CN102816591A - Catalytic cracking method - Google Patents
Catalytic cracking method Download PDFInfo
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- CN102816591A CN102816591A CN2011101532261A CN201110153226A CN102816591A CN 102816591 A CN102816591 A CN 102816591A CN 2011101532261 A CN2011101532261 A CN 2011101532261A CN 201110153226 A CN201110153226 A CN 201110153226A CN 102816591 A CN102816591 A CN 102816591A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A catalytic cracking method includes: hydrocarbon oil cracking raw materials and catalyst regenerant lifted by steam and entering a riser reactor are contacted for the cracking reaction under the cracking reaction condition, the mixture of catalysts and cracking reaction oil gas is obtained at an outlet of a riser and separated in a settler to obtain cracking reaction oil gas and carbon deposit catalysts, the reaction oil gas ascends to enter a product separation system through an oil gas pipeline on the top of the settler, the deposit catalysts descend to enter a steam stripping section, the deposit catalysts subjected to steam stripping enter a regenerator through a spent catalyst circulation line to react with prevailing wind to be burnt, the obtained regenerated fume enters a fume energy recovery system through a fume pipe on the top of the regenerator, and the obtained catalyst regenerant returns to the riser reactor. The catalytic cracking method is characterized by further including steps of cooling 10-50wt% of the carbon deposit catalysts by means of an external heat collection type steam generator, and entering a fluidized bed reactor to contact with an oxygenated compound heated in heat exchange to complete the dehydration reaction, wherein the obtained mixture of catalysts and oil gas products of the dehydration reaction returns to the settler via the top of the fluidized bed reactor to be mixed with the cracking reaction oil gas and the carbon deposit catalysts in the settler.
Description
Technical field
The invention relates to a kind of integrating heavy oil catalytic cracking with oxygen-containing compound catalyzed conversion increases the method for 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 (like oxyethane, Vilaterm, SE and Vestolen PP 7052 etc.).Along with the raising of China's rapid economy development and 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 technology productions such as petroleum naphthas; The whole world surpasses the ethene of ultimate production 90% and about 70% propylene is made by cracking petroleum hydrocarbon vapor, and remaining about 28% propylene is from catalytic cracking of petroleum hydrocarbon technology.But since two thousand five, world's crude production rate descends from peak value continuously, and oil price continues high-order operation, makes that the raw material supply of light olefin is nervous, production cost rises.The crude oil in China shortage of resources, the external interdependency of oil is high, and not only energy security is on the hazard, and the development of the insufficient problem restriction of crude resources petrochemical industry, therefore develops and renewablely produces ethene with alternative materials, propylene becomes Development Trend.
Methyl alcohol is as a kind of substitute energy, and wide material sources can be by coal, Sweet natural gas and biomass production, and its overall throughput worldwide constantly increases, and supplies with to continue to surpass demand.At present, also be tending towards ripe, become the technology that is hopeful to substitute petroleum naphtha route system alkene most by low-carbon alkenes such as methyl alcohol system ethene, propylene (Methanol to Olefin is called for short MTO) technology.
With the technology of methanol production light olefin (MTO) and last century the eighties at first propose by Mobil company.Nineteen ninety-five UOP/Hydro has developed jointly successfully fluidized-bed MTO technology; Adopt aperture SAPO-34 silicoaluminophosphamolecular molecular sieves catalyzer; The SAPO-34 molecular sieve is by the silicoaluminophosphamolecular molecular sieves (USP4440871) of U.S. UCC company in the invention early 1980s, in methanol to olefins reaction, shows the high olefin selectivity; After the cracking of olefins technology (OCP) of this MTO technology and Total company was integrated, the ethene of new MTO technology and the carbon back selectivity of propylene can reach more than 90%.The DMTO technology 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 sieves catalyzer, and the carbon back selectivity of the ethene of catalyzer of new generation and propylene can reach more than 90%.The FMTP technology of Tsing-Hua University exploitation adopts aperture CHA/AEI intergrowth phase silicoaluminophosphamolecular molecular sieves catalyzer, 2008 in Huaihe River group has carried out industrial demonstration, year process 30,000 tons of 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) technology, adopts ZSM-5 sieve catalyst (EP 0448000), and the MTP fixed-bed reactor that methyl alcohol partly is converted into 3 parallel connections of the laggard people of dme (DME) react, and reactor drum is two to open one and be equipped with.During normal running, single reactor methanol transformation efficiency reaches more than 90%, and through the cyclical operation of product alkene, the propylene selectivity is improved, and the carbon back selectivity of propylene can reach more than 71%.(petrochemical technology and economy, 2008,24 (4): 34)
This shows that it is ripe that the methanol-to-olefins technology has been tending towards, but it is huge to build large-scale complete MTO process unit investment, the methanol-to-olefins project is still located in the 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 reduced to about 20%, enterprise production operation 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 replenish product demands such as low-carbon alkene.Because the reaction-regeneration system and the existing RFCC technology of fluidized-bed MTO technology have similarity, two kinds of reaction process conditions are also had something in common, and the researchist endeavours two kinds of Technology couplings can be reduced investment outlay.
CN 86101079A discloses methyl alcohol as reactant with the petroleum hydrocarbon method of gas oil catalytic cracking for example; Reactant contacts with fine grain ZSM-5 catalyzer, the catalytic cracking reaction heat balance haply of methanol conversion reaction and heat absorption that makes heat release.
Microporous and Mesoporous Materials, 1999, (29): 145-157 also with the Dehydration of methanol of heat release and the cracking hydrocarbon reaction coupling of heat absorption, has obtained thermally equilibrated reaction process.Utilize modified ZSM-5 zeolite to be catalyzer,, reduced the productive rate of methane and COx in the independent Dehydration of methanol, hydrogen when obtaining higher yield of light olefin 600-680 ℃ of reaction.
CN1206319A discloses the approach that utilizes the differential responses PROCESS COUPLING to reduce reaction heat effect; The organic oxygen-containing compound of heat release is transformed and the cracking petroleum hydrocarbons reaction coupling of absorbing heat; Adopt fluidized-bed reactor; Containing the Si/Al weight ratio is 25-100, and the aperture is the method for carrying out catalytic cracking to prepare lower carbon olefin under the effect of solid acid catalyst and high-temperature vapor of molecular sieve of 0.4-0.7nm.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 " have studied methyl alcohol as catalytic cracking part charging reaction process; The influence of methyl alcohol adding mode wherein has been discussed; Comprise the charging simultaneously of methyl alcohol and raw 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 raw oil chargings; Inject stripping stage, settling section for methyl alcohol; The generation that is unfavorable for low-carbon alkene is thought in this research, and confirmed methyl alcohol suitable add implantation site and mode for bottom riser reactor, and prior to the raw oil charging.
" chemical industry journal; 2006; 57 (4): 785-790 " studied the reaction process of methyl alcohol as the catalytic cracking part material, on the 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 is formed.
" petrochemical complex; 2009; 38 (3): 267-272 " studied the research of methyl alcohol and the mixing upgrading of FCC gasoline on the small-sized riser reactor, and the result shows that methyl alcohol and FCC gasoline are mixing when improving quality of gasoline, helps increasing production reacted gas and improves liquid yield.The mixing suitable condition of gained methyl alcohol and FCC gasoline is: 400～420 ℃ of temperature of reaction, mixing ratio are 5%～10%, agent-oil ratio 10～12, and the product content of olefin in gasoline descends 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; Other tells a part of catalytic cracking regenerated catalyst cooling back and contacts with ethanol raw material; Said catalyzer contains y-type zeolite, and the gained reaction product separator of flowing through obtains carbon deposited catalyst and purpose product ethene, and carbon deposited catalyst gets into revivifier and carries out coke burning regeneration.This method ethanol conversion is up to more than 99%, and the content of ethene is up to more than the 95 body % in the reformed gas product.
US2006/0229481A1 discloses the ethers that in hydro carbons heat or catalytic cracking process, adds CxH2x+1OCyH2y+1 (x and y are 1-30), ethers in reaction at least partial cracking become alkene and corresponding alcohol, and reduce the hydrocarbon cracking green coke.This is invented employed catalyzer and contains the tetrahedral crystal oxide material, and is optional from zeolite, silicate, aluminium phosphate molecular sieve (AlPOs) and silicoaluminophosphamolecular molecular sieves (SAPOs), preferred zeolite.
CN101210190A discloses the method that a kind of heavy petroleum hydrocarbon and methyl alcohol co-fed are produced low-carbon alkene and gasoline.This method utilizes methyl alcohol to replace the part heavy feed stock on fluidized catalystic cracker; Containing mass ratio is 1: on the shape-selective molecular sieve of 0.1-1.0 and the composite molecular sieve catalyst of large pore molecular sieve; Refine out the premium product jointly, simultaneously increased low carbon olefine output.Used methyl alcohol accounts for the 1.5-50% (weight) of raw oil, and water injection rate accounts for the 5-50% of raw 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.
Visible from prior art, methanol conversion and catalytic cracking of petroleum hydrocarbon coupling reaction receive 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 lot of test; The viewpoint conclusion that is different from prior art is; After in cracking catalyst, adding a kind of active ingredient that is used for oxygenate; Even this cracking catalyst under catalytic cracking condition coking deactivation, need return revivifier and carry out under the regenerated situation, the active component that wherein is used for oxygenate does not receive cracking hydrocarbon ils contamination of raw material effect of coke deposition, still can be in the catalyzed conversion function that provides for oxygenatedchemicals; Oxygenatedchemicals has the transformation efficiency near 100%, thereby improves the yield that comprises the whole low-carbon alkene of ethene and propylene in the cracking hydrocarbon oil reaction product.
Therefore, main purpose of the present invention is to provide a kind of prior art that is different from, and can expand the catalyzed cracking processing raw material; Improve the ethene of catalytic cracking process and the catalyst cracking method of productivity of propylene; But the ratio of this method flexible catalytic cracking light olefin productive rate and olefin product kind, technology is simple, technology maturation; Less investment is easy to realize.
Catalyst cracking method provided by the invention; The catalyst regeneration agent that under the cracking reaction condition, petroleum hydrocarbon raw material and the steam that gets into riser reactor is promoted contacts carries out cracking reaction, and the riser tube outlet obtains cracking reaction oil gas and mixture of catalysts, in settling vessel, separates obtaining cracking reaction oil gas and carbon deposited catalyst; Wherein, Reaction oil gas rises, and gas pipeline gets into product separation system through the settling vessel top, and carbon deposited catalyst falls to getting into stripping stage, and the carbon deposited catalyst behind the stripping burns through spent agent circular route entering revivifier and main air reaction; The flue gas pipeline gets into smoke energy recovering system to the regenerated flue gas that obtains from the revivifier top; Riser reactor is returned in the catalyst regeneration agent that obtains, and it is characterized in that, this method also comprises the 10-50 weight % in the said carbon deposited catalyst through an outside heat removing steam generator cooling; Get into fluidized-bed reactor again; Contact with oxygenatedchemicals that heat exchange heats up and to carry out dehydration reaction, gained dehydration reaction oil gas product and catalyst mixture return settling vessel through the fluidized-bed reactor top, mix with cracking reaction oil gas and carbon deposited catalyst in the settling vessel.Wherein, to contain with weight be the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct of benchmark 1～90% to said catalyzer.
The beneficial effect of method provided by the invention is:
The present invention carries out existing heavy oil catalytically cracking equipment and oxygenate integrated, makes the products scheme of catalytic cracking process more flexible, and it is more extensive to process raw material.Because the primary product of oxygenate is ethene and propylene, therefore increased the yield of high-value product light olefin.
Simultaneously, the water that oxygenate generates substitutes part stripping steam, can reduce the consumption of original catalytic cracking process stripping steam.
Because the oxygenatedchemicals dehydration reaction takes place in newly-increased reactor drum; And spent agent has reduced temperature through outside heat removing steam generator generation steam earlier; Again with the oxygenatedchemicals contact reacts, thereby the dehydration reaction condition of oxygenatedchemicals is controlled more easily, it is higher to generate olefine selective.
The technology of apparatus of the present invention is simple, and the reaction-regeneration system device, the product separation that make full use of catalytic cracking process reclaim technology and Cooling and Heat Source, technology maturation, and less investment is easy to realize.
Description of drawings
Fig. 1 is the integrated processing oxygenatedchemicals of a RFCC of the present invention successive reaction reclaiming process system schematic.Among the figure, catalytically cracked stock 1, riser reactor 2, water vapour 3, settling vessel 4, reaction oil gas 5; Stripping stage 6, water vapour 7, reclaimable catalyst circular route 8, revivifier 9, regenerated catalyst circular route 10, main air air 11; Burn flue gas 12, oxygen-containing compound material 13, interchanger 14, oxygenatedchemicals dehydration reactor 15, circular route 16; Transfer limes 17, spent agent circular route 18, softening water 19, steam 20, outside heat removing vapour generator 21.
Embodiment
Catalyst cracking method provided by the invention; The catalyst regeneration agent that under the cracking reaction condition, petroleum hydrocarbon raw material and the steam that gets into riser reactor is promoted contacts carries out cracking reaction, and the riser tube outlet obtains cracking reaction oil gas and mixture of catalysts, in settling vessel, separates obtaining cracking reaction oil gas and carbon deposited catalyst; Wherein, Reaction oil gas rises, and gas pipeline gets into product separation system through the settling vessel top, and carbon deposited catalyst falls to getting into stripping stage, and the carbon deposited catalyst behind the stripping burns through spent agent circular route entering revivifier and main air reaction; The flue gas pipeline gets into smoke energy recovering system to the regenerated flue gas that obtains from the revivifier top; Riser reactor is returned in the catalyst regeneration agent that obtains, and it is characterized in that, this method also comprises the 10-50 weight % in the said carbon deposited catalyst through an outside heat removing steam generator cooling; Get into fluidized-bed reactor again; Contact with oxygenatedchemicals that heat exchange heats up and to carry out dehydration reaction, gained dehydration reaction oil gas product and catalyst mixture return settling vessel through the fluidized-bed reactor top, mix with cracking reaction oil gas and carbon deposited catalyst in the settling vessel.Wherein, to contain with weight be the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct of benchmark 1～90% to said catalyzer.
In the method provided by the invention, can in various cracking petroleum hydrocarbons reaction methods, implement, comprise catalytic cracking, catalytic pyrolysis and family's Technology thereof such as ARGG, MIP, DCC, CPP etc.Said 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 obtained by 70% decompressed wax oil and the mixing of 30% vacuum residuum.
In the method provided by the invention, said cracking petroleum hydrocarbons reaction, reaction conditions is temperature 400-650 ℃ in its riser reactor; Pressure 0.01-0.50MPa; Reaction times 1-600s, agent-oil ratio 1-20, the mass ratio of water vapour and petroleum hydrocarbon raw material are 0.01～1.0; Preferred reaction conditions is temperature 450-550 ℃, 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 are 0.05～0.5.
In the method provided by the invention; Said oxygenatedchemicals can be selected from one or more in the group that comprises methyl alcohol, dme, ethanol; In perhaps above-mentioned group one or more 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 the method provided by the invention, the reaction conditions of said oxygenate is that temperature of reaction is 300-600 ℃, and reaction pressure is 0.01-0.50MPa, oxygen-containing compound material reaction velocity 0.1-100h
-1, the oxygen-containing compound material preheating temperature is 50-500 ℃.Preferable reaction temperature 350-550 ℃, pressure 0.1-0.4MPa, oxygen-containing compound material reaction velocity 0.5-10h
-1, the oxygen-containing compound material preheating temperature is 150-400 ℃.
In the method provided by the invention, upflow tube, the 10-50 weight % in the carbon deposited catalyst are set at the stripping stage middle part; Get into the spent agent circulation line through upflow tube; The spent agent temperature here flows to outside heat removing vapour generator shell down for being lower than 10～30 ℃ of riser tube outlets, and the softening water after the deoxidation then gets into from outside heat removing steam generator layer; The steam that takes place is gone out drum from outside heat removing vapour generator overhead stream, further after bakingout process, incorporates steam pipe system into; Get into the oxygenatedchemicals dehydration reactor from the effusive spent agent of outside heat removing vapour generator shell through the spent agent circular route.
In the method provided by the invention, said catalyzer preferably is that benchmark has following composition with weight: 1～90% the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct, 0～50% the mesoporous silicon aluminum molecular screen with ten-ring window duct, 10～50% the macropore Si-Al molecular sieve with twelve-ring window duct, 4～50% inorganic oxide binder and 0～70% clay; It more preferably has following composition: 5～60% have octatomic ring window duct the mesoporous silicon aluminum molecular screen, 12～40% of silicoaluminophosphamolecular molecular sieves, 0～30% with ten-ring window duct have macropore Si-Al molecular sieve, 10～30% inorganic oxide binder and 10～50% the clay in twelve-ring window duct.
The present invention provides in the catalyzer of method, said silicoaluminophosphamolecular molecular sieves be selected from have CHA, the mixture of one or more molecular sieves of 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 has CHA/AEI intergrowth phase structure, and this molecular sieve X-ray diffraction spectral data contains the diffraction peak shown in the table 1 at least, and the structure expression of this molecular sieve is Al
2O
3: 0.1～1.7P
2O
5: 0.01～3SiO
2, in the 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, the contriver finds, after with Me1 and Me2 modification; This molecular sieve is used for the reaction of methanol-to-olefins reaction, has better product selectivity and less by product, and said Me1 is selected from a kind of element or boron or the gallium in IIA family in the periodic table of elements, the VB family; A kind of in preferably magnesium, vanadium, copper and the boron wherein; X representes that Me1 accounts for the molecular fraction of this molecular sieve in oxide compound, x=5～25, preferred x=10～20; Said Me2 is selected from a kind of element or the aluminium in the IVB family in the periodic table of elements, and a kind of y in wherein preferred aluminium, titanium and the zirconium representes that Me2 accounts for the molecular fraction of this molecular sieve, y=2～20, preferred y=3～10 in oxide compound.When modulation modifying element Me1 and the molecular fraction of Me2 in silicoaluminophosphamolecular molecular sieves; Particularly the ratio of x and y is when a suitable scope; Silicoaluminophosphamolecular molecular sieves acidity through modification is moderate, makes when keeping the high yield of title product ethene and propylene in the converting oxygen-containing compound to low-carbon olefins process yield minimizing of by product alkane and coke; 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 for example can be 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:
The silicoaluminophosphamolecular molecular sieves that 1) will be used for modification at first adds the mixing salt solution of two kinds of soluble elements, and concentration of salt solution is respectively 0.0001～0.3 mol, and the exchange temperature is a room temperature, and be 0.5～5 hour swap time;
2) silicoaluminophosphamolecular molecular sieves after the step 1) exchange is carried out 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, 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:
The silicoaluminophosphamolecular molecular sieves that 1) will be used for modification at first adds the soluble salt solution of soluble a kind of element, and concentration of salt solution is 0.0001～0.3 mol, and the exchange temperature is a room temperature, and be 0.5～5 hour swap time;
2) silicoaluminophosphamolecular molecular sieves after step 1 exchange is carried out 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) with step 2) silicoaluminophosphamolecular molecular sieves after the roasting puts in the soluble salt solution of another kind of element again, and strength of solution is 0.0001～0.3 mol, and the exchange temperature is a room temperature, and be 0.5～5 hour swap time;
4) silicoaluminophosphamolecular molecular sieves after the step 3) exchange is carried out 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, obtains described modified silicon aluminum phosphoric acid molecular sieve.
The present invention provides the catalyzer in the method, can also contain the mesoporous silicon aluminum molecular screen in ten-ring window duct, be selected from have MFI, the mixture of one or more molecular sieves of crystalline structure such as AEL.The ZSM-5 molecular sieve is a kind of widely used MFI crystalline structure molecular sieve; By those skilled in the art are known; Include or the organic-free template synthetic through the Hydrogen ZSM-5 of exchange later, calcination process preparation; 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 earth alkali metal is selected from magnesium and/or calcium, one or more in said transition metal chosen from Fe, cobalt, nickel, copper, zinc, titanium and the manganese.PFeZSM-5 of modified ZSM-5 preference such as phosphorus and magnesium-modified PMgZSM-5, phosphorus and iron modification or the like.
The present invention provides the catalyzer in the method, contains the macropore Si-Al molecular sieve in 10～50% twelve-ring window duct, be selected from have FAU, the mixture of one or more molecular sieves of crystalline structure such as MOR, MAZ, BEA.Y zeolite is a kind of molecular sieve of widely used FAU crystalline structure, is known by those skilled in the art know, 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 combine with the chemical treatment super-stable Y molecular sieves (USY) of method preparation of hydro-thermal, contain REUSY, REHY, the REY of REE, and phosphorated PUSY, PREHY, PREY etc.
The present invention provides the catalyzer in the method, can also contain inorganic oxide binder.The instance of said inorganic oxide binder includes but not limited to following kind: the mixture of one or more in aluminum oxide, silicon oxide, phosphagel phosphaljel, amorphous aluminum silicide, zirconium white and the 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 present invention provides the catalyzer in the method, can also contain clay.Said clay comprises the material of synthetic or natural generation, like one or more the mixture in kaolin, kaolinite, smectite, talcum and the wilkinite, also can be by the product of above-mentioned clay after peracid or the processing of alkaline purification process.Preferred clay is a kaolin and through the product of acid or alkaline purification.
The present invention provides in the method, and the most preferred composition of catalyzer is SAPO-34 or SRM silicoaluminophosphamolecular molecular sieves, the USY molecular sieve of 10-35%, the ZSM-5 molecular sieve of 2-20%, the silicon oxide of 15-30% or the kaolin of aluminum oxide (is that silicon sol or aluminium colloidal sol are counted in its precursor) and 15-40% that contains 10-20% in the embodiment.
The present invention provides the catalyzer in the method, and spray drying process moulding that its preparation process adopts this area researchist to say to know or extrusion, compressing tablet sieve the process for granulating moulding then.
Below in conjunction with accompanying drawing and concrete embodiment the present invention is done further detailed description,
Referring to accompanying drawing, accompanying drawing is the schematic flow sheet of catalyst cracking method provided by the invention.
Catalytically cracked stock 1 through preheating gets into riser reactor 2; Contact with the regenerated catalyst that promotes through water vapour 3 from regenerated catalyst circular route 10; The reaction oil gas and the mixture of catalysts of riser tube outlet get into settling vessel 4 behind the gas-solid sharp separation, the effusive reaction oil gas 5 in settling vessel 4 tops gets into fractionating system to be separated; The catalyzer of carbon deposit falls to getting into stripping stage 6; The partial product Pd/carbon catalyst gets into outside heat removing vapour generator 21 through spent agent circular route 18 and carries out heat exchange generation steam 20 with softening water 19; Carbon deposited catalyst after the cooling gets into oxygenatedchemicals dehydration reactor 15 and oxygen-containing compound material 13 contact reactss through circular route 16; Oxygen-containing compound material 13 is through the interchanger 14 laggard fluidized-bed reactor 15 of going into that heats up; Reaction oil gas product and catalyst mixture in the oxygenatedchemicals dehydration reactor 15 return settling vessel 4 behind the gas-solid sharp separation through reactor top transfer limes 17, and carbon deposited catalyst descends and gets into stripping stage 6, and reaction oil gas rises and flows out from settling vessel 4 tops; The reaction oil gas that carbon deposit reclaimable catalysts in the stripping stage 6 carry gets into settling vessel 4 top reaction oil air-flows after via water vapour 7 strippings that get into stripping stage 6; Reclaimable catalyst behind the stripping gets into revivifier 9 through circular route 8 to be generated; Contact coke burning regeneration with the main air air 11 that gets into revivifier; Burn flue gas 12 and remove smoke energy recovering system, regenerated catalyst gets into riser reactor 2 through regenerator circular route 10.
Following embodiment will be described further method provided by the invention, but therefore not limit content of the present invention.
Embodiment 1
Embodiment 1 explanation catalyst cracking method provided by the invention.
Catalytically cracked stock is the Wuhan mixing oil, mixes (feedstock property is seen table 2) by 70% decompressed wax oil and 30% vacuum residuum.Methanol aqueous solution contains 80% weight methyl alcohol, is 97% industrial methanol adding deionized water allotment by purity.
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, ℃ | |
| Over point | 243 |
| 5％ | 294 |
| 70％ | 473 |
Catalyst preparation process is following: with butt meter (molecular sieve weight basis, down together) ZSM-5 zeolite (ZSP-2, iron oxide content 2.2wt%; Phosphorus pentoxide content 2.5wt%, Sinopec catalyzer Shandong branch office product, down together) 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, percent crystallinity 68%, Sinopec catalyzer Shandong branch office product; 10kg down together), (SRM-8, elementary composition amount of substance is than being Al to add the SRM molecular sieve again
2O
3:, 0.81P
2O
5: 0.29SiO
2, the XRD diffraction data is seen table 3, the Sinopec catalyzer is built long branch office product) and 10kg, making beating is evenly.With aluminium colloidal sol (commercially available, Al
2O
3Content is 25%, down with) the 80kg making beating, add butt meter 40Kg kaolin (China Kaolin Co., Ltd's product, down with), making beating evenly adds above-mentioned molecular sieve pulp again, making beating evenly, spraying drying is collected 30-150 mu m range microsphere particle.Above-mentioned catalyzer microballoon in 500 ℃ of calcination process 1h, is used 1%NH then
4The Cl aqueous solution is handled 0.5h 60 ℃ of exchanges, filters, washes, and promptly gets the catalyst A of using in the inventive method in 120 ℃ of dry 16h.
Table 3
Catalyst A is formed as follows: ZSP-2 zeolite 20%, DASY2.0 molecular sieve 10%, SRM-8 molecular sieve 10%, aluminium colloidal sol (in aluminum oxide, down together) 20%, kaolin 40%.
Catalyst A carry out integrated reaction estimate before under 800 ℃ on the warp, 100% water vapour, hydrothermal treatment consists 17h.
The petroleum hydrocarbon catalytic cracking reactor form is a riser tube, and its internal diameter is 16 millimeters, highly is 4 meters; The 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 gets into 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 of the lifting vapor quality flow rate of entering riser tube and the mass flow rate of catalytically cracked stock charging is 0.25: 1; Reaction times is 3 seconds, and the riser tube temperature out is 520 ℃.
The carbon deposited catalyst of riser tube outlet gets into stripping stage under action of gravity, the stripping stage internal diameter is 100 millimeters, highly is 2.5 meters; Water vapour gets into the stripping stage bottom, and the carbon deposited catalyst behind the stripping gets into revivifier regeneration, and the catalyzer after the regeneration turns back to riser reactor; The reaction oil gas that stripping stage goes out through the water vapour stripping rises to the reaction oil gas outlet of settling vessel top and send subsequent separation system.The stripping stage middle part is provided with upflow tube; Spent agent gets into the spent agent circulation line (in the accompanying drawing 18 through upflow tube; The spent agent temperature is 515 ℃); Under flow to outside heat removing vapour generator (in the accompanying drawing 21) shell, softening water (in the accompanying drawing 19) then gets into from outside heat removing steam generator layer bottom, the steam of generation (in the accompanying drawing 20) flows out from outside heat removing vapour generator top; From the effusive spent agent of outside heat removing vapour generator shell through the spent agent circular route (the accompanying drawing 16; The spent agent temperature is 475 ℃;) under flow to Dehydration of methanol device (in the accompanying drawing 15), 15 millimeters of Dehydration of methanol device internal diameters, 3 meters of height; Directly get into dehydration reactor bottom and carbon deposited catalyst contact reacts after methanol aqueous solution is preheating to 200 ℃, transfer limes (in the accompanying drawing 17) returns that the realization finish separates in the settling vessel through the dehydration reactor top for reaction oil gas and mixture of catalysts.Weight hourly space velocity in the reaction of methyl alcohol methanol conversion is 2h
-1, the methanol conversion temperature out is 515 ℃, reaction pressure 0.1Mpa (gauge pressure).The methanol feeding amount is 0.81 with the ratio of catalytically cracked stock inlet amount.The unified metering of integrated reaction products therefrom, products therefrom distributes and calculates according to the catalytically cracked stock meter, and the gained reaction result is seen table 4.
Comparative Examples 1
Comparative Examples 1 explanation adopts conventional catalytic cracking catalyst to carry out the effect of heavy oil catalytic cracking reaction on the middle-scale device of successive reaction-regenerative operation.
Adopt catalytically cracked stock with embodiment 1; Reactor types and embodiment 1 difference are that stripping stage adopts the water vapour stripping, do not have spent agent circulation line shown in the accompanying drawing 1 (in the accompanying drawing 18), outside heat removing vapour generator (in the accompanying drawing 21); Spent agent circulation line (in the accompanying drawing 16); Dehydration of methanol device (in the accompanying drawing 15), reactor top transfer limes (in the accompanying drawing 17), reaction process does not have methanol feeding.
The preparation method is following:
(20kg adds the making beating of 35kg deionized water, adds DASY2.0 molecular sieve 10kg, and making beating evenly with butt meter ZSP-2 zeolite.With aluminium colloidal sol 80kg making beating, add butt meter 50Kg kaolin, making beating evenly adds above-mentioned molecular sieve pulp again, pulls an oar evenly, and spraying drying is collected 30-150 mu m range microsphere particle.Above-mentioned catalyzer microballoon in 500 ℃ of calcination process 1h, is used 1%NH then
4The Cl aqueous solution is handled 0.5h 60 ℃ of exchanges, filters, washes, and promptly gets conventional catalytic cracking catalyst A0 in 120 ℃ of dry 16h.
Catalyst A 0 is formed as follows: ZSP-2 zeolite 20%, DASY2.0 molecular sieve 10%, aluminium colloidal sol 20%, kaolin 50%.
Catalyst A 0 carry out integrated reaction estimate before under 800 ℃ on the warp, 100% water vapour, hydrothermal treatment consists 17h.
The gained reaction result is seen table 4.
Comparative Examples 2
Comparative Examples 2 explanations adopt conventional catalytic cracking catalyst A0 to carry out catalytic cracking on the middle-scale device of successive reaction-regenerative operation.
Adopt catalytically cracked stock and methanol feedstock with embodiment 1; Reactor types is identical with embodiment 1 with reaction conditions, and wherein, spent agent gets into the spent agent circulation line (in the accompanying drawing 18 through stripping stage middle part upflow tube; The spent agent temperature is 515 ℃); Under flow to outside heat removing vapour generator (in the accompanying drawing 21) shell, softening water (in the accompanying drawing 19) then gets into from outside heat removing steam generator layer bottom, the steam of generation (in the accompanying drawing 20) flows out from outside heat removing vapour generator top; From the effusive spent agent of outside heat removing vapour generator shell through the spent agent circular route (the accompanying drawing 16; The spent agent temperature is 495 ℃) under flow to Dehydration of methanol device (in the accompanying drawing 15); Directly get into dehydration reactor bottom and carbon deposited catalyst contact reacts after methanol aqueous solution is preheating to 200 ℃, transfer limes (in the accompanying drawing 17) returns that the realization finish separates in the settling vessel through the dehydration reactor top for reaction oil gas and mixture of catalysts.The methanol conversion temperature out is 515 ℃.
Catalyzer adopts the conventional catalytic cracking catalyst A0 in the Comparative Examples 1, and the methanol feeding amount is 0.85 with the ratio of catalytically cracked stock inlet amount.
The gained reaction result is seen table 4.
Comparative Examples 3
The explanation of this Comparative Examples adopts the catalyst A of embodiment 1 to carry out the effect of catalytic cracking reaction on the middle-scale device of successive reaction-regenerative operation.
Adopt catalytically cracked stock and catalyzer with embodiment 1; Reactor types and embodiment 1 difference is: stripping stage adopts the water vapour stripping, does not have the circulation line of spent agent shown in the accompanying drawing (in the accompanying drawing 18), outside heat removing vapour generator (in the accompanying drawing 21); Spent agent circulation line (in the accompanying drawing 16); Dehydration of methanol device (in the accompanying drawing 15), reactor top transfer limes (in the accompanying drawing 17), reaction process does not have methanol feeding.
The gained reaction result is seen table 4.
Embodiment 2
Catalyst cracking method provided by the invention is carried out in embodiment 2 explanations on the middle-scale device of successive reaction-regenerative operation.
The catalyzer of using in the present embodiment, its preparation method is following:
With butt meter ZSP-2 zeolite 20kg, add the making beating of 35kg deionized water, add DASY2.0 molecular sieve 10kg, add SAPO-34 molecular sieve (the Sinopec catalyzer is built long branch office pilot product) 20kg again, making beating is evenly.With aluminium colloidal sol 80kg making beating, add butt meter 30Kg kaolin, making beating evenly adds above-mentioned molecular sieve pulp again, pulls an oar evenly, and spraying drying is collected 30-150 mu m range microsphere particle.Above-mentioned catalyzer microballoon in 400 ℃ of calcination process 1h, is used 0.5%NH then
4The Cl aqueous solution is handled 0.5h 80 ℃ of exchanges, filters, washes, and promptly gets special-purpose catalyst B of the present invention in 120 ℃ of dry 16h.
Catalyst B is formed 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 estimate before under 800 ℃ on the warp, 100% water vapour, hydrothermal treatment consists 17h.
The petroleum hydrocarbon catalytic cracking reactor form is a riser tube, and its internal diameter is 16 millimeters, highly is 4 meters; The 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 gets into 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 of the lifting vapor quality flow rate of entering riser tube and the mass flow rate of catalytically cracked stock charging is 0.25: 1; Reaction times is 4 seconds, and the riser tube temperature out is 510 ℃.
The carbon deposited catalyst of riser tube outlet gets into stripping stage under action of gravity, the stripping stage internal diameter is 100 millimeters, highly is 2.5 meters; Water vapour gets into the stripping stage bottom, and the carbon deposited catalyst behind the stripping gets into revivifier regeneration, and the catalyzer after the regeneration turns back to riser reactor; The reaction oil gas that stripping stage goes out through the water vapour stripping rises to the reaction oil gas outlet of settling vessel top and send subsequent separation system.The stripping stage middle part is provided with upflow tube; Spent agent gets into the spent agent circulation line (in the accompanying drawing 18 through upflow tube; The spent agent temperature is 505 ℃); Under flow to outside heat removing vapour generator (in the accompanying drawing 21) shell, softening water (in the accompanying drawing 19) then gets into from outside heat removing steam generator layer bottom, the steam of generation (in the accompanying drawing 1 20) flows out from outside heat removing vapour generator top; From the effusive spent agent of outside heat removing vapour generator shell through the spent agent circular route (the accompanying drawing 1 16; The spent agent temperature is 470 ℃) under flow to Dehydration of methanol device (in the accompanying drawing 15); 15 millimeters of Dehydration of methanol device internal diameters; 3 meters of height directly get into dehydration reactor bottom and carbon deposited catalyst contact reacts after methanol aqueous solution is preheating to 200 ℃, transfer limes (in the accompanying drawing 17) returns that the realization finish separates in the settling vessel through the dehydration reactor top for reaction oil gas and mixture of catalysts.Weight hourly space velocity in the methyl alcohol methanol conversion is 1h
-1, the methanol conversion temperature of reaction is 510 ℃, reaction pressure 0.13Mpa (gauge pressure).The methanol feeding amount is 0.81 with the ratio of catalytically cracked stock inlet amount.
Catalytically cracked stock is the mixing oil that is mixed by 70% decompressed wax oil and 30% vacuum residuum with embodiment 1.Oxygenate feedstock is methanol aqueous solution (containing 80% weight methyl alcohol, is 97% industrial methanol adding deionized water allotment by purity).
The unified metering of reaction products therefrom, products therefrom distributes and calculates according to the catalytically cracked stock meter, and the gained reaction result is seen table 1.
Table 4
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Embodiment 1 | Embodiment 2 | |
| Product distributes, wt% | |||||
| Dry gas | 3.52 | 15.68 | 4.26 | 17.76 | 17.04 |
| Liquefied gas | 24.37 | 43.14 | 25.00 | 37.78 | 35.09 |
| Gasoline | 21.45 | 24.94 | 19.95 | 21.74 | 23.86 |
| Diesel oil | 15.93 | 18.19 | 15.91 | 16.64 | 17.20 |
| Heavy oil | 26.17 | 26.04 | 23.73 | 24.42 | 27.66 |
| Coke | 8.57 | 14.94 | 11.16 | 14.12 | 12.61 |
| The raw oil transformation efficiency, wt% | 57.91 | 60.36 | |||
| Methanol conversion, wt% | 77.63 | 99.24 | 99.30 | ||
| Yield of ethene, wt% | 1.28 | 2.29 | 2.01 | 13.13 | 12.70 |
| Propene yield, wt% | 9.98 | 12.97 | 9.59 | 18.36 | 16.78 |
Can find out by table 4; Method provided by the present invention, with respect to existing catalyst cracking method with the existing integrated methyl alcohol method for processing of catalytic cracking catalyst, methanol conversion obviously improves; Methyl alcohol is near transforming fully; 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
Embodiment 3 explanation methyl alcohol and ethanol in catalyst cracking method provided by the invention inject the experimental result of oxygenatedchemicals dehydration reactor simultaneously.
Present embodiment Preparation of catalysts process is following:
With butt meter (molecular sieve weight basis, down together) ZSM-5 zeolite (ZSP-3, iron oxide content 2.5wt%; Phosphorus pentoxide content 2.9wt%, Sinopec catalyzer Shandong branch office 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; Percent crystallinity 46%, Sinopec catalyzer Chang Ling branch office product) 35kg, add SRM molecular sieve (SRM-8 again; The Sinopec catalyzer is built long branch office product) 15kg, making beating is evenly.Butt meter 15Kg pseudo-boehmite (Chalco Shandong Aluminum Plant product, down together) is added the making beating of 100kg deionized water, and adding 2kg concentrated hydrochloric acid is (commercially available; HCl content 31.5% weight, down together) pull an oar evenly, add aluminium colloidal sol 60kg making beating again; Add butt meter 18Kg kaolin, making beating evenly adds above-mentioned molecular sieve pulp again; Making beating is even, and spraying drying is collected 30-150 mu m range microsphere particle.Above-mentioned catalyzer microballoon in 400 ℃ of calcination process 2h, is used 0.5%NH then
4The Cl aqueous solution is handled 1.5h 80 ℃ of exchanges, filters, washes, and promptly gets catalyzer C in 120 ℃ of dry 16h.
Catalyzer C forms as follows: ZSP-3 zeolite 2%, CDY molecular sieve 35%, SRM-8 molecular sieve 15%, aluminium colloidal sol 15%, pseudo-boehmite (in aluminum oxide, down together) 15%, kaolin 18%.
Catalyzer C carry out integrated reaction estimate before under 800 ℃ on the warp, 100% water vapour, hydrothermal treatment consists 17h.
Catalytically cracked stock is the Wuhan mixing oil with embodiment 1, is mixed by 70% decompressed wax oil and 30% vacuum residuum.Methyl alcohol and aqueous ethanolic solution contain 34% weight methyl alcohol and 46% weight ethanol, are that 97% industrial methanol and purity are that 95% industrial alcohol adds the deionized water allotment by purity.
The petroleum hydrocarbon catalytic cracking reactor form is a riser tube, and its internal diameter is 16 millimeters, highly is 4 meters; The 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 gets into 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 of the lifting vapor quality flow rate of entering riser tube and the mass flow rate of catalytically cracked stock charging is 0.25: 1; Reaction times is 4 seconds, and the riser tube temperature out is 500 ℃.
The carbon deposited catalyst of riser tube outlet gets into stripping stage under action of gravity, the stripping stage internal diameter is 100 millimeters, highly is 2.5 meters; Water vapour gets into the stripping stage bottom, and the carbon deposited catalyst behind the stripping gets into revivifier regeneration, and the catalyzer after the regeneration turns back to riser reactor; The reaction oil gas that stripping stage goes out through the water vapour stripping rises to the reaction oil gas outlet of settling vessel top and send subsequent separation system.The stripping stage middle part is provided with upflow tube; Spent agent gets into the spent agent circulation line (in the accompanying drawing 18 through upflow tube; The spent agent temperature is 495 ℃); Under flow to outside heat removing vapour generator (in the accompanying drawing 21) shell, softening water (in the accompanying drawing 19) then gets into from outside heat removing steam generator layer bottom, the steam of generation (in the accompanying drawing 20) flows out from outside heat removing vapour generator top; From the effusive spent agent of outside heat removing vapour generator shell through the spent agent circular route (the accompanying drawing 1 16; The spent agent temperature is 480 ℃) under flow to Dehydration of methanol device (in the accompanying drawing 15); 15 millimeters of Dehydration of methanol device internal diameters; 3 meters of height directly get into dehydration reactor bottom and carbon deposited catalyst contact reacts after methyl alcohol and the alcoholic acid aqueous solution are preheating to 200 ℃, transfer limes (in the accompanying drawing 17) returns that the realization finish separates in the settling vessel through the dehydration reactor top for reaction oil gas and mixture of catalysts.Weight hourly space velocity in the reaction of methyl alcohol methanol conversion is 4h
-1, the methanol conversion temperature of reaction is 500 ℃, reaction pressure 0.14Mpa (gauge pressure).Methyl alcohol and ethanol inlet amount are 0.71 with the ratio of catalytically cracked stock inlet amount.
Embodiment 4
The effect of the SRM molecular sieve of modification is adopted in the present embodiment explanation.
With embodiment 3, difference is that catalyzer wherein is numbered D, and the SRM molecular sieve among the catalyzer D is with magnesium and aluminium modification.Its method of modifying is following: 18.75Kg nine water aluminum nitrates are dissolved in the 500Kg deionized water, stir, and then (the Sinopec catalyzer is built long branch office product to add 50kg SRM-8 molecular sieve; Removed template method); At room temperature stirred 1 hour, and to wherein adding the 12.9Kg magnesium nitrate hexahydrate again, at room temperature stirred 1 hour then; Filter then, wash; 100 ℃ of following dry nights, dried molecular sieve obtains the silicoaluminophosphamolecular molecular sieves of magnesium and aluminium modification 600 ℃ of following roastings 2 hours.Sample after the roasting is measured its result data such as table 5 through the X-ray powder diffraction.The mole of modification sample consists of: 16MgO: 3.5Al
2O
3: (100Al
2O
3: 76P
2O
5: 30SiO
2).
Table 5
Catalyzer D prepares process with embodiment 3, and it is formed as follows: ZSP-3 zeolite 2%, CDY molecular sieve 35%, the SRM-8 molecular sieve 15% of magnesium and aluminium modification, aluminium colloidal sol 15%, pseudo-boehmite 15%, kaolin 18%.
Catalyzer D before carrying out reaction evaluating under 800 ℃, 100% water vapour, hydrothermal treatment consists 17h.
The unified metering of integrated reaction products therefrom, products therefrom distributes and calculates according to the catalytically cracked stock meter, and the gained reaction result is seen table 6.
Comparative Examples 4
Comparative Examples 4 explanations adopt conventional catalytic cracking catalyst to carry out catalytic cracking reaction on the middle-scale device of successive reaction-regenerative operation.
Adopt catalytically cracked stock with embodiment 1; Reactor types and embodiment 1 difference are that stripping stage adopts the water vapour stripping, do not have the circulation line of spent agent shown in the accompanying drawing (in the accompanying drawing 18), outside heat removing vapour generator (in the accompanying drawing 21); Spent agent circulation line (in the accompanying drawing 16); Dehydration of methanol device (in the accompanying drawing 15), reactor top transfer limes (in the accompanying drawing 17), reaction process does not have methanol feeding.
The preparation method is following:
With 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 the making beating of 100kg deionized water, add the making beating of 2kg concentrated hydrochloric acid evenly, add aluminium colloidal sol 60kg making beating again; Add butt meter 33Kg kaolin; Making beating evenly adds above-mentioned molecular sieve pulp again, and making beating evenly; Spraying drying is collected 30-150 mu m range microsphere particle.Above-mentioned catalyzer microballoon in 500 ℃ of calcination process 2h, is used 1%NH then
4The Cl aqueous solution is handled 1.5h 70 ℃ of exchanges, filters, washes, and promptly gets conventional catalytic cracking catalyst C0 in 120 ℃ of dry 24h.
Catalyzer C0 forms as follows: ZSP-3 zeolite 2%, CDY molecular sieve 35%, aluminium colloidal sol 15%, pseudo-boehmite 15%, kaolin 33%.
Catalyzer C0 carry out integrated reaction estimate before under 800 ℃ on the warp, 100% water vapour, hydrothermal treatment consists 17h.
The gained reaction result is seen table 6.
Table 6
| Comparative Examples 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 |
| The raw oil transformation efficiency, wt% | 66.45 | ||
| Methanol conversion, wt% | 99.12 | 100.00 | |
| The 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 |
Can find out by table 6; Catalyst cracking method provided by the present invention, methyl alcohol and ethanol are near transform fully, and 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 an ethene, increases considerably so yield of ethene has been obtained, the ratio of ethylene/propene obviously improves.After particularly employing contains the catalyzer of modification SRM molecular sieve; Because modification SRM molecular sieve further improves the activity and the selectivity of oxygenatedchemicals dehydration reaction; Not only make the oxygenatedchemicals that adds in the hydrocarbon oil catalytic cracking method transform fully, and the yield of ethene and propylene further improve.
Claims (25)
1. catalyst cracking method; The catalyst regeneration agent that under the cracking reaction condition, petroleum hydrocarbon raw material and the steam that gets into riser reactor is promoted contacts carries out cracking reaction, and the riser tube outlet obtains cracking reaction oil gas and mixture of catalysts, in settling vessel, separates obtaining cracking reaction oil gas and carbon deposited catalyst; Wherein, Reaction oil gas rises, and gas pipeline gets into product separation system through the settling vessel top, and carbon deposited catalyst falls to getting into stripping stage, and the carbon deposited catalyst behind the stripping burns through spent agent circular route entering revivifier and main air reaction; The flue gas pipeline gets into smoke energy recovering system to the regenerated flue gas that obtains from the revivifier top; Riser reactor is returned in the catalyst regeneration agent that obtains, and it is characterized in that, this method also comprises the 10-50 weight % in the said carbon deposited catalyst through an outside heat removing steam generator cooling; Get into fluidized-bed reactor again; Contact with oxygenatedchemicals that heat exchange heats up and to carry out dehydration reaction, gained dehydration reaction oil gas product and catalyst mixture return settling vessel through the fluidized-bed reactor top, mix with cracking reaction oil gas and carbon deposited catalyst in the settling vessel.Wherein, to contain with weight be the silicoaluminophosphamolecular molecular sieves with octatomic ring window duct of benchmark 1～90% to said catalyzer.
2. according to the method for claim 1; Wherein, said catalyzer is that benchmark has following composition with weight: 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 is that benchmark has following composition with weight: 5～60% have octatomic ring window duct the mesoporous silicon aluminum molecular screen, 12～40% of silicoaluminophosphamolecular molecular sieves, 0～30% with ten-ring window duct have 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, Said silicoaluminophosphamolecular molecular sieves with octatomic ring window duct be selected from have CHA, in the silicoaluminophosphamolecular molecular sieves of AEI, RHO crystalline structure one or more, or silicoaluminophosphamolecular molecular sieves with one or more intergrowth phases in the above-mentioned crystalline structure.
5. according to the method for claim 4, wherein, said silicoaluminophosphamolecular molecular sieves with octatomic ring window duct is selected from one or more in SAPO-34, SAPO-18 and the SRM molecular sieve.
6. according to the method for claim 5, wherein said SRM molecular sieve, the X-ray diffraction spectral data contains the diffraction peak shown in the following table at least, and the structure expression of this molecular sieve is Al
2O
3: 0.1～1.7P
2O
5: 0.01～3SiO
2, in the 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, the SRM molecular sieve is with Me1 and Me2 modification, and 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, the VB family, and said Me2 is selected from a kind of element or the aluminium in the IVB family in the periodic table of elements, and x representes that Me1 accounts for the molecular fraction of this molecular sieve in oxide compound; X=5～25; Y representes 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 the boron.
9. according to the method for claim 7, wherein, Me2 is selected from a kind of in aluminium, titanium and the zirconium.
10. according to the method for claim 2 or 3, wherein, said mesoporous silicon aluminum molecular screen with ten-ring window duct, be selected from have MFI, in the AEL crystalline structure Si-Al molecular sieve one or more.
11. according to the method for claim 10, wherein, the said MFI of having crystalline structure Si-Al molecular sieve is ZSM-5.
12. according to the method for claim 11, wherein, said ZSM-5 is Hydrogen ZSM-5, perhaps is the ZSM-5 through the phosphorus modification, perhaps is phosphorus and alkali-earth metal modified ZSM-5, perhaps is phosphorus and transition metal modified ZSM-5.
13. according to the method for claim 12, said earth alkali metal is selected from magnesium and/or calcium, one or more in said transition metal chosen from Fe, cobalt, nickel, copper, zinc, titanium and the manganese.
14. according to the method for claim 2 or 3, wherein, said macropore Si-Al molecular sieve with twelve-ring window duct, be selected from have FAU, in MOR, MAZ and the BEA crystalline structure Si-Al molecular sieve one or more.
15. according to the method for claim 14, wherein, the said FAU of having crystalline structure Si-Al molecular sieve is a Y zeolite.
16. according to the method for claim 15, 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 the 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 the hydrogenation tail oil.
20. according to the process of claim 1 wherein, the reaction conditions of said petroleum hydrocarbon raw material cracking reaction is temperature 400-650 ℃; 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 are 0.01～1.0.
21. according to the method for claim 20, wherein, the reaction conditions of said cracking petroleum hydrocarbons reaction is temperature 450-550 ℃; Pressure 0.1-0.40MPa; Reaction times 3-100s, agent-oil ratio 4.0-15.0, the mass ratio of water vapour and petroleum hydrocarbon raw material are 0.05～0.5.
22. according to the process of claim 1 wherein, said fluidized-bed reactor is fast bed or bubbling bed.
23. according to the process of claim 1 wherein, said oxygenatedchemicals is selected from one or more in methyl alcohol, ethanol, the dme.
24. according to the process of claim 1 wherein, the condition of said oxygenatedchemicals dehydration reaction is temperature 400-600 ℃, pressure 0.01-0.50MPa, oxygen-containing compound material reaction velocity 0.1-100h
-1, the oxygen-containing compound material preheating temperature is 50-500 ℃.
25. according to the method for claim 24, wherein, the condition of said oxygenatedchemicals dehydration reaction is temperature 450-550 ℃, pressure 0.1-0.4MPa, oxygen-containing compound material reaction velocity 0.5-10h
-1, the oxygen-containing compound material preheating temperature is 150-400 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| WO2015081489A1 (en) * | 2013-12-03 | 2015-06-11 | 中国科学院大连化学物理研究所 | Method for preparing a light olefin using an oxygen-containing compound |
| CN109777516A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method of heavy-oil hydrogenation aromatic hydrocarbons |
| CN115746906A (en) * | 2022-12-01 | 2023-03-07 | 黄河三角洲京博化工研究院有限公司 | Method and system for preparing chemical products by catalytic cracking of oxygen-containing compounds and light hydrocarbons |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672044A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefins by using oxygen-containing compounds |
| WO2015081489A1 (en) * | 2013-12-03 | 2015-06-11 | 中国科学院大连化学物理研究所 | Method for preparing a light olefin using an oxygen-containing compound |
| CN104672044B (en) * | 2013-12-03 | 2016-06-08 | 中国科学院大连化学物理研究所 | A kind of method of preparing low-carbon olefin from oxygen-containing compounds |
| AU2013407180B2 (en) * | 2013-12-03 | 2017-05-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing a light olefin using an oxygen-containing compound |
| US9725375B2 (en) | 2013-12-03 | 2017-08-08 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing a light olefin with an oxygen-containing compound |
| RU2632905C1 (en) * | 2013-12-03 | 2017-10-11 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайенсез | Method of producing light olefins by oxygen-containing compound |
| KR101847474B1 (en) | 2013-12-03 | 2018-04-10 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Method for preparing a light olefin using an oxygen-containing compound |
| CN109777516A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method of heavy-oil hydrogenation aromatic hydrocarbons |
| CN109777516B (en) * | 2017-11-14 | 2021-07-09 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon by heavy oil hydrogenation |
| CN115746906A (en) * | 2022-12-01 | 2023-03-07 | 黄河三角洲京博化工研究院有限公司 | Method and system for preparing chemical products by catalytic cracking of oxygen-containing compounds and light hydrocarbons |
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