CN105457569B - Double the regenerator reaction units and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons - Google Patents
Double the regenerator reaction units and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons Download PDFInfo
- Publication number
- CN105457569B CN105457569B CN201410454386.3A CN201410454386A CN105457569B CN 105457569 B CN105457569 B CN 105457569B CN 201410454386 A CN201410454386 A CN 201410454386A CN 105457569 B CN105457569 B CN 105457569B
- Authority
- CN
- China
- Prior art keywords
- regenerator
- catalyst
- bed
- bed regenerator
- fast
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- Y02P30/40—Ethylene production
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methanol and/or double the regenerator fluidized bed reactions and its reaction method of dimethyl ether conversion propylene and aromatic hydrocarbons, mainly solve the problems, such as alkene in the prior art and aromatics yield is low, catalyst hydrothermal deactivation is serious.The present invention is by including reactor, fast bed regenerator, turbulent bed regenerator, stripper, settler, the device of degassing tank, raw material enters reactor and catalyst haptoreaction from reactor lower part, reacted carbon deposited catalyst strips through stripper enters fast bed regenerator and/or turbulent bed regenerator, continue to regenerate into turbulent bed regenerator after the partial catalyst of fast bed regenerator regeneration goes upward to settler sedimentation, regenerate the technical scheme of Returning reactor after the degassed tank of complete catalyst deaerates, preferably solves the problem, available in alkene and arene industrial production.
Description
Technical field
The present invention relates to a kind of methanol and/or double regenerator fluidized bed reactions of dimethyl ether conversion alkene and aromatic hydrocarbons
And its reaction method.
Background technology
Alkene and aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) are important
Basic organic synthesis raw material.Driven by downstream derivative thing demand, the market demand sustainable growth of alkene and aromatic hydrocarbons.
It is alkene and aromatic hydrocarbons with the steam cracking process that liquid hydrocarbon (such as naphtha, diesel oil, secondary operation oil) is raw material
Main production.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 is continuously increased.By factor, alternative materials prepare alkene and aromatic hydrocarbons technology causes and closed more and more widely
Note.Wherein, for coal-based methanol, dimethyl ether raw material, due to rich coal resources in China, it is increasingly becoming a kind of important chemical industry
Raw materials for production, turn into the important supplement of petroleum.Accordingly, it is considered to alkene and virtue are prepared as raw material using methanol and/or dimethyl ether
Hydrocarbon.
In various existing methanol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons is simultaneously
Including alkene and aromatic hydrocarbons.The technology initially see Chang of Mobil companies in 1977 et al. (Journal of Catalysis,
1977,47,249) methanol and its oxygenatedchemicals conversion on ZSM-5 molecular sieve catalyst are reported and prepares hydrocarbonization such as aromatic hydrocarbons
The method of compound.1985, Mobil companies disclosed methanol, diformazan first in its United States Patent (USP) applied US1590321
The result of study of ether conversion for preparing arene, it is catalyst that the research, which uses the phosphorous ZSM-5 molecular sieve for 2.7 weight %, reaction temperature
Spend for 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, and alkene belongs to secondary
Product, yield are low.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 alkene and low aromatics yield in above-mentioned patented technology all be present.The present invention pointedly proposes technical side
Case, 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 alkene and aromatics yield are low in the prior art, and catalyst hydro-thermal is lost
A kind of serious technical problem living, there is provided double regenerator fluidized-bed reactions of methanol and/or dimethyl ether conversion alkene and aromatic hydrocarbons
Device.The device has alkene and aromatics yield height, effectively mitigates the advantages of catalyst hydrothermal deactivation.
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 conversion system
Double regenerator fluidized bed reactions of alkene and aromatic hydrocarbons, including reactor 1, fast bed regenerator 2, turbulent bed regenerator 3, stripping
The device of device 4, settler 5；Raw material 14 enters reactor 1 and catalyst haptoreaction, reacted carbon deposit from the bottom of reactor 1
Stripping standpipe 8 of being passed through under catalyst is promoted to stripper 4 and stripped；Stripping rear catalyst enters fast bed regenerator 2 and/or turbulent bed
Regenerator 3；Settler 5 is advanced on the semi regeneration catalyst obtained through the regeneration of fast bed regenerator 2, the semi regeneration catalysis after sedimentation
Agent continues to regenerate into turbulent bed regenerator 3；It is de- into degassing tank 6 that obtained regenerated catalyst is regenerated through turbulent bed regenerator 3
Returning reactor 1 after gas；Fast bed regenerator 2 is from bottom to top the first regenerator section 25, changeover portion 26, the second regenerator section 27, regeneration
Temperature is 500~600 DEG C, and the content of oxygen is 2~21 volume % in regenerating medium 17；Fast bed regenerator 2 and settler 5 are coaxial
Arrangement, the top of the second regenerator section 27 of fast bed regenerator 2 is located in settler 5；Turbulent bed regenerator 3 is close phase section from bottom to top
28th, changeover portion 29, dilute phase section 30；Regeneration temperature is 580~750 DEG C, and the content of oxygen is 21~30 bodies in regenerating medium 19
Product %.
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 7, then it is promoted to stripper 4 through stripping standpipe 8；Strip rear catalyst part and enter the regeneration of fast bed through fast bed inclined tube 13 to be generated
The regenerator section 25 of device 2 first, partly enter 3 close phase section 28 of turbulent bed regenerator through turbulent bed inclined tube 9 to be generated, or only through turbulent bed
Inclined tube 9 to be generated enters 3 close phase section 28 of turbulent bed regenerator；Advanced on the semi regeneration catalyst obtained through the regeneration of fast bed regenerator 2
Enter settler 5, the semi regeneration catalyst after sedimentation enters 3 close phase section 28 of turbulent bed regenerator through semi regeneration agent delivery pipe 10 to be continued
Regeneration；The obtained degassed tank inclined tube 11 of regenerated catalyst is regenerated through turbulent bed regenerator 3 to deaerate into degassing tank 6；After degassing
Regenerated catalyst is through the Returning reactor 1 of regenerator sloped tube 12.
In above-mentioned technical proposal, the height of the fast regenerator section 25 of bed regenerator 2 first account for fast bed regenerator total height 70~
90%；The diameter of second regenerator section 27 and the diameter ratio of the first regenerator section 25 are 0.3~1.2:1, preferably 0.4~0.9:1；Second again
The raw height of section 27 accounts for the 9~27% of fast bed regenerator total height；The height of changeover portion 26 accounts for the 1~3% of fast bed regenerator total height.
In above-mentioned technical proposal, the height of the close phase section 28 of turbulent bed regenerator 3 account for turbulent bed regenerator total height 60~
90%；The diameter of dilute phase section 27 and the diameter ratio of close phase section 25 are 1.1~3:1, preferably 1.1~2:1；Dilute phase section highly accounts for turbulent bed
The 9~37% of regenerator total height；The height of changeover portion 29 accounts for the 1~3% of turbulent bed regenerator total height；
In above-mentioned technical proposal, turbulent bed regenerator 3 is internal or external to set heat collector, and heat collector highly accounts for turbulent bed again
The 30%~80% of raw device height.
In above-mentioned technical proposal, the top of turbulent bed regenerator 3 is provided with one group of gas-solid cyclone separator 32, is 1~3 grade；It is heavy
The top of drop device 5 is provided with one group of gas-solid cyclone separator 31, is 1~3 grade
In above-mentioned technical proposal, reactor 1, for raw material 14 and catalyst haptoreaction to be converted into alkene and aromatic hydrocarbons
Based on product；Fast bed regenerator 2, for removing the hydrogen on carbon deposited catalyst in coke, generates semi regeneration catalyst；Turbulent bed
Regenerator 3, for the coke on semi regeneration catalyst, generate regenerated catalyst；Stripper 4, for carbon deposited catalyst to be stripped off
The product of upper carrying；Settler 5, the semi regeneration catalyst obtained for settling fast bed regenerator；Degassing tank 6, for further
Remove the regenerated flue gas of the regenerated catalyst entrainment after the regeneration of turbulent bed regenerator.
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 conversion system
Double regenerator fluidized bed reaction methods of alkene and aromatic hydrocarbons, using above-mentioned device, described method includes following steps：
A) raw material 14 enters reactor 1 and catalyst haptoreaction, reaction of formation product 24 and carbon deposit from the bottom of reactor 1
Catalyst, reaction product 24 enter later separation device；
B) the stripping inclined tube 7 being connected with the bottom of reactor 1 is advanced under carbon deposited catalyst, stripping standpipe 8 is entered back into, through carrying
Rise medium 23 and be promoted to stripper 4, and the contact stripping of stripping fluid 15, obtained stripped product 16 and the carbon deposit catalysis after stripping
Agent, stripped product 16 enter later separation device；
C) the carbon deposited catalyst part after stripping enters the fast regenerator section 25 of bed regenerator 2 first through fast bed inclined tube 13 to be generated,
Part enters 3 close phase section 28 of turbulent bed regenerator through turbulent bed inclined tube 9 to be generated, or only enters rapids through turbulent bed inclined tube 9 to be generated
Dynamic 3 close phase section 28 of bed regenerator；
D) carbon deposited catalyst after stripping obtains partly again in fast bed regenerator 2 with the contact of regenerating medium 17 annealing in hydrogen atmosphere, burning carbon
Raw catalyst and flue gas 18, are above advanced into settler 5, semi regeneration catalyst sedimentation, flue gas 18 divides through gas-solid cyclone separator 31
From follow-up flue gas energy recovery device is entered after semi regeneration catalyst, the semi regeneration catalyst of sedimentation is through semi regeneration agent delivery pipe 10
Into the close phase section 28 of turbulent bed regenerator 3；
E) semi regeneration catalyst and/or stripping after carbon deposited catalyst in turbulent bed regenerator 3 and regenerating medium 19 connect
Touch and make charcoal to obtain regenerated catalyst and flue gas 20, flue gas 20 enters follow-up after gas-solid cyclone separator 32 separates regenerated catalyst
Flue gas energy recovery device or the regenerating medium as fast bed regenerator 2；
F) the degassed tank inclined tube 11 of regenerated catalyst enters degassing tank 6 and degassing medium 21 contacts, and further removes flue gas
22, flue gas 22 enters follow-up flue gas energy recovery device or the regenerating medium as fast bed 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 fast bed regenerator 2 is 500~600 DEG C, preferably 530~570 DEG C；It is average
Empty tower gas velocity is 1~8 meter per second, preferably 1.5~5 meter per seconds,
In above-mentioned technical proposal, the content of oxygen is 2~21 volume % in the regenerating medium 17 of fast bed regenerator 2, preferably 3
~15 volume %；Can be the mixed of the flue gas 22 that the obtained flue gas 20 of air or turbulent bed regenerator 3 and/or degassing tank 6 obtain
The mixture for the flue gas 22 that the flue gas 20 and/or degassing tank 6 that compound or air and turbulent bed regenerator 3 obtain obtain.
In above-mentioned technical proposal, the regeneration temperature of turbulent bed regenerator 3 is 580~750 DEG C, preferably 630~700 DEG C；It is flat
Equal empty tower gas velocity is 0.5~2 meter per second, preferably 0.8~1.5 meter per second.
In above-mentioned technical proposal, the content of oxygen is 21~30 volume % in the regenerating medium 19 of turbulent bed regenerator 3, excellent
Select 21~25 volume %；Can be air or air and O2Mixture.
In above-mentioned technical proposal, the charcoal in regenerated catalyst that turbulent bed regenerator 3 obtains, with the quality percentage of catalyst
Than meter, content is 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 14 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 14 is 0.01~30 weight %, preferably shorter than 10 weights
Measure %.
In above-mentioned technical proposal, stripping fluid 15 is water vapour or N2Or water vapour and N2Mixture, lifting medium 23 be
Water vapour or N2Or water vapour and N2Mixture, degassing medium 21 be water vapour or N2Or water vapour and N2Mixture.
Technical scheme provided by the invention, using double regenerators regenerate, reclaimable catalyst in fast bed 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 alkene and aromatic hydrocarbons.
Using technical scheme, using methanol as raw material, water content is 5 weight %；Fast bed regenerator regeneration temperature
For 560 DEG C, average gas superficial velocity is 2 meter per seconds, and regenerating medium is air；Turbulent bed regenerator regeneration temperature is 650 DEG C, average
Empty tower gas velocity is 0.8 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 0.2；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 is the schematic device of technical scheme of the present invention, and Fig. 2 is the schematic diagram of fast bed regenerator, and Fig. 3 is turbulence
The schematic diagram of bed regenerator.
1 is reactor in 1~2 in figure；2 be fast bed regenerator；3 be turbulent bed regenerator；4 be stripper；5 be sedimentation
Device；6 be degassing tank；7 be stripping inclined tube；8 be stripping standpipe；9 be turbulent bed inclined tube to be generated；10 be semi regeneration agent delivery pipe；11
For degassing tank inclined tube；12 be regenerator sloped tube；13 be fast bed inclined tube to be generated；14 be raw material；15 be stripping fluid；16 be stripping production
Thing；17 be fast bed regenerator regenerating medium；18 be fast bed regenerator flue gas；19 be turbulent bed regenerator regenerating medium；20 be rapids
Dynamic bed regenerator flue gas；21 be degassing medium；22 be degassing tank flue gas；23 be lifting medium；24 be reaction product；25 be fast bed
The regenerator section of regenerator first；26 be fast bed regenerator changeover portion；27 be the fast regenerator section of bed regenerator second；28 be that turbulent bed regenerates
The close phase section of device；29 be turbulent bed regenerator changeover portion；30 be turbulent bed regenerator dilute phase section.
Raw material 14 enters reactor 1 and catalyst haptoreaction, the He of reaction of formation product 24 from the bottom of reactor 1 in Fig. 1
Carbon deposited catalyst, reaction product 24 enter later separation device after gas-solid cyclone separator separates carbon deposited catalyst；Carbon deposit is urged
The stripping inclined tube 7 being connected with the bottom of reactor 1 is advanced under agent, enters back into stripping standpipe 8, boosted medium 23 is promoted to vapour
Device 4 is carried, and the contact stripping of stripping fluid 15, obtained stripped product 16 pass through with the carbon deposited catalyst after stripping, stripped product 16
Enter later separation device after gas-solid cyclone separator separation carbon deposited catalyst；Treated through fast bed carbon deposited catalyst part after stripping
Raw inclined tube 13 enters the fast regenerator section 25 of bed regenerator 2 first, and it is close partly to enter turbulent bed regenerator 3 through turbulent bed inclined tube 9 to be generated
Phase section 28, or only enter 3 close phase section 28 of turbulent bed regenerator through turbulent bed inclined tube 9 to be generated；Carbon deposited catalyst after stripping exists
In fast bed regenerator 2 and regenerating medium 17 contacts annealing in hydrogen atmosphere, burning carbon obtains semi regeneration catalyst and flue gas 18, is above advanced into settler
5, semi regeneration catalyst sedimentation, flue gas 18 enters follow-up gas energy after gas-solid cyclone separator separates semi regeneration catalyst and returned
Receiving apparatus, the semi regeneration catalyst of sedimentation enter 3 close phase section 28 of turbulent bed regenerator through semi regeneration agent delivery pipe 10；Semi regeneration is urged
Carbon deposited catalyst after agent and/or stripping contacts with regenerating medium 19 in turbulent bed regenerator 3 and makes charcoal to obtain regeneration catalyzing
Agent and flue gas 20, flue gas 20 enter follow-up flue gas energy recovery device or work after gas-solid cyclone separator separates regenerated catalyst
For the regenerating medium of fast bed regenerator 2；The degassed tank inclined tube 11 of regenerated catalyst enters degassing tank 6 and degassing medium 21 contacts,
Flue gas 22 is further removed, flue gas 22 enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator 2, takes off
Passed through under regenerated catalyst after gas 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.Fast a diameter of 1.5 meters of bed the first regenerator section of regenerator, its height accounts for fast bed regenerator
The diameter ratio of the 80% of height, the second regenerator section diameter and the first regenerator section is 0.8:1, its height accounts for fast bed regenerator height
15%.Regeneration temperature is 560 DEG C, and average gas superficial velocity is 2 meter per seconds.Regenerating medium is air, and oxygen content is 21 bodies
Product %.
A diameter of 3 meters of the close phase section of turbulent bed regenerator, its height account for the 70% of turbulent bed regenerator height, dilute phase section diameter
It is 1.3 with close phase section diameter ratio:1, its height accounts for the 27% of turbulent bed regenerator height.The height of external heat collector accounts for regeneration
The 70% of device height.Regeneration temperature is 650 DEG C, and average gas superficial velocity is 0.8 meter per second.Regenerating medium is air, and oxygen content is
21 volume %.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 0.2.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.Fast a diameter of 1.8 meters of bed the first regenerator section of regenerator, its height account for fast bed regeneration
The diameter ratio of the 90% of device height, the second regenerator section diameter and the first regenerator section is 0.3:1, it is high that its height accounts for fast bed regenerator
The 9% of degree.Regeneration temperature is 500 DEG C, and average gas superficial velocity is 1 meter per second.Regenerating medium is air, and oxygen content is 21 bodies
Product %.
A diameter of 2.6 meters of the close phase section of turbulent bed regenerator, its height accounts for the 90% of turbulent bed regenerator height, dilute phase Duan Zhi
Footpath and close phase section diameter ratio are 3:1, its height accounts for the 9% of turbulent bed regenerator height.The height of external heat collector accounts for regeneration
The 80% of device height.Regeneration temperature is 580 DEG C, and average gas superficial velocity is 0.5 meter per second.Regenerating medium is the mixed of air and oxygen
Compound, oxygen content are 30 volume %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content 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 0.17.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.
Fast bed regenerator regeneration temperature is 600 DEG C, and average gas superficial velocity is 8 meter per seconds.Regenerating medium is turbulent bed regenerator
The mixture for the flue gas that obtained flue gas and degassing tank obtains, oxygen content are 2~4 volume %.
Turbulent bed regenerator regeneration temperature is 750 DEG C, and average gas superficial velocity is 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.Fast a diameter of 2.5 meters of bed the first regenerator section of regenerator, its height account for fast bed regeneration
The diameter ratio of the 70% of device height, the second regenerator section diameter and the first regenerator section is 1.2:1, it is high that its height accounts for fast bed regenerator
The 27% of degree.Regeneration temperature is 540 DEG C, and average gas superficial velocity is 3 meter per seconds.Regenerating medium is the cigarette that turbulent bed regenerator obtains
Gas, oxygen content are 3~6 volume %.
A diameter of 4 meters of the close phase section of turbulent bed regenerator, its height account for the 60% of turbulent bed regenerator height, dilute phase section diameter
It is 1.1 with close phase section diameter ratio:1, its height accounts for the 37% of turbulent bed regenerator height.The height of external heat collector accounts for regeneration
The 30% of device height.Regeneration temperature is 720 DEG C, and average gas superficial velocity is 1.5 meter per seconds.Regenerating medium is air, and oxygen content is
21 volume %.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.
Fast bed regenerator regeneration temperature is 580 DEG C, and average gas superficial velocity is 5 meter per seconds.Regenerating medium is air and turbulent bed
Regenerator obtains the mixture of flue gas, and oxygen content is 10~15 volume %.
Turbulent bed regenerator regeneration temperature is 700 DEG C, and average gas superficial velocity is 1.2 meter per seconds.Regenerating medium is air and oxygen
Gas mixture, oxygen content are 27 volume %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content
For 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.Fast a diameter of 2 meters of bed the first regenerator section of regenerator, it is high that its height accounts for fast bed regenerator
The diameter ratio of the 80% of degree, the second regenerator section diameter and the first regenerator section is 1.1:1, its height accounts for fast bed regenerator height
18%.Regeneration temperature is 530 DEG C, and average gas superficial velocity is 3 meter per seconds.Regenerating medium is that air and turbulent bed regenerator 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 turbulent bed regenerator, its height account for the 80% of turbulent bed regenerator height, dilute phase section diameter
It is 2 with close phase section diameter ratio:1, its height accounts for the 17% of turbulent bed regenerator height.The height of built-in heat collector accounts for regenerator
The 30% of height.Regeneration temperature is 720 DEG C, and average gas superficial velocity is 1.8 meter per seconds.Regenerating medium is air, oxygen content 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 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.
Fast bed regenerator regeneration temperature is 550 DEG C, and average gas superficial velocity is 2 meter per seconds.Regenerating medium is air, and oxygen contains
Measure as 21 volume %.
Turbulent bed regenerator regeneration temperature is 650 DEG C, and average gas superficial velocity is 0.8 meter per second.Regenerating medium is air, oxygen
Gas content is 21 volume %.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.07 weight
Measure %.
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.Fast a diameter of 1.7 meters of bed the first regenerator section of regenerator, its height account for fast bed regeneration
The diameter ratio of the 85% of device height, the second regenerator section diameter and the first regenerator section is 0.7:1, it is high that its height accounts for fast bed regenerator
The 12% of degree.Regeneration temperature is 590 DEG C, and average gas superficial velocity is 6 meter per seconds.Regenerating medium is air, and oxygen content is 21 bodies
Product %.
A diameter of 2 meters of the close phase section of turbulent bed regenerator, its height account for the 70% of turbulent bed regenerator height, dilute phase section diameter
It is 2.2 with close phase section diameter ratio:1, its height accounts for the 28% of turbulent bed regenerator height.The height of built-in heat collector accounts for regeneration
The 80% of device height.Regeneration temperature is 740 DEG C, and average gas superficial velocity is 1.5 meter per seconds.Regenerating medium is air, and oxygen content is
21 volume %.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
Claims (8)
1. double regenerator fluidized bed reactions of a kind of methanol and/or dimethyl ether conversion alkene and aromatic hydrocarbons, including reactor
(1), fast bed regenerator (2), turbulent bed regenerator (3), stripper (4), the device of settler (5)；Raw material (14) is from reactor
(1) bottom enters reactor (1) and catalyst haptoreaction, stripping standpipe (8) lifting of being passed through under reacted carbon deposited catalyst
Stripped to stripper (4)；Stripping rear catalyst enters fast bed regenerator (2) and/or turbulent bed regenerator (3)；Regenerated through fast bed
Settler (5) is advanced on the semi regeneration catalyst that device (2) regeneration obtains, the semi regeneration catalyst after sedimentation enters turbulent bed again
Raw device (3) continues to regenerate；The regenerated catalyst obtained through turbulent bed regenerator (3) regeneration returns after entering degassing tank (6) degassing
Reactor (1)；
Fast bed regenerator (2) is from bottom to top the first regenerator section (25), changeover portion (26), the second regenerator section (27)；Regeneration temperature
For 500~600 DEG C, the content of oxygen is 2~21 volume % in regenerating medium (17)；
Fast bed regenerator (2) and settler (5) are coaxially arranged, and the second regenerator section (27) top of fast bed regenerator (2) is positioned at heavy
Drop in device (5)；
Turbulent bed regenerator (3) is from bottom to top close phase section (28), changeover portion (29), dilute phase section (30)；Regeneration temperature be 580~
750 DEG C, the content of oxygen is 21~30 volume % in regenerating medium (19)；
The height of the fast regenerator section (25) of bed regenerator (2) first accounts for the 70~90% of fast bed regenerator total height；Second regenerator section
(27) diameter and the first regenerator section (25) diameter ratio are 0.3~1.2:1, the second regenerator section highly accounts for fast bed regenerator total height
9~27%；Changeover portion (26) highly accounts for the 1~3% of fast bed regenerator total height；
The height of turbulent bed regenerator (3) close phase section (28) accounts for the 60~90% of turbulent bed regenerator total height；Dilute phase section (27)
Diameter and close phase section (25) diameter ratio are 1.1~3:1, dilute phase section highly accounts for the 9~37% of turbulent bed regenerator total height；Cross
Cross section (29) highly accounts for turbulent bed regenerator total height 1~3%；Turbulent bed regenerator (3) is internal or external to set heat collector,
Heat collector highly accounts for the 30%~80% of turbulent bed regenerator height.
2. double regenerator fluidized-bed reactions of methanol according to claim 1 and/or dimethyl ether conversion alkene and aromatic hydrocarbons
Device, it is characterised in that be advanced into the stripping inclined tube being connected with reactor (1) bottom under the carbon deposited catalyst of reactor (1) generation
(7), then through stripping standpipe (8) it is promoted to stripper (4)；Strip rear catalyst part and enter fast bed through fast bed inclined tube to be generated (13)
The regenerator section (25) of regenerator (2) first, partly enter turbulent bed regenerator (3) close phase section (28) through turbulent bed inclined tube to be generated (9),
Or only enter turbulent bed regenerator (3) close phase section (28) through turbulent bed inclined tube to be generated (9)；Regenerated through fast bed regenerator (2)
To semi regeneration catalyst on be advanced into settler (5), the semi regeneration catalyst after sedimentation enters through semi regeneration agent delivery pipe (10)
Enter turbulent bed regenerator (3) close phase section (28) to continue to regenerate；The regenerated catalyst obtained through turbulent bed regenerator (3) regeneration is through de-
Gas tank inclined tube (11) deaerates into degassing tank (6)；Regenerated catalyst is through regenerator sloped tube (12) Returning reactor (1) after degassing.
3. double regenerator fluidized-bed reactions of methanol according to claim 1 and/or dimethyl ether conversion alkene and aromatic hydrocarbons
Device, it is characterised in that be provided with one group of gas-solid cyclone separator (32) at the top of turbulent bed regenerator (3), be 1~3 grade；Settler
(5) top is provided with one group of gas-solid cyclone separator (31), is 1~3 grade.
4. double regenerator fluidized bed reaction methods of a kind of methanol and/or dimethyl ether conversion alkene and aromatic hydrocarbons, will using right
The device described in 1 or 2 is sought, described method includes following steps：
A) raw material (14) enters reactor (1) and catalyst haptoreaction from reactor (1) bottom, reaction of formation product (24) and
Carbon deposited catalyst, reaction product (24) enter later separation device；
B) the stripping inclined tube (7) being connected with reactor (1) bottom is advanced under carbon deposited catalyst, enters back into stripping standpipe (8), warp
Lifting medium (23) is promoted to stripper (4), and stripping fluid (15) contact strips, after obtained stripped product (16) and stripping
Carbon deposited catalyst, stripped product (16) enters later separation device；
C) the carbon deposited catalyst part after stripping enters the fast regenerator section of bed regenerator (2) first through fast bed inclined tube to be generated (13)
(25), partly turbulent bed regenerator (3) close phase section (28) is entered through turbulent bed inclined tube to be generated (9), or it is only to be generated through turbulent bed
Inclined tube (9) enters turbulent bed regenerator (3) close phase section (28)；
E) carbon deposited catalyst after stripping obtains partly again in fast bed regenerator (2) neutralization regenerating medium (17) contact annealing in hydrogen atmosphere, burning carbon
Raw catalyst and flue gas (18), are above advanced into settler (5), semi regeneration catalyst sedimentation, flue gas (18) separates through gas-solid cyclone
Enter follow-up flue gas energy recovery device after device (31) separation semi regeneration catalyst, the semi regeneration catalyst of sedimentation is through semi regeneration agent
Delivery pipe (10) enters turbulent bed regenerator (3) close phase section (28)；
F) semi regeneration catalyst and/or stripping after carbon deposited catalyst turbulent bed regenerator (3) neutralize regenerating medium (19) connect
Touch and make charcoal to obtain regenerated catalyst and flue gas (20), flue gas (20) is laggard through gas-solid cyclone separator (32) separation regenerated catalyst
Enter follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator (2)；
G) the degassed tank inclined tube (11) of regenerated catalyst enters degassing tank (6) and degassing medium (21) contact, further removes cigarette
Gas (22), flue gas (22) enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator (2), after degassing
Passed through under regenerated catalyst regenerator sloped tube (12) Returning reactor (1).
5. double regenerator fluidized-bed reactions of methanol according to claim 4 and/or dimethyl ether conversion alkene and aromatic hydrocarbons
Method, it is characterised in that the regeneration temperature of fast bed regenerator (2) is 500~600 DEG C, and average gas superficial velocity is 1~8 meter per second,
The content of oxygen is 2~21 volume % in regenerating medium (17), the flue gas (20) that is obtained for air, turbulent bed regenerator (3) or
The one or more for the flue gas (22) that degassing tank (6) obtains；The regeneration temperature of turbulent bed regenerator (3) is 580~750 DEG C, is put down
Equal empty tower gas velocity be 0.5~2 meter per second, and the content of oxygen be 21~30 volume % in regenerating medium (19), for air or air with
O2Mixture；The charcoal in regenerated catalyst that turbulent bed regenerator (3) regeneration obtains, in terms of the mass percent of catalyst,
Content is less than 0.1 weight %.
6. double regenerator fluidized-bed reactions of methanol according to claim 4 and/or dimethyl ether conversion alkene and aromatic hydrocarbons
Method, it is characterised in that the reaction temperature of reactor (1) is 400~550 DEG C, the weight space velocity of raw material (14) for 0.1~10 gram/
Hour/gram catalyst, reaction pressure is counted as 0~0.5 MPa using gauge pressure, the quality of catalyst internal circulating load and raw material (14) inlet amount
Than for 3~40: 1, density of catalyst is 50~200 kgs/m3, the meter per second of average gas superficial velocity 0.01~1.
7. double regenerator fluidized-bed reactions of methanol according to claim 4 and/or dimethyl ether conversion alkene and aromatic hydrocarbons
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 mutual
The composite molecular screen of formation；Carrier is kaolin, aluminum oxide, silica；The mass ratio of active component and carrier for (10~
50): (50~90)；Catalyst is loaded with one or more elements in Zn, Ag, P, Ga, Cu, Mn, Mg, with the quality hundred of catalyst
Divide than meter, its content is 0.01~15 weight %.
8. double regenerator fluidized-bed reactions of methanol according to claim 4 and/or dimethyl ether conversion alkene and aromatic hydrocarbons
Method, it is characterised in that raw material (14) is the mixture of methanol or dimethyl ether or both, the weight/mass percentage composition of water for 0.01~
30 weight %；Stripping fluid (15) is water vapour or N2Or water vapour and N2Mixture, lifting medium (23) be water vapour or N2
Or water vapour and N2Mixture；The medium (21) that deaerates is water vapour or N2Or water vapour and N2Mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410454386.3A CN105457569B (en) | 2014-09-09 | 2014-09-09 | Double the regenerator reaction units and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410454386.3A CN105457569B (en) | 2014-09-09 | 2014-09-09 | Double the regenerator reaction units and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105457569A CN105457569A (en) | 2016-04-06 |
| CN105457569B true CN105457569B (en) | 2018-02-13 |
Family
ID=55595988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410454386.3A Active CN105457569B (en) | 2014-09-09 | 2014-09-09 | Double the regenerator reaction units and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105457569B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107540495A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Methanol or the method for dimethyl ether conversion production aromatic hydrocarbons and low-carbon alkene |
| CN107540496A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene |
| CN107540493A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene |
| CN107540501B (en) * | 2016-06-29 | 2020-10-30 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon from methanol raw material |
| CN107540494A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene method |
| CN107540492A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | By methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene |
| CN107540498A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | By methanol or the method for dimethyl ether conversion preparing aromatic hydrocarbon and low-carbon alkene |
| CN108786672B (en) * | 2017-04-27 | 2021-01-26 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing low-carbon olefin by using methanol and/or dimethyl ether and benzene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2624762B1 (en) * | 1987-12-21 | 1990-06-08 | Total France | METHOD AND DEVICE FOR REGENERATING A FLUIDIZED BED CATALYST |
| US7347930B2 (en) * | 2003-10-16 | 2008-03-25 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| BRPI1009534A2 (en) * | 2009-03-04 | 2016-03-15 | Uop Llc | fluid catalytic cracking process and apparatus. |
| CN103721743B (en) * | 2012-10-12 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of catalyst recovery process reducing CO2 emission |
-
2014
- 2014-09-09 CN CN201410454386.3A patent/CN105457569B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105457569A (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105457570B (en) | The coaxial-type two-stage regeneration reaction unit and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons | |
| CN105457568B (en) | Methanol and/or dimethyl ether catalysis convert double the regenerator reaction units and its reaction method of ethene and aromatic hydrocarbons processed | |
| CN105457569B (en) | Double the regenerator reaction units and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons | |
| CN104549074B (en) | The coaxial-type segmental fluidized bed reaction unit of methanol and/or dimethyl ether conversion ethylene, propylene and aromatic hydrocarbons and reaction method thereof | |
| CN104549072B (en) | Fluidized bed reaction system and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether | |
| CN104557365B (en) | The coaxial-type fluidized bed reaction system of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons and reaction method thereof | |
| CN106588527B (en) | Produce the regenerative response system and reaction method of aromatic hydrocarbons and low-carbon alkene | |
| CN105461497B (en) | The two-stage regeneration reaction unit and its reaction method of methanol and/or dimethyl ether conversion producing light olefins and aromatic hydrocarbons | |
| CN101844089A (en) | Method for partially regenerating catalyst for preparing low-carbon alkenes from methanol or dimethyl ether | |
| CN103059926B (en) | Method for producing low carbon olefin by catalytic conversion of lightweight hydrocarbon oil | |
| CN103059923B (en) | A kind of Light hydrocarbon oil catalytic conversion method with heat exchange | |
| CN101928598B (en) | Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion | |
| CN103059924B (en) | With the Light hydrocarbon oil catalytic conversion method of heat exchange | |
| CN104557415A (en) | System and method for preparing aromatic hydrocarbon and coproducing liquefied gas by converting methanol and/or dimethyl ether | |
| CN107540497A (en) | The method of oxygen-containing compound material catalytic cracking ethene, propylene and aromatic hydrocarbons | |
| CN104557366B (en) | System and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether | |
| CN103509595B (en) | A kind of Light hydrocarbon oil catalytic conversion method | |
| CN104557370B (en) | The double-fluidized-bed response system of methanol and/or dimethyl ether conversion ethylene, propylene and aromatic hydrocarbons and method thereof | |
| CN104557363B (en) | Methanol and/or the reaction unit of dimethyl ether conversion ethylene, propylene and aromatic hydrocarbons and reaction method thereof | |
| CN103372404A (en) | Novel circulating fluidization device for preparing low-carbon olefin from methanol | |
| CN103059925B (en) | Method for producing low carbon olefin by catalytic conversion of lightweight petroleum hydrocarbon | |
| CN107540503A (en) | The method of oxygen-containing compound material ethene, propylene and aromatic hydrocarbons | |
| CN103509593B (en) | A kind of Light hydrocarbon oil catalytic conversion method | |
| CN103509594B (en) | A kind of Light hydrocarbon oil catalytic conversion method | |
| CN112723971A (en) | Method for producing ethylene and propylene from carbon-tetrahydrocarbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |