CN105457568B - Methanol and/or dimethyl ether catalysis convert double the regenerator reaction units and its reaction method of ethene and aromatic hydrocarbons processed - Google Patents

Methanol and/or dimethyl ether catalysis convert double the regenerator reaction units and its reaction method of ethene and aromatic hydrocarbons processed Download PDF

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CN105457568B
CN105457568B CN201410454255.5A CN201410454255A CN105457568B CN 105457568 B CN105457568 B CN 105457568B CN 201410454255 A CN201410454255 A CN 201410454255A CN 105457568 B CN105457568 B CN 105457568B
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catalyst
regenerator
reactivator
phase section
reactor
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CN105457568A (en
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顾松园
李晓红
齐国祯
王洪涛
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

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Abstract

The present invention relates to the double regenerator fluidized bed reactions and its method that a kind of methanol and/or dimethyl ether catalysis convert ethene processed, propylene and aromatic hydrocarbons, mainly solve the problems, such as ethene, propylene in the prior art and aromatics yield is low, catalyst hydrothermal deactivation is serious.The present invention by including reactor, the first regenerator, Second reactivator, stripper, degassing tank device, raw material enters reactor and catalyst haptoreaction from reactor lower part, reacted carbon deposited catalyst enters the first regenerator and/or Second reactivator through stripper stripping, the partial catalyst regenerated through the first regenerator continues to regenerate into Second reactivator, regenerate the technical scheme of Returning reactor after the degassed tank of complete catalyst deaerates, preferably solves the problem, available in ethene, propylene and arene industrial production.

Description

Methanol and/or dimethyl ether catalysis convert double regenerators reaction dress of ethene and aromatic hydrocarbons processed Put and its reaction method
Technical field
The present invention relates to double regenerators fluidisation of a kind of methanol and/or dimethyl ether catalysis conversion ethene processed, propylene and aromatic hydrocarbons Bed reaction device and its reaction method.
Background technology
Ethene, propylene and aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) It is important basic organic synthesis raw material.Driven by downstream derivative thing demand, the market demand of ethene, propylene and aromatic hydrocarbons continues Increase.
It is ethene, propylene and virtue with the steam cracking process that liquid hydrocarbon (such as naphtha, diesel oil, secondary operation oil) is raw material The main production of hydrocarbon.The technique belongs to petroleum path production technology, in recent years, due to the limited supply of petroleum resources and Higher price, cost of material are continuously increased.By factor, alternative materials prepare ethene, propylene and aromatic hydrocarbons technology cause it is more next More widely pay close attention to.Wherein, for coal-based methanol, dimethyl ether raw material, due to rich coal resources in China, it is increasingly becoming one kind Important Chemical Manufacture raw material, turn into the important supplement of petroleum.Accordingly, it is considered to using methanol and/or dimethyl ether as raw material system Standby ethene, propylene and aromatic hydrocarbons.
In various existing methanol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons is simultaneously Including ethene, propylene and aromatic hydrocarbons.The technology initially sees Chang of Mobil companies in 1977 et al. (Journal of Catalysis, 1977,47,249) report methanol and its oxygenatedchemicals conversion preparation virtue on ZSM-5 molecular sieve catalyst The method of the hydrocarbons such as hydrocarbon.1985, Mobil companies disclosed first in its United States Patent (USP) applied US1590321 The result of study of methanol, dimethyl ether conversion aromatic hydrocarbons, it is catalysis that the research, which uses the phosphorous ZSM-5 molecular sieve for 2.7 weight %, Agent, reaction temperature are 400~450 DEG C, methanol, dimethyl ether air speed 1.3 (Grams Per Hour)/gram catalyst.
The relevant report and patent in the field are more, but the purpose product of most of technologies is aromatic hydrocarbons, ethene, propylene category It is low in accessory substance, yield.Such as the patent in terms of methanol arenes catalytic agent:Chinese patent CN102372535, CN102371176、CN102371177、CN102372550、CN102372536、CN102371178、CN102416342、 CN101550051, United States Patent (USP) US4615995, US2002/0099249A1 etc..Such as in terms of methanol aromatics process Patent:United States Patent (USP) US4686312, Chinese patent ZL101244969, ZL1880288, CN101602646, CN101823929, CN101671226, CN102199069, CN102199446, CN1880288 etc..
In addition, while technology path disclosed in some patents is methanol aromatic hydrocarbons co-producing light olefins, gasoline etc. other Product, such as patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537.
Wherein, Multi-function methanol processing method disclosed in patent CN102775261 and device utilize methanol production low-carbon alkene Hydrocarbon, gasoline, aromatic hydrocarbons.This method uses two-step method production technology, and first step methanol feedstock produces low under the effect of special-purpose catalyst 1 Carbon olefin, second step by the reaction gas containing low-carbon alkene after heat exchange, chilling, carrying out washing treatment, in the presence of special-purpose catalyst 2 Synthesize aromatic hydrocarbons and/or gasoline.The reactor of two courses of reaction can be fixed bed or fluid bed.This method uses two-step method, technique Flow is complicated.
Patent CN102146010 discloses the work that low-carbon alkene and arene parallel cogeneration gasoline are produced using methanol as raw material Skill.Low-carbon alkene and aromatic hydrocarbons are produced using methanol as raw material and using molecular sieve catalyst through methanol alkylation reaction and aromatization Co-production gasoline.The reactor of methanol alkylation reaction and aromatization is various types of fixed bed reactors, pressure 0.01 ~0.5 MPa, 180~600 DEG C of temperature.Total liquid yield is more than 70 weight %, and triphen yield is more than 90 weight %.This method also uses Two reactors, technological process are complicated.
Patent CN102531821 discloses methanol and the method for the co-feeding production low-carbon alkene of naphtha and/or aromatic hydrocarbons, Using load 2.2~6.0 weight %La and 1.0~2.8 weight %P ZSM-5 catalyst, fixed bed reactors or stream can be used Fluidized bed reactor.Reaction temperature is 550~670 DEG C, air speed 1.0~5 (Grams Per Hour)/gram catalyst.The triolefin yield of this method It is higher, but BTX yields are low, only 5~17 weight %.
The method that patent CN102372537 and CN102190546 disclose preparing propylene by methanol transformation and aromatic hydrocarbons.This two specially Profit is developed on the basis of preparing propylene by methanol transformation technology, and propylene is main purpose product, and aromatics yield is relatively low.
The problem of ethene, propylene and aromatics yield are low all be present in above-mentioned patented technology.The present invention pointedly proposes Technical scheme, solves above mentioned problem.
The above-mentioned existing fluidization that aromatic hydrocarbons is produced using methanol and/or dimethyl ether as raw material all uses single regenerator Carry out catalyst circular response regeneration.For guarantee high activity of catalyst, it is necessary to which the carbon content of regenerated catalyst is as far as possible low, Below 0.05~0.1 weight %, therefore high temperature regeneration is unavoidably needed, typically at 650~730 DEG C or so.Catalyst reaction The coke of generation contains protium, and protium oxidation reaction can produce vapor.For molecular sieve catalyst, in this hydro-thermal atmosphere Under can lose activity because of framework of molecular sieve dealuminzation, this inactivation is permanent and irreversible.Reacted for single regenerator Device, the overwhelming majority of catalyst total amount are present in regenerator, and catalyst inventory is excessive in regenerator, and catalyst is in regenerator Interior residence time length, catalyst hydrothermal deactivation is serious, and service life reduces, production cost increase.The present invention pointedly carries Go out the technical scheme of double regenerators, solve above mentioned problem.
The content of the invention
One of technical problems to be solved by the invention are that ethene, propylene and aromatics yield are low in the prior art, catalyst The serious technical problem of hydrothermal deactivation, there is provided a kind of methanol and/or dimethyl ether catalysis convert ethene processed, propylene and aromatic hydrocarbons it is double again Raw device fluidized bed reaction.The device has the excellent of high, the effective mitigation catalyst hydrothermal deactivation of ethene, propylene and aromatics yield Point.
The two of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem corresponding method.
One of to solve the above problems, the technical solution adopted by the present invention is as follows:A kind of methanol and/or dimethyl ether catalysis turn Change double regenerator fluidized bed reactions of ethene and aromatic hydrocarbons processed, including reactor 1, the first regenerator 2, Second reactivator 3, vapour Carry the device of device 4;Raw material 13 enters reactor 1 and catalyst haptoreaction, reacted carbon deposited catalyst from the bottom of reactor 1 Under stripping standpipe 7 of passing through be promoted to stripper 4 and strip;Stripping rear catalyst enters the first regenerator 2 and/or Second reactivator 3; The semi regeneration catalyst obtained through the regeneration of the first regenerator 2 continues to regenerate into Second reactivator 3;Regenerated through Second reactivator 3 Obtained regenerated catalyst enters Returning reactor 1 after degassing tank 5 deaerates;First regenerator 2 is from bottom to top close phase section 26, mistake Cross section 27, dilute phase section 28;Regeneration temperature is 500~600 DEG C, and the content of oxygen is 2~21 volume % in regenerating medium 18;Second Regenerator 3 is from bottom to top close phase section 29, changeover portion 30, dilute phase section 31;Regeneration temperature is 580~750 DEG C, in regenerating medium 20 The content of oxygen is 21~30 volume %.
In above-mentioned technical proposal, the stripping being connected with the bottom of reactor 1 is advanced under the carbon deposited catalyst that reactor 1 generates Inclined tube 6, then it is promoted to stripper 4 through stripping standpipe 7;Strip rear catalyst the first regenerator of part inclined tube 8 to be generated and enter the One regenerator, 2 close phase section 26, partly enter the close phase section 29 of Second reactivator 3 through Second reactivator inclined tube 9 to be generated, or only through rapids Dynamic bed inclined tube 9 to be generated enters the close phase section 28 of Second reactivator 3;The semi regeneration catalyst obtained through the regeneration of the first regenerator 2 is through half Regenerative agent delivery pipe 10 continues to regenerate into the close phase section 29 of Second reactivator 3;Obtained regeneration catalyzing is regenerated through Second reactivator 3 The degassed tank inclined tube 11 of agent deaerates into degassing tank 5;Regenerated catalyst is through the Returning reactor 1 of regenerator sloped tube 12 after degassing.
In above-mentioned technical proposal, the height of 2 close phase section 26 of the first regenerator accounts for the 70~90% of the first regenerator total height; The diameter of dilute phase section 28 and the diameter ratio of close phase section 26 are 1.1~2:1, its height accounts for the 9~27% of the first regenerator total height;Cross Cross the height of section 27 accounts for the first regenerator total height 1~3%.
In above-mentioned technical proposal, the height of the close phase section 29 of Second reactivator 3 accounts for the 50~85% of Second reactivator total height; The diameter of dilute phase section 31 and the diameter ratio of close phase section 29 are 1.1~2:1, its height accounts for the 14~47% of Second reactivator total height; The height of changeover portion 30 accounts for the 1~3% of Second reactivator total height.
In above-mentioned technical proposal, Second reactivator 3 internally and/or externally sets heat collector, and heat collector highly accounts for second again The 30%~80% of raw device height.
In above-mentioned technical proposal, the top of the first regenerator 2 is provided with one group of gas-solid cyclone separator 24, is 1~3 grade;Second The top of regenerator 3 is provided with one group of gas-solid cyclone separator 25, is 1~3 grade.
In above-mentioned technical proposal, reactor 1, for raw material 14 and catalyst haptoreaction to be converted into ethene, propylene With the product based on aromatic hydrocarbons;First regenerator 2, for removing the hydrogen on carbon deposited catalyst in coke, generate semi regeneration catalyst; Second reactivator 3, for the coke on semi regeneration catalyst, generate regenerated catalyst;Stripper 4, urged for carbon deposit to be stripped off The product carried in agent;Degassing tank 5, for further removing the regeneration of the regenerated catalyst entrainment after Second reactivator regenerates Flue gas.
For solve the above problems two, the technical solution adopted by the present invention is as follows:A kind of methanol and/or dimethyl ether catalysis turn Change double regenerator fluidized bed reaction methods of ethene and aromatic hydrocarbons processed, using above-mentioned device, described method includes following Step:
A) raw material 13 enters reactor 1 and catalyst haptoreaction, reaction of formation product 14 and carbon deposit from the bottom of reactor 1 Catalyst, reaction product 14 enter later separation device;
B) the stripping inclined tube 6 being connected with the bottom of reactor 1 is advanced under carbon deposited catalyst, stripping standpipe 7 is entered back into, through carrying Rise medium 15 and be promoted to stripper 4, and the contact stripping of stripping fluid 16, obtained stripped product 17 and the carbon deposit catalysis after stripping Agent, stripped product 17 enter later separation device;
C) regenerator of carbon deposited catalyst part first inclined tube 8 to be generated after stripping enters 2 close phase section 26 of the first regenerator, Part enters the close phase section 29 of Second reactivator 3 through Second reactivator inclined tube 9 to be generated, or only through Second reactivator inclined tube 9 to be generated Into the close phase section 29 of Second reactivator 3;
D) carbon deposited catalyst after stripping obtains partly again in the first regenerator 2 with the contact of regenerating medium 18 annealing in hydrogen atmosphere, burning carbon Raw catalyst and flue gas 19, flue gas 19 enter follow-up gas energy after gas-solid cyclone separator 24 separates semi regeneration catalyst and returned Receiving apparatus, semi regeneration catalyst enter the close phase section 29 of Second reactivator 3 through semi regeneration agent delivery pipe 10;
E) semi regeneration catalyst and/or stripping after carbon deposited catalyst in Second reactivator 3 and regenerating medium 20 contact Make charcoal to obtain regenerated catalyst and flue gas 21, flue gas 21 enters follow-up cigarette after gas-solid cyclone separator 25 separates regenerated catalyst Gas energy recycle device or the regenerating medium as the first regenerator 2;
F) the degassed tank inclined tube 11 of regenerated catalyst enters degassing tank 5 and degassing medium 22 contacts, and further removes flue gas 23, flue gas 23 enters follow-up flue gas energy recovery device or the regenerating medium as the first regenerator 2, the regeneration catalyzing after degassing Passed through under agent the Returning reactor 1 of regenerator sloped tube 12.
In above-mentioned technical proposal, the regeneration temperature of the first regenerator 2 is 500~600 DEG C, preferably 530~570 DEG C;It is average Empty tower gas velocity is 0.1~0.8 meter per second, preferably 0.2~0.6 meter per second.
In above-mentioned technical proposal, the content of oxygen is 2~21 volume % in the regenerating medium 18 of the first regenerator 2, can be The mixture for the flue gas 23 that air flue gas 21 and/or degassing tank 5 that either Second reactivator 3 obtains obtain or air and second The mixture for the flue gas 23 that the flue gas 21 and/or degassing tank 5 that regenerator 3 obtains obtain.
In above-mentioned technical proposal, the regeneration temperature of Second reactivator 3 is 580~750 DEG C, preferably 630~700 DEG C;It is average Empty tower gas velocity is 0.5~1.2 meter per second, preferably 0.6~1 meter per second.
In above-mentioned technical proposal, the content of oxygen is 21~30 volume % in the regenerating medium 20 of Second reactivator 3, preferably 21~25 volume %;Can be air or air and O2Mixture.
In above-mentioned technical proposal, the charcoal in regenerated catalyst that Second reactivator 3 obtains, with the mass percent of catalyst Meter, content are less than 0.1 weight %, even more preferably below 0.08 weight %.
In above-mentioned technical proposal, the reaction temperature of reactor 1 is 400~550 DEG C, the weight space velocity of raw material 14 for 0.1~ 10 (Grams Per Hours)/gram catalyst, reaction pressure is counted as 0~0.5 MPa using gauge pressure, catalyst internal circulating load and the inlet amount of raw material 14 Mass ratio be 3~40: 1, density of catalyst be 50~200 kgs/m3, the meter per second of average gas superficial velocity 0.01~1.
In above-mentioned technical proposal, catalyst activity component ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, Y molecular sieve or The composite molecular screen formed each other, preferably ZSM-5;Carrier is kaolin, aluminum oxide, silica;Active component and carrier Mass ratio be (10~50): (50~90), preferably (20~40): (60~80).
In above-mentioned technical proposal, catalyst is loaded with one or more elements or oxidation in Zn, Ag, P, Ga, Cu, Mn, Mg Thing, preferably Zn, P;In terms of the mass percent of catalyst, the content of the element of load on a catalyst is 0.01~15 weight Measure %, preferably 0.02~8 weight %.
In above-mentioned technical proposal, the active component of catalyst is selected from ZSM-5 molecular sieve, with the percentage by weight of catalyst Count, 0.01~5 weight % Zn elements or oxide, 0.1~8 weight % P element or oxide are loaded on catalyst.
In above-mentioned technical proposal, raw material 13 is the mixture of methanol or dimethyl ether or both, preferably methanol.
In above-mentioned technical proposal, the weight/mass percentage composition of the reclaimed water of raw material 13 is 0.01~30 weight %, preferably shorter than 10 weights Measure %.
In above-mentioned technical proposal, stripping fluid 16 is water vapour or N2Or water vapour and N2Mixture, lifting medium 15 be Water vapour or N2Or water vapour and N2Mixture, degassing medium 22 be water vapour or N2Or water vapour and N2Mixture.
Technical scheme provided by the invention, using double regenerators regenerate, reclaimable catalyst in the first regenerator low temperature, Oxygen deprivation, quick annealing in hydrogen atmosphere in the short period, the semi regeneration catalyst after annealing in hydrogen atmosphere enter turbulent bed regenerator in high temperature, oxygen-enriched, longer Carbon is thoroughly burnt in time, finally gives the relatively low high activity regenerated catalyst of carbon content.The semi regeneration catalyst of burned hydrogen exists Due to that will not generate substantial amounts of water when continuing to burn carbon under 580~750 DEG C of hot conditions, catalyst hydrothermal dealumination phenomenon substantially subtracts It is weak.
Technical scheme provided by the invention, using catalyst and the fluidized-bed reactor of reaction mass countercurrent movement, can have Effect promotes contact of the reaction mass with catalyst active center, and reduction extends influence, and improves mass-transfer efficiency;It can also expand simultaneously Air speed adjustable range, conveniently realize the purpose of maximum production ethene, propylene and aromatic hydrocarbons.
Using technical scheme, using methanol as raw material, water content is 5 weight %;First regenerator regeneration temperature For 560 DEG C, average gas superficial velocity is 0.3 meter per second, and regenerating medium is air;Second reactivator regeneration temperature is 680 DEG C, average Empty tower gas velocity is 0.7 meter per second, and regenerating medium is air;The reaction temperature of reactor is 480 DEG C, and reaction pressure is in terms of gauge pressure 0.2 MPa, weight space velocity is 2 (Grams Per Hours)/gram catalyst, and the mass ratio of catalyst internal circulating load and feedstock amount is 12: 1, The density of catalyst of reaction zone is double centner/rice in reactor3, the meter per second of average gas superficial velocity 0.7;It is catalyzed using Cu-ZSM-5 Agent;Ethene carbon base absorption rate is 21.7 weight %, propylene carbon base absorption rate is 18.3 weight %, aromatic hydrocarbons carbon base absorption rate is 41.0 weights % is measured, BTX carbon base absorption rates are 32.8 weight %.
Brief description of the drawings
Fig. 1 be technical scheme of the present invention schematic device, Fig. 2 be the first regenerator schematic diagram, Fig. 3 second The schematic diagram of regenerator.
1 is reactor in 1~2 in figure;2 be the first regenerator;3 be Second reactivator;4 be stripper;5 be degassing tank;6 To strip inclined tube;7 be stripping standpipe;8 be the first regenerator inclined tube to be generated;9 be Second reactivator inclined tube to be generated;10 be semi regeneration Agent delivery pipe;11 be degassing tank inclined tube;12 be regenerator sloped tube;13 be raw material;14 be reaction product;15 be lifting medium;16 are Stripping fluid;17 be stripped product;18 be the first regenerator regenerating medium;19 be the first regenerator flue gas;20 be the second regeneration Device regenerating medium;21 be Second reactivator flue gas;22 be degassing medium;23 be degassing tank flue gas;24 be the first regenerator whirlwind Separator;25 be Second reactivator cyclone separator;26 be the close phase section of the first regenerator;27 be the first regenerator changeover portion;28 For the first regenerator dilute phase section;29 be the close phase section of Second reactivator;30 be Second reactivator changeover portion;31 be that Second reactivator is dilute Phase section.
Raw material 13 enters reactor 1 and catalyst haptoreaction, the He of reaction of formation product 14 from the bottom of reactor 1 in Fig. 1 Carbon deposited catalyst, reaction product 14 enter later separation device;The vapour being connected with the bottom of reactor 1 is advanced under carbon deposited catalyst Inclined tube 6 is carried, enters back into stripping standpipe 7, boosted medium 15 is promoted to stripper 4, and the contact stripping of stripping fluid 16, obtained Carbon deposited catalyst after stripped product 17 and stripping, stripped product 17 enter later separation device;Carbon deposited catalyst after stripping Part enters 2 close phase section 26 of the first regenerator through the first regenerator inclined tube 8 to be generated, partly enters through Second reactivator inclined tube 9 to be generated Enter the close phase section 29 of Second reactivator 3, or only enter the close phase section 29 of Second reactivator 3 through Second reactivator inclined tube 9 to be generated;Stripping Carbon deposited catalyst afterwards is in the first regenerator 2 and regenerating medium 18 contacts annealing in hydrogen atmosphere, burning carbon obtains semi regeneration catalyst and flue gas 19, flue gas 19 enters follow-up flue gas energy recovery device, semi regeneration after gas-solid cyclone separator 24 separates semi regeneration catalyst Catalyst enters the close phase section 29 of Second reactivator 3 through semi regeneration agent delivery pipe 10;Carbon deposit after semi regeneration catalyst and/or stripping Catalyst is in Second reactivator 3 and the contact of regenerating medium 20 makes charcoal to obtain regenerated catalyst and flue gas 21, and flue gas 21 is through gas-solid Cyclone separator 25 enters follow-up flue gas energy recovery device after separating regenerated catalyst or the regeneration as the first regenerator 2 is situated between Matter;The degassed tank inclined tube 11 of regenerated catalyst enters degassing tank 5 and degassing medium 22 contacts, and further removes flue gas 23, flue gas 23 is descending into follow-up flue gas energy recovery device or the regenerating medium as the first regenerator 2, the regenerated catalyst after degassing Through the Returning reactor 1 of regenerator sloped tube 12.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
Using device as shown in Figure 1.A diameter of 2 meters of the close phase section of first regenerator, its height accounts for the first regenerator height 80%, the diameter ratio of dilute phase section diameter and close phase section is 1.3:1, its height accounts for the 18% of the first regenerator height.Regeneration temperature Spend for 560 DEG C, average gas superficial velocity is 0.3 meter per second.Regenerating medium is air, and oxygen content is 21 volume %.
A diameter of 1.5 meters of the close phase section of Second reactivator, its height account for the 70% of Second reactivator height, dilute phase section diameter and Close phase section diameter ratio is 1.1:1, its height accounts for the 27% of Second reactivator height.The height of external heat collector accounts for regenerator height The 70% of degree.Regeneration temperature is 680 DEG C, and average gas superficial velocity is 0.7 meter per second.Regenerating medium is air, and oxygen content is 21 bodies Product %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.04 weight %.
The reaction condition of reactor is:Temperature is 480 DEG C, counts reaction pressure as 0.2 MPa using gauge pressure, weight space velocity 2 The mass ratio of (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 12: 1, and reaction zone urges in reactor Agent density is double centner/rice3, the meter per second of average gas superficial velocity 0.7.Using methanol as raw material, water content is 5 weight %.
Stripping fluid is water vapour.Lifting medium is vapor.Degassing medium is N2
Using Cu-ZSM-5 catalyst.
The preparation process of Cu-ZSM-5 catalyst:By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add appropriate Water, HCl, control pH value are not less than 3, and slurries stir urges after spray shaping at 500 DEG C, the ZSM-5 that 60~300 mesh are made Agent intermediate.ZSM-5 molecular sieve and the mass ratio of matrix are 4:6;The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25;Matrix is The mixture of kaolin and alundum (Al2O3), both mass ratioes are 7:3.By Cu mass of ions percentage composition be 5% solution, Using the weight of solution and catalyst ratio as 1.74:1 is impregnated, and is dried 5 hours at 120 DEG C, is placed into Muffle furnace in 550 DEG C Lower roasting is prepared into the Cu-ZSM-5 catalyst that Cu constituent contents are 8 weight % for 6 hours.
【Embodiment 2】
Using device as shown in Figure 1.A diameter of 2.6 meters of the close phase section of first regenerator, its height account for the first regenerator height The diameter ratio of the 90% of degree, the second regenerator section diameter and the first regenerator section is 2:1, its height accounts for the first regenerator height 9%.Regeneration temperature is 500 DEG C, and average gas superficial velocity is 0.1 meter per second.Regenerating medium is air, and oxygen content is 21 volume %.
A diameter of 1.8 meters of the close phase section of Second reactivator, its height account for the 85% of Second reactivator height, dilute phase section diameter and Close phase section diameter ratio is 2:1, its height accounts for the 14% of Second reactivator height.The height of external heat collector accounts for regenerator height 80%.Regeneration temperature is 580 DEG C, and average gas superficial velocity is 0.5 meter per second.Regenerating medium is the mixture of air and oxygen, oxygen Gas content is 30 volume %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.1 weight %.
The reaction condition of reactor is:Temperature is 400 DEG C, counts reaction pressure as 0.5 MPa using gauge pressure, weight space velocity 10 The mass ratio of (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 3: 1, the catalysis of reaction zone in reactor Agent density is 90 kgs/m3, the meter per second of average gas superficial velocity 0.01.Using methanol as raw material, water content is 30 weight %.
Stripping fluid is N2.Lifting medium is N2.Degassing medium is vapor.
Using Ag-Y-ZSM-23 catalyst.
The preparation process of Ag-Y-ZSM-23 catalyst:Y molecular sieve, ZSM-23 molecular screen, carrier and binding agent machinery is mixed Close, add suitable quantity of water, HCl, control pH value is not less than 3, and slurries stir after spray shaping at 500 DEG C, are made 60~300 Purpose Y-ZSM-23 catalyst intermediates.Molecular sieve and the mass ratio of matrix are 1:9;Y molecular sieve and ZSM-23 molecular screen quality Than for 3:7;The silicoaluminophosphate molecular ratio of Y molecular sieve is 10;The silicoaluminophosphate molecular ratio of ZSM-23 molecular screen is 60;Matrix is kaolin and three The mixture of Al 2 O, both mass ratioes are 8:2.By the solution that Ag mass of ions percentage composition is 1%, with solution and urge Agent weight ratio is 0.1:1 is impregnated, and is dried 5 hours at 120 DEG C, places into Muffle furnace and 6 hours systems are calcined at 550 DEG C The standby Ag-Y-ZSM-23 catalyst into Ag constituent contents for 0.1 weight %.
【Embodiment 3】
Using the device of embodiment 1.
First regenerator regeneration temperature is 600 DEG C, and average gas superficial velocity is 0.8 meter per second.Regenerating medium is Second reactivator The mixture for the flue gas that obtained flue gas and degassing tank obtains, oxygen content are 2~4 volume %.
Second reactivator regeneration temperature is 750 DEG C, and average gas superficial velocity is 1.2 meter per seconds.Regenerating medium is air, oxygen Content is 21 volume %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.01 weight %.
The reaction condition of reactor is:Temperature is 550 DEG C, counts reaction pressure as 0 MPa using gauge pressure, weight space velocity 10 The mass ratio of (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 30: 1, and reaction zone urges in reactor Agent density is 50 kgs/m3, the meter per second of average gas superficial velocity 1.Using methanol as raw material, water content is 0.01 weight %.Reaction The height of the external heat collector of device accounts for the 30% of height for reactor.
Stripping fluid is water vapour.Lifting medium is N2.Degassing medium is N2With the mixture of vapor, volume ratio 5: 5。
Using Ga- beta catalysts.
The preparation process of Ga- beta catalysts:By beta-molecular sieve, carrier and binding agent mechanical mixture, suitable quantity of water, HCl, control are added PH value processed is not less than 4, and slurries stir after spray shaping at 500 DEG C, and the beta catalyst intermediate of 60~300 mesh is made.β Molecular sieve and the mass ratio of matrix are 5:5;The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20;Matrix is kaolin, silica and three oxygen Change the mixture of two aluminium, the mass ratio of three is 7:1:2.By the solution that Ga mass of ions percentage composition is 2%, with solution and urge Agent weight ratio is 0.4:1 is impregnated, and is dried 5 hours at 120 DEG C, places into Muffle furnace and 6 hours systems are calcined at 550 DEG C The standby Ga- beta catalysts into Ga constituent contents for 0.8 weight %.
【Embodiment 4】
Using device as shown in Figure 1.A diameter of 3 meters of the close phase section of first regenerator, its height account for the first regenerator height 70%, the diameter ratio of the second regenerator section diameter and the first regenerator section is 1.1:1, its height accounts for the first regenerator height 27%.Regeneration temperature is 540 DEG C, and average gas superficial velocity is 0.7 meter per second.The flue gas that regenerating medium obtains for Second reactivator, oxygen Gas content is 3~6 volume %.
A diameter of 2.2 meters of the close phase section of Second reactivator, its height account for the 50% of Second reactivator height, dilute phase section diameter and Close phase section diameter ratio is 1.1:1, its height accounts for the 47% of Second reactivator height.The height of external heat collector accounts for regenerator height The 30% of degree.Regeneration temperature is 720 DEG C, and average gas superficial velocity is 1 meter per second.Regenerating medium is air, and oxygen content is 21 bodies Product %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.08 weight %.
The reaction condition of reactor is:Temperature is 470 DEG C, counts reaction pressure as 0.3 MPa using gauge pressure, weight space velocity 1 The mass ratio of (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 25: 1, and reaction zone urges in reactor Agent density is 200 kgs/m3, the meter per second of average gas superficial velocity 0.01.Using dimethyl ether as raw material.
Stripping fluid is water vapour and N2Mixture, volume ratio 5: 5.Lifting medium is N2.Degassing medium is N2And water The mixture of steam, volume ratio 9:1.
Using Mn-ZSM-11 catalyst.
The preparation process of Mn-ZSM-11 catalyst:By ZSM-11 molecular sieves, carrier and binding agent mechanical mixture, add suitable Water, HCl are measured, control pH value is not less than 3, and slurries stir after spray shaping at 500 DEG C, and the ZSM- of 60~300 mesh is made 11 catalyst intermediates.ZSM-11 molecular sieves and the mass ratio of matrix are 3:7;The silicoaluminophosphate molecular ratio of ZSM-11 molecular sieves is 50; Matrix is the mixture of kaolin and alundum (Al2O3), and both mass ratioes are 7:3.It is 10% by Mn mass of ions percentage composition Solution, using the weight of solution and catalyst ratio as 1:1 is impregnated, at 120 DEG C dry 5 hours, place into Muffle furnace in The Mn-ZSM-11 catalyst for being prepared into that Mn constituent contents are 9.09 weight % for 6 hours is calcined at 550 DEG C.
【Embodiment 5】
Using the device of embodiment 4.
First regenerator regeneration temperature is 580 DEG C, and average gas superficial velocity is 0.4 meter per second.Regenerating medium is air and second Regenerator obtains the mixture of flue gas, and oxygen content is 10~15 volume %.
Second reactivator regeneration temperature is 700 DEG C, and average gas superficial velocity is 1.2 meter per seconds.Regenerating medium is air and oxygen Mixture, oxygen content are 27 volume %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.07 weight %.
The reaction condition of reactor is:Temperature is 465 DEG C, counts reaction pressure as 0.25 MPa using gauge pressure, weight space velocity is The mass ratio of 0.3 (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 10: 1, reaction zone in reactor Density of catalyst is 180 kgs/m3, the meter per second of average gas superficial velocity 0.05.Using methanol as raw material, water content is 10 weight %.
Stripping fluid is water vapour.It is water vapour and N to lift medium2Mixture, volume ratio 1: 9.Degassing medium be N2
Using Zn-P-ZSM-5 catalyst.
The preparation process of Zn-P-ZSM-5 catalyst:By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add suitable Measure water, H3PO4, not less than 3, slurries stir after spray shaping at 500 DEG C control pH value, and the P- of 60~300 mesh is made ZSM-5 catalyst intermediates.H3PO4The concentration of solution is 1 weight %, and the weight ratio of solution and molecular sieve is 1.53:1.ZSM-5 Molecular sieve and the mass ratio of matrix are 3.5:6.5;The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25;Matrix is kaolin and three oxygen Change the mixture of two aluminium, both mass ratioes are 7:3.By Zn mass of ions percentage composition be 5% solution, with solution and P- ZSM-5 catalyst weights ratio is 0.6:1 is impregnated, and is dried 5 hours at 120 DEG C, is placed into Muffle furnace and be calcined at 550 DEG C 6 hours, it was 2.87 weight % to be prepared into Zn constituent contents, and P element content is 1.48 weight % Zn-P-ZSM-5 catalyst.
【Embodiment 6】
Using device as shown in Figure 1.A diameter of 1.7 meters of the close phase section of first regenerator, its height account for the first regenerator height 80%, the diameter ratio of the second regenerator section diameter and the first regenerator section is 1.1:1, its height accounts for the first regenerator height 18%.Regeneration temperature is 530 DEG C, and average gas superficial velocity is 0.2 meter per second.Regenerating medium is that air and Second reactivator obtain The mixture for the flue gas that flue gas and degassing tank obtain, oxygen content are 16~18 volume %.
A diameter of 2 meters of the close phase section of Second reactivator, its height account for the 60% of Second reactivator height, dilute phase section diameter and close Phase section diameter ratio is 1.8:1, its height accounts for the 37% of Second reactivator height.The height of built-in heat collector accounts for regenerator height 30%, the height of external heat collector accounts for the 50% of regenerator height.Regeneration temperature is 720 DEG C, average gas superficial velocity 1.8 Meter per second.Regenerating medium is air, and oxygen content is 21 volume %.The charcoal on catalyst after regeneration, with the quality hundred of catalyst Divide than meter, content is 0.07 weight %.
The reaction condition of reactor is:Temperature is 480 DEG C, counts reaction pressure as 0.1 MPa using gauge pressure, weight space velocity 2 The mass ratio of (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 20: 1, and reaction zone urges in reactor Agent density is 80 kgs/m3, the meter per second of average gas superficial velocity 0.5.Using dimethyl ether as raw material.
Stripping fluid is water vapour and N2Mixture, volume ratio 2: 8.It is water vapour and N to lift medium2Mixture, Volume ratio is 2: 8.Degassing medium is N2With the mixture of vapor, volume ratio 7:3.
Using ZSM-5- beta catalysts.
The preparation process of ZSM-5- beta catalysts:By ZSM-5 molecular sieve, beta-molecular sieve, carrier and binding agent mechanical mixture, add Enter suitable quantity of water, HCl, control pH value is not less than 3, and slurries stir after spray shaping at 500 DEG C, and 60~300 purposes are made ZSM-5- beta catalysts.ZSM-5 and beta-molecular sieve and the mass ratio of matrix are 3.5: 6.5.The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 38;The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20;The mass ratio of ZSM-5 and beta-molecular sieve is 9:1.Matrix is kaolin, silica With the mixture of alundum (Al2O3), the mass ratio of three is 5:2:3.
【Embodiment 7】
Using the device of embodiment 6.
First regenerator regeneration temperature is 550 DEG C, and average gas superficial velocity is 0.4 meter per second.Regenerating medium is air, oxygen Content is 21 volume %.
Second reactivator regeneration temperature is 650 DEG C, and average gas superficial velocity is 0.8 meter per second.Regenerating medium is air, oxygen Content is 21 volume %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.07 weight %.
The reaction condition of reactor is:Temperature is 450 DEG C, counts reaction pressure as 0.15 MPa using gauge pressure, weight space velocity is The mass ratio of 0.8 (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 15: 1, reaction zone in reactor Density of catalyst is double centner/rice3, the meter per second of average gas superficial velocity 0.3.Using methanol, dimethyl ether mixture as raw material, both Mass ratio is 8:2.
Stripping fluid is water vapour.It is water vapour and N to lift medium2Mixture, volume ratio 8: 2.Degassing medium is N2 With the mixture of vapor, volume ratio 2:8.
Using Zn-Ag-P-ZSM-5 catalyst.
The preparation process of Zn-Ag-P-ZSM-5 catalyst:By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add Suitable quantity of water, H3PO4, not less than 3, slurries stir after spray shaping at 500 DEG C control pH value, and the P- of 60~300 mesh is made ZSM-5 catalyst intermediates.H3PO4The concentration of solution is 2.5 weight %, and the weight ratio of solution and molecular sieve is 2:1.ZSM-5 points Son sieve and the mass ratio of matrix are 3.5:6.5;The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 28;Matrix is kaolin and three oxidations The mixture of two aluminium, both mass ratioes are 8:2.Be 1% by Ag mass of ion percentage compositions, Zn mass of ion percentage compositions be 3% solution, using solution and P-ZSM-5 catalyst weights ratio as 0.8:1 is impregnated, and is dried 5 hours at 120 DEG C, then put Enter Muffle furnace to be calcined 6 hours at 550 DEG C, it is that 2.32 weight %, Ag constituent contents are 0.78 weight to be prepared into Zn constituent contents % is measured, P element content is 1.51 weight % Zn-Ag-P-ZSM-5 catalyst.
【Embodiment 8】
Using device as shown in Figure 1.A diameter of 1 meter of the close phase section of first regenerator, its height account for the first regenerator height 85%, the diameter ratio of the second regenerator section diameter and the first regenerator section is 0.7:1, its height accounts for the first regenerator height 12%.Regeneration temperature is 590 DEG C, and average gas superficial velocity is 0.75 meter per second.Regenerating medium is air, and oxygen content is 21 bodies Product %.
A diameter of 2 meters of the close phase section of Second reactivator, its height account for the 70% of Second reactivator height, dilute phase section diameter and close Phase section diameter ratio is 1.7:1, its height accounts for the 28% of Second reactivator height.The height of built-in heat collector accounts for regenerator height 80%.Regeneration temperature is 740 DEG C, and average gas superficial velocity is 0.9 meter per second.Regenerating medium is air, and oxygen content is 21 bodies Product %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.08 weight %.
The reaction condition of reactor is:Temperature is 460 DEG C, counts reaction pressure as 0.2 MPa using gauge pressure, weight space velocity is The mass ratio of 0.5 (Grams Per Hour)/gram catalyst, catalyst internal circulating load and feedstock amount is 30: 1, reaction zone in reactor Density of catalyst is 150 kgs/m3, the meter per second of average gas superficial velocity 0.1.Using methanol as raw material, water content is 0.01 weight %.
Stripping fluid is water vapour and N2Mixture, volume ratio 8: 2.It is water vapour and N to lift medium2Mixture, Volume ratio is 5: 5.Degassing medium is N2
Using Zn-Mg-P-ZSM-5 catalyst.
The preparation process of Zn-Mg-P-ZSM-5 catalyst:By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add Suitable quantity of water, H3PO4, not less than 3, slurries stir after spray shaping at 500 DEG C control pH value, and the P- of 60~300 mesh is made ZSM-5 catalyst intermediates.H3PO4The concentration of solution is 4 weight %, and the weight ratio of solution and molecular sieve is 2:1.ZSM-5 molecules Sieve and the mass ratio of matrix are 3:7;The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 32;Matrix is kaolin and alundum (Al2O3) Mixture, both mass ratioes are 7:3.Be 2% by Mg mass of ion percentage compositions, Zn mass of ion percentage compositions be 3% Solution, using solution and P-ZSM-5 catalyst weights ratio as 1:1 is impregnated, and is dried 5 hours at 120 DEG C, is placed into Muffle furnace It is calcined 6 hours at 550 DEG C, it is that 2.86 weight %, Mg constituent contents are 1.9 weight % to be prepared into Zn constituent contents, and P element contains Measure as 2.35 weight % Zn-Mg-P-ZSM-5 catalyst.Table 1
Yield of ethene, weight % Propene yield, weight % Aromatics yield, weight %
Embodiment 1 21.7 18.3 41.0
Embodiment 2 12.3 10.4 57.2
Embodiment 3 20.2 17.9 43.1
Embodiment 4 13.8 10.2 58.3
Embodiment 5 11.1 7.8 62.2
Embodiment 6 15.9 14.2 52.4
Embodiment 7 12.6 8.8 60.2
Embodiment 8 16.5 12.0 53.5

Claims (7)

1. a kind of methanol and/or dimethyl ether catalysis convert double regenerator fluidized bed reactions of ethene and aromatic hydrocarbons processed, including anti- Answer device (1), the first regenerator (2), Second reactivator (3), the device of stripper (4);Raw material (13) enters from reactor (1) bottom Enter reactor (1) and catalyst haptoreaction, stripping standpipe (7) of being passed through under reacted carbon deposited catalyst is promoted to stripper (4) strip;Stripping rear catalyst enters the first regenerator (2) and/or Second reactivator (3);Regenerated through the first regenerator (2) To semi regeneration catalyst continue to regenerate into Second reactivator (3);The regenerated catalyst obtained through Second reactivator (3) regeneration Returning reactor (1) after being deaerated into degassing tank (5);
First regenerator (2) is from bottom to top close phase section (26), changeover portion (27), dilute phase section (28);Regeneration temperature be 500~ 600 DEG C, the content of oxygen is 2~21 volume % in regenerating medium (18);
Second reactivator (3) is from bottom to top close phase section (29), changeover portion (30), dilute phase section (31);Regeneration temperature be 580~ 750 DEG C, the content of oxygen is 21~30 volume % in regenerating medium (20);
The stripping inclined tube (6) being connected with reactor (1) bottom is advanced under the carbon deposited catalyst of reactor (1) generation, then through vapour Carry standpipe (7) and be promoted to stripper (4);Strip rear catalyst the first regenerator of part inclined tube to be generated (8) and enter the first regeneration Device (2) close phase section (26), partly enter Second reactivator (3) close phase section (29) through Second reactivator inclined tube to be generated (9), or only Enter Second reactivator (3) close phase section (28) through turbulent bed inclined tube to be generated (9);Through the first regenerator (2) regeneration obtain partly again Raw catalyst continues to regenerate through semi regeneration agent delivery pipe (10) into Second reactivator (3) close phase section (29);Through Second reactivator (3) the degassed tank inclined tube (11) of regenerated catalyst that regeneration obtains deaerates into degassing tank (5);Regenerated catalyst is through again after degassing Raw inclined tube (12) Returning reactor (1);
The height of first regenerator (2) close phase section (26) accounts for the 70~90% of the first regenerator total height;Dilute phase section (28) diameter It is 1.1~2 with close phase section (26) diameter ratio:1, its height accounts for the 9~27% of the first regenerator total height;Changeover portion (27) is high Degree accounts for the 1~3% of the first regenerator total height;
The height of Second reactivator (3) close phase section (29) accounts for the 50~85% of Second reactivator total height;Dilute phase section (31) diameter It is 1.1~2 with close phase section (29) diameter ratio:1, its height accounts for the 14~47% of Second reactivator total height;Changeover portion (30) Highly account for the 1~3% of Second reactivator total height;Second reactivator (3) internally and/or externally sets heat collector, heat collector height Degree accounts for the 30%~80% of Second reactivator height.
2. methanol according to claim 1 and/or dimethyl ether catalysis convert double regenerator fluid beds of ethene and aromatic hydrocarbons processed Reaction unit, it is characterised in that be provided with one group of gas-solid cyclone separator (24) at the top of the first regenerator (2), be 1~3 grade;Second One group of gas-solid cyclone separator (25) is provided with the top of regenerator (3), is 1~3 grade.
3. a kind of methanol and/or dimethyl ether catalysis convert double regenerator fluidized bed reaction methods of ethene and aromatic hydrocarbons processed, using power Profit requires the device described in 1 or 2, and described method includes following steps:
A) raw material (13) enters reactor (1) and catalyst haptoreaction from reactor (1) bottom, reaction of formation product (14) and Carbon deposited catalyst, reaction product (14) enter later separation device;
B) the stripping inclined tube (6) being connected with reactor (1) bottom is advanced under carbon deposited catalyst, enters back into stripping standpipe (7), warp Lifting medium (15) is promoted to stripper (4), and stripping fluid (16) contact strips, after obtained stripped product (17) and stripping Carbon deposited catalyst, stripped product (17) enters later separation device;
C) regenerator of carbon deposited catalyst part first inclined tube to be generated (8) after stripping enters the first regenerator (2) close phase section (26), partly Second reactivator (3) close phase section (29) is entered through Second reactivator inclined tube to be generated (9), or only through the second regeneration Device inclined tube to be generated (9) enters Second reactivator (3) close phase section (29);
E) carbon deposited catalyst after stripping obtains partly again in the first regenerator (2) neutralization regenerating medium (18) contact annealing in hydrogen atmosphere, burning carbon Raw catalyst and flue gas (19), flue gas (19) enter follow-up flue gas after gas-solid cyclone separator (24) separates semi regeneration catalyst Energy recycle device, semi regeneration catalyst enter Second reactivator (3) close phase section (29) through semi regeneration agent delivery pipe (10);
F) semi regeneration catalyst and/or stripping after carbon deposited catalyst Second reactivator (3) neutralize regenerating medium (20) contact Make charcoal to obtain regenerated catalyst and flue gas (21), flue gas (21) enters after gas-solid cyclone separator (25) separates regenerated catalyst Follow-up flue gas energy recovery device or the regenerating medium as the first regenerator (2);
G) the degassed tank inclined tube (11) of regenerated catalyst enters degassing tank (5) and degassing medium (22) contact, further removes cigarette Gas (23), flue gas (23) enters follow-up flue gas energy recovery device or the regenerating medium as the first regenerator (2), after degassing Passed through under regenerated catalyst regenerator sloped tube (12) Returning reactor (1).
4. methanol according to claim 3 and/or dimethyl ether catalysis convert double regenerator fluid beds of ethene and aromatic hydrocarbons processed Reaction method, it is characterised in that the regeneration temperature of the first regenerator (2) be 500~600 DEG C, average gas superficial velocity be 0.1~ 0.8 meter per second, the content of oxygen is 2~21 volume % in regenerating medium (18), is obtained for air or Second reactivator (3) The flue gas that the mixture or air and Second reactivator (3) for the flue gas (23) that flue gas (21) and/or degassing tank (5) obtain obtain And/or the obtained mixture of flue gas (23) of degassing tank (5) (21);The regeneration temperature of Second reactivator (3) is 580~750 DEG C, Average gas superficial velocity is 0.5~1.2 meter per second, and the content of oxygen is 21~30 volume % in regenerating medium (20), is air or sky Gas and O2Mixture;The charcoal in regenerated catalyst that Second reactivator (3) regeneration obtains, with the mass percent of catalyst Meter, content are less than 0.1 weight %.
5. methanol according to claim 3 and/or dimethyl ether catalysis convert double regenerator fluid beds of ethene and aromatic hydrocarbons processed Reaction method, it is characterised in that the reaction temperature of reactor (1) is 400~550 DEG C, the weight space velocity of raw material (13) for 0.1~ 10 (Grams Per Hours)/gram catalyst, reaction pressure is counted as 0~0.5 MPa using gauge pressure, catalyst internal circulating load and raw material (13) charging The mass ratio of amount is 3~40: 1, and density of catalyst is 50~200 kgs/m3, the meter per second of average gas superficial velocity 0.01~1.
6. methanol according to claim 3 and/or dimethyl ether catalysis convert double regenerator fluid beds of ethene and aromatic hydrocarbons processed Reaction method, it is characterised in that the active component of catalyst is ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, Y molecular sieve or phase The composite molecular screen formed between mutually;Carrier is kaolin, aluminum oxide, silica;The mass ratio of active component and carrier is (10 ~50): (50~90);Catalyst is loaded with one or more elements or oxide in Zn, Ag, P, Ga, Cu, Mn, Mg, with catalysis The mass percent meter of agent, its content are 0.01~15 weight %.
7. methanol according to claim 3 and/or dimethyl ether catalysis convert double regenerator fluid beds of ethene and aromatic hydrocarbons processed Reaction method, it is characterised in that raw material (13) is the mixture of methanol or dimethyl ether or both, and the weight/mass percentage composition of water is 0.01~30 weight %;Stripping fluid (16) is water vapour or N2Or water vapour and N2Mixture, lifting medium (15) be water steaming Vapour or N2Or water vapour and N2Mixture;The medium (22) that deaerates is water vapour or N2Or water vapour and N2Mixture.
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CN109694293B (en) * 2017-10-20 2022-02-01 中国石油化工股份有限公司 Method for preparing aromatic hydrocarbon by catalytic conversion of methanol
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CN111056901B (en) * 2018-10-17 2022-10-11 中国石油化工股份有限公司 Reaction system and reaction method for preparing aromatic hydrocarbon through catalytic conversion of methanol
KR20230013253A (en) * 2020-10-16 2023-01-26 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 Recycling device, device for producing low carbon olefin and its application

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