CN102816589B - Hydrocarbon oil catalytic cracking method - Google Patents
Hydrocarbon oil catalytic cracking method Download PDFInfo
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- CN102816589B CN102816589B CN201110153197.9A CN201110153197A CN102816589B CN 102816589 B CN102816589 B CN 102816589B CN 201110153197 A CN201110153197 A CN 201110153197A CN 102816589 B CN102816589 B CN 102816589B
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
A hydrocarbon oil catalytic cracking method includes: hydrocarbon oil cracking raw materials and catalyst regenerant lifted by steam and entering a riser reactor are contacted for the cracking reaction, the mixture of catalysts and cracking reaction oil gas obtained at an outlet of a riser enters a settler for separation, the separated cracking reaction oil gas ascends to enter a subsequent product separation system through an oil gas pipeline on the top of the settler, the separated carbon deposit catalysts descend to enter a steam stripping section and then enter a regenerator through a spent catalyst circulation line to react with prevailing wind to be burnt, the obtained regenerated fume enters a fume energy recovery system through a fume pipe on the top of the regenerator, and the obtained catalyst regenerant returns to the riser reactor through a regenerant circulation line and lifted by steam to react with the hydrocarbon oil cracking raw materials. The hydrocarbon oil catalytic cracking method is characterized by further including steps of preheating oxygenated compound materials to directly enter the steam stripping section, or mixing all or part of oxygenated compound materials with stripping steam to enter the steam stripping section, and contacting with the carbon deposit catalysts falling into the steam stripping section to perform an oxygenated compound conversion reaction, wherein reaction oil gas generated in the conversion reaction ascends to be mixed with the cracking reaction oil gas to enter an oil gas pipeline on the top of the settler.
Description
Technical field
The invention relates to a kind of catalytic cracking method for hydrocarbon oil, more specifically say a kind of method of yield of light olefins such as increasing ethene and propylene of being combined with oxygenatedchemicals catalyzed conversion about petroleum hydrocarbon catalytic cracking process.
Background technology
Light olefin comprises ethene and propylene, is the basic material of producing multiple important Chemicals (as oxyethane, polyethylene, polyvinyl chloride and polypropylene etc.).Along with the fast development of China's economy and the raising of people's living standard, ethene and propylene demand are also rapidly increased, and annual growth surpasses world average level.
The preparation method of light olefin is a lot, generally adopt in the world with light hydrocarbon feedstocks steam cracking technologies such as petroleum naphthas and produce, the whole world surpasses the ethene of ultimate production 90% and approximately 70% propylene is made by cracking petroleum hydrocarbon vapor, and remaining approximately 28% propylene is from catalytic cracking of petroleum hydrocarbon technique.But since two thousand five, world's crude production rate declines continuously from peak value, and oil price continues run at high level, make raw material supply anxiety, the production cost of light olefin increase.Crude oil in China shortage of resources, dependence on foreign countries for oil is high, and not only energy security is on the hazard, and the development of the problem of crude resources deficiency restriction petrochemical industry, therefore develops the trend that renewable and alternative materials preparing ethylene, propylene become development.
Methyl alcohol is as a kind of substitute energy, and wide material sources, can be produced by coal, Sweet natural gas and biomass, and its overall throughput worldwide constantly increases, and supplies with and continues to surpass demand.At present, by the low-carbon alkenes such as Methanol ethene, propylene (Methanol to Olefin is called for short MTO) technology, be also tending towards ripe, become the technique that is hopeful to substitute petroleum naphtha route alkene processed most.
With the technology of methanol production light olefin (MTO) and last century the eighties first by Mobil company, proposed.Nineteen ninety-five UOP/Hydro has developed jointly successfully fluidized-bed MTO technique, adopt aperture SAPO-34 silicoaluminophosphamolecular molecular sieve catalyst, SAPO-34 molecular sieve Shi You U.S. UCC company, at the silicoaluminophosphamolecular molecular sieves (USP4440871) of the invention early 1980s, shows high olefin selectivity in methanol to olefins reaction; After the cracking of olefins technique (OCP) of this MTO technique and Total company is integrated, the new ethene of MTO technique and the carbon back selectivity of propylene can reach more than 90%.The DMTO technique that the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences and Luoyang Petrochemical engineering corporation develop jointly, also adopts aperture SAPO-34 silicoaluminophosphamolecular molecular sieve catalyst, and the carbon back selectivity of the ethene of catalyzer of new generation and propylene can reach more than 90%.The FMTP technique of Tsing-Hua University's exploitation, adopts aperture CHA/AEI intergrowth phase silicoaluminophosphamolecular molecular sieve catalyst, and 2008 Nian Huaihua groups have carried out Industrial demonstration, and 30,000 tons of year processing methyl alcohol, can produce 10,000 tons of propylene.(chemical industry, 2009,27 (1-2): 18-22)
Germany Lurgi company has developed preparing propylene from methanol (MTP) technique, adopt ZSM-5 molecular sieve catalyzer (EP0448000), methyl alcohol Partial Conversion is that 3 MTP fixed-bed reactor in parallel of the laggard people of dme (DME) react, reactor be two open one standby.During normal running, single reactor methanol transformation efficiency reaches more than 90%, and through the cyclical operation of product alkene, Propylene Selectivity is improved, and the carbon back selectivity of propylene can reach more than 71%.(petrochemical technology and economy, 2008,24 (4): 34)
As can be seen here, it is ripe that methanol-to-olefins technology has been tending towards, but it is huge to build large-scale complete MTO process unit investment, and methanol-to-olefins project is still located in demonstration.The throughput of China's methyl alcohol has broken through 3,000 ten thousand tons at present, and derived product outlet deficiency causes alcohol ether industry working rate very low, and the whole working rate of methyl alcohol industry is less than 50%, and the average working rate of dme device has been down to 20% left and right, enterprise's production run difficulty.And China's methyl alcohol industry production capacity dispersion, concentrate the large-scale methanol conversion process investment of construction huge, therefore, be badly in need of new technology and promote that methyl alcohol transforms nearby, not only solve the outlet of methyl alcohol, also can supplement the product demands such as low-carbon alkene.Because reaction-regeneration system and the existing Catalytic Cracking Technique of Heavy Oil of fluidized-bed MTO technology has similarity, two kinds of reaction process conditions are also had something in common, and researchist endeavours, by two kinds of Technologies couplings, can reduce investment outlay.
CN86101079A discloses methyl alcohol as reactant and the petroleum hydrocarbon method of catalytic cracking together with gas oil for example, reactant contacts with fine grain ZSM-5 catalyzer, makes the reaction of methanol conversion of heat release and the catalytic cracking reaction of heat absorption heat balance haply.
Microporous and Mesoporous Materials, 1999, (29): 145-157 also, by the cracking hydrocarbon reaction coupling of the Dehydration of methanol of heat release and heat absorption, has obtained thermally equilibrated reaction process.Utilize modified ZSM-5 zeolite for catalyzer, 600-680 ℃ of reaction, when obtaining higher yield of light olefin, reduced the productive rate of methane and COx in independent Dehydration of methanol, hydrogen.
CN1206319A discloses the approach that utilizes differential responses PROCESS COUPLING to reduce reaction heat effect, the organic oxygen-containing compound of heat release is transformed with the cracking petroleum hydrocarbons of heat absorption and reacts coupling, adopt fluidized-bed reactor, containing Si/Al weight ratio, be 25-100, under the solid acid catalyst of the molecular sieve that aperture is 0.4-0.7nm and the effect of high-temperature vapor, carry out the method for catalytic cracking to prepare lower carbon olefin.Reaction conditions is: temperature 500-720 ℃, and the weight ratio 5-40 of catalyzer and petroleum hydrocarbon: 1, the weight ratio 0.01-2 of organic oxygen-containing compound and petroleum hydrocarbon: 1, the weight ratio 0-1 of water vapour and petroleum hydrocarbon: 1.
" petrochemical complex; 2005; 34 (12) 1153-1158 " studied methyl alcohol as catalytic cracking part charging reaction process, the impact that methyl alcohol adds mode has wherein been discussed, comprise the charging simultaneously of methyl alcohol and stock oil, the top of methyl alcohol injecting lift pipe reactor, methyl alcohol injects stripping stage, settling section and methyl alcohol prior to modes such as stock oil chargings, for methyl alcohol, inject stripping stage, settling section, this research is thought and is unfavorable for the generation of low-carbon alkene, and determined methyl alcohol suitable add implantation site and mode in riser reactor bottom, and prior to stock oil charging.
" Journal of Chemical Industry and Engineering; 2006; 57 (4): 785-790 " studied methyl alcohol as the charging of catalytic cracking part with increased low carbon olefine output, under the condition of fresh catalytic cracking catalyst, temperature of reaction 550-600 ℃, adopt the charging of 40% (massfraction) methanol aqueous solution, the hydrocarbon productive rate of methanol conversion can reach 26.3%-28.1% (massfraction), and low-carbon alkene accounts for the 67.8%-66.5% (massfraction) that hydrocarbon forms.
" petrochemical complex; 2009; 38 (3): 267-272 " studied the research of methyl alcohol and the mixing upgrading of fluid catalytic cracking gasoline on small riser reactor, result show methyl alcohol and FCC gasoline mixing when improving quality of gasoline, be conducive to increase production reacted gas and improve liquid yield.The mixing suitable condition of gained methyl alcohol and FCC gasoline is: 400～420 ℃ of temperature of reaction, mixing ratio are 5%～10%, agent-oil ratio 10～12, and product content of olefin in gasoline declines more than 50%.
CN101104571A and CN101104576A disclose a kind of method of producing ethylene from ethanol by combination hydrocarbons catalytic conversion, catalytic cracking process remains unchanged, separately separating a part of catalytic cracking regenerated catalyst contacts with ethanol raw material after cooling, described catalyzer contains y-type zeolite, the gained reaction product separator of flowing through obtains carbon deposited catalyst and object product ethene, and carbon deposited catalyst enters revivifier and carries out coke burning regeneration.The method ethanol conversion is up to more than 99%, and in reformed gas product, the content of ethene is up to more than 95 volume %.
US2006/0229481A1 discloses the ethers that adds CxH2x+10CyH2y+1 (x and y are 1-30) in hydro carbons heat or catalytic cracking process, and ethers is cracked at least partly alkene and corresponding alcohol in reaction, and reduces hydrocarbon cracking green coke.The catalyzer that this invention is used contains tetrahedral crystal oxide material, optional from zeolite, silicate, aluminium phosphate molecular sieve (AlPOs) and silicoaluminophosphamolecular molecular sieves (SAPOs), preferred zeolite.
CN101210190A discloses a kind of method of heavy petroleum hydrocarbon and the common charging preparing low-carbon olefins of methyl alcohol and gasoline.The method utilizes methyl alcohol to replace part heavy feed stock on fluidized catalytic cracker, containing mass ratio, be 1: on the shape-selective molecular sieve of 0.1-1.0 and the composite molecular sieve catalyst of large pore molecular sieve, jointly refine out premium product, simultaneously increased low carbon olefine output.Methyl alcohol used accounts for the 1.5-50% (weight) of stock oil, and water injection rate accounts for the 5-50% of stock oil, and operational condition is temperature 480-600 ℃, pressure 0.01-0.51MPa, weight hourly space velocity 1.01-20.1h-1, agent-oil ratio 1.0-20.1.
From prior art, methanol conversion and catalytic cracking of petroleum hydrocarbon coupling reaction are subject to processing condition, catalyst activity and selectivity restriction, and methanol conversion and olefine selective are all not high enough.Therefore, the integrated complete processing of development of new catalytic cracking and methyl alcohol, the transformation efficiency and the olefine selective that improve methanol conversion are very meaningful.
Summary of the invention
The inventor is surprised to find that through a large amount of tests, the viewpoint conclusion that is different from prior art is, in cracking catalyst, add after a kind of active ingredient transforming for oxygenatedchemicals, even if this cracking catalyst is coking deactivation under catalytic cracking condition, need to return in the situation that revivifier regenerates, the active component wherein transforming for oxygenatedchemicals is not by the impact of cracking hydrocarbon ils contamination of raw material carbon deposit, still can in stripping stage, provide the catalyzed conversion function for oxygenatedchemicals, oxygenatedchemicals has the transformation efficiency that approaches 100%, thereby improve cracking hydrocarbon oil reaction product and comprise that ethene and propylene are at the yield of interior whole low-carbon alkene.
Therefore, main purpose of the present invention is to provide a kind of prior art that is different from, can expand catalyzed cracking processing raw material, improve the ethene of catalytic cracking process and the catalytic cracking method for hydrocarbon oil of productivity of propylene, the method can flexible catalytic cracking light olefin productive rate and the ratio of olefin product kind, and technique is simple, technology maturation, less investment, is easy to realize.
Catalytic cracking method for hydrocarbon oil provided by the invention, cracking hydrocarbon oil raw material is contacted and carries out cracking reaction with the catalyst regeneration agent being promoted by steam that enters riser reactor, riser reactor outlet gained cracking reaction oil gas enters settling vessel with the mixture of catalyzer and carries out separated, wherein, isolated cracking reaction oil gas rises, gas pipeline through settling vessel top enters subsequent products separation system, and isolated carbon deposited catalyst falls to entering stripping stage, through spent agent circular route, enter revivifier, react and burn with main air, gained regenerated flue gas enters smoke energy recovering system from revivifier top flue gas pipeline, the agent of gained catalyst regeneration is returned to riser reactor through regenerator circular route, by steam, promoted and cracking hydrocarbon oil raw material reaction, it is characterized in that, the method also comprises oxygen-containing compound material preheating, directly enter stripping stage, or, to after part or all of oxygen-containing compound material and the mixing of stripping steam, enter stripping stage, the carbon deposited catalyst that enters stripping stage with whereabouts contacts and carries out oxygenate conversion reaction, the reaction oil gas that this conversion reaction generates rises and enters the gas pipeline at settling vessel top with cracking reaction air-fuel mixture, wherein, said catalyzer be take catalyst weight and is contained 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct as benchmark.
Method provided by the invention is that existing catalytic cracking unit and oxygenatedchemicals conversion are carried out integrated, being different from prior art is, the conversion reaction of oxygenatedchemicals is carried out under the catalyzer of stripping stage, carbon deposit exists, and contains the active ingredient that a kind of oxygenatedchemicals transforms in catalyzer.The present invention can, so that the products scheme of catalytic cracking process is more flexible, process raw material more extensive.The primary product transforming due to oxygenatedchemicals is ethene and propylene, has therefore increased the yield of high-value product light olefin.Meanwhile, oxygenatedchemicals transforms the water Substitute For Partial stripping steam generating, and can reduce the consumption of original catalytic cracking process stripping steam.
The technique of apparatus of the present invention is simple, makes full use of reaction-regeneration system device, product separation recovery process and the Cooling and Heat Source of catalytic cracking process, technology maturation, and less investment, is easy to realize.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of integrating heavy oil catalytic cracking with oxygen-containing compound working method of the present invention.
In figure, cracking hydrocarbon oil raw material 1, riser reactor 2, water vapour 3, settling vessel 4, reaction oil gas 5, stripping stage 6, water vapour 7, catalyzer circular route 8 to be generated, revivifier 9, regenerated catalyst circular route 10, main air air 11, flue gas 12, oxygen-containing compound material 13, interchanger 14, feeding line 15, former stockline 16.
Embodiment
Catalytic cracking method for hydrocarbon oil provided by the invention, cracking hydrocarbon oil raw material is contacted and carries out cracking reaction with the catalyst regeneration agent being promoted by steam that enters riser reactor, riser reactor outlet gained cracking reaction oil gas enters settling vessel with the mixture of catalyzer and carries out separated, wherein, isolated cracking reaction oil gas rises, gas pipeline through settling vessel top enters subsequent products separation system, and isolated carbon deposited catalyst falls to entering stripping stage, through spent agent circular route, enter revivifier, react and burn with main air, gained regenerated flue gas enters smoke energy recovering system from revivifier top flue gas pipeline, the agent of gained catalyst regeneration is returned to riser reactor through regenerator circular route, by steam, promoted and cracking hydrocarbon oil raw material reaction, it is characterized in that, the method also comprises oxygen-containing compound material preheating, directly enter stripping stage, or, to after part or all of oxygen-containing compound material and the mixing of stripping steam, enter stripping stage, the carbon deposited catalyst that enters stripping stage with whereabouts contacts and carries out oxygenate conversion reaction, the reaction oil gas that this conversion reaction generates rises and enters the gas pipeline at settling vessel top with cracking reaction air-fuel mixture, wherein, said catalyzer be take catalyst weight and is contained 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct as benchmark.
In method provided by the invention, can in various cracking petroleum hydrocarbons reaction methods, implement, comprise that catalytic cracking, catalytic pyrolysis and family's Technology thereof are as ARGG, MIP, DCC, CPP etc.Described petroleum hydrocarbon raw material comprises all kinds of catalytic cracking reaction raw material well known to those skilled in the art, can be selected from one or more mixture of crude oil, gasoline, diesel oil, decompressed wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil, hydrogenation tail oil.The petroleum hydrocarbon raw material of the more suitable processing of method provided by the invention is selected from one or more mixture of decompressed wax oil, long residuum, vacuum residuum, wax tailings, hydrogenation tail oil.In a concrete embodiment of the present invention, petroleum hydrocarbon raw material is mixed to get by 70% decompressed wax oil and 30% vacuum residuum.
In method provided by the invention, described cracking petroleum hydrocarbons reaction, in its riser reactor, reaction conditions is temperature 400-650 ℃, pressure 0.01-0.50MPa, reaction times 1-600s, agent-oil ratio 1-20, the mass ratio of water vapour and cracking hydrocarbon oil raw material is 0.01～1.0; Preferred temperature 450-550 ℃, pressure 0.1-0.40MPa, reaction times 3-100s, agent-oil ratio 4.0-15.0, the mass ratio of water vapour and cracking hydrocarbon oil raw material is 0.05～0.5.
In method provided by the invention, described oxygenatedchemicals can be selected from one or more in the group that comprises methyl alcohol, dme, ethanol, or one or more in above-mentioned group again with any mixture of water, preferred oxygenatedchemicals is selected from methyl alcohol and/or dme, or the mixture of methyl alcohol and/or dme and water.
In method provided by the invention, after said oxygen-containing compound material preheating, can all directly enter the middle part of stripping stage inner catalyst dense-phase bed; Also whole cracking hydrocarbon oil raw materials and stripping steam can be mixed into the bottom of stripping stage; The minimizing green coke that can expect, increases the object of olefin yields, maybe can adopt and enter the middle part of stripping stage inner catalyst dense-phase bed by 10～90% of oxygen-containing compound material, and remaining part and stripping steam are mixed into the mode bottom stripping stage.
In method provided by the invention, the reaction conditions that described oxygenatedchemicals transforms is that temperature of reaction is 400-600 ℃, and reaction pressure is 0.01-0.50MPa, oxygen-containing compound material reaction velocity 0.1-100h
-1, oxygen-containing compound material preheating temperature is 50-500 ℃, and the mass ratio of charging oxygenatedchemicals and cracking hydrocarbon oil raw material is 0.01～5, and oxygen-containing compound material is 0.01～5 with the mass ratio that enters the stripped vapor of stripping stage; Preferred reaction conditions is temperature of reaction 450-550 ℃, pressure 0.1-0.4MPa, oxygen-containing compound material reaction velocity 0.5-10h
-1, oxygen-containing compound material preheating temperature is 150-400 ℃, and the mass ratio of charging oxygenatedchemicals and stock oil is 0.05～1, and oxygen-containing compound material is 0.05～1 with the mass ratio that enters the stripped vapor of stripping stage.
In method provided by the invention, said catalyzer preferably take weight as benchmark has following composition: 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct, 0～50% the mesoporous silicon aluminum molecular screen with ten-ring window duct, 10～50% the macropore Si-Al molecular sieve with twelve-ring window duct, 4～50% inorganic oxide binder and 0～70% clay; It more preferably has following composition: the mesoporous silicon aluminum molecular screen, 12～40% that 5～60% silicoaluminophosphamolecular molecular sieves, 0～30% with octatomic ring window duct have a ten-ring window duct has macropore Si-Al molecular sieve, 10～30% inorganic oxide binder and 10～50% the clay in twelve-ring window duct.
The invention provides in the catalyzer of method, said silicoaluminophosphamolecular molecular sieves be selected from there is CHA, the mixture of one or more molecular sieves of the crystalline structure such as AEI, CHA/AEI intergrowth phase, RHO.Wherein, preferred silicoaluminophosphamolecular molecular sieves is for comprising SAPO-34, SAPO-18, SRM molecular sieve.
Said SRM silicoaluminophosphamolecular molecular sieves, this molecular sieve X-ray diffraction spectral data at least contains the diffraction peak shown in table 1, and the structure expression of this molecular sieve is Al
2o
3: 0.1～1.7P
2o
5: 0.01～3SiO
2, in table, VS, M and W represent the relative intensity of diffraction peak, and W is > 0～20%, and M is > 20～60%, and VS is > 80～100%,
Table 1
In said SRM molecular sieve, contriver finds, after using Me1 and Me2 modification, this molecular sieve, for the reaction of methanol-to-olefins reaction, has better product selectivity and less by product, and said Me1 is selected from a kind of element or boron or the gallium in periodic table of elements ZhongIIA family, VB family, a kind of in preferably magnesium, vanadium, copper and boron wherein, x represents that Me1 accounts for the molecular fraction of this molecular sieve in oxide compound, x=5～25, preferably x=10～20; Said Me2 is selected from a kind of element or the aluminium in periodic table of elements ZhongIVB family, and wherein a kind of y in preferred aluminium, titanium and zirconium represents that Me2 accounts for the molecular fraction of this molecular sieve in oxide compound, y=2～20, preferably y=3～10.The molecular fraction in silicoaluminophosphamolecular molecular sieves as modulation modifying element Me1 and Me2, particularly the ratio of x and y is when a suitable scope, silicoaluminophosphamolecular molecular sieves acidity through modification is moderate, when making to keep in converting oxygen-containing compound to low-carbon olefins process the high yield of target product ethene and propylene, the yield of by product alkane and coke reduces, the ratio of x and y is 0.5～10, and the ratio of preferred x and y is 1～6.In most preferred embodiment of the present invention, the combination of the element of two kinds of modifications is such as being magnesium and aluminium, magnesium and zirconium, magnesium and copper etc.
The SRM molecular sieve of said Me1 and Me2 modification, can obtain according to following preparation process:
1) first the silicoaluminophosphamolecular molecular sieves for modification is added to the mixing salt solution of two kinds of soluble elements, concentration of salt solution is respectively 0.0001～0.3 mol/L, and exchange temperature is room temperature, and be 0.5～5 hour swap time;
2) by step 1) silicoaluminophosphamolecular molecular sieves after exchange carries out drying and roasting, and drying temperature is 80～140 ℃, and be 2～12 hours time of drying, and maturing temperature is 400～700 ℃, roasting time is 1～8 hour, obtains described modified silicon aluminum phosphoric acid molecular sieve.
The SRM molecular sieve of said Me1 and Me2 modification, can also obtain according to following preparation process:
1) first the silicoaluminophosphamolecular molecular sieves for modification is added to the soluble salt solution of soluble a kind of element, concentration of salt solution is 0.0001～0.3 mol/L, and exchange temperature is room temperature, and be 0.5～5 hour swap time;
2) silicoaluminophosphamolecular molecular sieves after step 1 exchange is carried out to drying and roasting, drying temperature is 80～140 ℃, and be 2～12 hours time of drying, and maturing temperature is 400～700 ℃, and roasting time is 1～8 hour;
3) by step 2) silicoaluminophosphamolecular molecular sieves after roasting puts in the soluble salt solution of another kind of element again, and strength of solution is 0.0001～0.3 mol/L, and exchange temperature is room temperature, and be 0.5～5 hour swap time;
4) by step 3) silicoaluminophosphamolecular molecular sieves after exchange carries out drying and roasting, and drying temperature is 80～140 ℃, and be 2～12 hours time of drying, and maturing temperature is 400～700 ℃, roasting time is 1～8 hour, obtains described modified silicon aluminum phosphoric acid molecular sieve.
The invention provides the catalyzer in method, can also contain the mesoporous silicon aluminum molecular screen in ten-ring window duct, be selected from there is MFI, the mixture of one or more molecular sieves of the crystalline structure such as AEL.ZSM-5 molecular sieve is a kind of widely used MFI crystalline structure molecular sieve, dawn known to those skilled in the art, include or organic-free template is synthetic through Hydrogen ZSM-5 that later prepared by exchange, calcination process, PZSM-5 through phosphorus modification, and phosphorous and alkali-earth metal modified ZSM-5, or through phosphorus and transition metal modified ZSM-5.Said alkaline-earth metal is selected from magnesium and/or calcium, one or more in said transition metal chosen from Fe, cobalt, nickel, copper, zinc, titanium and manganese.Modified ZSM-5 preference is as PFeZSM-5 of phosphorus and magnesium-modified PMgZSM-5, phosphorus and iron modification etc.
The invention provides the catalyzer in method, the macropore Si-Al molecular sieve that contains 10～50% twelve-ring window duct, be selected from there is FAU, the mixture of one or more molecular sieves of the crystalline structure such as MOR, MAZ, BEA.Y zeolite is a kind of molecular sieve of widely used FAU crystalline structure, known to those skilled in the artly knows, and can comprise hydrothermal method, method of chemical treatment (mineral acid logos, silicofluoric acid aluminium-eliminating and silicon-replenishing method and SiCl
4vapor phase process) or the hydro-thermal standby super-stable Y molecular sieves of legal system (USY) that combines with chemical treatment, the REUSY that contains rare earth element, REHY, REY, and phosphorous PUSY, PREHY, PREY etc.
The invention provides the catalyzer in method, can also contain inorganic oxide binder.The example of said inorganic oxide binder includes but not limited to following kind: the mixture of one or more in aluminum oxide, silicon oxide, aluminum phosphate, amorphous aluminum silicide, zirconium white and titanium oxide.Its precursor of said aluminum oxide comprises the acidifying colloid of aluminium colloidal sol, aluminium chlorohydroxide, boehmite and pseudo-boehmite etc.; Said silicon-dioxide precursor comprises water glass, silicon sol etc.
The invention provides the catalyzer in method, can also contain clay.The material that said clay comprises synthetic or natural generation, as one or more the mixture in kaolin, kaolinite, montmorillonite, talcum and wilkinite, can be also the product after peracid or the processing of alkaline purification process by above-mentioned clay.Preferred clay is kaolin and through the product of acid or alkaline purification.
The invention provides in method, in embodiment, the most preferred composition of catalyzer is the USY molecular sieve, the ZSM-5 molecular sieve of 2-20%, the silicon oxide of 15-30% or aluminum oxide (take its precursor count for silicon sol or aluminium colloidal sol) of the SAPO-34 that contains 10-20% or SRM silicoaluminophosphamolecular molecular sieves, 10-35% and the kaolin of 15-40%.
The invention provides the catalyzer in method, then the spray drying process moulding that its preparation process adopts this area researchist to say to know or extrusion, compressing tablet sieve the method moulding of granulation.
Below in conjunction with drawings and Examples, the invention will be further described, but content not thereby limiting the invention.
Accompanying drawing is the schematic flow sheet of catalytic cracking method for hydrocarbon oil technique provided by the invention.
The inventive method adopts successive reaction regenerative operation, cracking hydrocarbon oil raw material 1 through preheating enters riser reactor 2, contact with the regenerated catalyst from regenerated catalyst circular route 10 promoting through water vapour 3, the reaction oil gas of riser reactor outlet and the mixture of catalyzer enter settling vessel 4 after gas-solid sharp separation, and the reaction oil gas 5 that flow out on settling vessel top enters fractionating system and carries out separation, the catalyzer of carbon deposit falls to entering stripping stage 6, oxygen-containing compound material 13 enters stripping stage 6 by feeding line 15 and contacts with carbon deposited catalyst after interchanger 14 heats up, or after mixing with water vapour 7 by former stockline 16, entering stripping stage 6 contacts with carbon deposited catalyst, or oxygen-containing compound material 13 parts that heat up enter stripping stage 6 by feeding line 15, part enters stripping stage after mixing with water vapour 7 by former stockline 16, the reaction oil gas that carbon deposit reclaimable catalyst in stripping stage 6 carries enters settling vessel 4 top reaction oil air-flows after stripping, reclaimable catalyst after stripping enters revivifier 9 through circular route 8 to be generated, contact coke burning regeneration with the main air air 11 that enters revivifier, burn flue gas 12 and remove smoke energy recovering system, regenerated catalyst enters riser reactor 2 through regenerator circular route 10.
Embodiment 1
The present embodiment illustrates catalytic cracking method for hydrocarbon oil provided by the invention.
Catalytically cracked stock is Wuhan mixing oil, the mixing oil (feedstock property is in Table 2) being mixed by 70% decompressed wax oil and 30% vacuum residuum.Oxygenate feedstock is methanol aqueous solution (containing 80% weight methyl alcohol, the industrial methanol that is 97% by purity adds deionized water to allocate).
Table 2
| Project | |
| Density (20 ℃), g/cm 3 | 0.9044 |
| Refractive power (20 ℃) | 1.5217 |
| Viscosity (100 ℃) mm 2/s | 9.96 |
| Zero pour, ℃ | 40 |
| Aniline point, ℃ | 95.8 |
| C wt％ | 85.98 |
| H wt％ | 12.86 |
| S wt％ | 0.55 |
| N wt％ | 0.18 |
| Carbon residue wt% | 3.0 |
| Boiling range, ℃ | |
| Initial boiling point | 243 |
| 5％ | 294 |
| 70％ | 473 |
In the present embodiment, the preparation method of used catalyst is as follows:
By butt meter (molecular sieve weight basis, lower same) ZSM-5 molecular sieve (ZSP-2, iron oxide content 2.2wt%, phosphorus pentoxide content 2.5wt%, Sinopec catalyzer asphalt in Shenli Refinery product) 20kg, adds the making beating of 35kg deionized water, adds USY molecular sieve (DASY2.0, rare earth oxide content 1.8%, lattice constant 2.445nm, degree of crystallinity 68%, Sinopec catalyzer asphalt in Shenli Refinery product) 10kg, (SRM-8, elementary composition is Al to add SRM molecular sieve again
2o
3:, 0.81P
2o
5: 0.29SiO
2, XRD diffraction data is in Table 3, Sinopec catalyzer Jian Chang branch office product, lower with) 10kg, making beating evenly, obtains molecular sieve pulp.By aluminium colloidal sol (commercially available, Al
2o
3content is 25%) 80kg making beating, add butt meter 40Kg kaolin (China Kaolin Co., Ltd's product), making beating is even, then adds above-mentioned molecular sieve pulp, and evenly, spraying is dry, collects 30-150 μ m scope microsphere particle in making beating.Above-mentioned catalyst microspheres, in 500 ℃ of calcination process 1h, is then used to 1%NH
4the Cl aqueous solution is processed 0.5h 60 ℃ of exchanges, filters, washes, in 120 ℃ of dry 16h, the catalyst A that obtains adopting in the inventive method.
Table 3
Catalyst A is composed as follows: ZSP-2 zeolite 20%, DASY2.0 molecular sieve 10%, SRM-8 molecular sieve 10%, aluminium colloidal sol (in aluminum oxide) 20%, kaolin 40%.
Catalyst A before reaction evaluating under 800 ℃, 100% water vapour, hydrothermal treatment consists 17h.
Hydrocarbon oil catalytic cracking reactor types is riser tube, and its internal diameter is 16 millimeters, is highly 4 meters; Riser reactor outlet is positioned at settling vessel, realizes catalyzer and reaction oil gas sharp separation, and reaction product is sent into subsequent separation system; Catalytically cracked stock is heated to 300 ℃ and enters riser tube and regenerated catalyst contact reacts, the ratio of the mass flow rate of regenerator mass flow rate and catalytically cracked stock charging is 8: 1, the ratio that enters the lifting vapor quality flow rate of riser tube and the mass flow rate of catalytically cracked stock charging is 0.25: 1, reaction times is 3 seconds, and outlet temperature of riser is 520 ℃.
The carbon deposited catalyst of leg outlet enters stripping stage under action of gravity, and stripping stage internal diameter is 100 millimeters, is highly 2.5 meters; Stripping stage bottom through the steam stripped carbon deposited catalyst of water vapour, enter revivifier regeneration, the catalyzer after regeneration turns back to riser reactor; The reaction oil gas that stripping stage goes out through water vapour stripping rises to the reaction oil gas outlet of settling vessel top and send subsequent separation system.
Methanol aqueous solution directly enters, 0.5 meter, stripping stage stripping vapour inlet top and carbon deposited catalyst contact reacts after being preheating to 200 ℃, stripping steam enters stripping stage bottom, and the weight hourly space velocity of methyl alcohol methanol conversion of take is 2h
-1, the ratio of the mass flow rate of stripping steam and methyl alcohol is 0.1: 1, the reaction of methanol conversion temperature is 520 ℃, reaction pressure 0.1Mpa (gauge pressure).Methanol feeding amount is 0.81 with the ratio of catalytically cracked stock inlet amount.
The unified metering of products therefrom, products distribution is calculated according to catalytically cracked stock meter, and gained reaction result is in Table 4.
Comparative example 1
The explanation of this comparative example adopts the effect of conventional catalytic cracking catalyst A0.Catalytically cracked stock is with embodiment 1, and reactor types is identical with embodiment 1, only at stripping stage, adopts water vapour stripping, does not add methanol feeding.
Method for preparing catalyst is as follows:
By butt meter ZSM-5 zeolite (ZSP-2, Sinopec catalyzer asphalt in Shenli Refinery product) 20kg, adds the making beating of 35kg deionized water, adds USY molecular sieve (DASY2.0, Sinopec catalyzer asphalt in Shenli Refinery product) 10kg, the uniform molecular sieve pulp of pulling an oar.By aluminium colloidal sol (commercially available, Al
2o
3content is 25%) 80kg making beating, add butt meter 50Kg kaolin (China Kaolin Co., Ltd's product), making beating is even, then adds above-mentioned molecular sieve pulp, and evenly, spraying is dry, collects 30-150 μ m scope microsphere particle in making beating.Above-mentioned catalyst microspheres, in 500 ℃ of calcination process 1h, is then used to 1%NH
4the Cl aqueous solution is processed 0.5h 60 ℃ of exchanges, filters, washes, and in 120 ℃ of dry 16h, obtains conventional catalytic cracking catalyst A0.
A0 is composed as follows: ZSP-2 zeolite 20%, DASY2.0 molecular sieve 10%, aluminium colloidal sol 20%, kaolin 50%.
Catalyst A 0 carry out integrated reaction evaluate before under 800 ℃, 100% water vapour, hydrothermal treatment consists 17h.
Gained reaction result is in Table 4.
Comparative example 2
The explanation of this comparative example adopts the not conventional catalytic cracking catalyst A0 of containing silica alumina phosphate molecular sieve, adopts the effect of oxygenate feedstock.
Catalytically cracked stock and methanol feedstock are with embodiment 1, and reactor types and reaction conditions are identical with embodiment 1, methanol feeding, and methanol feeding amount is 0.85 with the ratio of catalytically cracked stock inlet amount.
Gained reaction result is in Table 4.
Comparative example 3
In this comparative example 3 explanation catalyzer, contain silicoaluminophosphamolecular molecular sieves, but effect during without oxygenate feedstock.
Catalytically cracked stock and catalyzer are with embodiment 1, and reactor types is identical with embodiment 1, only at stripping stage, adopt water vapour stripping, do not add methanol feeding.
Gained reaction result is in Table 4.
Embodiment 2
The present embodiment illustrates in method provided by the invention and adopts oxygen-containing compound material segmentation to inject the effect of stripper mode.
Catalytically cracked stock, with embodiment 1, is the mixing oil being mixed by 70% decompressed wax oil and 30% vacuum residuum.Oxygenate feedstock is methanol aqueous solution (containing 80% weight methyl alcohol, the industrial methanol that is 97% by purity adds deionized water to allocate).
Method for preparing catalyst is as follows:
By butt meter ZSM-5 zeolite (ZSP-2, Sinopec catalyzer asphalt in Shenli Refinery product) 20kg, add the making beating of 35kg deionized water, add USY molecular sieve (DASY2.0 Sinopec catalyzer asphalt in Shenli Refinery product) 10kg, add SAPO-34 molecular sieve (Sinopec catalyzer Jian Chang branch office pilot product) 20kg, making beating evenly again.By aluminium colloidal sol (commercially available, Al
2o
3content is 25%) 80kg making beating, add butt meter 30Kg kaolin (China Kaolin Co., Ltd's product), making beating is even, then adds above-mentioned molecular sieve pulp, and evenly, spraying is dry, collects 30-150 μ m scope microsphere particle in making beating.Above-mentioned catalyst microspheres, in 400 ℃ of calcination process 1h, is then used to 0.5%NH
4the Cl aqueous solution is processed 0.5h 80 ℃ of exchanges, filters, washes, and in 120 ℃ of dry 16h, obtains catalyst B.
Catalyst B is composed as follows: ZSP-2 zeolite 20%, DASY2.0 molecular sieve 10%, SAPO-34 molecular sieve 20%, aluminium colloidal sol 20%, kaolin 30%.
Catalyst B carry out integrated reaction evaluate before under 800 ℃, 100% water vapour, hydrothermal treatment consists 17h.
Petroleum hydrocarbon catalytic cracking reactor form is riser tube, and its internal diameter is 16 millimeters, is highly 4 meters; Riser reactor outlet is positioned at settling vessel, realizes catalyzer and reaction oil gas sharp separation, and reaction product is sent into subsequent separation system; Catalytically cracked stock is heated to 320 ℃ and enters riser tube and regenerated catalyst contact reacts, the ratio of the mass flow rate of regenerator mass flow rate and catalytically cracked stock charging is 7: 1, the ratio that enters the lifting vapor quality flow rate of riser tube and the mass flow rate of catalytically cracked stock charging is 0.25: 1, reaction times is 4 seconds, and outlet temperature of riser is 510 ℃.
The carbon deposited catalyst of leg outlet enters stripping stage under action of gravity, and stripping stage internal diameter is 100 millimeters, is highly 2.5 meters; Stripping stage bottom through the steam stripped carbon deposited catalyst of water vapour, enter revivifier regeneration, the catalyzer after regeneration turns back to riser reactor; The reaction oil gas that stripping stage goes out through water vapour stripping rises to the reaction oil gas outlet of settling vessel top and send subsequent separation system.After methanol aqueous solution is preheating to 200 ℃, 50% directly enters, 0.5 meter, stripping stage stripping vapour inlet top and carbon deposited catalyst contact reacts, and remaining 50% enters stripping stage bottom with stripping steam, and the weight hourly space velocity of methyl alcohol methanol conversion of take is 1h
-1, the ratio of the mass flow rate of stripping steam and methyl alcohol is 0.1: 1, the reaction of methanol conversion temperature is 510 ℃, reaction pressure 0.13Mpa (gauge pressure).Methanol feeding amount is 0.81 with the ratio of catalytically cracked stock inlet amount.
The unified metering of reaction products therefrom, products distribution is calculated according to catalytically cracked stock meter, and gained reaction result is in Table 4.
Table 4
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 | Embodiment 2 | |
| Product distributes, wt% | |||||
| Dry gas | 3.52 | 15.68 | 4.26 | 17.76 | 17.04 |
| Liquefied gas | 24.37 | 43.14 | 25.00 | 37.78 | 35.09 |
| Gasoline | 21.45 | 24.94 | 19.95 | 21.74 | 23.86 |
| Diesel oil | 15.93 | 18.19 | 15.91 | 16.64 | 17.20 |
| Heavy oil | 26.17 | 26.04 | 23.73 | 24.42 | 27.66 |
| Coke | 8.57 | 14.94 | 11.16 | 14.12 | 12.61 |
| Stock oil transformation efficiency, wt% | 57.91 | 60.36 | |||
| Methanol conversion, wt% | 77.63 | 99.84 | 99.30 | ||
| Yield of ethene, wt% | 1.28 | 2.29 | 2.01 | 13.13 | 12.70 |
| Propene yield, wt% | 9.98 | 12.97 | 9.59 | 18.36 | 16.78 |
As can be seen from Table 4, method provided by the invention, with respect to existing catalyst cracking method with the method for the integrated methyl alcohol of existing catalytic cracking catalyst processing, methanol conversion obviously improves, methyl alcohol approaches completely and transforms, ethene+propene yield also obviously increases, and particularly yield of ethene has been obtained and increased considerably, and the ratio of ethylene/propene obviously improves.
Embodiment 3
The present embodiment illustrates in method provided by the invention and adopts methyl alcohol and ethanol to inject the result of stripping stage mode simultaneously.
The preparation process of the present embodiment catalyzer is as follows:
By butt meter ZSM-5 zeolite (ZSP-3, iron oxide content 2.5wt%, phosphorus pentoxide content 2.9wt%, Sinopec catalyzer asphalt in Shenli Refinery product) 2kg, add the making beating of 45kg deionized water, add REY molecular sieve (REY, rare earth oxide content 18.7%, lattice constant 2.469nm, degree of crystallinity 46% performance index, Sinopec catalyzer asphalt in Shenli Refinery product) 35kg, then add SRM-8 molecular sieve 15kg, making beating is evenly.Butt meter 15Kg pseudo-boehmite (Chalco Shandong Aluminum Plant product) is added to 100kg deionized water making beating, adds 2kg concentrated hydrochloric acid (commercially available, HCl content 31.5% weight) making beating evenly, then add aluminium colloidal sol (commercially available, Al
2o
3content is 25%) 60kg making beating, add butt meter 18Kg kaolin (China Kaolin Co., Ltd's product), making beating is even, then adds above-mentioned molecular sieve pulp, and evenly, spraying is dry, collects 30-150 μ m scope microsphere particle in making beating.Above-mentioned catalyst microspheres, in 400 ℃ of calcination process 2h, is then used to 0.5%NH
4the Cl aqueous solution is processed 1.5h 80 ℃ of exchanges, filters, washes, and in 120 ℃ of dry 16h, obtains catalyzer C.
Catalyzer C is composed as follows: ZSP-3 zeolite 2%, REY molecular sieve 35%, SRM-8 molecular sieve 15%, aluminium colloidal sol 15%, pseudo-boehmite 15%, kaolin 18%.
Catalyzer C carry out integrated reaction evaluate before under 800 ℃, 100% water vapour, hydrothermal treatment consists 17h.
Catalytically cracked stock, with embodiment 1, is Wuhan mixing oil, by 70% decompressed wax oil and 30% vacuum residuum, is mixed.Methyl alcohol and aqueous ethanolic solution are containing 34% weight methyl alcohol and 46% weight ethanol, and the industrial alcohol that the industrial methanol that is 97% by purity and purity are 95% adds deionized water to allocate.
Petroleum hydrocarbon catalytic cracking reactor form is riser tube, and its internal diameter is 16 millimeters, is highly 4 meters; Riser reactor outlet is positioned at settling vessel, realizes catalyzer and reaction oil gas sharp separation, and reaction product is sent into subsequent separation system; Catalytically cracked stock is heated to 280 ℃ and enters riser tube and regenerated catalyst contact reacts, the ratio of the mass flow rate of regenerator mass flow rate and catalytically cracked stock charging is 5: 1, the ratio that enters the lifting vapor quality flow rate of riser tube and the mass flow rate of catalytically cracked stock charging is 0.25: 1, reaction times is 4 seconds, and outlet temperature of riser is 500 ℃.
The carbon deposited catalyst of leg outlet enters stripping stage under action of gravity, and stripping stage internal diameter is 100 millimeters, is highly 2.5 meters; Stripping stage bottom through the steam stripped carbon deposited catalyst of water vapour, enter revivifier regeneration, the catalyzer after regeneration turns back to riser reactor; The reaction oil gas that stripping stage goes out through water vapour stripping rises to the reaction oil gas outlet of settling vessel top and send subsequent separation system.The aqueous solution of methyl alcohol and ethanol enters stripping stage stripping vapour inlet after being preheating to 200 ℃ mixes with stripped vapor, and with carbon deposited catalyst contact reacts, the weight hourly space velocity of methyl alcohol the reaction of methanol conversion of take is 4h
-1, the ratio of the mass flow rate of stripping steam and methyl alcohol is 0.2: 1, the reaction of methanol conversion temperature is 500 ℃, reaction pressure 0.14Mpa (gauge pressure).Methyl alcohol and ethanol inlet amount are 0.58 with the ratio of catalytically cracked stock inlet amount.
The unified metering of reaction products therefrom, products therefrom distributes and calculates according to catalytically cracked stock meter, and gained reaction result is in Table 6.
Comparative example 4
The explanation of this comparative example adopts conventional catalytic cracking catalyst to carry out the effect of catalytic cracking reaction.
Adopt catalytically cracked stock with embodiment 1, reactor types is identical with embodiment 1, only at stripping stage, adopts water vapour stripping, does not add oxygenate feedstock.
Method for preparing catalyst is as follows: by butt meter ZSM-5 zeolite (ZSP-3, Sinopec catalyzer asphalt in Shenli Refinery product) 2kg, add the making beating of 35kg deionized water, add REY molecular sieve (Sinopec catalyzer asphalt in Shenli Refinery product) 35kg, making beating evenly.Butt meter 15Kg pseudo-boehmite (Chalco Shandong Aluminum Plant product) is added to 100kg deionized water making beating, adds 2kg concentrated hydrochloric acid (commercially available, HCl content 31.5% weight) making beating evenly, then add aluminium colloidal sol (commercially available, Al
2o
3content is 25%) 60kg making beating, add butt meter 33Kg kaolin (China Kaolin Co., Ltd's product), making beating is even, then adds above-mentioned molecular sieve pulp, and evenly, spraying is dry, collects 30-150 μ m scope microsphere particle in making beating.Above-mentioned catalyst microspheres, in 500 ℃ of calcination process 2h, is then used to 1%NH
4the Cl aqueous solution is processed 1.5h 70 ℃ of exchanges, filters, washes, and in 120 ℃ of dry 24h, obtains catalytic cracking catalyst C0.
Catalyzer C0 is composed as follows: ZSP-3 zeolite 2%, REY molecular sieve 35%, aluminium colloidal sol (in aluminum oxide) 15%, pseudo-boehmite (in aluminum oxide) 15%, kaolin 33%.
Catalyzer C0 carry out integrated reaction evaluate before under 800 ℃, 100% water vapour, hydrothermal treatment consists 17h.
Gained reaction result is in Table 6.
Embodiment 4
The present embodiment explanation adopts the effect of the SRM molecular sieve of modification.
With embodiment 3, difference is, catalyzer is wherein numbered D, magnesium and aluminium modification for the SRM-8 molecular sieve in catalyzer D.Its method of modifying is as follows:
18.75Kg nine water aluminum nitrates are dissolved in 500Kg deionized water, stir, and then add 50kg SRM-8 molecular sieve (Sinopec catalyzer Jian Chang branch office product, removed template method), at room temperature stir 1 hour, then add again wherein 12.9Kg magnesium nitrate hexahydrate, at room temperature stir 1 hour, then filter, wash, a dry night at 100 ℃, the roasting 2 hours at 600 ℃ of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification.
Sample after roasting is measured through X-ray powder diffraction, and its result data is as table 5.Mole consisting of of modified sample: 16MgO: 3.5Al
2o
3: (100Al
2o
3: 76P
2o
5: 30SiO
2).
Table 5
Catalyzer D preparation process is with embodiment 3, and it is composed as follows: ZSP-3 zeolite 2%, REY molecular sieve 35%, the SRM-8 molecular sieve 15% of magnesium and aluminium modification, aluminium colloidal sol 15%, pseudo-boehmite 15%, kaolin 18%.
Catalyzer D before carrying out reaction evaluating under 800 ℃, 100% water vapour, hydrothermal treatment consists 17h.
Gained reaction result is in Table 6.
Table 6
| Comparative example 4 | Embodiment 3 | Embodiment 4 | |
| Product distributes, wt% | |||
| Dry gas | 3.60 | 23.18 | 23.30 |
| Liquefied gas | 17.09 | 25.21 | 25.46 |
| Gasoline | 35.24 | 36.64 | 36.54 |
| Diesel oil | 19.10 | 19.22 | 19.25 |
| Heavy oil | 14.45 | 14.39 | 14.31 |
| Coke | 10.51 | 11.47 | 11.27 |
| Stock oil transformation efficiency, wt% | 66.45 | ||
| Methanol conversion, wt% | 99.71 | 100.00 | |
| Ethanol conversion, wt% | 99.93 | 100.00 | |
| Yield of ethene, wt% | 0.79 | 19.33 | 19.45 |
| Propene yield, wt% | 5.66 | 10.10 | 10.35 |
As can be seen from Table 6, catalytic cracking method for hydrocarbon oil provided by the present invention, methyl alcohol and ethanol approach completely and transform, the total recovery of ethene and propylene also obviously increases, because the primary product of ethanol dehydration reaction is ethene, so yield of ethene has been obtained, increase considerably, the ratio of ethylene/propene obviously improves.Particularly adopt containing after the catalyzer of modification SRM molecular sieve, because the SRM-8 molecular sieve of modification further improves the activity and selectivity of oxygenatedchemicals dehydration reaction, not only make the oxygenatedchemicals adding in catalytic cracking method for hydrocarbon oil transform completely, and the yield of ethene and propylene further improves, by oxygenatedchemicals, transform the green coke causing and decline.
Claims (25)
1. a catalytic cracking method for hydrocarbon oil, cracking hydrocarbon oil raw material is contacted and carries out cracking reaction with the catalyst regeneration agent being promoted by steam that enters riser reactor, riser reactor outlet gained cracking reaction oil gas enters settling vessel with the mixture of catalyzer and carries out separated, wherein, isolated cracking reaction oil gas rises, gas pipeline through settling vessel top enters subsequent products separation system, and isolated carbon deposited catalyst falls to entering stripping stage, through spent agent circular route, enter revivifier, react and burn with main air, gained regenerated flue gas enters smoke energy recovering system from revivifier top flue gas pipeline, the agent of gained catalyst regeneration is returned to riser reactor through regenerator circular route, by steam, promoted and cracking hydrocarbon oil raw material reaction, it is characterized in that, the method also comprises oxygen-containing compound material preheating, directly enter stripping stage, or, to after part or all of oxygen-containing compound material and the mixing of stripping steam, enter stripping stage, the carbon deposited catalyst that enters stripping stage with whereabouts contacts and carries out oxygenate conversion reaction, the reaction oil gas that this conversion reaction generates rises and enters the gas pipeline at settling vessel top with cracking reaction air-fuel mixture, wherein, said catalyzer be take catalyst weight and is contained 1～90% the silicon aluminium phosphate SRM molecular sieve with octatomic ring window duct as benchmark, said SRM molecular sieve, X-ray diffraction spectral data at least contains the diffraction peak shown in following table, the structure expression of this molecular sieve is Al
2o
3: 0.1～1.7P
2o
5: 0.01～3SiO
2, in table, VS, M and W represent the relative intensity of diffraction peak, and W is > 0～20%, and M is > 20～60%, and VS is > 80～100%,
2. according to the method for claim 1, wherein, said catalyzer take weight as benchmark has following composition: 1～90% the silicon aluminium phosphate SRM molecular sieve with octatomic ring window duct, 0～50% the mesoporous silicon aluminum molecular screen with ten-ring window duct, 10～50% the macropore Si-Al molecular sieve with twelve-ring window duct, 4～50% inorganic oxide binder and 0～70% clay.
3. according to the method for claim 2, wherein, said catalyzer take weight as benchmark has following composition: the mesoporous silicon aluminum molecular screen, 12～40% that 5～60% silicon aluminium phosphate SRM molecular sieves, 0～30% with octatomic ring window duct have a ten-ring window duct has macropore Si-Al molecular sieve, 10～30% inorganic oxide binder and 10～50% the clay in twelve-ring window duct.
4. according to the process of claim 1 wherein, Me1 and Me2 modification for SRM molecular sieve, the structure expression of this molecular sieve is xMe1:yMe2:(Al
2o
3: 0.1～1.7P
2o
5: 0.01～3SiO
2), said Me1 is selected from a kind of element or boron or the gallium in periodic table of elements ZhongIIA family, VB family, said Me2 is selected from a kind of element or the aluminium in periodic table of elements ZhongIVB family, x represents that Me1 accounts for the molecular fraction of this molecular sieve in oxide compound, x=5～25, y represents that Me2 accounts for the molecular fraction of this molecular sieve in oxide compound, y=2～20, and the ratio of x and y is 0.5～10.
5. according to the method for claim 4, wherein Me1 is selected from a kind of in magnesium, vanadium, copper and boron.
6. according to the method for claim 4, wherein, Me2 is selected from a kind of element or the aluminium in periodic table of elements ZhongIVB family.
7. according to the method for claim 6, wherein, Me2 is selected from a kind of in aluminium, titanium and zirconium.
8. according to the method for claim 2 or 3, wherein, the said mesoporous silicon aluminum molecular screen with ten-ring window duct, be selected from there is MFI, one or more in AEL crystalline structure Si-Al molecular sieve.
9. according to the method for claim 8, wherein, the said MFI of having crystalline structure Si-Al molecular sieve is ZSM-5.
10. according to the method for claim 9, wherein, said ZSM-5 is Hydrogen ZSM-5, or is the ZSM-5 through phosphorus modification, or is phosphorus and alkali-earth metal modified ZSM-5, or is phosphorus and transition metal modified ZSM-5.
11. according to the method for claim 10, and said alkaline-earth metal is selected from magnesium and/or calcium, one or more in said transition metal chosen from Fe, cobalt, nickel, copper, zinc, titanium and manganese.
12. according to the method for claim 2 or 3, wherein, the said macropore Si-Al molecular sieve with twelve-ring window duct, be selected from there is FAU, one or more in MOR, MAZ and BEA crystalline structure Si-Al molecular sieve.
13. according to the method for claim 12, and wherein, the said FAU of having crystalline structure Si-Al molecular sieve is Y zeolite.
14. according to the method for claim 13, and wherein, said Y zeolite is selected from USY, phosphorus and/or rare earth modified Y zeolite.
15. according to the process of claim 1 wherein, said catalyzer contains silicon aluminium phosphate SRM molecular sieve, USY and/or ZSM-5 Si-Al molecular sieve, silicon oxide or aluminum oxide and kaolin.
16. according to the process of claim 1 wherein, said cracking hydrocarbon oil raw material is selected from one or more the mixture in crude oil, gasoline, diesel oil, decompressed wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil and hydrogenation tail oil.
17. according to the process of claim 1 wherein, said petroleum hydrocarbon raw material is selected from one or more the mixture in decompressed wax oil, long residuum, vacuum residuum, wax tailings and hydrogenation tail oil.
18. according to the process of claim 1 wherein, the condition of said cracking hydrocarbon oil reaction is 400～650 ℃ of temperature, pressure 0.01～0.50MPa, and reaction times 1～600s, agent-oil ratio 1～20, the mass ratio of water vapour and cracking hydrocarbon oil raw material is 0.01～1.0.
19. according to the method for claim 18, and wherein, the condition of said cracking hydrocarbon oil reaction is 450～550 ℃ of temperature, pressure 0.1～0.40MPa, and reaction times 3～100s, agent-oil ratio 4～15, the mass ratio of water vapour and cracking hydrocarbon oil raw material is 0.05～0.5.
20. according to the process of claim 1 wherein, said oxygenatedchemicals is selected from one or more in methyl alcohol, ethanol, dme.
21. according to the method for claim 1 or 20, and wherein, the condition of said oxygenate conversion reaction is that temperature is 400～600 ℃, and pressure is 0.01～0.50MPa, oxygen-containing compound material reaction velocity 0.1～100h
-1, oxygen-containing compound material preheating temperature is 50～500 ℃, and the mass ratio of oxygen-containing compound material and cracking hydrocarbon oil raw material is 0.01～5, and oxygen-containing compound material is 0.01～5 with the mass ratio that enters the stripped vapor of stripping stage.
22. according to the method for claim 21, and wherein, the condition of said oxygenate conversion reaction is 450～550 ℃ of temperature, pressure 0.1～0.4MPa, oxygen-containing compound material reaction velocity 0.5～10h
-1, oxygen-containing compound material preheating temperature is 150～400 ℃, and the mass ratio of oxygen-containing compound material and cracking hydrocarbon oil raw material is 0.05～1, and oxygen-containing compound material is 0.05～1 with the mass ratio that enters the stripped vapor of stripping stage.
23. according to the process of claim 1 wherein, directly enters the middle part of stripping stage inner catalyst dense-phase bed after oxygen-containing compound material preheating.
24. according to the process of claim 1 wherein, all oxygen-containing compound material and stripping steam are mixed into stripping stage bottom.
25. according to the process of claim 1 wherein, 10～90% oxygen-containing compound material enters the middle part of stripping stage inner catalyst dense-phase bed, and remaining part oxygen-containing compound material and stripping steam are mixed into stripping stage bottom.
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