CN103450921B - Method for selectively preparing propylene and clean gasoline through using methanol - Google Patents
Method for selectively preparing propylene and clean gasoline through using methanol Download PDFInfo
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- CN103450921B CN103450921B CN201210179763.8A CN201210179763A CN103450921B CN 103450921 B CN103450921 B CN 103450921B CN 201210179763 A CN201210179763 A CN 201210179763A CN 103450921 B CN103450921 B CN 103450921B
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention relates to a method for selectively preparing propylene and clean gasoline through using methanol. The method comprises the following steps: methanol enters a double arc bottom turbulent bed reactor through a methanol feeding ring tube to contact and react with a catalyst at 300-500DEG C for 2-5s; an obtained gas enters a conveying bed reactor after reducing, wherein the gas retention time is 1-3s; the gas and the catalyst are separated by a cyclone separator in a settlement device, and the gas gets away off a reaction regeneration system separating system from the top of the settlement device to a separation system; the settled catalyst is added to a reactivator for scorching regeneration; and the regenerated catalyst returns to the double arc bottom turbulent bed reactor, and a pre-riser outlet is arranged on a cross section in which a highest nozzle outlet of the feeding ring tube. The methanol conversion rate is 99.48wt%, generated hydrocarbons contain higher-content gasoline, lower-content liquefied gas and lowest-content dry gas and coke, the content of propylene in the liquefied gas reaches 62.13%, and the content of ethylene in the dry gas reaches 82wt%.
Description
Technical field:
The present invention relates to a kind of method for methyl alcohol selectively producing propene and clean gasoline.
Background technology
Mobil Corp. (Mobil) proposes a kind of use ZSM-5 catalyzer, and in shell and tube reactor, carry out the technical process of preparing olefin by conversion of methanol, and carried out the pilot experiment of 9 months in 1984, experimental scale is 100 barrels/day.In technological process, methyl alcohol is diffused in catalyst pores and reacts, and first generates dme, then generates ethene, reaction proceeds, generate propylene, butylene and higher alkene, also can generate dipolymer and ring compound, based on carbon selectivity, it is heavy that yield of ethene can reach 60%(), it is heavy that alkene total recovery can reach 80%(), about the same in the twice adopting conventional naphtha/gas oil pyrolysis in tubular furnace method yield, but the life-span of catalyzer is still undesirable.
BASF AG (BASF) adopts zeolite catalyst, and summer in 1980 establishes the pilot plant of a set of daily consumption 30 tons of methyl alcohol at Ludwigshafen, Germany.Its temperature of reaction is 300-450 DEG C, and pressure is 0.1-0.5Mpa, uses various zeolites as catalysts, and Preliminary experiment results is the weight yield of C2-C4 alkene is 50-60%, and yield is too low.
The catalyzer that Praxair Technology, Inc (UOP) filters out is called MTO-100.MTO-100 is the combination of the SAPO-34 of union carbide corporation's exploitation and the binder materials of a series of special selection.SAPO-34 is the matrix of MTO-100 catalyzer, and developed the eighties in 20th century by Union Carbide molecule sieve part, main chemical compositions comprises the elements such as silicon (Si), aluminium (Al), phosphorus (P), oxygen (O).It has suitable inner duct scantlings of the structure and solid acid intensity, can reduce the alkene generation oligomerisation reaction generation macromolecule hydrocarbon that initial reaction stage generates as far as possible, thus improve target product--the selectivity of alkene.Although SPAO-34 is desirable catalytic material, be not robust material, and selected tamanori can increase catalyst strength and wear resistance to fluidized bed process.By inference, the tamanori adopted in MTO-100 is the silicon-dioxide and aluminum oxide that processed.SAPO-34 molecular sieve catalyst aperture only allows ethene, propylene and a small amount of C
4pass through, heavy hydrocarbon products can not be produced.Ethene, polypropylene ratio can regulate between 0.75 ~ 1.5, and the productive rate of ethene+propylene is more stable (about 80%), and the purity of ethene and propylene is all more than 99.6%, directly can meet the requirement of polymerization-grade propylene and ethene.
Ac.cn, as the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, University of Petroleum, Shi Ke institute of China Petrochemical Industry have also carried out the research of similar catalyzer, has obtained the result close with UOP, and this has turned preparation into for catalyzer from now on domestic.
MTO technique adopts and is similar to ripe FCC processing method, the i.e. fluid catalytic cracking technology that carries out continuously of conversion reaction and catalyzer coke burning regeneration, catalyzer after continuous compensation regeneration, ensures that the reactive behavior of catalyzer and selectivity are stablized, conversion reaction is steadily carried out.
UOP and Hai De company (Norsk Hydro) is the MTO technique demonstration unit of 0.75t/d in a set of crude carbinol working ability of Cooperative construction in June nineteen ninety-five, and device has operated 90 days continuously, and the operation of each system is normal, stable.In running in 90 days, catalyzer is through 450 secondary responses-reprocessing cycle, and its performance is still highly stable, and by sampling analysis after reaction, the intensity of catalyzer also meets the demands, and can change the yield ratio that operational condition regulates ethene and propylene.The purity of ethene and propylene, all more than 99.6%, directly can meet the requirement of polymerization-grade propylene and ethene.
Praxair Technology, Inc in November nineteen ninety-five (UOP) and Hai Deluo company (Norsk Hydro) disclose their the natural gas via synthesizing methanol of joint development first and produce the MTO process of alkene (ethene, propylene and butylene) and the service data of demonstration unit further in the 4th the conversion of natural gas international conference in South Africa, and claim this process can realize the suitability for industrialized production of annual output 500000 tons of ethene, can obtain from Praxair Technology, Inc (UOP), Hai Deluo company (Norsk Hydro) license licensed licenser licence of founding the factory.
The gas chemical industry associated enterprises being positioned at Nigeria adopts the MTO technique of UOP/Hydro company exploitation, material benzenemethanol comes from 7500t/d methanol device, MTO designs production 400,000 tons/year of ethene and 400,000 tons/year of propylene, ethene and propylene are used further to production 400,000 tons/year of HDPE and 400,000 ton/year PP, completed basic design in 2003, this machinery was gone into operation due to 2006.Design and preconsolidation stress work that Norway and the Middle East are also utilizing this technology to carry out 200,000 tons and 500,000 tons ethene.
From a large amount of bibliographical informations, catalyzer aspect, object product is if ethene, and active ingredient is all SAPO-34 molecular sieve substantially; If object product is propylene or gasoline, active ingredient is generally ZSM-5 molecular sieve.Reactor aspect, by the considerably less (patent: US4929780 of fixed bed, CN 1084431A), majority is all adopt fluidized-bed, but, the form of the fluidized-bed that different technology adopts varies, some employings be fast bed (US6166282, US4076796), some employings conveying bed (CN 1688522A, CN2339296Y, US 7385099B2), some employing turbulent beds (CN 101152998A, CN 101172937A, CN101172936A), the then employing fast bed+turbulent bed (US 4328384) had.
Summary of the invention
The object of this invention is to provide a kind of method for methyl alcohol selectively producing propene and clean gasoline.Be with the difference of disclosed patent: 1. the active ingredient of catalyzer is nanometer rod grafting ZSM-11 Quito level porous molecular sieve material (synthetic method has applied for national inventing patent CN201210003750.5); 2. reactor adopts instant contact high-density turbulent bed+conveying bed; 3. object product is clean gasoline with high octane and propylene, and both ratios can be adjusted flexibly by the silica alumina ratio of adjustment ZSM-11.
Method for methyl alcohol selectively producing propene and clean gasoline of the present invention; Comprise the catalyzer that methanol oxidation transforms stop bracket gasoline processed and propylene and the circulating fluidized bed reaction regeneration device matched with this catalyzer.
The active ingredient of the catalyzer nanometer rod grafting ZSM-11 Quito level porous molecular sieve material of method synthesis for announcing by CN201210003750.5, this material has abundant micropore and mesopore, and micropore canals is straight and short, be convenient to methyl alcohol to the diffusion in hole and product to hole external diffusion, reduce converting propylene and become alkane.The content of this molecular screen material in the catalyzer prepared through mist projection granulating accounts for 5 ~ 50wt%.Other component of catalyzer (catalyzer all prepared with mist projection granulating is for benchmark) also comprises kaolin (5 ~ 50wt%), silicon-dioxide (0.1 ~ 20wt%, be transformed from the silicon sol as binding agent), aluminium sesquioxide (0.1 ~ 20wt%, be transformed from as the Alumina gel of binding agent or the pseudo-boehmite of acidifying), Vanadium Pentoxide in FLAKES (0.1 ~ 15wt%, the phposphate again before mist projection granulating in slurries).
Methyl alcohol reacts on the catalyzer prepared as stated above, and methyl alcohol be made fully to transform, except temperature of reaction at 300 ° of C with upper outside, also must must ensure that methyl alcohol can fully contact with catalyzer; Want selectivity to produce gasoline and propylene, except temperature of reaction can not more than except 500 ° of C, also strictly must control gas (product generated after nail alcohol and reaction thereof) solid (referring to catalyzer) duration of contact can not more than 10s, preferably within 5s; In methyl alcohol reaction process, catalyzer can coking deactivation, but deactivation rate is unhappy, reacts on a fixed bed, catalyzer completely because of carbon deposit the time of inactivation different because of the difference of concrete reaction conditions, generally at several minutes to dozens of minutes; Here catalyzer belongs to solid acid catalyst, if the alkene that methyl alcohol reaction generates can not separate in time with catalyzer, alkene hydrogen transfer reactions can occur and changes into alkane, and thus reactor should reduce the back-mixing of gas as far as possible; In addition, in the gasoline that methyl alcohol reaction generates, if transform insufficient, may a certain amount of oxygenatedchemicals be contained, these oxygenatedchemicalss thus must be allowed fully to transform, to ensure quality of gasoline.For above-mentioned requirements, invent be reactor with " instant contact turbulent bed+conveying bed " as shown in drawings can the circulating fluidized bed device of successive reaction and regeneration.
Being in the turbulent bed of dense fluidized, is ensure methyl alcohol and catalyzer high-efficient contact and the abundant key transformed.For this reason, methyl alcohol adopts endless tube charging, and the feed nozzle on endless tube is totally in downward direction, and each nozzle can be different from the angle in reactor axis direction; For ensureing catalyst distribution as far as possible evenly, from reactor along the profile of axis, bottom is bicircular arcs bottom structure; For ensureing that catalyzer can steady fluidisation, pre-lift pipe exports at least will on the cross section residing for the highest jet exit in charging endless tube position.Calculate quickly by the blank pipe gas of the gas generated after methanol conversion under real reaction condition, the mean residence time of gas in turbulent bed can not more than 5s, preferably within 2s.Turbulent bed top, through undergauge, is connected with transport bed reactor, and oil gas undergauge from turbulent bed exports to transport bed reactor, and the mean residence time (calculating by real reaction condition) of gas is not more than 5s, is preferably less than 3s.What be connected with conveying bed top is settling vessel, and in settling vessel, gas and catalyzer are after cyclonic separator is separated, gas leaves reaction-regeneration system from settling vessel top, get separation system, the catalyzer settled down enters revivifier through inclined tube to be generated, carries out the coke burning regeneration of catalyzer with air; If the coke burning on catalyzer is not enough to maintain temperature condition required for catalyst regeneration, warm air can be added at auxiliary chamber afterburning, also can direct afterburning in a regenerator.Catalyzer after regeneration enters reactor bottom through regenerator sloped tube, and the dry gas generated through water vapor or reaction carries out pre-lift, and catalyzer is returned in turbulent bed reactor.
Major technique advantage of the present invention is the following aspects:
(1) advantages such as catalyzer is with the nanometer rod grafting ZSM-11 multi-stage porous molecular screen material of low diffusional resistance for active ingredient, and have high added value product yield high, gasoline octane rating is high, and Propylene Selectivity is high.
(2) the turbulent bed reactor of instant contact dense fluidized combines with the transport bed reactor of low fluid density by reactor, turbulent bed reactor is also by the innovation of structure and feeding manner, reduce the channeling that turbulent bed occurs usually, thus improve gas-solid contact efficiency.The turbulent bed reactor of high gas-solid contact efficiency ensures that methyl alcohol fully contacts with catalyzer and reacts, thus ensures the transformation efficiency of methyl alcohol; In the turbulent bed of dense fluidized, the residence time of gas is short, can reduce back-mixing and the secondary reaction of propylene.Transport bed reactor fluid density is low, if can reduce the secondary reaction of the propylene of adsorptive power, ensures the selectivity of propylene; The fluid density that conveying bed is low, does not hinder absorption and the reaction of the oxygenatedchemicals in the gasoline fraction of high adsorption capacity, thus ensures the abundant conversion of oxygenatedchemicals in gasoline fraction.
(3) ratio of gasoline and propylene, can be adjusted than neatly by the Si/Al of adjustment ZSM-11 molecular screen material, also can be adjusted by adjustment temperature of reaction.
Accompanying drawing explanation
Fig. 1 reaction and reprocessing cycle fluidizer
Wherein: 1. methanol feeding endless tube; 2. pre-lift pipe; 3. turbulent bed reactor at the bottom of pair arc; 4. pre-lift medium; 5. regenerator sloped tube; 6. air; 7. revivifier; 8. flue gas; 9. inclined tube to be generated; 10. settling vessel; The gas that 11. reactions generate; 12. transport bed reactors.
Embodiment
Method for methyl alcohol selectively producing propene and clean gasoline of the present invention comprises the catalyzer that methanol oxidation transforms stop bracket gasoline processed and propylene and the circulating fluidized bed reaction regeneration device matched with this catalyzer; Methanol feedstock exports top methanol feeding endless tube 1 by being positioned at pre-lift pipe 2 enters turbulent bed reactor 3 at the bottom of two arc, downward by general direction on endless tube, the feed nozzle different from the angle in reactor axis direction sprays to turbulent bed reactor bottom and catalyzer uniform contact at the bottom of two arc and reacts; Temperature of reaction is at 300 ~ 500 ° of C, and the time is 2 ~ 5s; At the bottom of two arc, turbulent bed reactor 3 top is through undergauge, is connected with transport bed reactor 12, and oil gas undergauge from turbulent bed reactor 3 at the bottom of two arc exports to transport bed reactor, and the mean residence time of gas is 1 ~ 3s; What be connected with transport bed reactor top is settling vessel 10, and in settling vessel, gas and catalyzer are after cyclonic separator is separated, and the gas that reaction generates leaves reaction-regeneration system and goes separation system from settling vessel top; The catalyzer settled down enters revivifier 7 through inclined tube 9 to be generated, carries out the coke burning regeneration of catalyzer with air 6; Catalyzer after regeneration enters bottom pre-lift pipe 2 through regenerator sloped tube 5, pre-lift is carried out through pre-lift medium 4, make catalyzer return in turbulent bed reactor at the bottom of two arc, pre-lift pipe 2 outlet is located on the highest cross section residing for jet exit in charging endless tube position.
Embodiment 1:
In stirring tank, add the pseudo-boehmite of 11.76kg, inject 700kg deionized water, under the condition of continuously stirring, add salt acid for adjusting pH value is 3-4.After pseudo-boehmite changes into jelly completely, in still, add the ZSM-11 molecular screen material (SiO changing into Hydrogen through ion-exchange of 60kg
2/ Al
2o
3than being 100), then add 106kg kaolin, after stirring, then add 40kg silicon sol and 14kg phosphoric acid.After stirring 2h, carry out mist projection granulating.
By for subsequent use after aging 4h under 800 ° of C, 100% water vapor condition for the microspherical catalyst obtained.
Catalyzer 50kg after aging is loaded in the pilot plant by structure building shown in the drawings.Temperature of reaction in turbulent bed controls at 420 ° of C; The average linear velocity of gas in turbulent bed is 0.45m/s, and mean residence time is about 2s; The average linear speed of gas in conveying bed is 7m/s, and mean residence time is about 1.5s.Temperature in revivifier controls at 700 ° of C, and the amount of air is dryouied only (coke content ≯ 0.15wt% on regenerator) completely with the carbon deposit ensureing on catalyzer and is advisable.
With pure methyl alcohol for raw material, inlet amount is 40kg/h, and reaction result as in the attached table.
Measure the methanol content in water, the methanol conversion calculated thus is 99.48wt%, almost transforms completely.In reaction product, the yield of water is close to theoretical value 56wt%; In the hydrocarbon generated, the amount of gasoline is maximum, and be secondly liquefied gas, the yield of dry gas and coke is all very low.In liquefied gas, the content of propylene reaches 62.13%; In dry gas, the content of ethene reaches more than 82wt% especially.
Reaction result in subordinate list, has absolutely proved the catalyzer and the excellent properties of supporting reactor in methanol oxidation conversion selectivities production gasoline and propylene invented.
1. subordinate list
Methyl alcohol distribution of reaction products
Claims (1)
1., for a method for methyl alcohol selectively producing propene and clean gasoline, it is characterized in that:
With the catalyzer that nanometer rod grafting ZSM-11 multilevel hole material is active ingredient, be equipped with circulating fluidized bed reaction regeneration device, transform to produce for methyl alcohol selective catalysis and be main oil product with clean stop bracket gasoline, be main low-carbon alkene product with propylene;
Methanol feedstock enters turbulent bed reactor at the bottom of two arc by the methanol feeding endless tube being positioned at pre-lift pipe outlet top, downward by general direction on endless tube, the feed nozzle different from the angle in reactor axis direction sprays to turbulent bed reactor bottom and catalyzer uniform contact at the bottom of two arc and reacts; Temperature of reaction is at 300 ~ 500 DEG C, and the time is 2 ~ 5s; At the bottom of two arc, turbulent bed reactor top is through undergauge, is connected with transport bed reactor, and oil gas undergauge from turbulent bed reactor at the bottom of two arc exports to transport bed reactor, and the mean residence time of gas is 1 ~ 3s; What be connected with transport bed reactor top is settling vessel, and in settling vessel, gas and catalyzer are after cyclonic separator is separated, and the gas that reaction generates leaves reaction-regeneration system and goes separation system from settling vessel top; The catalyzer settled down enters revivifier through inclined tube to be generated, carries out the coke burning regeneration of catalyzer with air; Catalyzer after regeneration enters bottom pre-lift pipe through regenerator sloped tube, carries out pre-lift through pre-lift medium, and make catalyzer return in turbulent bed reactor at the bottom of two arc, the outlet of pre-lift pipe is located on the highest cross section residing for jet exit in charging endless tube position;
At the bottom of described two arcs, turbulent bed reactor is from reactor along the profile of axis, and bottom is bicircular arcs bottom structure.
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| CN105018129B (en) * | 2014-04-18 | 2017-01-18 | 中石化洛阳工程有限公司 | Device and method for producing gasoline from methyl alcohol by fluidized bed |
| CN108654526B (en) * | 2017-04-01 | 2021-04-16 | 中国石油大学(华东) | Reactor capable of reducing back mixing and used for preparing olefin through alkane dehydrogenation and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049573A (en) * | 1976-02-05 | 1977-09-20 | Mobil Oil Corporation | Zeolite catalyst containing oxide of boron or magnesium |
| CN1356927A (en) * | 1999-05-20 | 2002-07-03 | 埃克森美孚化学专利公司 | Metal-contg. macrostructures of porous inorganic oxide, prepn. thereof, and use |
| CN1678715A (en) * | 2002-08-01 | 2005-10-05 | 埃克森美孚化学专利公司 | Two stage hydrocarbon conversion reaction system |
| JP2007290991A (en) * | 2006-04-24 | 2007-11-08 | Idemitsu Kosan Co Ltd | Method for producing olefin from oxygen-containing compound |
| CN101244971A (en) * | 2008-02-27 | 2008-08-20 | 大连理工大学 | Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8357826B2 (en) * | 2008-10-16 | 2013-01-22 | Karl Kharas | Methods and apparatus for synthesis of alcohols from syngas |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049573A (en) * | 1976-02-05 | 1977-09-20 | Mobil Oil Corporation | Zeolite catalyst containing oxide of boron or magnesium |
| CN1356927A (en) * | 1999-05-20 | 2002-07-03 | 埃克森美孚化学专利公司 | Metal-contg. macrostructures of porous inorganic oxide, prepn. thereof, and use |
| CN1678715A (en) * | 2002-08-01 | 2005-10-05 | 埃克森美孚化学专利公司 | Two stage hydrocarbon conversion reaction system |
| JP2007290991A (en) * | 2006-04-24 | 2007-11-08 | Idemitsu Kosan Co Ltd | Method for producing olefin from oxygen-containing compound |
| CN101244971A (en) * | 2008-02-27 | 2008-08-20 | 大连理工大学 | Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol |
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