPa, catalyzer and the easy weight ratio 1.0～30 of cracking stock oil, water vapor and the easy weight ratio of cracking stock oil are to carry out cracking reaction under 0.05～1.0 the condition;
(3) reclaimable catalyst separates by cyclonic separator with reaction oil gas; Randomly, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration; Reaction oil gas obtains comprising the reaction product of propylene, stop bracket gasoline, catalytic wax oil through separation;
(4) described catalytic wax oil enters a kind of, two or three device in hydrotreater, aromatic extraction unit, the hydroeracking unit, these three kinds of devices obtain respectively that hydrogenation catalyst wax oil, catalytic wax oil are raffinated oil, the catalytic wax oil hydrocracking tail oil, described hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil as difficult cracking stock oil easily cracking stock oil turn back to step (1) or/and in the step (2).
Described catalytic wax oil hydrocracking tail oil can turn back to step (1) or/and in the step (2), also can be used as the stock oil of voluminous gasoline device, steam cracking device and other device.
In a more preferred embodiment, described difficult cracking stock grease separation from or comprise that slurry oil, diesel oil, gasoline, carbonatoms are one or more the mixture in the hydrocarbon of 4-8; Described easy cracking stock grease separation from or comprise petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, the long residuum, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.Described gasoline is selected from or comprises 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 selected from or comprises 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.Described carbonatoms is that 4～8 hydrocarbon can be from catalytic cracking method of the present invention, also can be from technologies such as conventional catalytic cracking, coking, thermally splitting, hydrogenation.
In a more preferred embodiment, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can be to above-mentioned mesopore zeolite with non-metallic element and/or iron such as phosphorus, cobalt, transition metals such as nickel carry out modification, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, the mixture of one or more among the zeolite of 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 the Y series zeolite, comprises super steady Y, high silicon Y that Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods obtain.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 can be identical, also can be different.
The size composition of the catalyzer that described coarse grain directly distributes is lower than 10% and is preferably lower than 5% for account for all particulate volume ratios less than 40 microns particle.
In a more preferred embodiment, the more excellent size composition of the catalyzer that described coarse grain directly distributes should be lower than 10% for accounting for all particulate volume ratios less than 40 microns particle, is preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and should be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
In a more preferred embodiment, also can to obtain boiling range be 180～260 ℃ cut to the described reaction oil gas of step (3) through separating, this cut as difficult cracking stock oil or/and easily cracking stock oil turn back to step (1) or/and in the step (2).Described boiling range scope is that 180～260 ℃ cut can also can comprise any cut that is rich in mononuclear aromatics from technologies such as conventional catalytic cracking, coking, thermally splitting and hydrogenation simultaneously from catalytic cracking method of the present invention.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.Wherein the gas speed of fluidized-bed is 0.1 meter per second～2 meter per seconds, and the gas speed of riser tube is 2 meter per seconds～30 meter per seconds (disregarding catalyzer).
Preferred forms of the present invention is to carry out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.
In order to increase the agent-oil ratio of reaction catchment, improve the catalytic activity of catalyzer, can be by supplemental heat or cold regenerated catalyst, half regenerated catalyst, catalyzer, live catalyst to be generated.Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively, 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.
Method such as separation of propylene is identical with the method that those of ordinary skills know from reaction product; Separate described 180～260 ℃ cut, preferred 190～250 ℃ cut can separate in existing FCC separation column also and can separate in the separation column separately; Greater than heavy aromatics and separating of non-aromatics in the catalytic wax oil of 250 ℃ or 260 ℃ (or greater than 330 ℃ catalytic wax oil) adopting the catalytic wax oil extraction plant, perhaps greater than the stock oil of the cut of 250 ℃ or 260 ℃ (or greater than 330 ℃ cut), perhaps adopt the catalytic wax oil hydrogenation unit greater than the catalytic wax oil of 250 ℃ or 260 ℃ (or greater than 330 ℃ catalytic wax oil) hydrogenation mode as catalytic cracking unit.
The catalytic wax oil extraction solvent is selected from methyl-sulphoxide, furfural, dimethyl formamide, monoethanolamine, ethylene glycol, 1, the mixture of one or more in the materials such as 2-propylene glycol.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.Extractum is one of a purpose product heavy aromatics, and it is non-aromatics as one of raw material of catalytic pyrolysis that catalytic wax oil is raffinated oil.
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 carry out hydrotreatment reaction.
The catalytic wax oil hydrocracking is under there is situation in hydrogen, contacts with hydrocracking 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 hydrocracking reaction.
This technical scheme organically combines technologies such as catalytic pyrolysis and the extracting of catalytic wax oil aromatic solvent, catalytic wax oil hydrogenation and catalytic wax oil hydrocracking, produces the stop bracket gasoline low-carbon alkene to greatest extent from the lower heavy feed stock of hydrogen richness, especially propylene.The present invention compared with prior art has following technique effect:
1, productivity of propylene and the propylene selectivity in liquefied gas increases considerably; Gasoline yield increases significantly, and gasoline octane rating improves significantly.
2, under the situation that productivity of propylene increases considerably, dry gas yied and coke yield reduce significantly.
3, yield of light oil increases significantly, and the slurry oil productive rate reduces significantly, thereby the petroleum resources utilising efficiency improves.
4, catalyzer is more even because of particle, thereby partial temperature distribution is also more even in regenerative process, and the catalyst breakage tendency also correspondingly reduces.
5, catalyst consumption reduces, and the catalyst content in the catalytic wax oil reduces.
Description of drawings
Fig. 1 is the synoptic diagram of the catalysis conversion method of first kind of embodiment of the present invention.
Fig. 2 is the synoptic diagram of the catalytic cracking method of second kind of embodiment of the present invention.
Fig. 3 is the synoptic diagram of the catalytic cracking method of the third embodiment of the present invention, and it is a catalysis conversion method schematic flow sheet of producing propylene and stop bracket gasoline provided by the invention.
Fig. 4 is the synoptic diagram of the catalytic cracking method of the 4th kind of embodiment of the present invention.
Above-mentioned accompanying drawing is intended to the present invention schematically is described and unrestricted the present invention.
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 synoptic diagram of the catalysis conversion method of first kind of embodiment of the present invention.
Its technical process is as follows:
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 in the accelerated motion that makes progress of the pre-castering action lower edge riser tube that promotes medium, part material oil through pipeline 3 with 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 takes place in stock oil on the catalyzer of heat, and upwards accelerated motion.Part material oil through pipeline 5 with middle and upper part from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 6, mix with the existing logistics of riser reactor, cracking reaction takes place in stock oil on the lower catalyzer that contains certain charcoal, and upwards accelerated motion enters reaction zone II continuation reaction, the reaction product oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 8 through pipeline 7, the realization reclaimable catalyst separates with reaction product oil gas, reaction product oil gas enters collection chamber 9, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 10 in the settling vessel, contacts with steam from pipeline 11.The reaction product oil gas that stripping goes out from reclaimable catalyst enters collection chamber 9 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, 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 15.Catalyzer after the regeneration enters riser tube through inclined tube 16.
Reaction product oil gas in the collection chamber 9 enters follow-up separation system 18 through main oil gas piping 17, separates the liquefied gas that obtains and draws through pipeline 20; Separating the gasoline that obtains draws through pipeline 21; Separating the dry gas that obtains draws through pipeline 19; Separating the diesel oil that obtains draws through pipeline 22; Separating the catalytic wax oil that obtains draws through pipeline 23.Wherein each cut boiling range is regulated according to refinery's actual needs.
Fig. 2 is the catalytic cracking method synoptic diagram of second kind of embodiment of the present invention.
Its technical process is as follows:
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 in the accelerated motion that makes progress of the pre-castering action lower edge riser tube that promotes medium, difficult cracking stock oil through pipeline 3 with 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 takes place in difficult cracking stock oil on the catalyzer of heat, and upwards accelerated motion.Easily cracking stock oil through pipeline 5 with middle and upper part from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 6, mix with the existing logistics of riser reactor, easily cracking reaction takes place in cracking stock oil on the lower catalyzer that contains certain charcoal, and upwards accelerated motion enters reaction zone II continuation reaction, the reaction product oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 8 through pipeline 7, the realization reclaimable catalyst separates with reaction product oil gas, reaction product oil gas enters collection chamber 9, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 10 in the settling vessel, contacts with steam from pipeline 11.The reaction product oil gas that stripping goes out from reclaimable catalyst enters collection chamber 9 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, 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 15.Catalyzer after the regeneration enters riser tube through inclined tube 16.
Reaction product oil gas in the collection chamber 9 enters follow-up separation system 18 through main oil gas piping 17, separates the propylene that obtains and draws through pipeline 219; Separating the propane that obtains draws through pipeline 228; And C 4 olefin is drawn through pipeline 220, and the part C 4 olefin returns riser reactor 2; The catalytic pyrolysis dry gas is drawn through pipeline 221; Boiling range is that 180～260 ℃ cut is drawn through pipeline 222 and returned riser tube 2; Boiling range is that 260～330 ℃ diesel oil distillate can be drawn through pipeline 229, also can draw with catalytic wax oil and enter catalytic wax oil extracting unit; The catalytic wax oil raw material is drawn out to catalytic wax oil extracting unit 224 through pipeline 223, and isolated heavy aromatics is drawn through pipeline 226, and catalytic wax oil is raffinated oil and returned riser tube 2 through pipeline 225; Catalytic pyrolysis C5-180 ℃ stop bracket gasoline is drawn through pipeline 227.Wherein each cut boiling range is regulated according to refinery's actual needs.
Fig. 3 is the catalytic cracking method synoptic diagram of the third embodiment of the present invention.
Its technical process is as follows:
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 in the accelerated motion that makes progress of the pre-castering action lower edge riser tube that promotes medium, difficult cracking stock oil through pipeline 3 with 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 takes place in difficult cracking stock oil on the catalyzer of heat, and upwards accelerated motion.Easily cracking stock oil through pipeline 5 with middle and upper part from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 6, mix with the existing logistics of riser reactor, easily cracking reaction takes place in cracking stock oil on the lower catalyzer that contains certain charcoal, and upwards accelerated motion enters reaction zone II continuation reaction, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 8 through pipeline 7, the realization reclaimable catalyst separates with oil gas, oil gas enters collection chamber 9, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 10 in the settling vessel, contacts with steam from pipeline 11.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 9 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, 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 15.Catalyzer after the regeneration enters riser tube through inclined tube 16.
Reaction product oil gas in the collection chamber 9 is through main oil gas piping 17, enter follow-up separation system 18, separating the propylene that obtains draws through pipeline 319, separating the propane that obtains draws through pipeline 328, and carbon four hydrocarbon are drawn through pipeline 320, also can return the reaction zone I bottom of riser tube 2, the catalytic pyrolysis dry gas is drawn through pipeline 321, catalytic cracking gasoline is drawn through pipeline 327, boiling range is 180～260 ℃ cut returns riser tube 2 through pipeline 322 reaction zone I bottom, the cut of boiling range＞260 ℃ enters hydrotreatment unit 324 through pipeline 323, isolates light constituent and draws through pipeline 325, and hydrogenation heavy oil returns the reaction zone I middle and upper part of riser tube 2 through pipeline 326.
Fig. 4 is the catalytic cracking method synoptic diagram of the 4th kind of embodiment of the present invention.
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 in the accelerated motion that makes progress of the pre-castering action lower edge riser tube that promotes medium, again cracking stock oil through pipeline 3 with 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 takes place in cracking stock on the catalyzer of heat again, and upwards accelerated motion.Cracking stock oil through pipeline 5 with middle and lower part from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 6, mix with the existing logistics of riser reactor, cracking reaction takes place in cracking stock on the lower catalyzer that contains certain charcoal, and upwards accelerated motion enters reaction zone II continuation reaction, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 8 through pipeline 7, the realization reclaimable catalyst separates with oil gas, oil gas enters collection chamber 9, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 10 in the settling vessel, contacts with steam from pipeline 11.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 9 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, 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 15.Catalyzer after the regeneration enters riser tube through inclined tube 16.
Oil gas in the collection chamber 9 enters follow-up separation system 18 through main oil gas piping 17, separates the propylene that obtains and draws through pipeline 419, separates the propane that obtains and draws through pipeline 428; And carbon four hydrocarbon are drawn through pipeline 420, also can return riser tube 2; The catalytic pyrolysis dry gas is drawn through pipeline 421; Catalytic cracking gasoline is drawn through pipeline 427, and preferred boiling range is drawn conduct cracking stock Returning reactor again less than 65～110 ℃ of gasoline fractions through pipeline 422; Diesel oil distillate is drawn through pipeline 429, also the heavy gas oil cut can be drawn with catalytic wax oil and enter the hydrocracking unit; The catalytic wax oil raw material is drawn out to hydrocracking unit 424 through pipeline 423, and isolated hydrocracking product further separates through pipeline 425, and hydrocracking tail oil is sent into this reactor or/and voluminous gasoline device 427 through pipeline 426.The oil gas that fecund gasoline device generates can enter fractionating system 18 or/and enter other fractionating system and separate through gas pipeline 430.Wherein each cut boiling range is regulated according to refinery's actual needs.
The following examples will give further instruction to present method, but therefore not limit present method.
Used stock oil is VGO among the embodiment, and its character is as shown in table 1.
Catalytic cracking catalyst preparation method used among the embodiment is summarized as follows:
1), with 20gNH
4Cl is dissolved in the 1000g water, and (Qilu Petrochemical company catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP-1 zeolite 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 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 handle 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 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%) again, its PH is transferred to 2-4 with hydrochloric acid, 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), the MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (the Qilu Petrochemical company catalyst plant Industrial products of the phosphorous and iron that step 1) is prepared, 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 the catalytic cracking catalyst sample, consist of 18 heavy % MFI structure mesopore zeolite, 2 heavy %DASY zeolites, the 28 heavy % pseudo-boehmites, 7 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
4) prepared catalyzer wears out through 800 ℃ and 100% water vapor, the aged catalyst property is listed in table 2, its code name is DW-1, again elutriation is carried out in the aging agent of part, remove fine particle and greater than 100 microns particle, obtain the catalyzer that coarse grain directly distributes, its code name is DL-1, and its character is listed in table 2.
Embodiment 1
This embodiment tests according to the flow process of Fig. 1, and stock oil A directly as the stock oil of catalytic pyrolysis, tests on the middle-scale device of riser reactor, and stock oil A enters reaction zone I.530 ℃ of temperature of reaction, weight hourly space velocity 30h
-1The weight ratio of catalyzer DL-1 and stock oil is 10, the weight ratio of water vapor and stock oil is to carry out cracking reaction under 0.15 condition, reaction product oil gas separates at settling vessel with band charcoal catalyzer to be generated, product cuts by boiling range in separation system, thereby obtains products such as propylene, gasoline and catalytic wax oil.Operational condition and product distribute and list in table 3.
Comparative Examples 1
This Comparative Examples is also tested according to the flow process of Fig. 1, and stock oil A directly as the stock oil of catalytic pyrolysis, tests on the middle-scale device of riser reactor, and stock oil A enters reaction zone I.530 ℃ of temperature of reaction, weight hourly space velocity 30h
-1The weight ratio of catalyzer DW-1 and stock oil is 10, the weight ratio of water vapor and stock oil is to carry out cracking reaction under 0.15 condition, reaction product oil gas separates at settling vessel with band charcoal catalyzer to be generated, product cuts by boiling range in separation system, thereby obtains products such as propylene, gasoline and catalytic wax oil.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, with respect to embodiment 1, the dry gas yied and the coke yield of Comparative Examples 1 increase significantly, and the catalytic wax oil productive rate slightly reduces.
This embodiment tests according to the flow process of accompanying drawing 3, the employing catalyzer is DL-1, stock oil A is directly as the stock oil of catalytic pyrolysis, on middle-scale device, test by riser reactor, easily cracking stock oil enters reaction zone I middle and upper part, difficult cracking stock oil enters reaction zone I bottom, and in reaction zone I bottom, difficult cracking stock oil is at 640 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, the weight ratio 60 of catalyzer DL-1 and difficult cracking stock oil, the weight ratio of water vapor and difficult cracking stock oil are to carry out cracking reaction under 0.20 condition; In reaction zone I middle and upper part, easily cracking stock oil is at 580 ℃ of temperature of reaction, weight hourly space velocity 60h
-1, the weight ratio 10 of catalytic cracking catalyst and easy cracking stock oil, water vapor is to carry out cracking reaction under 0.15 condition with the weight ratio of easy cracking stock oil, at reaction zone II, reactant flow oil gas is at 540 ℃ of temperature of reaction, weight hourly space velocity 30h
-1Water vapor is to carry out cracking reaction under 0.15 condition with the weight ratio of easy cracking stock oil, reaction product oil gas separates at settling vessel with catalyzer to be generated, product cuts by boiling range in separation system, thereby obtain propylene and gasoline, part carbon four hydrocarbon, boiling range are that 180～260 ℃ cut carries out cracking again, and (its productive rate is 29.32 heavy % to the catalytic wax oil of boiling range＞260 ℃, and hydrogen richness is 11.1 heavy %.) through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1500v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, the hydrogenation catalyst wax oil behind the hydrogenation loops back above-mentioned kitty cracker.Operational condition and product distribute and list in table 4.
Comparative Examples 2
This Comparative Examples is also tested according to the flow process of Fig. 3, and the stock oil of test and testing sequence and method and embodiment 2 are identical, and just the catalyzer that adopts changes catalyzer DW-1 into by DL-1.
Operational condition and product distribute and list in table 4.
As can be seen from Table 4, with respect to embodiment 2, the dry gas yied and the coke yield of Comparative Examples 2 increase significantly.
Embodiment 3
This embodiment tests according to the flow process of Fig. 4, stock oil B is directly as the stock oil of catalytic pyrolysis, on middle-scale device, test by riser reactor, cracking stock oil enters reaction zone I middle and upper part, butylene conduct cracking stock oil again enters reaction zone I bottom, in reaction zone I bottom, cracking stock oil is at 630 ℃ of temperature of reaction, weight hourly space velocity 180h again
-1, the catalytic cracking catalyst and the weight ratio 62 of cracking stock oil again, water vapor is to carry out cracking reaction under 0.20 condition with the weight ratio of cracking stock oil again; In reaction zone I middle and upper part, cracking stock oil is at 575 ℃ of temperature of reaction, weight hourly space velocity 65h
-1The weight ratio 10 of catalytic cracking catalyst and cracking stock oil, the weight ratio of water vapor and cracking stock oil is to carry out cracking reaction under 0.15 condition, in addition, replenish the steam stripped reclaimable catalyst of part from stripping stage and enter reaction zone II bottom, with temperature and the reaction weight hourly space velocity that reduces reaction zone II.At reaction zone II, oil gas is at 530 ℃ of temperature of reaction, weight hourly space velocity 20h
-1The weight ratio of water vapor and cracking stock oil is to carry out cracking reaction under 0.15 condition, and oil gas separates at settling vessel with the catalyzer for the treatment of charcoal, and product cuts by boiling range in separation system, thereby obtain propylene and gasoline, the catalytic wax oil of part carbon four hydrocarbon, boiling range＞260 ℃.Catalytic wax oil is delivered to hydroeracking unit and is handled, and the reactive system of this hydroeracking unit comprises refining reaction device and two reactors of cracking case, at hydrogen dividing potential drop 16.5/16.0MPa, 375/371 ℃ of temperature of reaction, volume space velocity 0.90/1.1h
-1Reaction conditions under carry out hydrotreatment, the hydrocracking tail oil behind the hydrogenation returns this riser reactor reaction zone I middle and upper part.Operational condition and product distribute and list in table 5.
As can be seen from Table 5, productivity of propylene is up to 15.21 heavy %, and gasoline yield is 37.41 heavy %, and aviation fuel is 13.89 heavy %.
Comparative Examples 3
This Comparative Examples is also tested according to the flow process of Fig. 4, and the stock oil of test and testing sequence and method and embodiment 3 are identical, and just the catalyzer that adopts changes catalyzer DW-1 into by DL-1.Operational condition and product distribute and list in table 5.
As can be seen from Table 5, with respect to embodiment 3, the dry gas yied and the coke yield of Comparative Examples 2 increase significantly.
Table 1
| The stock oil numbering | A | B |
| Stock oil character | ||
| Density (20 ℃), g/cm 3 | 0.8886 | 0.8997 |
| Sulphur content, μ g/g | 4700 | 2000 |
| Nitrogen content, μ g/g | 1600 | 1500 |
| Aromatic hydrocarbons, heavy % | 26.3 | 23.4 |
| Carbon, heavy % | 86.46 | 86.61 |
| Hydrogen, heavy % | 12.86 | 12.73 |
| Boiling range (ASTM D-1160), ℃ | ||
| IBP | 312 | 283 |
| 10％ | 361 | 376 |
| 30％ | 412 | 410 |
| 50％ | 452 | 433 |
| 70％ | 478 | 460 |
| 90％ | 506 | 511 |
| 95％ | 532 | 523 |
| EP | 546 | 541 |
Table 2
| The catalyzer title | DW-1 | DL-1 |
| Grain type | Conventional particle diameter | The coarse grain footpath |
| Chemical property, w% | ||
| Al 2O 3 | 50.4 | 50.1 |
| Fe 2O 3 | 0.6 | 0.6 |
| Na 2O | 0.07 | 0.06 |
| Physical properties | ||
| Tap density, g/cm 3 | 0.78 | 0.80 |
| Specific surface, m 2/g | 104 | 97 |
| Pore volume, ml/g | 0.22 | 0.20 |
| Size-grade distribution, volume % | ||
| 0～40μm | 25.8 | 6.8 |
| 40～80μm | 57.5 | 78.6 |
| ＞80μm | 16.7 | 14.6 |
| Median size, μ m | 69 | 72 |
Table 3
| Embodiment 1 | Comparative Examples 1 | |
| The stock oil numbering | A | A |
| The catalyzer title | DL-1 | DW-1 |
| Operational condition | ||
| Temperature of reaction, ℃ | 530 | 530 |
| Weight hourly space velocity (WHSV), h -1 | 30 | 30 |
| Steam/stock oil weight ratio, m/m | 0.15 | 0.15 |
| Catalystoil ratio, m/ |
10 | 10 |
| Products distribution, heavy % | ||
| Dry gas | 2.04 | 2.36 |
| Liquefied gas | 39.16 | 39.68 |
| Propylene | 18.52 | 18.29 |
| Gasoline | 21.05 | 21.53 |
| Diesel oil | 2.53 | 2.36 |
| Catalytic wax oil (FGO) | 31.57 | 30.12 |
| Hydrogen richness, heavy % | 11.15 | 11.08 |
| Boiling range, ℃ | ||
| Initial boiling point | 265 | 263 |
| Final boiling point | 555 | 554 |
| Coke | 3.65 | 3.95 |
| Amount to | 100.00 | 100.00 |
Table 4
| |
Comparative Examples 2 | |
| The stock oil numbering | A | A |
| The catalyzer title | DL-1 | DW-1 |
| Catalytic unit | ||
| The riser tube temperature out, ℃ | 530 | 530 |
| Second reaction zone | ||
| Temperature of reaction, ℃ | 540 | 540 |
| Weight hourly space velocity (WHSV), h -1 | 30 | 30 |
| Steam/stock oil weight ratio, m/m | 0.15 | 0.15 |
| First reaction zone | ||
| Temperature of reaction, ℃ | 640/580 | 640/580 |
| Catalystoil ratio, m/m | 60/10 | 60/10 |
| Weight hourly space velocity (WHSV), h -1 | 180/60 | 180/60 |
| Steam/stock oil weight ratio, m/m | 0.20/0.15 | 0.20/0.15 |
| Hydrogenation unit | ||
| The hydrogen dividing potential drop, MPa | 18.0 | 18.0 |
| Temperature of reaction, ℃ | 350 | 350 |
| Hydrogen-oil ratio, v/v | 1500 | 1500 |
| Volume space velocity, h -1 | 1.5 | 1.5 |
| Products distribution, heavy % | ||
| Dry gas | 2.98 | 3.32 |
| Liquefied gas | 51.21 | 51.23 |
| Propylene | 31.10 | 30.02 |
| Gasoline | 32.11 | 31.12 |
| Diesel oil | 8.50 | 8.33 |
| Coke | 5.20 | 6.0 |
| Amount to | 100.0 | 100.00 |
Table 5
| Embodiment 3 | Comparative Examples 3 | |
| The stock oil numbering | B | B |
| The catalyzer title | DL-1 | DW-1 |
| The catalytic pyrolysis unit | ||
| Operational condition | ||
| The riser tube temperature out, ℃ | 515 | 515 |
| Riser reaction zone II | ||
| Temperature of reaction, ℃ | 530 | 530 |
| Weight hourly space velocity, |
20 | 20 |
| The weight ratio of water vapor/stock oil | 0.15 | 0.15 |
| Riser reaction zone I | ||
| Medial temperature, ℃ | 630/575 | 630/575 |
| Agent-oil ratio, m/m | 62/10 | 62/10 |
| Weight hourly space velocity, h -1 | 180/60 | 180/60 |
| The weight ratio of water vapor/stock oil | 0.20/0.15 | 0.20/0.15 |
| The hydrocracking unit | ||
| The hydrogen dividing potential drop, MPa | 16.5/16.0 | 16.5/16.0 |
| Temperature of reaction, ℃ | 375/371 | 375/371 |
| Volume space velocity, h -1 | 0.90/1.10 | 0.90/1.10 |
| Product distributes, m% | ||
| Dry gas | 3.00 | 3.35 |
| Liquefied gas | 31.67 | 31.73 |
| Propylene | 15.21 | 14.84 |
| Gasoline | 37.41 | 36.79 |
| Aviation fuel | 13.89 | 13.46 |
| Diesel oil | 8.87 | 8.79 |
| Coke | 4.67 | 5.38 |
| Loss | 0.50 | 0.50 |
| Add up to | 100.00 | 100.00 |
The said products distributed data is data behind the normalizing.
Above-mentioned all reference are all incorporated this paper for all useful purposes into through quoting.
Although show and described concrete manifestation some embodiment of the present invention, but those skilled in the art it is evident that, can under the situation that does not deviate from the spirit and scope that constitute principle of the present invention, make various variations and modification, and this is not limited to the illustrational specific form of this paper.
Claims (34)
1. catalysis conversion method of producing propylene and stop bracket gasoline, wherein the catalyzer that directly distributes with the coarse grain that is rich in mesopore zeolite in reactor of stock oil contacts and reacts, the size composition of the catalyzer that described coarse grain directly distributes is lower than 10% and account for all particulate volume ratios greater than 80 microns particle and be lower than 15% for account for all particulate volume ratios less than 40 microns particle, temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil, and wherein said weight hourly space velocity is 25～100h
-1, described temperature of reaction is 450～600 ℃, described catalyzer and stock oil weight ratio are 1～30; Described catalytic wax oil is that initial boiling point is not less than 260 ℃ cut, and hydrogen richness is not less than 10.5 heavy %.
2. according to the method for claim 1, it is characterized in that described stock oil is selected from petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, the long residuum, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
3. according to the method for claim 1, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y series zeolite.
4. according to the method for claim 1, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 5% for accounting for all particulate volume ratios less than 40 microns particle.
5. according to the method for claim 1, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios greater than 80 microns particle.
6. according to the method for claim 1, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
7. according to the method for claim 1, it is characterized in that described stock oil being introduced in the reactor, or described stock oil is introduced in the reactor in the position of identical or different height more than a position.
8. according to the method for claim 1, it is characterized in that temperature of reaction is 460～580 ℃, weight hourly space velocity is 30～80h
-1, catalyzer and stock oil weight ratio be 2～15.
9. according to the method for claim 1, it is characterized in that temperature of reaction is 480～540 ℃.
10. according to the method for claim 1, it is characterized in that weight hourly space velocity is 40～60h
-1
11., it is characterized in that catalyzer and stock oil weight ratio are 3～14 according to the method for claim 1.
12., it is characterized in that the described pressure that is reflected at is to carry out under 0.10MPa～1.0MPa according to the method for claim 1.
13. according to the method for claim 1, it is characterized in that described method also comprises separates reaction product with catalyzer, catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises propylene, stop bracket gasoline and catalytic wax oil.
14. according to the method for claim 1, it is characterized in that described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, hydrogen richness is not less than 10.8 heavy %.
15. catalysis conversion method, wherein the catalyzer that directly distributes with the coarse grain that is rich in mesopore zeolite in reactor of stock oil contacts and reacts, the size composition of the catalyzer that described coarse grain directly distributes is lower than 10% and account for all particulate volume ratios greater than 80 microns particle and be lower than 15% for account for all particulate volume ratios less than 40 microns particle, and this method comprises:
(1) stock oil comprises difficult cracking stock oil and easy cracking stock oil, a position described stock oil is introduced in the reactor, or described stock oil is introduced in the reactor in the position of identical or different height more than, described difficult cracking stock grease separation is from slurry oil, diesel oil, gasoline, carbonatoms is one or more the mixture in the hydrocarbon of 4-8, easily cracking stock grease separation is from petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, the mixture of one or more in the long residuum, other mineral oil are liquefied coal coil, tar sand oil, the mixture of one or more in the shale oil;
(2) difficult cracking stock oil is not later than easy cracking stock oil and reacts in reactor;
(3) weight ratio of temperature of reaction, weight hourly space velocity, catalyzer and stock oil is enough to make reaction to obtain comprising to account for the reaction product of easy cracking stock oil 12～60 heavy % catalytic wax oil, described catalytic wax oil is that initial boiling point is not less than 260 ℃ cut, and hydrogen richness is not less than 10.5 heavy %;
(4) easily the described temperature of reaction of cracking stock oil is 460-580 ℃, and weight hourly space velocity is 5～100h
-1, catalyzer and stock oil weight ratio are 3～14.
16. method according to claim 15, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y series zeolite.
17. according to the method for claim 15, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 5% for accounting for all particulate volume ratios less than 40 microns particle.
18. according to the method for claim 15, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios greater than 80 microns particle.
19. method according to claim 15, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
20., it is characterized in that the reaction conditions of difficult cracking stock oil is: 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h according to the method for claim 15
-1, reaction pressure 0.10～1.0MPa, catalyzer and difficult cracking stock oil weight ratio 30～150, the weight ratio of water vapor and difficult cracking stock oil is 0.05～1.0.
21., it is characterized in that the reaction conditions of easy cracking stock oil is: 450～600 ℃ of temperature of reaction, weight hourly space velocity 5～100h according to the method for claim 15
-1, reaction pressure 0.10～1.0MPa, catalyzer and the easy weight ratio 1.0～30 of cracking stock oil, water vapor is 0.05～1.0 with the easy weight ratio of cracking stock oil.
22. according to the method for claim 15, the weight hourly space velocity that it is characterized in that easy cracking stock oil is 10～90h
-1
23. according to the method for claim 15, it is characterized in that described method also comprises separates reaction product with catalyzer, catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises propylene, stop bracket gasoline and catalytic wax oil.
24. according to the method for claim 15, it is characterized in that described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, hydrogen richness is not less than 10.8 heavy %.
25. a catalysis conversion method of producing propylene and stop bracket gasoline is characterized in that this method comprises the following steps:
(1) raw material that contains difficult cracking stock oil earlier and the catalyzer that the coarse grain that is rich in mesopore zeolite directly distributes contact, the size composition of the catalyzer that described coarse grain directly distributes is lower than 10% and account for all particulate volume ratios greater than 80 microns particle and be lower than 15% for account for all particulate volume ratios less than 40 microns particle, at 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10～1.0MPa, catalyzer and difficult cracking stock oil weight ratio 30～150, the weight ratio of water vapor and difficult cracking stock oil is to carry out cracking reaction under 0.05～1.0 the condition;
(2) reactant flow that contains difficult cracking stock oil again with easy cracking stock oil at 450～600 ℃ of temperature of reaction, weight hourly space velocity 5～100h
-1, reaction pressure 0.10～1.0MPa, catalyzer and the easy weight ratio 1.0～30 of cracking stock oil, water vapor and the easy weight ratio of cracking stock oil are to carry out cracking reaction under 0.05～1.0 the condition;
(3) reclaimable catalyst separates by cyclonic separator with reaction oil gas; Randomly, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration; Reaction oil gas obtains comprising the reaction product of propylene, stop bracket gasoline, catalytic wax oil through separation, and described catalytic wax oil is that initial boiling point is not less than 260 ℃ cut, and hydrogen richness is not less than 10.5 heavy %;
(4) described catalytic wax oil enters a kind of, two or three device in hydrotreater, aromatic extraction unit, the hydroeracking unit, these three kinds of devices obtain respectively that hydrogenation catalyst wax oil, catalytic wax oil are raffinated oil, the catalytic wax oil hydrocracking tail oil, described hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil as difficult cracking stock oil easily cracking stock oil turn back to step (1) or/and in the step (2);
Described difficult cracking stock grease separation is one or more mixture in 4～8 the hydrocarbon from slurry oil, diesel oil, gasoline, carbonatoms; Described easy cracking stock grease separation is from petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, the long residuum, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
26. method according to claim 25, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51～100 heavy % of zeolite gross weight, large pore zeolite accounts for 0～49 heavy % of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y series zeolite.
27. according to the method for claim 25, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 5% for accounting for all particulate volume ratios less than 40 microns particle.
28. according to the method for claim 25, the size composition that it is characterized in that the catalyzer that described coarse grain directly distributes is lower than 10% for accounting for all particulate volume ratios greater than 80 microns particle.
29. according to the method for claim 25, it is characterized in that described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, hydrogen richness is not less than 10.8 heavy %.
30. method according to claim 25, it is characterized in that also can to obtain boiling range be 180～260 ℃ cut to the described reaction oil gas of step (3) through separating, this cut as difficult cracking stock oil or/and easily cracking stock oil turn back to step (1) or/and in the step (2).
31., it is characterized in that described catalyzer mesopore zeolite accounts for the heavy % in 70 heavy % of zeolite gross weight～100 according to the method for claim 26.
32. method according to claim 25, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
33., it is characterized in that described catalytic wax oil hydrocracking tail oil turns back to step (1) or/and in the step (2) according to the method for claim 25.
34., it is characterized in that the stock oil of described catalytic wax oil hydrocracking tail oil as voluminous gasoline device, steam cracking device and other device according to the method for claim 25.
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| CN102806100B (en) * | 2011-05-31 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for producing propane and high octane number gasoline by using butane, and preparation method thereof |
| CN104549458B (en) * | 2013-10-23 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of maximum produces ethylene raw hydrocracking catalyst and preparation method thereof |
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| CN1232070A (en) * | 1999-04-23 | 1999-10-20 | 中国石油化工集团公司 | Catalytic conversion method for preparing propylene, isobutane and isoalkane-enriched gasoline |
| CN1307088A (en) * | 2000-01-21 | 2001-08-08 | 中国石油化工集团公司 | Method for increasing liquefied gas yield and gasoline octane number |
| CN101362959A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing propone and high-octane number gasoline |
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| CN1232070A (en) * | 1999-04-23 | 1999-10-20 | 中国石油化工集团公司 | Catalytic conversion method for preparing propylene, isobutane and isoalkane-enriched gasoline |
| CN1307088A (en) * | 2000-01-21 | 2001-08-08 | 中国石油化工集团公司 | Method for increasing liquefied gas yield and gasoline octane number |
| CN101362959A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing propone and high-octane number gasoline |
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