CN102816590B - Method for producing low-carbon olefin through petroleum hydrocarbon oil catalytic cracking - Google Patents

Abstract

Provided is a method for producing low-carbon olefin through petroleum hydrocarbon oil catalytic cracking. A petroleum hydrocarbon raw material and a catalyst regenerating agent which enters a lift pipe reactor and is used for steam lifting are contacted and perform cracking reaction under the condition of the cracking reaction. The method is characterized by further comprising the step of introducing 10-50 weight% of carbon deposit catalyst into a fluidized bed reactor to be contacted with and react with an oxygen-containing compound raw material, wherein the feeding of the oxygen-containing compound raw material includes two portions, one feeding portion containing ethanol and/or diethyl ether enters from the bottom of the fluidized bed reactor after subjected to heat exchange, the other feeding portion with no ethanol and/or diethyl ether enters from the middle-lower portion of the reactor after subjected to heat exchange and temperature rise, and a mixture of a reaction oil-gas product and the catalyst returns to a precipitator through a conveying line at the top of the fluidized bed reactor to be mixed with cracking reaction oil and gas and the carbon deposit catalyst.

Description

A kind of method of oil hydrocarbon oil catalytic cracking low-carbon olefines high-output

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 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 Material s, 1999, (29): 145157 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 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 ℃, 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) 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: temperature of reaction 400-420 ℃, 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, 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.

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 subject to the impact of cracking hydrocarbon ils contamination of raw material carbon deposit, still can be in the catalyzed conversion function providing 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 catalytic cracking method for hydrocarbon oil of the productivity of low carbon olefin hydrocarbon of catalytic cracking process, 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.

The method of a kind of oil hydrocarbon oil catalytic cracking low-carbon olefines high-output provided by the invention, the catalyst regeneration agent under cracking reaction condition, petroleum hydrocarbon raw material being promoted with the steam that enters riser reactor contacts carries out cracking reaction, leg outlet obtains the mixture of cracking reaction oil gas and carbon deposited catalyst, in settling vessel, separation obtains 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 deposited catalyst falls to entering stripping stage, carbon deposited 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 catalyst regeneration agent obtaining, it is characterized in that the method also comprises carbon deposited catalyst introducing fluidized-bed reactor and the oxygen-containing compound material contact reacts of 10-50 % by weight, the charging of said oxygen-containing compound material is divided into two strands, wherein one charging of ethanol and/or ether enters from fluidized-bed reactor bottom after heat exchange, after other one oxygen-containing compound material heat exchange intensification containing ethanol and/or ether, in the middle and lower part of reactor, do not enter, reaction oil gas product and catalyst mixture return to settling vessel through fluidized-bed reactor top transfer limes to be mixed with cracking reaction oil gas and carbon deposited catalyst, said catalyzer be take weight and is contained 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct as benchmark.

The beneficial effect of method provided by the invention is:

The present invention carries out the dehydration of existing catalytic cracking unit and oxygenatedchemicals integrated, makes the products scheme of catalytic cracking process more flexible, processes raw material more extensive.The primary product dewatering due to oxygenatedchemicals 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 catalytic cracking process stripping steam.Because oxygenatedchemicals dehydration reaction occurs in newly-increased reactor, wherein one oxygen-containing compound material dehydration reaction for ethanol and/or ether is thermo-negative reaction, other oxygen-containing compound materials are as methyl alcohol, the dehydration reaction of dme is thermopositive reaction, two kinds of oxygen-containing compound material sectional feedings, spent agent is the oxygenatedchemicals dehydration reaction through absorbing heat first, catalyst temperature reduces, again with other one oxygenatedchemicals as methyl alcohol and/or dme contact reacts, thereby the dehydration reaction condition of methyl alcohol and/or dme is more easily controlled, generate olefine selective higher.

Method of the present invention, device, technique 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, less investment, is easy to realize.

Accompanying drawing explanation

Accompanying drawing is the process system schematic diagram of the inventive method.

Embodiment

A kind of method of oil hydrocarbon oil catalytic cracking low-carbon olefines high-output, the catalyst regeneration agent under cracking reaction condition, petroleum hydrocarbon raw material being promoted with the steam that enters riser reactor contacts carries out cracking reaction, leg outlet obtains the mixture of cracking reaction oil gas and carbon deposited catalyst, in settling vessel, separation obtains 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 deposited catalyst falls to entering stripping stage, carbon deposited 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 catalyst regeneration agent obtaining, it is characterized in that the method also comprises carbon deposited catalyst introducing fluidized-bed reactor and the oxygen-containing compound material contact reacts of 10-50 % by weight, the charging of said oxygen-containing compound material is divided into two strands, wherein one charging of ethanol and/or ether enters from fluidized-bed reactor bottom after heat exchange, after other one oxygen-containing compound material heat exchange intensification containing ethanol and/or ether, in the middle and lower part of reactor, do not enter, reaction oil gas product and catalyst mixture return to settling vessel through fluidized-bed reactor top transfer limes to be mixed with cracking reaction oil gas and carbon deposited catalyst, said catalyzer be take 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, the reaction conditions of described cracking petroleum hydrocarbons reaction is temperature 300-650 ℃, pressure 0.01-0.50MPa, and 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; Preferred reaction conditions is temperature of reaction 350-550 ℃, 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.

In method provided by the invention, said ethanol and/or ether can be any mixture, preferred alcohol and the aqueous solution thereof of ethanol, ether or they and water.Said other one oxygen-containing compound material that does not contain ethanol and/or ether is preferably methyl alcohol and/or dme.Ethanol and/or ether raw material dehydration reaction are thermo-negative reaction, other oxygen-containing compound materials as the dehydration reaction of methyl alcohol, dme be thermopositive reaction, oxygen-containing compound material divides two stock section feedings, spent agent first carries out dehydration reaction through ethanol and/or the ether of heat absorption, catalyst temperature reduces, again with methyl alcohol and/or dme contact reacts, thereby the dehydration reaction condition of methyl alcohol and/or dme is more easily controlled, generated olefine selective higher.

In method provided by the invention, said carbon deposited catalyst reacts with oxygenatedchemicals in fluidized-bed reactor, oxygenatedchemicals dehydration, reaction conditions is temperature of reaction 400-600 ℃, reaction pressure 0.01-0.50MPa, in two bursts of oxygen-containing compound material total amounts, reaction velocity 0.1-100h ^-1, oxygen-containing compound material preheating temperature 50-500 ℃; Preferred reaction conditions is temperature of reaction 450-550 ℃, pressure 0.1-0.4MPa, reaction velocity 0.5-10h ^-1, oxygen-containing compound material preheating temperature 150-400 ℃.

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.More preferably there is 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.

In the catalyzer of method provided by the invention, 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, 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 the structure expression of 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, a kind of in preferably magnesium, vanadium, copper and boron wherein, 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 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 methanol-to-olefins reaction 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, said catalyzer contains SRM silicoaluminophosphamolecular molecular sieves, REY molecular sieve, ZSM-5 molecular sieve, aluminum oxide and kaolin.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 accompanying drawing and specific embodiment, the present invention is described in further detail.

Referring to accompanying drawing, the schematic flow sheet of the technique that accompanying drawing is method provided by the invention.

Adopt 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 on settling vessel top enters fractionating system and carries out separation, the catalyzer of carbon deposit falls to entering stripping stage 6, partial product Pd/carbon catalyst enters oxygenatedchemicals dehydration reactor 15 and oxygenatedchemicals contact reacts through spent agent circular route 16, the oxygen-containing compound material charging of oxygenatedchemicals dehydration reactor 15 is divided into 2 strands, wherein the oxygen-containing compound material 18 containing ethanol and/or ether enters with carbon deposited catalyst and contacts from dehydration reactor 15 bottoms after interchanger 19 heats up, other oxygen-containing compound materials 13 containing methyl alcohol and/or dme enter with catalyzer and contact in the middle and lower part of reactor 15 after interchanger 14 heats up, reaction oil gas product in dehydration reactor 15 and catalyst mixture return to settling vessel after gas-solid sharp separation through reactor top transfer limes 17, carbon deposited catalyst declines and enters stripping stage, reaction oil gas rises and flows out from settling vessel top, 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 6, 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.

Below by embodiment, the invention will be further described, but not thereby limiting the invention.

Embodiment 1

Method of the present invention is carried out in the present embodiment explanation on the middle-scale device of successive reaction-regenerative operation.

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 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; 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 ethanolic solution of 80% weight directly enters dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 200 ℃, the methanol aqueous solution of 80% weight enters, 1 meter of dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 220 ℃, the mixture of reaction oil gas and catalyzer returns to through dehydration reactor top transfer limes (in accompanying drawing 17) that in settling vessel, to realize finish separated.The weight hourly space velocity of methyl alcohol the reaction of methanol conversion of take is 2h ^-1, methanol conversion temperature out is 520 ℃, reaction pressure 0.1Mpa (gauge pressure).Methanol feeding amount is 0.85 with the ratio of catalytically cracked stock inlet amount, and the ratio of methyl alcohol and ethanol feed weight is 2.04.

Catalytically cracked stock is Wuhan mixing oil, by 70% decompressed wax oil and 30% vacuum residuum, mixes (feedstock property is in Table 2).The industrial methanol that methanol aqueous solution is 97% by purity adds deionized water to allocate, and the industrial alcohol that aqueous ethanolic solution is 95% 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

The cracking catalyst A preparation method who uses in the present embodiment 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, lower same) 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, lower same) 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%, lower same) 80kg making beating, add butt meter 40Kg kaolin (China Kaolin Co., Ltd's product, lower same), making beating is even, then adds above-mentioned molecular sieve pulp, pulls an oar evenly, sprays dry, collects 30-150 μ m scope microsphere particle.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 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 20%, kaolin 40%.

Catalyst A carry out integrated reaction evaluate before under 800 ℃, 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 4.

Comparative example 1

Comparative example 1 explanation 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 at stripping stage, adopts water vapour stripping, does not add methyl alcohol and ethanol charging in Dehydration of methanol device.Catalyzer is A0.

The preparation process of catalyst A 0 is as follows:

By butt meter ZSP-2 zeolite 20kg, add the making beating of 35kg deionized water, add DASY2.0 molecular sieve 10kg, the uniform molecular sieve pulp of pulling an oar.By aluminium colloidal sol 80kg making beating, add butt meter 50Kg kaolin, 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.

Catalyst A 0 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

This comparative example explanation adopts the catalyzer of containing silica alumina phosphate molecular sieve on the middle-scale device of successive reaction-regenerative operation, but carries out the effect of catalytic cracking reaction during without oxygenate feedstock.

Adopt catalytically cracked stock and catalyzer with embodiment 1, reactor types is identical with embodiment 1, only at stripping stage, adopts water vapour stripping, does not add methyl alcohol and ethanol charging in Dehydration of methanol device.

Gained reaction result is in Table 4.

Embodiment 2

Method provided by the invention is carried out in embodiment 2 explanations on the middle-scale device of successive reaction-regenerative operation.

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; 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 ethanolic solution of 80% weight directly enters dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 200 ℃, the methanol aqueous solution of 80% weight enters, 1 meter of dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 220 ℃, the mixture of reaction oil gas and catalyzer returns to through dehydration reactor top transfer limes (in accompanying drawing 1 17) that in settling vessel, to realize finish separated.The weight hourly space velocity of methyl alcohol methanol conversion of take is 1h ^-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, and the ratio of methyl alcohol and ethanol feed weight is 0.74.

Catalytically cracked stock is Wuhan mixing oil, by 70% decompressed wax oil and 30% vacuum residuum, is mixed.The industrial methanol that methanol aqueous solution is 97% by purity adds deionized water to allocate, and the industrial alcohol that aqueous ethanolic solution is 95% by purity adds deionized water to allocate.

Preparation method is as follows:

By butt meter ZSP-2 zeolite 20kg, add the making beating of 35kg deionized water, add DASY2.0 molecular sieve 10kg, then add SAPO-34 molecular sieve (Sinopec catalyzer Jian Chang branch office pilot product) 20kg, making beating is evenly.By aluminium colloidal sol 80kg making beating, add butt meter 30Kg kaolin, 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 the catalyst B in the inventive method.

Catalyst B is composed as follows: ZSP-2 zeolite 20%, DASY2.0 molecular sieve 10%, has the SAPO-34 molecular sieve 20% of CHA structure, aluminium colloidal sol 20%, kaolin 30%.

Catalyst B carry out integrated reaction evaluate before under 800 ℃, 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 4.

Table 4

?	Comparative example 1	Comparative example 2	Embodiment 1	Embodiment 2
					Product distributes, wt%	?	?	?	?
Dry gas	3.52	4.26	25.59	33.72
					Liquefied gas	24.37	25.00	38.53	35.92
Gasoline	21.45	19.95	22.07	22.05
					Diesel oil	15.93	15.91	16.16	16.07
Heavy oil	26.17	23.73	23.75	23.65
					Coke	8.57	11.16	12.83	12.64
Stock oil transformation efficiency, wt%	57.91	60.36	?	?
					Methanol conversion, wt%	?	?	97.44	99.12
Ethanol conversion, wt%	?	?	99.57	99.53
					Yield of ethene, wt%	1.28	2.01	21.29	30.14
Propene yield, wt%	9.98	9.59	16.97	16.47

As can be seen from Table 4, method provided by the present invention, with respect to existing catalyst cracking method, methyl alcohol and ethanol approach completely and transform, and ethene+propene yield obviously increases, and particularly yield of ethene has been obtained and has been increased considerably, and the ratio of ethylene/propene obviously improves.

Embodiment 3

The experimental result of the inventive method is carried out in the present embodiment explanation on the middle-scale device of successive reaction-regenerative operation.

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; 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 oxygenatedchemicals dehydration reactor (in accompanying drawing 15), 15 millimeters of dehydration reactor internal diameters, 3 meters of height, the aqueous ethanolic solution of 80% weight directly enters dehydration reactor bottom and carbon deposited catalyst contact reacts after being preheating to 200 ℃, the methanol aqueous solution of 80% weight enters dehydration reactor bottom after being preheating to 200 ℃, apart from 1 meter of eminence of reactor bottom and carbon deposited catalyst contact reacts, the mixture of reaction oil gas and catalyzer returns to through dehydration reactor top transfer limes (in accompanying drawing 17) that in settling vessel, to realize finish separated.The weight hourly space velocity of methyl alcohol the reaction of methanol conversion of take is 4h ^-1, the reaction of methanol conversion temperature is 500 ℃, reaction pressure 0.14Mpa (gauge pressure).Methyl alcohol and total ethanol inlet amount are 0.71 with the ratio of catalytically cracked stock inlet amount, and the ratio of methyl alcohol and ethanol feed weight is 0.74.

Catalytically cracked stock, with embodiment 1, is Wuhan mixing oil, by 70% decompressed wax oil and 30% vacuum residuum, is mixed.The industrial methanol that methanol aqueous solution is 97% by purity adds deionized water to allocate, and the industrial alcohol that aqueous ethanolic solution is 95% by purity adds deionized water to allocate.

In the present embodiment, catalyzer C preparation method 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, lower same) 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, lower same) 35kg, then add SRM molecular sieve (SRM-8, Sinopec catalyzer Jian Chang branch office product) 15kg, making beating evenly.By butt meter 15Kg pseudo-boehmite (Chalco Shandong Aluminum Plant product, lower with) add the making beating of 100kg deionized water, add 2kg concentrated hydrochloric acid (commercially available, HCl content 31.5% weight, lower same) making beating is evenly, add aluminium colloidal sol 60kg making beating again, add butt meter 18Kg kaolin, making beating evenly, add again above-mentioned molecular sieve pulp, 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 special-purpose catalyst C of the present invention.

Catalyzer C is composed as follows: ZSP-3 zeolite 2%, CDY 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.

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.

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, and 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%, CDY molecular sieve 35%, the SRM 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.

Comparative example 3

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 at stripping stage, adopts water vapour stripping, does not add oxygenate feedstock in Dehydration of methanol device.

Conventional catalytic cracking catalyst preparation method is as follows:

By butt meter ZSP-3 zeolite 2kg, add the making beating of 35kg deionized water, add CDY molecular sieve 35kg, making beating is evenly.Butt meter 15Kg pseudo-boehmite is added to the making beating of 100kg deionized water, add the making beating of 2kg concentrated hydrochloric acid evenly, add again aluminium colloidal sol 60kg making beating, add butt meter 33Kg kaolin, making beating is even, then adds above-mentioned molecular sieve pulp, and making beating evenly, spraying is dry, collects 30-150 μ m scope microsphere particle.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 conventional catalytic cracking catalyst C0.

Catalyzer C0 is composed as follows: containing the ZSP-3 zeolite 2% with MFI structure, CDY molecular sieve 35%, aluminium colloidal sol 15%, pseudo-boehmite 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.

Table 6

?	Comparative example 3	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 alcohol 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, method provided by the present invention, methyl alcohol and ethanol approach completely and transform, ethene+propene yield also obviously increases, particularly yield of ethene has been obtained and has been increased considerably, because the primary product of ethanol dehydration reaction is ethene, so having obtained, yield of ethene increases considerably, the ratio of ethylene/propene obviously improves.Particularly adopt containing after the catalyzer of modification SRM molecular sieve, because modification SRM molecular sieve 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 (24)

1. the method for an oil hydrocarbon oil catalytic cracking low-carbon olefines high-output, the catalyst regeneration agent under cracking reaction condition, petroleum hydrocarbon raw material being promoted with the steam that enters riser reactor contacts carries out cracking reaction, leg outlet obtains the mixture of cracking reaction oil gas and carbon deposited catalyst, in settling vessel, separation obtains 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 deposited catalyst falls to entering stripping stage, carbon deposited 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 catalyst regeneration agent obtaining, it is characterized in that the method also comprises carbon deposited catalyst introducing fluidized-bed reactor and the oxygen-containing compound material contact reacts of 10-50 % by weight, the charging of said oxygen-containing compound material is divided into two strands, wherein one charging of ethanol and/or ether enters from fluidized-bed reactor bottom after heat exchange, after other one oxygen-containing compound material heat exchange intensification containing ethanol and/or ether, in the middle and lower part of reactor, do not enter, reaction oil gas product and catalyst mixture return to settling vessel through fluidized-bed reactor top transfer limes to be mixed with cracking reaction oil gas and carbon deposited catalyst, said catalyzer be take weight and is contained 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct as benchmark.

2. according to the method for claim 1, wherein, said catalyzer 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.

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% 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 claim 1,2 or 3 method, wherein, the said silicoaluminophosphamolecular molecular sieves with octatomic ring window duct be selected from there is CHA, one or more in the silicoaluminophosphamolecular molecular sieves of AEI, RHO crystalline structure, or there is the silicoaluminophosphamolecular molecular sieves of CHA/AEI intergrowth phase.

5. according to the method for claim 4, wherein, the said silicoaluminophosphamolecular molecular sieves with octatomic ring window duct is selected from one or more in SAPO-34, SAPO-18 and SRM molecular sieve.

6. according to the method for claim 5, wherein, said SRM molecular sieve, X-ray diffraction spectral data at least contains the diffraction peak shown in following table, 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%,

7. according to the method for claim 6, 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.

8. according to the method for claim 7, wherein Me1 is selected from a kind of in magnesium, vanadium, copper and boron.

9. according to the method for claim 7, wherein, Me2 is selected from a kind of in aluminium, titanium and zirconium.

10. 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.

11. according to the method for claim 10, and wherein, the said MFI of having crystalline structure Si-Al molecular sieve is ZSM-5.

12. according to the method for claim 11, and 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.

13. according to the method for claim 12, 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.

14. 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.

15. according to the method for claim 14, and wherein, the said FAU of having crystalline structure Si-Al molecular sieve is Y zeolite.

16. according to the method for claim 15, and wherein, said Y zeolite is selected from USY, phosphorus and/or rare earth modified Y zeolite.

17. according to the process of claim 1 wherein, said catalyzer contains SRM silicoaluminophosphamolecular molecular sieves, REY molecular sieve, ZSM-5 molecular sieve, aluminum oxide and kaolin.

18. 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.

19. 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.

20. according to the process of claim 1 wherein, the reaction conditions of said cracking petroleum hydrocarbons reaction is temperature 300-650 ℃, 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.

21. according to the process of claim 1 wherein, the reaction conditions of said cracking petroleum hydrocarbons reaction is temperature 350-550 ℃, pressure 0.1-0.40MPa, 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.

22. according to the process of claim 1 wherein, said in addition one oxygen-containing compound material be methyl alcohol and/dme.

23. according to the process of claim 1 wherein, in said fluidized-bed reactor, the catalytic condition of carbon deposited catalyst and oxygen-containing compound material is temperature 400-600 ℃, and pressure is 0.01-0.50MPa, oxygen-containing compound material reaction velocity 0.1-100h ^-1.

24. according to the method for claim 23, wherein, and said temperature 450-550 ℃, pressure 0.1-0.4MPa, oxygen-containing compound material reaction velocity 0.5-10h ^-1.