CN104419459A - Catalytic conversion method for producing propylene and fuel oil - Google Patents
Catalytic conversion method for producing propylene and fuel oil Download PDFInfo
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- CN104419459A CN104419459A CN201310388931.9A CN201310388931A CN104419459A CN 104419459 A CN104419459 A CN 104419459A CN 201310388931 A CN201310388931 A CN 201310388931A CN 104419459 A CN104419459 A CN 104419459A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a catalytic conversion method for producing propylene and fuel oil. The method comprises the following steps: enabling raw material oil of which the paraffin content is 40-90wt% and methane to contact with a catalytic cracking catalyst under the catalytic cracking condition; separating out pyrolysis gas oil from a contacted mixture; and carrying out aromatics extraction on the pyrolysis gas oil to obtain extract oil and raffinate oil. According to the method provided by the invention, the raw material oil (for example, straight-run diesel oil), which is relatively high in paraffin content can be adopted as a raw material; low-carbon olefin, particularly propylene and fuel oil can be produced at high selectivity; the problem of shortage of petrochemical materials is solved; and the economic benefits of a refinery plant are improved.
Description
Technical field
The present invention relates to a kind of catalysis conversion method producing propylene and oil fuel.
Background technology
Propylene is important Organic Chemicals, and according to analysis, global propylene demand growth amount about 4.0%, about 83Mt in 2012, propylene supply and demand ratio is about 1.0.Over nearly 10 years, the rate of increase of World Propylene demand, always higher than ethene, estimates that, at 20 years from now on, the rate of increase of World Propylene demand will exceed the rate of increase of ethylene requirements.At present, the byproduct of ethene produced by the propylene of 61% from steam cracking in the world, 34% produces the byproduct of gasoline, diesel oil from refinery catalytic cracking unit, wherein, steam cracking with lightweight oils such as petroleum naphthas for raw material produces ethene and propylene by thermo-cracking, but the productive rate of propylene is only about 15 % by weight, in Conventional catalytic cracking technology, productivity of propylene is about 3-5%, and in mink cell focus deep catalytic cracking technology, productivity of propylene is about 15-20%.Along with heaviness and the in poor quality aggravation of crude oil, technical superiority and the economy of from mink cell focus, producing propylene will be subject to challenge greatly.
By the increasingly strict promotion that environmental regulation requires and automobile industry requires fuel mass, global motor spirit increased quality is very rapid in recent years, and oil quality upgrading paces are also obviously accelerated.At present, FCC gasoline accounts for more than 70% of motor spirit total amount, and reformed gasoline is too low with other high-quality high octane gasoline component content, and less than 9%, and low-octane straight-run spirit proportion is higher, reaches about 13%.Therefore, FCC gasoline quality plays a part very important to gasoline aggregate level.FCC gasoline octane value RON is up to 90-92, and minimum is 87-88, average out to 89-90; MON is up to 80.6, and minimum is 78, average out to 79, the gap that existence is larger compared with the quality of gasoline of some other developed country, therefore, improves gasoline octane rating, and realizing gasoline upgrading is trend of the times.
In addition, in gasoline cleaning process, some measures are as controlled content of olefin in gasoline, desulfurization, and all cause octane value to lose to some extent, the contradiction of octane value shortage will be more outstanding.In sum, Development and Production propylene produces high-grade fuel oil as the catalytic cracking technology of stop bracket gasoline simultaneously, to meet the industrial chemicals and the oily Production requirement of high-grade fuel that specification of quality improves constantly, has important practical significance undoubtedly.
It is the feedstock of 160-260 DEG C and Conventional catalytic cracking catalyst exposure that CN101362960A proposes boiling range, and in fluidized-bed reactor, carry out cracking reaction, reaction oil gas is isolated to object product stop bracket gasoline.The method increase octane value and the productive rate of gasoline, by-product part small-numerator olefin is as ethene and propylene simultaneously.
CN101362959A proposes the raw material of difficult cracking first to contact with hot regenerated catalyst, cracking reaction is carried out after mixing with the stock oil of easy cracking again, obtain the raw material of object product propylene and stop bracket gasoline and cracking again, then the raw material packet of cracking is raffinated oil containing cut, the heavy aromatics that boiling range is 180-260 DEG C.Productive rate and the selectivity of the method propylene significantly increase, and gasoline yield and octane value improve significantly, and dry gas yied reduces amplitude up to 80 heavy more than %.
CN101531923A proposes the raw material of difficult cracking first to contact with hot recycling catalytic cracking catalyst, reactant flow again with the stock oil hybrid reaction of easy cracking, obtain propylene and gasoline, using the cut of >260 DEG C through the hydrogenation heavy oil of hydrotreatment gained as stock oil.The method increase productivity of propylene and selectivity, and stop bracket gasoline gain in yield, dry gas yied reduces, and liquid yield increases considerably.
CN101724430A proposes inferior feedstock oil to inject successively the first reaction zone of catalytic conversion reactor and second reaction zone and catalytic converting catalyst contact reacts, obtain propylene, gasoline, catalytic wax oil and other products, wherein, catalytic wax oil enters aromatic extraction unit, is separated and obtains extracting oil out and raffinating oil; Raffinate oil be circulated to reactor the first reaction zone or/and other catalytic convention design is obtained by reacting object product propylene and gasoline further.
The differential responses district that the stock oil that CN101760227A proposes different cracking performance enters the first riser reactor contacts with catalytic cracking catalyst and carries out cracking reaction, obtain the product comprising propylene, gasoline, again cracking stock, wherein, cracking stock is sent in the second riser reactor again, and the reclaimable catalyst of two riser reactors returns two riser reactors respectively in same revivifier after coke burning regeneration.The method propylene and gasoline yield increase significantly, and gasoline octane rating improves significantly, and when productivity of propylene increases considerably, dry gas yied reduces significantly, can reduce and reach more than 80 % by weight.
CN102453540A proposes high quality raw material oil and the lower contacts generation cracking reaction of the lower and hot regenerated catalyst that activity distribution is relatively uniform of average activity at reactor, diesel oil distillate in reaction product is cut into solar oil cut and heavy gas oil cut, heavy gas oil cut is separately or/and recycle stock cut, slurry oil cut carry out hydrotreatment obtain hydrogenation heavy gas oil cut, and hydrogenation heavy gas oil cut is separately or/and solar oil cut returns this reactor or/and other reactors react further.The method not only improves gasoline yield, and improves gasoline octane rating, reduces dry gas and coke yield simultaneously.
From the prior art, the exploitation that hydrocarbons catalytic conversion produces low-carbon alkene and oil fuel technology mainly concentrates on mink cell focus catalytic cracking technology aspect, due to mink cell focus boiling range a wider range, hydrocarbon molecules is larger, product structure numerous and complicated, in order to improve propene yield, adopts higher temperature of reaction, cause in increase productivity of propylene situation, dry gas yied especially methane production increases considerably.
Adopt intermediate oil as straight-run diesel oil be raw material time, owing to containing more paraffinic hydrocarbons in raw material, by a cracking reaction, although the productive rate of byproduct methane is higher in product, but still there is higher alkene and gasoline fraction yield, again because raw molecule is less relative to mink cell focus molecule, need the effectively cracking of higher reaction temperatures ability, even if but in high reaction temperatures, scission reaction green coke amount is still less, namely bring the problem of obvious reaction heat deficiency, make easily to occur revivifier carbon build-up in plant running process, finally cause products distribution to worsen.
In addition, prior art is underused gasoline potential content in high-octane number component in gasoline and diesel oil, causes gasoline yield on the low side.In order to meet the demand of growing propylene and high-grade fuel oil, be necessary that developing a kind of take intermediate oil as the catalysis conversion method that raw material is converted into propylene and high-grade fuel oil to greatest extent, to realize the efficiency utilization rate of petroleum resources.
Summary of the invention
The object of the invention is on the basis of existing technology, provide that a kind of dry gas yied is low, the catalysis conversion method of propylene and the high production propylene of fuel oil yield and oil fuel.
For realizing aforementioned object, the invention provides a kind of catalysis conversion method producing propylene and oil fuel, wherein, the method comprises: under catalytic cracking conditions, be that stock oil, the methane of 40-90 quality % contacts with catalytic cracking catalyst by paraffinicity, from the mixture after contact, isolate Pyrolysis gas oil PGO; Described Pyrolysis gas oil PGO is carried out Aromatics Extractive Project to obtain extracting oil out and raffinating oil.
Method provided by the invention is for the chemical constitution characteristic of the higher stock oil (such as straight-run diesel oil) of paraffinicity, catalysis conversion method is adopted to reduce hydrocarbon cracking reaction activity, in catalytic conversion process, add methane feed simultaneously, and to make in raw material more the hydro carbons generation scission reaction such as multichain alkane and naphthenic hydrocarbon and open loop scission reaction generate small molecules hydro carbons, improve the selectivity of low-carbon alkene particularly propylene; And of the present invention preferred embodiment in, preheating after reclaimable catalyst air lift is regenerated, makes reclaimable catalyst be that revivifier has been taken more heat, decrease the possibility that in revivifier, carbon build-up occurs, improve operational stability.And the high-temperature flue gas preheating reclaimable catalyst that the present invention adopts regeneration to produce, has effectively saved energy consumption.
Method of the present invention effectively can improve the productive rate of low-carbon alkene particularly propylene, and the present invention by rational Controlling Technology parameter and catalyst property, can adjust the product mix flexibly.
Method provided by the invention, stock oil (such as straight-run diesel oil) that paraffinicity is higher can be adopted as raw material, production low-carbon alkene particularly propylene and the oil fuel of highly selective, overcome the higher stock oil of traditional paraffinicity (such as straight-run diesel oil) high for the dry gas yied caused as catalytic pyrolysis raw material, the defect that productivity of low carbon olefin hydrocarbon is low, and make petroleum chemical enterprise that catalysis processing method can be adopted to substitute thermal processing method and produce low-carbon alkene particularly propylene and oil fuel to greatest extent from fraction oil of petroleum, thus realize the technological breakthrough of refinery's concept, change from traditional fuel type and fuel-Lube Type refinery production model to chemical industry type, make refinery from single oil refining to industrial chemicals and the production development of high added value derived product and extension, both the problem of petrochemical material shortage had been solved, turn improve the economic benefit of refinery.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schematic flow sheet of catalysis conversion method conventionally.
Fig. 2 is the schematic flow sheet of the catalysis conversion method according to a kind of production propylene preferred embodiment of the present invention and oil fuel.
Description of reference numerals
1-riser reactor; 2-revivifier; 3-settling vessel; 4-stripping stage; 5-degassing vessel;
6-(riser reactor 1 exit end) cyclonic separator;
7-(is communicated with pneumatic outlet and the main oil gas piping 20 of cyclonic separator 6) collection chamber;
8-reclaimable catalyst inclined tube pipeline; 9-guiding valve to be generated;
10-(is communicated with catalyst outlet and the degassing vessel 5 of described revivifier 2) pipeline;
11-(is communicated with degassing vessel 5 pneumatic outlet and revivifier 2) pipeline;
12-(is communicated with degassing vessel 5 and riser reactor 1) regenerated catalyst inclined tube;
13-regenerates guiding valve;
14-is the pipeline that pre-lift medium carried by riser reactor 1;
15-is the pipeline of riser reactor 1 transferring raw material;
16-is the pipeline of riser reactor 1 delivery of mist steam transferring raw material;
17-is the pipeline that hybrid C 4 component carried by riser reactor 1;
18-is the pipeline of riser reactor 1 delivery of mist steam and/or conveying hybrid C 4 component;
19-is the pipeline of stripping stage 4 delivery of mist steam;
20-main oil gas piping; 21-(revivifier 2) main air source line; 22-air distributor;
The pipeline of 23-degassing vessel 5 delivery of mist steam; 24-revivifier cyclonic separator;
25-(is communicated with cyclonic separator 24 pneumatic outlet) flue;
30-separation system (separation column); 31-carries the pipeline of dry gas; The pipeline of 32-delivering propane;
33-carries the pipeline of propylene; 34-carries the pipeline of hybrid C 4 component;
35-carries the pipeline of hybrid C 4 component freshening; 36-carries the pipeline of pyrolysis gasoline;
37-carries the pipeline of Pyrolysis gas oil PGO; 38-carries the pipeline of slurry oil; 40-Aromatics Extractive Project unit;
41-carries the pipeline of raffinating oil; The pipeline of oil is extracted in 42-conveying out;
50-hydrotreating unit; 51-carries the pipeline of hydrotreating unit lighter products;
52-carries hydrogenation to extract the pipeline of oil out;
70-interchanger; 71-high-temperature flue gas pipeline; 72-low-temperature flue gas pipeline;
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of catalysis conversion method producing propylene and oil fuel, wherein, the method comprises: under catalytic cracking conditions, is that stock oil, the methane of 30-90 quality % contacts with catalytic cracking catalyst by paraffinicity, from the mixture after contact, isolate Pyrolysis gas oil PGO; Described Pyrolysis gas oil PGO is carried out Aromatics Extractive Project to obtain extracting oil out and raffinating oil.
In the present invention, the flammable cut obtained through each step of the present invention all can use as oil fuel, but oil fuel described in the present invention mainly refers to the pyrolysis gasoline finally obtained according to catalysis conversion method of the present invention.
According to catalysis conversion method of the present invention; the method of described Aromatics Extractive Project is the ordinary method of this area; for the present invention, the extraction solvent that preferred aromatic hydrocarbons extracting uses be selected from tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether one or more.More preferably, extractive process solvent recuperation recycling in Aromatics Extractive Project.The temperature of preferred aromatic hydrocarbons extracting is 40-120 DEG C, and the volume ratio of the raw material Pyrolysis gas oil PGO of extraction solvent and Aromatics Extractive Project is 0.5-5.
According to catalysis conversion method of the present invention, described in i.e. non-aromatics of raffinating oil can return and contact with catalytic cracking catalyst.
Catalysis conversion method provided by the invention, can carry out in the various reactors of prior art, such as can carry out in riser reactor, fluidized-bed reactor (waiting the fluidized-bed of linear speed or isodiametric fluidized-bed), upstriker transfer limes or downstriker transfer limes, wherein, when carrying out in a fluidized bed reactor, preferred gas speed is 0.1-2 meter per second, and when carrying out in riser reactor, preferred gas speed is 2-30 meter per second.
For the present invention, preferably carry out in riser reactor, and when carrying out in riser reactor, optimization methane introduces reactor after described stock oil feed entrance point, can improve the selectivity of propylene thus further.
Catalysis conversion method provided by the invention, can introduce whole described stock oil in reactor at a feed entrance point, or is introduced in reactor according to identical or different ratio by described stock oil at least two different feed entrance points.
In the present invention, the catalytic cracking riser reactor of the routine that described riser reactor can be known to the skilled person, such as, described riser tube can be selected from equal diameter riser reactor and/or etc. linear speed riser reactor, preferably use equal diameter riser tube.More preferably in situation, described riser reactor comprises pre lift zone and at least one reaction zone from bottom to top successively, in order to enable stock oil fully react, and according to different object product qualities demands, described reaction zone can be 2-8, is preferably 2-3.
According to catalysis conversion method of the present invention, preferred described stock oil paraffin content is 35-80 quality %.
According to catalysis conversion method of the present invention, in order to improve the low-carbon alkene particularly productive rate of propylene and the productive rate of oil fuel further, the mass ratio of optimization methane and described stock oil is 1-20:100, is more preferably 2-15:100, more preferably 5-10:100.
It is 180-350 DEG C that catalysis conversion method of the present invention is particularly suitable for boiling range, preferred boiling range is the catalyzed conversion of the hydrocarbon-fraction of 190-330 DEG C, is more suitable for one or more the catalyzed conversion in straight-run diesel oil, catalytic diesel oil, coker gas oil, hydrogenated diesel oil and gelatin liquefaction diesel oil.Adopt method process aforementioned base materials of the present invention oil, greatly can improve the low-carbon alkene particularly productive rate of propylene and the productive rate of oil fuel, namely can improve the ratio of propylene and ethene.
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises: described extraction oil is carried out hydrogenation, obtains hydrogenation and extracts oil out; Described hydrogenation is extracted out oil and described raffinate oil to return contact with catalytic cracking catalyst together with described stock oil.
According to catalysis conversion method of the present invention, the condition that described extraction oil carries out hydrogenation can be selected for conventional, and the condition of preferred hydrogenation comprises: hydrogen dividing potential drop 1.2-8.0MPa(absolute pressure), temperature 150-400 DEG C, hydrogen to oil volume ratio 150-600Nm
3/ m
3, volume space velocity 1-20h
-1; Hydrogenation catalyst is with Ni-W, Co-Ni-W, Ni-Mo or Co-Mo for active ingredient, and activated alumina is the non-precious metal catalyst of carrier.
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises: from the mixture after contact, isolate reclaimable catalyst, methane, propylene, propane, hybrid C 4 component and pyrolysis gasoline.
According to catalysis conversion method of the present invention, general first separation with reaction oil gas by reclaimable catalyst obtains reclaimable catalyst and reaction oil gas, then the reaction oil gas obtained is separated dry gas through follow-up separation system (such as cyclonic separator), liquefied gas, the cut such as pyrolysis gasoline and Pyrolysis gas oil PGO, then dry gas and liquefied gas are separated further through gas separation equipment and obtain methane, propylene, propane, hybrid C 4 component etc., separating propane from reaction product, the methods such as propylene are similar to this area convenient technical process, the present invention is not limited in this respect, be not described in detail at this.
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises: returned by the methane that separation obtains and contact with catalytic cracking catalyst as methane feed.
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises: regenerated by described reclaimable catalyst; And preferred described catalytic cracking catalyst is the catalyzer after regeneration at least partially.
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises carries out air lift (generally using water vapour air lift) slough the impurity such as gas by regenerating the regenerated catalyst that obtains.
According to catalysis conversion method of the present invention, in regenerative process, generally introduce oxygen-containing gas from the bottom of revivifier, oxygen-containing gas such as can for after air introducing revivifier, reclaimable catalyst contacts coke burning regeneration with oxygen, the flue gas generated after catalyzer coke burning regeneration is in revivifier top gas solid separation, and such as, after cyclonic separator gas solid separation, isolated regenerated flue gas discharges revivifier for the pre-thermal source as reclaimable catalyst.
According to catalysis conversion method of the present invention, the operational condition of described reclaimable catalyst regeneration is preferably: temperature is 550-750 DEG C, is more preferably 600-730 DEG C, more preferably 650-700 DEG C; Gas superficial linear speed is 0.5-3 meter per second, is preferably 0.8-2.5 meter per second, is more preferably 1-2 meter per second, and reclaimable catalyst mean residence time is 0.6-3 minute, preferably 0.8-2.5 minute, more preferably 1-2 minute.
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises: before by described reclaimable catalyst regeneration, by described reclaimable catalyst air lift (adopting water vapour air lift), then regenerates the high-temperature flue gas produced with reclaimable catalyst and carries out heat exchange.So make reclaimable catalyst be that revivifier has been taken more heat, decrease the possibility that in revivifier, carbon build-up occurs, improve operational stability.And the high-temperature flue gas preheating reclaimable catalyst that the present invention adopts regeneration to produce, has effectively saved energy consumption.The method of air lift is conventionally known to one of skill in the art, is not described in detail at this.
According to catalysis conversion method of the present invention, preferably with described high-temperature flue gas heat exchange after reclaimable catalyst temperature be 550-750 DEG C, be preferably 580-720 DEG C, be more preferably 600-700 DEG C.
According to catalysis conversion method of the present invention, described catalytic cracking catalyst can be that the routine of this area is selected, for the present invention, preferably with the total weight of catalyzer, described catalytic cracking catalyst contains: zeolite 1-60 % by weight, inorganic oxide 5-99 % by weight and clay 0-70 % by weight.
According to catalysis conversion method of the present invention, wherein, described zeolite is as active ingredient, preferred described zeolite is selected from mesopore zeolite and/or large pore zeolite, and preferably mesopore zeolite accounts for the 50-100 % by weight of zeolite gross weight, more preferably mesopore zeolite accounts for the 70-100 % by weight of zeolite gross weight, and large pore zeolite accounts for the 0-50 % by weight of zeolite gross weight, and preferred large pore zeolite accounts for the 0-30 % by weight of zeolite gross weight.
In the present invention, described mesopore zeolite and large pore zeolite continue to use the definition of this area routine, i.e. the mean pore size 0.5-0.6nm of mesopore zeolite, the mean pore size 0.7-1.0nm of large pore zeolite.Such as, described large pore zeolite can be selected from by Rare Earth Y (REY), rare earth hydrogen Y(REHY), one or more of mixture in this group zeolite of forming of the different methods super steady Y, the high silicon Y that obtain.
Described mesopore zeolite can be selected from the zeolite with MFI structure, such as ZSM series zeolite and/or ZRP zeolite, also modification can be carried out to transition metals such as the non-metallic elements such as above-mentioned mesopore zeolite phosphorus and/or iron, cobalt, nickel, about the more detailed description of ZRP is see US5,232,675, ZSM series zeolite is selected from the one or more of mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, about the more detailed description of ZSM-5 is see US3,702,886.
In the present invention, described inorganic oxide, as caking agent, is preferably selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).
In the present invention, described clay, as matrix (i.e. carrier), is preferably selected from kaolin and/or halloysite.
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises: described hybrid C 4 component (also can be described as C4 hydrocarbon-fraction, refer to C4 alkane and C4 alkene mixture) returned and contact with described catalytic cracking catalyst together with described stock oil.
According to catalysis conversion method of the present invention, preferably described hybrid C 4 component is introduced reactor after described stock oil feed entrance point.
According to catalysis conversion method of the present invention, preferably, reactor (such as riser reactor) is introduced by being separated after the methane obtained mixes with described hybrid C 4 component
According to catalysis conversion method of the present invention, preferred method of the present invention also comprises: before being contacted with catalytic cracking catalyst by described stock oil, be gaseous state by described fuel oil preheating, such as fuel oil preheating being contacted with catalytic cracking catalyst to introducing reactor after 350-420 DEG C, being preferably preheated to 380-400 DEG C.
According to catalysis conversion method of the present invention, the condition of preferred described catalytic pyrolysis comprises: temperature is 500-750 DEG C, is preferably 550-750 DEG C, is more preferably 550-700 DEG C, is particularly preferably 580-680 DEG C; Time is 1-10s, is preferably 2-5s, is more preferably 2-4s; Reaction pressure is 0.05-1MPa, and agent-oil ratio is 1-100:1, is preferably 10-50:1, is more preferably 20-40:1.
According to catalysis conversion method of the present invention, more preferably, the condition of described catalytic pyrolysis also comprises: the weight ratio of pre-lift medium and stock oil is 0.05-1.0, and described carrier is conventional selection, such as, can be water vapour.Pre-lift medium is conventional selection, such as, can be one or more in water vapour, refinery dry gas, light paraffins, light olefin.The effect of pre-lift medium makes catalyzer accelerate to rise, and forms the catalyst activity plug flow of even density at reactor bottom.The consumption of pre-lift medium is well known for the person skilled in the art, and in general, the consumption of pre-lift medium accounts for the 1-30 % by weight of stock oil total amount, preferred 2-15 % by weight.
According to one of the present invention preferred embodiment, when method of the present invention is carried out in riser reactor, generally carry out as follows:
The regenerated catalyst (catalytic cracking catalyst) being rich in mesopore zeolite enters the pre lift zone of riser reactor, upwards flow under the effect of pre-lift medium, stock oil after preheating mixes with portion of methane, mixture flow is injecting lift pipe reactor bottom together with atomizing steam, contacts the while of carrying out catalytic cracking reaction upwards flow with regenerated catalyst; After reaction, logistics enters in cyclonic separator through riser reactor outlet, and isolated reaction oil gas caterpillar is separated further and obtains the cuts such as methane, propylene, propane, hybrid C 4 component, Pyrolysis gas oil PGO, pyrolysis gasoline; Wherein, portion of methane returns riser reactor, isolated reclaimable catalyst enters interchanger and the high-temperature flue gas heat exchange from revivifier after stripping, reclaimable catalyst after heating enters coke burning regeneration in revivifier, and the regenerated catalyst of activity recovery returns in riser reactor and recycles; Pyrolysis gas oil PGO enters aromatic extraction unit, is separated and is raffinated oil and extract oil out, wherein, raffinate oil and return bottom riser reactor; Extraction oil enters hydrotreater and carries out hydrotreatment, is then isolated to hydrogenation and extracts oil out; Described hydrogenation is extracted oil circulation being back to bottom riser reactor out and is obtained by reacting object product propylene and light-weight fuel oil further.
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Fig. 2 is the schematic flow sheet of the catalysis conversion method of production propylene provided by the invention and oil fuel.
Illustrate the technical process of method provided by the invention referring to Fig. 2, but the present invention is not therefore subject to any restriction; Shown in Fig. 2, pre-lift medium enters by bottom riser reactor 1 through pipeline 14, regenerated catalyst from pipeline 12 enters the bottom of riser reactor 1 after regeneration guiding valve 13 regulates, along riser tube upwards accelerated motion under the castering action of pre-lift medium, stock oil and portion of methane are after pipeline 15 mixes, the bottom of injecting lift pipe reactor 1 together with the atomizing steam from pipeline 16, mix with the existing logistics of riser reactor, scission reaction is there is in stock oil on the catalyzer of heat, and upwards accelerated motion.The reaction product oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator 6 in settling vessel 3, and realize being separated of reclaimable catalyst and reaction product oil gas, reaction product oil gas enters collection chamber 7, and catalyst fines returns settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 4, contacts with the steam from pipeline 19.The reaction product oil gas that stripping goes out from reclaimable catalyst enters collection chamber 7 after cyclonic separator 6.Reclaimable catalyst after stripping enters interchanger 70 through reclaimable catalyst inclined tube pipeline 8, after the high-temperature flue gas heat exchange of the pipeline 71 from exchanger base, reclaimable catalyst after heating enters revivifier 2 after guiding valve 9 to be generated regulates, air from pipeline 21 enters revivifier 2 after air distributor 22 distributes, burning-off is arranged in the coke on the dense-phase bed reclaimable catalyst bottom revivifier 2, the reclaimable catalyst of inactivation is regenerated, flue gas enters interchanger 70 through the upper smoke feed channel 25 of cyclonic separator 24, through with reclaimable catalyst heat exchange after enter subsequent power recovery system through pipeline 72.
The pipeline 10 of catalyzer after regeneration through being communicated with revivifier 2 catalyst outlet enters degassing vessel 5, contact with the stripping fluid from the pipeline 23 bottom degassing vessel 5, remove the flue gas that regenerated catalyst is carried secretly, regenerated catalyst after degassed is recycled to the bottom of riser reactor 1 through pipeline 12, catalyst recirculation amount can be controlled by regeneration guiding valve 13, gas returns in revivifier 2 through pipeline 11, and the reaction product oil gas in collection chamber 7 enters subsequent separation system through main oil gas piping 20.Wherein, described pre-lift medium can be dry gas, water vapour or their mixture.
Reaction product oil gas in collection chamber 7 is through main oil gas piping 20, enter follow-up separation system 30, catalytic pyrolysis dry gas is drawn separation through pipeline 31 and is obtained methane, riser reactor is returned through pipeline 15, through pipeline 17 injecting lift pipe reactor together with the atomizing steam from pipeline 18 after also can mixing with hybrid C 4 component after portion of methane can mix with stock oil.Be separated the propane obtained to draw through pipeline 32; Be separated the propylene obtained to draw through pipeline 33; Hybrid C 4 component is drawn through pipeline 34, after part hybrid C 4 component can mix with stock oil, returns riser reactor through pipeline 15, also can return riser reactor 1 through pipeline 35,17; High-octane catalytic cracking gasoline is drawn through pipeline 36.Slurry oil can be drawn through pipeline 38, Pyrolysis gas oil PGO can be drawn through pipeline 37, enter Aromatics Extractive Project unit 40, raffinate oil through pipeline 41 draw return riser reactor 1, extract oil out and enter hydrotreating unit 50 through pipeline 42, isolate the hydrocarbon component (hydrotreating unit lighter products) that hydrogenation obtains to draw through pipeline 51, the extraction oil after hydrogenation returns riser reactor 1 through pipeline 52; Wherein each cut boiling range regulates according to refinery's actual needs.
The following examples will be further described method of the present invention, but therefore not limit present method.
Extraction solvent used in embodiment is tetramethylene sulfone.The selective hydrogenation catalyst trade mark used in embodiment is RSDS-1, is produced by Sinopec catalyzer branch office.
Catalytic cracking catalyst preparation method used in embodiment is summarized as follows:
1) by 20gNH
4cl is dissolved in 1000g water, in this solution, add 100g(butt) crystallization product ZRP-1 zeolite (Qilu Petrochemical Company's catalyst plant is produced, Si/Al=30(mol ratio), content of rare earth RE
2o
3=2.0 heavy %), after exchanging 0.5h at 90 DEG C, filter to obtain filter cake; Add 4.0gH
3pO
4(concentration 85 % by weight) and 4.5gFe (NO
3)
3be dissolved in 90g water, dry with filter cake hybrid infusion; Then within 2 hours, obtain phosphorous and MFI structure mesopore zeolite that is iron 550 DEG C of roasting temperature process, its elementary analytical chemistry consists of:
0.1Na
2O·5.1Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2) use 250kg decationized Y sieve water by 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6 % by weight) making beating, add 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63 % by weight) again, with hydrochloric acid, its PH is adjusted to 2-4, stir, at 60-70 DEG C, leave standstill aging 1 hour, maintenance PH is 2-4, cools the temperature to less than 60 DEG C, add 41.5kg Alumina gel (Qilu Petrochemical Company's catalyst plant product, Al
2o
3content is 21.7 % by weight), stir 40 minutes, obtain mixed serum.
3) the MFI structure mesopore zeolite (butt is 22.5kg) of the phosphorous and iron prepared by step 1) and DASY zeolite (Qilu Petrochemical Company's catalyst plant Industrial products, 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 1 % by weight) washing, wash away free Na
+, be drying to obtain catalytic cracking catalyst sample, the MFI structure mesopore zeolite consisting of 18 % by weight phosphorous and iron of this catalyzer, 2 % by weight DASY zeolites, 28 % by weight pseudo-boehmites, 7 % by weight Alumina gel and balance kaolin.
Hydrotreating catalyst preparation method used in embodiment is summarized as follows: take ammonium metawolframate ((NH
4)
2w
4o
1318H
2o, chemical pure) and nickelous nitrate (Ni(NO
3)
218H
2o, chemical pure), be made into 200mL solution with water.Solution is joined in alumina supporter 50 grams, at room temperature flood 3 hours, in steeping process, use ultrasonication steeping fluid 30 minutes, cooling, filter, to be put in microwave oven drying about 15 minutes.Consisting of of this catalyzer: 30.0 heavy %WO
3, 3.1 heavy %NiO and remainder alumina.
Comparative example 1
(consistent with flow process shown in Fig. 2 according to the flow process of Fig. 1, unlike, do not comprise the heat exchanging part of interchanger, namely reclaimable catalyst does not carry out preheating and directly regenerates) test, Yanshan Mountain straight-run diesel oil (its character is as shown in table 1) is directly as catalytic pyrolysis raw material, riser reactor middle-scale device is tested, and the Aromatic raffinate obtained, hydrogenation are extracted out after oil mixes with straight-run diesel oil and are formed mixing raw material, and mixing raw material enters bottom reaction zone.Temperature of reaction be 620 DEG C, the reaction times is 2.5 seconds, the weight ratio of catalytic cracking catalyst and stock oil be 30 and the weight ratio of water vapour and stock oil be the condition of 0.25 under carry out scission reaction; Reaction product oil gas is separated in settling vessel with reclaimable catalyst, and reclaimable catalyst enters the reaction oil gas that stripping stage stripping is carried secretly, and the reclaimable catalyst after stripping enters into revivifier, contacts regenerate with air.Catalyzer after regeneration enters degassing vessel, with the non-hydrocarbon gas impurity removing regenerated catalyst absorption and carry.Regenerated catalyst after stripping turns back in riser reactor and recycles.Reaction oil gas cuts by boiling range in separation system, thus obtain the cuts such as methane, propylene, propane, hybrid C 4 component, pyrolysis gasoline and Pyrolysis gas oil PGO, wherein Pyrolysis gas oil PGO enters Aromatics Extractive Project unit through Sulfolane Extraction, extraction temperature is 100 DEG C, the volume ratio of solvent and Pyrolysis gas oil PGO is 3.0, separate and raffinate oil (being mainly stable hydrocarbon) and extract out oil (double ring arene), raffinate oil and return riser reactor.Extract oil out and enter hydrogenation unit, at hydrogen dividing potential drop 1.6MPa, temperature of reaction 270 DEG C, hydrogen to oil volume ratio 350, volume space velocity 4.0h
-1reaction conditions under carry out selective hydrogenation, extract oil after hydrogenation out and return lifting oil reactor.Operational condition and product slates list in table 2.
Comparative example 2
(consistent with flow process shown in Fig. 2 according to the flow process of Fig. 1, unlike, do not comprise the heat exchanging part of interchanger, namely reclaimable catalyst does not carry out preheating and directly regenerates) test, Yanshan Mountain straight-run diesel oil (its character is as shown in table 1) is directly as the raw material of catalytic pyrolysis, riser reactor middle-scale device is tested, and the Aromatic raffinate obtained, hydrogenation are extracted out after oil mixes with straight-run diesel oil and are formed mixing raw material, and mixing raw material enters bottom reaction zone.Temperature of reaction be 640 DEG C, the reaction times is 2 seconds, the weight ratio of catalytic cracking catalyst and stock oil be 25 and the weight ratio of water vapour and stock oil be the condition of 0.25 under carry out scission reaction, reaction product oil gas is separated at settling vessel with catalyzer to be generated, reclaimable catalyst enters the reaction oil gas that stripping stage stripping is carried secretly, reclaimable catalyst after stripping enters into revivifier, contacts regenerate with air.Catalyzer after regeneration enters degassing vessel, with the non-hydrocarbon gas impurity removing regenerated catalyst absorption and carry.Regenerated catalyst after stripping turns back in riser tube reaction again and recycles.Reaction oil gas cuts by boiling range in separation system, thus obtain the cuts such as methane, propylene, propane, hybrid C 4 component, pyrolysis gasoline and Pyrolysis gas oil PGO, wherein hybrid C 4 component returns riser reactor and reacts further and generate propylene and premium, Pyrolysis gas oil PGO enters Aromatics Extractive Project unit through Sulfolane Extraction, extraction temperature is 100 DEG C, the volume ratio of solvent and Pyrolysis gas oil PGO is 3.0, separate and raffinate oil (being mainly stable hydrocarbon) and extract out oil (double ring arene), raffinate oil and return riser reactor.Extract oil out and enter hydrogenation unit, hydrogen dividing potential drop be 1.6MPa, temperature of reaction is 270 DEG C, hydrogen to oil volume ratio is 350, volume space velocity is 4.0h
-1reaction conditions under carry out selective hydrogenation, extract oil after hydrogenation out and return riser reactor.Operational condition and product slates list in table 2.
Embodiment 1
Test according to the flow process of Fig. 2, straight-run diesel oil is directly as the raw material of catalytic pyrolysis, riser reactor middle-scale device is tested, after Yanshan Mountain straight-run diesel oil mixes with portion of methane (mass ratio of methane and stock oil straight-run diesel oil is 5:100), enters bottom riser reactor.Temperature of reaction be 620 DEG C, the reaction times is 2.5 seconds, the weight ratio of catalytic cracking catalyst and stock oil is 30, and the weight ratio of water vapour and stock oil is carry out scission reaction under the condition of 0.25; Reaction product oil gas is separated at settling vessel with catalyzer to be generated, reclaimable catalyst enters stripping stage under gravity, the hydrocarbon product that reclaimable catalyst adsorbs is gone out by water vapour stripping, reclaimable catalyst after stripping with enter into revivifier again from (temperature of reclaimable catalyst is 600 DEG C after heat exchange) after the high-temperature flue gas heat exchange of revivifier, contact with air and regenerate.Catalyzer after regeneration enters degassing vessel, with the non-hydrocarbon gas impurity removing regenerated catalyst absorption and carry.Regenerated catalyst after stripping turns back in riser tube reaction again and recycles.Reaction oil gas cuts by boiling range in separation system, thus obtain the cuts such as methane, propylene, propane, hybrid C 4 component, pyrolysis gasoline and Pyrolysis gas oil PGO, wherein portion of methane returns bottom riser tube, Pyrolysis gas oil PGO enters Aromatics Extractive Project unit through Sulfolane Extraction, extraction temperature is 100 DEG C, the volume ratio of solvent and diesel oil is 3.0, separates and raffinates oil (being mainly stable hydrocarbon) and extract out oil (double ring arene), raffinate oil and return riser reactor.Extract oil out and enter hydrogenation unit, hydrogen dividing potential drop be 1.6MPa, temperature of reaction is 270 DEG C, hydrogen to oil volume ratio is 350, volume space velocity is 4.0h
-1reaction conditions under carry out selective hydrogenation, extract oil after hydrogenation out and return riser reactor.Operational condition and product slates list in table 2.
Embodiment 2
This embodiment is tested according to the flow process of Fig. 2, Yanshan Mountain straight-run diesel oil is directly as the raw material of catalytic pyrolysis, testing by the middle-scale device of riser reactor, after straight-run diesel oil mixes with portion of methane (methane is 7.5:100 with the mass ratio of stock oil straight-run diesel oil), it is 640 DEG C in temperature of reaction, reaction times is 2.0 seconds, the weight ratio of catalytic cracking catalyst and stock oil is 25, the weight ratio of water vapour and stock oil is carry out cracking reaction under 0.25 condition, reaction product oil gas is separated at settling vessel with catalyzer to be generated, reclaimable catalyst enters stripping stage under gravity, the hydrocarbon product that reclaimable catalyst adsorbs is gone out by water vapour stripping, reclaimable catalyst after stripping with enter into revivifier again from (temperature of reclaimable catalyst is 600 DEG C after heat exchange) after the high-temperature flue gas heat exchange of revivifier, contact with air and regenerate.Catalyzer after regeneration enters degassing vessel, with the non-hydrocarbon gas impurity removing regenerated catalyst absorption and carry.Regenerated catalyst after stripping turns back in riser reactor and recycles.Reaction oil gas cuts by boiling range in separation system, thus obtains the cuts such as methane, propylene, hybrid C 4 component, pyrolysis gasoline and Pyrolysis gas oil PGO, and wherein methane and hybrid C 4 component Returning reactor react further; Wherein, Pyrolysis gas oil PGO enters Aromatics Extractive Project unit through Sulfolane Extraction, and extraction temperature is 100 DEG C, and the volume ratio of solvent and Pyrolysis gas oil PGO is 3.0, separates and raffinates oil (being mainly stable hydrocarbon) and extract out oil (double ring arene), raffinate oil and return riser reactor.Extract oil out and enter hydrogenation unit, at hydrogen dividing potential drop 1.6MPa, temperature of reaction 270 DEG C, hydrogen to oil volume ratio 350, volume space velocity 4.0h
-1reaction conditions under carry out selective hydrogenation, extract oil after hydrogenation out and return riser reactor.Operational condition and product slates list in table 2.
Embodiment 3
This embodiment is tested according to the flow process of Fig. 2, Yanshan Mountain straight-run diesel oil is directly as the raw material of catalytic pyrolysis, testing by the middle-scale device of riser reactor, methane enters bottom reaction zone after mixing with stock oil (methane is 10:100 with the mass ratio of stock oil straight-run diesel oil).It is 640 DEG C in temperature of reaction, reaction times is 2.5 seconds, the weight ratio of catalytic cracking catalyst and stock oil is 25, the weight ratio of water vapour and stock oil is carry out scission reaction under the condition of 0.25, reaction product oil gas is separated at settling vessel with catalyzer to be generated, reclaimable catalyst enters stripping stage under gravity, the hydrocarbon product that reclaimable catalyst adsorbs is gone out by water vapour stripping, reclaimable catalyst after stripping with enter into revivifier again from (temperature of reclaimable catalyst is 600 DEG C after heat exchange) after the high-temperature flue gas heat exchange of revivifier, contact with air and regenerate.Catalyzer after regeneration enters degassing vessel, with the non-hydrocarbon gas impurity removing regenerated catalyst absorption and carry.Regenerated catalyst after stripping turns back in riser reactor and recycles.Reaction oil gas cuts by boiling range in separation system, thus obtain the cuts such as methane, propylene, hybrid C 4 component, pyrolysis gasoline and Pyrolysis gas oil PGO, wherein methane and hybrid C 4 component return riser reactor after mixing and participate in reaction further, Pyrolysis gas oil PGO enters Aromatics Extractive Project unit through Sulfolane Extraction, extraction temperature is 100 DEG C, the volume ratio of solvent and Pyrolysis gas oil PGO is 3.0, separates and raffinates oil (being mainly stable hydrocarbon) and extract out oil (double ring arene), raffinate oil and return riser reactor.Extract oil out and enter hydrogenation unit, at hydrogen dividing potential drop 1.6MPa, temperature of reaction 270 DEG C, hydrogen to oil volume ratio 350, volume space velocity 4.0h
-1reaction conditions under carry out selective hydrogenation, extract oil after hydrogenation out and return riser reactor.Operational condition and product slates list in table 2.
Embodiment 4
Produce ethene and propylene according to the method for embodiment 3, the mass ratio unlike methane and stock oil is 20:100, and all the other conditions are all identical, the results are shown in Table 3.
Embodiment 5
Produce ethene and propylene according to the method for embodiment 3, unlike the use of stock oil be Cangzhou straight-run diesel oil (character is in table 1), all the other conditions are all identical, the results are shown in Table 3.
Embodiment 6
Produce ethene and propylene according to the method for embodiment 3, unlike the use of stock oil be Shijiazhuang straight-run diesel oil (character is in table 1), all the other conditions are all identical, the results are shown in Table 3.
Embodiment 7
Produce ethene and propylene according to the method for embodiment 3, enter bottom riser tube unlike the feed entrance point of portion of methane after the raw material of preheating, the reaction times of introducing stock oil during methane is 1s, and all the other conditions are all identical, the results are shown in Table 3.
Embodiment 8
Produce ethene and propylene according to the method for embodiment 3, unlike the use of stock oil be the Aromatic raffinate (character is in table 1) of diesel oil distillate, all the other conditions are all identical, the results are shown in Table 3.
Table 1
| Stock oil character | Yanshan Mountain straight-run diesel oil | Cangzhou straight-run diesel oil | Shijiazhuang straight-run diesel oil | Aromatic raffinate |
| Density (20 DEG C), g/cm 3 | 0.8342 | 0.8369 | 0.8412 | 0.8154 |
| Aniline point/DEG C | 73.3 | 67.9 | 61.5 | 91.0 |
| Elementary composition, % by weight | ||||
| Carbon | 86.33 | 86.36 | 86.62 | 84.89 |
| Hydrogen | 13.66 | 13.52 | 13.38 | 14.98 |
| Hydrocarbon composition, % by weight | ||||
| Paraffinic hydrocarbons | 44.8 | 36.2 | 35.6 | 77.06 |
| Naphthenic hydrocarbon | 33.7 | 39.9 | 36.3 | 16.82 |
| Aromatic hydrocarbons | 21.5 | 23.8 | 27.9 | 5.72 |
| Boiling range, DEG C | ||||
| IBP | 222 | 222 | 212 | 224 |
| 10% | 250 | 242 | 227 | 231 |
| 30% | 266 | 256 | 251 | 255 |
| 50% | 279 | 266 | 276 | 280 |
| 70% | 295 | 278 | 307 | 315 |
| 90% | 319 | 294 | 348 | 353 |
| Final boiling point | 342 | 306 | 362 | 368 |
Table 2
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Product slates, % by weight | |||||
| H 2-C 2 | 13.73 | 14.14 | 8.59 | 9.01 | 9.04 |
| Product forms | |||||
| （H 2-C 2) in, wherein methane | 12.90 | 13.17 | 7.61 | 7.76 | 7.64 |
| Propylene | 10.02 | 12.93 | 10.92 | 14.09 | 13.58 |
| Propane | 2.77 | 3.27 | 3.02 | 3.56 | 3.51 |
| Hybrid C 4 component | 14.83 | / | 15.74 | / | / |
| Pyrolysis gasoline | 55.92 | 65.63 | 58.72 | 68.91 | 69.54 |
| Slurry oil | 0.55 | 1.45 | 0.61 | 1.60 | 1.52 |
| Coke | 2.18 | 2.58 | 2.4 | 2.83 | 2.81 |
| Add up to | 100 | 100 | 100 | 100 | 100 |
| Gasoline octane rating | 93.1 | 93.7 | 94.1 | 94.7 | 94.3 |
Table 3
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Product slates, % by weight | |||||
| H 2-C 2 | 10.48 | 9.16 | 8.96 | 8.16 | 8.64 |
| Product forms | |||||
| （H 2-C 2) in, wherein methane | 8.72 | 7.79 | 7.49 | 6.13 | 7.03 |
| Propylene | 13.17 | 12.37 | 12.49 | 14.38 | 17.75 |
| Propane | 3.58 | 3.58 | 3.86 | 3.02 | 3.12 |
| Hybrid C 4 component | |||||
| Pyrolysis gasoline | 68.15 | 69.84 | 69.06 | 70.59 | 66.76 |
| Slurry oil | 1.67 | 1.77 | 1.98 | 1.35 | 1.31 |
| Coke | 2.95 | 3.28 | 3.65 | 2.50 | 2.42 |
| Add up to | 100 | 100.00 | 100.00 | 100.00 | 100.00 |
| Gasoline octane rating | 93.9 | 93.8 | 94 | 94.4 | 94 |
As can be seen from data in table, method of the present invention can obtain higher productivity of propylene and pyrolysis gasoline productive rate, and the pyrolysis gasoline octane value obtained is higher.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. produce the catalysis conversion method of propylene and oil fuel for one kind, it is characterized in that, the method comprises: under catalytic cracking conditions, is that stock oil, the methane of 30-90 quality % contacts with catalytic cracking catalyst by paraffinicity, from the mixture after contact, isolate Pyrolysis gas oil PGO; Described Pyrolysis gas oil PGO is carried out Aromatics Extractive Project to obtain extracting oil out and raffinating oil.
2. catalysis conversion method according to claim 1, wherein, described stock oil paraffin content is 35-80 quality %.
3. catalysis conversion method according to claim 1, wherein, the mass ratio of methane and described stock oil is 1-20:100.
4. catalysis conversion method according to claim 3, wherein, the mass ratio of methane and described stock oil is 5-10:100.
5. according to the catalysis conversion method in claim 1-4 described in any one, wherein, described stock oil to be boiling range the be hydrocarbon-fraction of 180-350 DEG C.
6. catalysis conversion method according to claim 5, wherein, described stock oil is one or more in straight-run diesel oil, catalytic diesel oil, coker gas oil, hydrogenated diesel oil and gelatin liquefaction diesel oil.
7. according to the catalysis conversion method in claim 1-4 described in any one, wherein, the method also comprises: described extraction oil is carried out hydrogenation, obtains hydrogenation and extracts oil out; Described hydrogenation is extracted out oil and described raffinate oil to return contact with catalytic cracking catalyst together with described stock oil.
8. the catalysis conversion method according to claim 1 or 7, wherein, the method also comprises: from the mixture after contact, isolate reclaimable catalyst, methane, propylene, propane, hybrid C 4 component and pyrolysis gasoline, and returns contact being separated the methane that obtains with catalytic cracking catalyst as methane feed.
9. catalysis conversion method according to claim 8, wherein, the method also comprises: regenerated by described reclaimable catalyst; Described catalytic cracking catalyst at least partially for regeneration after catalyzer.
10. catalysis conversion method according to claim 9, wherein, the method also comprises: before by described reclaimable catalyst regeneration, by described reclaimable catalyst air lift, then regenerate the high-temperature flue gas produced with reclaimable catalyst and carry out heat exchange.
11. catalysis conversion methods according to claim 8, wherein, the method also comprises: described hybrid C 4 component returned and contact with described catalytic cracking catalyst together with described stock oil.
12. according to the catalysis conversion method in claim 1-4 described in any one, and wherein, the method also comprises: before being contacted with catalytic cracking catalyst by described stock oil, by described fuel oil preheating to 350-420 DEG C.
13. according to the catalysis conversion method in claim 1-4 described in any one, wherein, the method also comprises: before being introduced by methane and contacting with catalytic cracking catalyst with stock oil, contacted with catalytic cracking catalyst in advance by described stock oil, the time of contact is 0.8-1.2s.
14. according to the catalysis conversion method in claim 1-4 described in any one, and wherein, described catalytic cracking conditions comprises: temperature is 500-750 DEG C, and the time is 1-10s, and reaction pressure is 0.05-1MPa, and agent-oil ratio is 1-100:1.
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