CN102816588B - Method for catalytic cracking process and oxygen-containing compound integrated process - Google Patents

Abstract

The invention relates to a method for a catalytic cracking process and an oxygen-containing compound integrated process. The method comprises the steps of guiding 10-50 wt% of a carbon cracking catalyst obtained by separating from a precipitator to a fluidized bed reactor; contacting with a heat-exchanged raw material of the oxygen-containing compound; performing a dehydration reaction; and returning a mixture consisting of oil and gas products of the dehydration reaction and the carbon cracking catalyst to the precipitator; wherein the oil and gas products of the dehydration reaction is mixed with oil and gas products of a cracking reaction and enters into a subsequent product separation system through an oil and gas pipeline on the top of the precipitator; and the cracking catalyst comprises, on basis of the weight of the catalyst, 1-90% of silicoaluminophosphate molecular sieves having octatomic ring window channels. Light olefin yield and proportion of olefin product types of the catalytic cracking process can be flexibly adjusted by adding a dehydration reactor of the oxygen-containing compound and material-feeding of the oxygen-containing compound. The method is simple in process, mature in technology, low in investment and easy to realize.

Description

A kind of method of catalytic cracking process and the integrated processing of oxygenatedchemicals

Technical field

The invention relates to a kind of integrating heavy oil catalytic cracking with oxygen-containing compound catalyzed conversion increases the method for the yield of light olefins such as ethene and propylene.

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 exceedes 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 propylene that the whole world exceedes the ethene of ultimate production 90% and approximately 70% 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 the raw material supply anxiety of light olefin, production cost 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, and therefore developing renewable and alternative materials preparing ethylene, propylene becomes the trend of 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 exceed demand.At present, be also tending towards ripe by the low-carbon alkenes such as Methanol ethene, propylene (Methanol to Olefin is called for short MTO) technology, 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 proposed by Mobil company.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 is the silicoaluminophosphamolecular molecular sieves (USP4440871) in the invention early 1980s by UCC company of the U.S., 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, within 2008, has carried out Industrial demonstration in Huai Hua group, and 30,000 tons of year processing methyl alcohol, can produce 10,000 tons of propylene.(chemical industry, 2009,27 (1-2): 18-22)

Lurgi company of Germany has developed preparing propylene from methanol (MTP) technique, adopt ZSM-5 molecular sieve catalyzer (EP 0448000), 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.When 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 methyl alcohol industry entirety working rate 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 have similarity, two kinds of reaction process conditions are also had something in common, and researchist endeavours, by two kinds of Technology couplings, can reduce investment outlay.

CN 86101079A discloses methyl alcohol as reactant and for example method of catalytic cracking together with gas oil of petroleum hydrocarbon, 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 DEG C 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, be 25-100 containing Si/Al weight ratio, 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 DEG C, 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, inject stripping stage, settling section for methyl alcohol, 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 has studied the reaction process of methyl alcohol as catalytic cracking part material, on fresh catalytic cracking catalyst, under the condition of temperature of reaction 550-600 DEG C, adopt the independent charging of 40% (weight) methanol aqueous solution, the hydrocarbon productive rate of methanol conversion can reach 26.3%-28.1% (weight), and low-carbon alkene accounts for the 67.8%-66.5% (weight) of hydrocarbon composition.

Petrochemical complex, 2009,38 (3): 267-272 has 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 in 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: temperature of reaction 400-420 DEG C, 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 body %.

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, be 1 containing mass ratio: 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 DEG C, 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 finds through a large amount of experiment accident ground, 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 subject to the impact of cracking hydrocarbon ils contamination of raw material carbon deposit, still the catalyzed conversion function of its oxygenatedchemicals can utilized, oxygenatedchemicals is had and approach 100% transformation efficiency, thereby improve cracking hydrocarbon oil reaction product and comprise ethene and the propylene yield at interior overall low-carbon alkene.

Therefore, the object of the invention is to provide a kind of integrated catalytic cracking process of prior art and method of the work oxygenatedchemicals course of processing of being different from, and makes the raw material expansion of catalyzed cracking processing, can improve ethene and the productivity of propylene of catalytic cracking process.

A kind of method of catalytic cracking process and the integrated processing of oxygenatedchemicals, the regenerated cracking catalyst agent under cracking reaction condition, petroleum hydrocarbon raw material being promoted with the steam that enters riser reactor contacts reacts, riser reactor exports the cracking reaction oil gas obtaining and separates in settling vessel with the mixture of catalyzer, obtain cracking reaction oil gas and carbon deposit cracking catalyst, wherein, carbon deposit cracking catalyst falls to entering stripping stage, the cracking reaction oil gas that carbon deposited catalyst in stripping stage carries enters settling vessel top gas pipeline after the water vapour stripping of stripping stage and enters product separation system via entering, carbon deposit cracking catalyst after stripping enters revivifier through spent agent circular route and reacts and burn with main air, the regenerated flue gas obtaining enters smoke energy recovering system from revivifier top flue gas pipeline, riser reactor is returned in the regenerated cracking catalyst agent obtaining, it is characterized in that, the method also comprises in the 10-50 % by weight importing fluidized-bed reactor separating in settling vessel in the carbon deposit cracking catalyst obtaining, contact with the oxygen-containing compound material heating up through heat exchange, carry out dehydration reaction, the mixture of dehydration reaction oil gas product and carbon deposit cracking catalyst returns in settling vessel, dehydration reaction oil gas product wherein and cracking reaction air-fuel mixture, through settling vessel top, gas pipeline enters subsequent products separation system, wherein, said cracking catalyst contains 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct taking catalyst weight as benchmark.

Method provided by the invention, carries out existing heavy oil catalytically cracking equipment and the oxygenatedchemicals course of processing integrated, makes the products scheme of catalytic cracking more flexible, processes raw material more extensive.Because the oxygenatedchemicals course of processing is mainly dehydration, its primary product is ethene and propylene, has therefore increased the yield of high-value product light olefin.Meanwhile, the water Substitute For Partial stripping steam that oxygenatedchemicals dehydration generates, can reduce the consumption of original catalyst cracking method stripping steam.Because oxygenatedchemicals dehydration reaction occurs in newly-increased fluidized-bed reactor, therefore easy control of reaction conditions.Method provided by the invention, only increasing oxygenatedchemicals dehydration reactor and oxygenate feedstock just can flexible catalytic cracking light olefin productive rate and the ratio of olefin product kind, device is simple, make full use of reaction-regeneration system device, product separation recovery process and the Cooling and Heat Source of catalytic cracking process, technology maturation, less investment, is easy to realize.

Brief description of the drawings

Accompanying drawing is the process system schematic diagram of the method for integrated catalytic cracking process provided by the invention and the oxygenatedchemicals course of processing.

Embodiment

The method of integrated catalytic cracking process provided by the invention and oxygenatedchemicals processing, the regenerated cracking catalyst agent under cracking reaction condition, petroleum hydrocarbon raw material being promoted with the steam that enters riser reactor contacts reacts, the cracking reaction oil gas that leg outlet obtains separates in settling vessel with the mixture of catalyzer, obtain cracking reaction oil gas and carbon deposited catalyst, wherein, cracking reaction oil gas rises and enters product separation system through settling vessel top gas pipeline, carbon deposit cracking catalyst falls to entering stripping stage, carbon deposit cracking catalyst after stripping enters revivifier through spent agent circular route and reacts and burn with main air, the regenerated flue gas obtaining enters smoke energy recovering system from revivifier top flue gas pipeline, riser reactor is returned in the regenerated cracking catalyst agent obtaining, it is characterized in that, the method also comprises and will in settling vessel, separate the 10-50 % by weight in the carbon deposit cracking catalyst obtaining, importing fluidized-bed reactor contacts and carries out dehydration reaction with the oxygenatedchemicals heating up through heat exchange, the mixture of dehydration reaction oil gas product and carbon deposit cracking catalyst returns in settling vessel, dehydration reaction oil gas product wherein and cracking reaction air-fuel mixture, through settling vessel top, gas pipeline enters subsequent products separation system, wherein, said cracking catalyst contains 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct taking catalyst weight 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, preferred petroleum hydrocarbon raw material 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 catalytic cracking, in its riser reactor, reaction conditions is temperature 400-650 DEG C, pressure 0.01-0.50MPa, reaction times 1-600s, agent-oil ratio 1.0-20, the mass ratio of water vapour and petroleum hydrocarbon raw material is 0.01～1.0; Preferable reaction temperature 450-550 DEG C, 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 carries out the fluidized-bed reactor of dehydration reaction for all kinds of fluidized-bed reactors that this area researchist knows, and comprises such as fast bed, bubbling bed etc.

In method provided by the invention, described oxygenatedchemicals can be selected from one or more in the group including 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, the condition of described oxygenatedchemicals dehydration reaction is that temperature is 400-600 DEG C, 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 DEG C.Preferable reaction temperature 450-550 DEG C, pressure 0.1-0.4MPa, oxygen-containing compound material reaction velocity 0.5-10h ^-1, oxygen-containing compound material preheating temperature is 150-400 DEG C., the mass ratio of described oxygenate feedstock and petroleum hydrocarbon raw material is 0.01～5.

In method provided by the invention, said cracking catalyst is taking the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct of catalyst weight following composition: 1-90% as benchmark has, the mesoporous silicon aluminum molecular screen with ten-ring window duct of 0-50%, the macropore Si-Al molecular sieve with twelve-ring window duct, the inorganic oxide binder of 4-50% and the clay of 0-70% of 10-50%; Preferred group becomes the silicoaluminophosphamolecular molecular sieves of 5-60%, the mesoporous silicon aluminum molecular screen of 0-30%, macropore Si-Al molecular sieve, the inorganic oxide binder of 10-30% and the clay of 10-50% of 12-40%.

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's discovery, when using after Me1 and Me2 modification, this molecular sieve is for the reaction of methanol-to-olefins reaction, have better product selectivity and less by product, 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 IIA family in the periodic table of elements, VB family, the wherein one in preferably magnesium, vanadium, copper and boron, and 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 IVB family in the periodic table of elements, 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 in the time of a suitable scope, silicoaluminophosphamolecular molecular sieves acidity through modification is moderate, when oxygen-containing compound material being transformed keep in preparing low carbon olefin hydrocarbon 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 method provided by the invention, the SRM molecular sieve adopting in most preferred embodiment, is to obtain with the combination modification of the element of two kinds of 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 SRM 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) exchange after silicoaluminophosphamolecular molecular sieves carry out drying and roasting, drying temperature is 80～140 DEG C, and be 2～12 hours time of drying, and maturing temperature is 400～700 DEG C, 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 SRM 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 is exchanged carries out drying and roasting, and drying temperature is 80～140 DEG C, and be 2～12 hours time of drying, and maturing temperature is 400～700 DEG C, 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) exchange after silicoaluminophosphamolecular molecular sieves carry out drying and roasting, drying temperature is 80～140 DEG C, and be 2～12 hours time of drying, and maturing temperature is 400～700 DEG C, 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 the mixture of one or more molecular sieves with the crystalline structure such as MFI, 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, through the PZSM-5 of 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 the product through acid or alkaline purification thereof.

The invention provides in method, in embodiment, the most preferred composition of catalyzer is the kaolin of the silicon oxide of ZSM-5 molecular sieve, 15-30% of USY molecular sieve, the 2-20% of the SAPO-34 that contains 10-20% or SRM silicoaluminophosphamolecular molecular sieves, 10-35% or aluminum oxide (taking its precursor as silicon sol or aluminium colloidal sol count) and 15-40%.

Method provided by the invention, considers oxygenatedchemicals amount of finish and stripping stage stable operation, can be derived 10～50% carbon deposited catalyst and entered by upflow tube the dehydration reaction fluidized-bed of oxygenatedchemicals.

Catalyzer provided by the invention, 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.

Referring to accompanying drawing, accompanying drawing is the process system schematic diagram of the method for integrated catalytic cracking process provided by the invention and the oxygenatedchemicals course of processing.

The integrated processing oxygenatedchemicals of catalytic cracking process using successive reaction regenerative operation, catalytically cracked stock 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 leg outlet and the mixture of catalyzer enter settling vessel 4 after gas-solid sharp separation, and the reaction oil gas 5 that flow out at settling vessel 4 tops goes fractionating system to separate; The catalyzer of carbon deposit falls to entering stripping stage 6, partial product Pd/carbon catalyst enters oxygenatedchemicals dehydration fluid bed reactor 15 through spent agent circular route 16 and contacts with the oxygen-containing compound material 13 heating up through interchanger 14, reaction oil gas product and catalyst mixture return to settling vessel 4 through dehydration fluid bed reactor 15 top transfer limess 17, after gas-solid sharp separation, carbon deposited catalyst declines and enters stripping stage 6, and reaction oil gas rises and flows out from settling vessel 4 tops; The reaction oil gas that carbon deposit reclaimable catalyst in stripping stage 6 carries enters settling vessel 4 top reaction oil air-flows after entering water vapour 7 strippings of stripping stage 4, 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 9, burn flue gas 12 and remove smoke energy recovering system, regenerated catalyst enters riser reactor 2 through regenerator circular route 10.

Embodiment 1

The method of integrated catalytic cracking process provided by the invention and the oxygenatedchemicals course of processing is carried out in the present embodiment explanation on the middle-scale device of successive reaction-regenerative operation.

Riser tube 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 DEG C 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 DEG C.

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; Water vapour enters stripping stage bottom, and the carbon deposited catalyst after stripping enters revivifier regeneration, and 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.Stripping stage middle part arranges upflow tube, spent agent enters spent agent circulation line (in accompanying drawing 16) by upflow tube, under flow to Dehydration of methanol device (in accompanying drawing 15), 15 millimeters of Dehydration of methanol device internal diameters, 3 meters of height, methanol aqueous solution directly enters dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 200 DEG C, the mixture of reaction oil gas and catalyzer returns and in settling vessel, realizes finish and separate through dehydration reactor top transfer limes (in accompanying drawing 17).

Taking the weight hourly space velocity of methyl alcohol the reaction of methanol conversion as 2h ^-1, methanol conversion temperature out is 520 DEG C, reaction pressure 0.1Mpa (gauge pressure).Methanol feeding amount is 0.60 with the ratio of catalytically cracked stock inlet amount.

Catalytically cracked stock is Wuhan mixing oil, mixes (feedstock property is in table 2) by 70% decompressed wax oil and 30% vacuum residuum.Oxygenatedchemicals is methanol aqueous solution, and containing 80% weight methyl alcohol, the industrial methanol that is 97% by purity adds deionized water allotment.

Table 2

Project	?
		Density (20 DEG C), g/cm 3	0.9044
Refractive power (20 DEG C)	1.5217
		Viscosity (100 DEG C) mm 2/s	9.96
Zero pour, DEG C	40
		Aniline point, DEG C	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, DEG C	?
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, add the making beating of 35kg deionized water, add 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) and 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 DEG C of calcination process 1h, is then used to 1%NH ₄the Cl aqueous solution is processed 0.5h 60 DEG C of exchanges, filters, washes, and obtains in 120 DEG C of dry 16h the catalyst A 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, lower same) 20%, kaolin 40%.

Catalyst A carry out integrated reaction evaluate before under 800 DEG C, 100% water vapour, hydrothermal treatment consists 17h.

The unified metering of integrated reaction products therefrom, products therefrom distributes and calculates according to catalytically cracked stock meter, and gained reaction result is in table 1.

Comparative example 1

The explanation of this comparative example adopts conventional catalytic cracking catalyst to carry out catalytic cracking reaction on the middle-scale device of successive reaction-regenerative operation, does not add the effect of methanol feeding in dehydration reactor.

Catalytically cracked stock is with embodiment 1, and reactor types is identical with embodiment 1, only adopts water vapour stripping at stripping stage, does not add methanol feeding in Dehydration of methanol device.

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, 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 DEG C of calcination process 1h, is then used to 1%NH ₄the Cl aqueous solution is processed 0.5h 60 DEG C of exchanges, filters, washes, and obtains conventional catalytic cracking catalyst A0 in 120 DEG C of dry 16h.

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 DEG C, 100% water vapour, hydrothermal treatment consists 17h.

Gained reaction result is in table 4.

Comparative example 2

This comparative example explanation adopts the conventional catalytic cracking catalyst A0 of containing silica alumina phosphate molecular sieve not to carry out the effect of the integrated oxygenatedchemicals course of processing of catalytic cracking process on the middle-scale device of successive reaction-regenerative operation.

Catalytically cracked stock and methanol feedstock are with embodiment 1, and reactor types and reaction conditions are identical with embodiment 1, and catalytic cracking catalyst is with the A0 of comparative example 1, 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

The catalyzer that the explanation of this comparative example adopts on the middle-scale device of successive reaction-regenerative operation contains silicoaluminophosphamolecular molecular sieves, but catalytic cracking reaction effect during without oxygen-containing compound material charging.

Catalytically cracked stock and catalyzer are with embodiment 1, and reactor types is identical with embodiment 1, only adopt water vapour stripping at stripping stage, do not add methanol feeding in Dehydration of methanol device.

Gained reaction result is in table 4.

Embodiment 2

The experimental result of the integrated oxygenatedchemicals course of processing of catalytic cracking process is carried out in the present embodiment explanation on the middle-scale device of successive reaction-regenerative operation.

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 allotment).

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 DEG C of calcination process 1h, is then used to 0.5%NH ₄the Cl aqueous solution is processed 0.5h 80 DEG C of exchanges, filters, washes, and in 120 DEG C 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 DEG C, 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 DEG C 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 DEG C.

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; Water vapour enters stripping stage bottom, and the carbon deposited catalyst after stripping enters revivifier regeneration, and 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.Stripping stage middle part arranges upflow tube, spent agent enters spent agent circulation line (in accompanying drawing 16) by upflow tube, under flow to Dehydration of methanol device (in accompanying drawing 15), 15 millimeters of Dehydration of methanol device internal diameters, 3 meters of height, methanol aqueous solution directly enters dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 200 DEG C, the mixture of reaction oil gas and catalyzer returns and in settling vessel, realizes finish and separate through dehydration reactor top transfer limes (in accompanying drawing 17).Taking the weight hourly space velocity of methyl alcohol methanol conversion as 1h ^-1, the reaction of methanol conversion temperature is 510 DEG C, reaction pressure 0.13Mpa (gauge pressure).Methanol feeding amount is 0.60 with the ratio of catalytically cracked stock inlet amount.

The unified metering of integrated reaction products therefrom, products therefrom distributes and calculates according to catalytically cracked stock meter, and gained reaction result is in table 4.

Table 4

As can be seen from Table 4, the integrated methyl alcohol processing of heavy oil fluid catalytic cracking provided by the present invention producing light olefins method, the method of processing with respect to existing catalyst cracking method with the integrated methyl alcohol of existing catalytic cracking catalyst, 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 experimental result of stripper is carried out the integrated methyl alcohol of heavy oil fluid catalytic cracking and ethanol and is injected simultaneously in the present embodiment explanation on the middle-scale device of successive reaction-regenerative operation of embodiment 1.

The preparation process of the present embodiment catalyzer is as follows: by butt meter (molecular sieve weight basis, lower same) 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 (CDY, rare earth oxide content 18.7%, lattice constant 2.469nm, degree of crystallinity 46%, Sinopec catalyzer Chang Ling branch office product) 35kg, add SRM molecular sieve 15kg, making beating evenly again.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 DEG C of calcination process 2h, is then used to 0.5%NH ₄the Cl aqueous solution is processed 1.5h 80 DEG C of exchanges, filters, washes, and obtains catalyzer C in 120 DEG C of dry 16h.

Catalyzer C is composed as follows: ZSP-3 zeolite 2%, REY molecular sieve 35%, SRM molecular sieve 15%, aluminium colloidal sol 15%, pseudo-boehmite (in aluminum oxide, lower same) 15%, kaolin 18%.

Catalyzer C carry out integrated reaction evaluate before under 800 DEG C, 100% water vapour, hydrothermal treatment consists 17h.

Catalytically cracked stock is Wuhan mixing oil, is mixed by 70% decompressed wax oil and 30% vacuum residuum.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 allotment.

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 DEG C 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 DEG C.

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; Water vapour enters stripping stage bottom, and the carbon deposited catalyst after stripping enters revivifier regeneration, and 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.Stripping stage middle part arranges upflow tube, spent agent enters spent agent circulation line (in accompanying drawing 16) by upflow tube, under flow to Dehydration of methanol device (in accompanying drawing 15), 15 millimeters of Dehydration of methanol device internal diameters, 3 meters of height, the aqueous solution of methyl alcohol and ethanol directly enters dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 200 DEG C, the mixture of reaction oil gas and catalyzer returns and in settling vessel, realizes finish and separate through dehydration reactor top transfer limes (in accompanying drawing 17).Taking the weight hourly space velocity of methyl alcohol the reaction of methanol conversion as 4h ^-1, the reaction of methanol conversion temperature is 500 DEG C, reaction pressure 0.14Mpa (gauge pressure).Methyl alcohol and ethanol inlet amount are 0.71 with the ratio of catalytically cracked stock inlet amount.

The unified metering of integrated 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 on the middle-scale device of successive reaction-regenerative operation.

Adopt catalytically cracked stock with embodiment 1, reactor types is identical with embodiment 1, only adopts water vapour stripping at stripping stage, does not add oxygenate feedstock in Dehydration of methanol device.

Preparation method 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 (CDY, Sinopec catalyzer Chang Ling branch office product) 35kg, 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 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 DEG C of calcination process 2h, is then used to 1%NH ₄the Cl aqueous solution is processed 1.5h 70 DEG C of exchanges, filters, washes, and in 120 DEG C 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 15%, pseudo-boehmite 15%, kaolin 33%.

Catalyzer C0 carry out integrated reaction evaluate before under 800 DEG C, 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 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 50 kg SRM-8 molecular sieves (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 DEG C, the roasting 2 hours at 600 DEG C of dried molecular sieve, obtains the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification.After roasting, the X-ray powder diffraction result data of sample 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 is carrying out before reaction evaluating under 800 DEG C, 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	27.56	29.43
				Liquefied gas	17.09	27.04	26.67
Gasoline	35.24	36.95	37.08
				Diesel oil	19.10	19.34	19.24
Heavy oil	14.45	14.28	14.38
				Coke	10.51	11.68	11.81
Stock oil transformation efficiency, wt%	66.45	?	?
				Methanol conversion, wt%	?	99.12	100.00
Ethanol conversion, wt%	?	99.53	100.00
				Yield of ethene, wt%	0.79	23.49	25.44
Propene yield, wt%	5.66	11.10	11.69

As can be seen from Table 6, the integrated methyl alcohol processing of heavy oil fluid catalytic cracking provided by the present invention producing light olefins method, methyl alcohol and ethanol approach completely and transform, ethene+propene yield also obviously increases, because the primary product of ethanol dehydration reaction is ethene, increase considerably so yield of ethene has been obtained, the ratio of ethylene/propene obviously improves.Particularly adopt containing after the catalyzer of modification SRM-8 molecular sieve, because modification SRM molecular sieve wherein 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 improve.

Claims (22)

1. the method for a catalytic cracking process and the integrated processing of oxygenatedchemicals, the regenerated cracking catalyst agent under cracking reaction condition, petroleum hydrocarbon raw material being promoted with the steam that enters riser reactor contacts reacts, riser reactor exports the cracking reaction oil gas obtaining and separates in settling vessel with the mixture of catalyzer, obtain cracking reaction oil gas and carbon deposit cracking catalyst, wherein, carbon deposit cracking catalyst falls to entering stripping stage, the cracking reaction oil gas that carbon deposited catalyst in stripping stage carries enters settling vessel top gas pipeline after the water vapour stripping of stripping stage and enters product separation system via entering, carbon deposit cracking catalyst after stripping enters revivifier through spent agent circular route and reacts and burn with main air, the regenerated flue gas obtaining enters smoke energy recovering system from revivifier top flue gas pipeline, riser reactor is returned in the regenerated cracking catalyst agent obtaining, it is characterized in that, the method also comprises in the 10-50 % by weight importing fluidized-bed reactor separating in settling vessel in the carbon deposit cracking catalyst obtaining, contact with the oxygen-containing compound material heating up through heat exchange, carry out dehydration reaction, the mixture of dehydration reaction oil gas product and carbon deposit cracking catalyst returns in settling vessel, dehydration reaction oil gas product wherein and cracking reaction air-fuel mixture, through settling vessel top, gas pipeline enters subsequent products separation system, wherein, said cracking catalyst contains 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct taking catalyst weight as benchmark, the said silicoaluminophosphamolecular molecular sieves with octatomic ring window duct is SRM molecular sieve, 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%,

The mass ratio of described oxygen-containing compound material and petroleum hydrocarbon raw material is 0.01～5.

2. according to the method for claim 1, wherein, said cracking catalyst, taking 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.

3. according to the method for claim 2, wherein, said cracking catalyst, taking weight as benchmark 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.

4. according to the process of claim 1 wherein, Me1 and Me2 modification for said 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 IIA family in the periodic table of elements, VB family, said Me2 is selected from a kind of element or the aluminium in IVB family in the periodic table of elements, 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 the one in magnesium, vanadium, copper and boron.

6. according to the method for claim 4, wherein, Me2 is selected from the one in aluminium, titanium and zirconium.

7. according to the method for claim 4, wherein, Me1 is selected from magnesium, and Me2 is selected from aluminium.

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 cracking catalyst by weight, USY, the 2-20%ZSM-5, silicon oxide or the aluminum oxide 15-40 % by weight kaolin that contain 10-20%SRM silicoaluminophosphamolecular molecular sieves, 10-35%.

16. according to the process of claim 1 wherein, said petroleum hydrocarbon 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, the condition of said cracking petroleum hydrocarbons reaction is temperature 400-650 DEG C, pressure 0.01-0.50MPa, reaction times 1-600s, agent-oil ratio 1.0-20.0, the mass ratio of water vapour and petroleum hydrocarbon raw material is 0.01～1.0.

18. according to the process of claim 1 wherein, the condition of said cracking petroleum hydrocarbons reaction is temperature 450-550 DEG C, pressure 0.1-0.40MPa, and reaction times 3-100s, agent-oil ratio 4.0-15.0, the mass ratio of water vapour and petroleum hydrocarbon raw material is 0.05～0.5.

19. according to the process of claim 1 wherein, said oxygenatedchemicals dehydration fluid bed reactor is fast bed or bubbling bed.

20. according to the process of claim 1 wherein, said oxygenatedchemicals is selected from one or more in methyl alcohol, dme and ethanol.

21. according to the process of claim 1 wherein, the condition of said oxygenatedchemicals dehydration reaction is temperature 400-600 DEG C, pressure 0.01-0.50MPa, oxygen-containing compound material reaction velocity 0.1-100h ^-1, oxygen-containing compound material preheating temperature is 50-500 DEG C.

22. according to the method for claim 21, and wherein, the condition of said oxygenatedchemicals dehydration reaction is temperature 450-550 DEG C, pressure 0.1-0.4MPa, oxygen-containing compound material reaction velocity 0.5-10h ^-1, oxygen-containing compound material preheating temperature is 150-400 DEG C.