CN105268381B - Down-flow fluidized bed using ECT reaction regeneration device and its reaction method for methanol-to-olefins - Google Patents
Down-flow fluidized bed using ECT reaction regeneration device and its reaction method for methanol-to-olefins Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 33
- 238000011069 regeneration method Methods 0.000 title claims abstract description 13
- 230000008929 regeneration Effects 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000013589 supplement Substances 0.000 claims abstract description 21
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- 238000003860 storage Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 12
- 230000001172 regenerating effect Effects 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000001154 acute effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of down-flow fluidized bed using ECT reaction regeneration device for methanol-to-olefins, the problem of mainly solving serious concentration distribution inequality, back-mixing in reactor, too low reaction second half section catalyst activity, temperature drift.The present invention mainly includes by using a kind of device of methanol-to-olefins：Settler (5), descending-bed reactor (7), regenerator (11), low temperature catalyst storage tank (14), supplement catalyst inclined tube (16), it is connected wherein at the posterior segment of descending-bed reactor (7) with supplement catalyst inclined tube (16), its outlet at bottom is connected with settler (5), stripper (2) is connected with riser (17) by inclined tube to be generated (18), the bottom of regenerator (11) respectively with gas-solid distributor (8), low temperature catalyst storage tank (14) is connected, the bottom of gas-solid distributor (8) is the technical scheme of descending-bed reactor (7), preferably resolve above-mentioned technical problem, it can be applied in methanol-to-olefins industrial production.
Description
Technical field
The present invention relates to a kind of down-flow fluidized bed using ECT reaction-regenerative device for MTO technology.
Background technology
Ethene, as two the most key big basic materials of modern petrochemical field, is industrial or agricultural, traffic, state with propylene
The field such as anti-provides industrial chemicals.A large amount of downstream product of ethene mainly have polyethylene, styrene, vinyl acetate, epoxy second
Alkane, ethylene glycol etc..The size of ethylene yield is to weigh the mark of petrochemical industry or even national economy.Propylene is mainly for the production of poly-
Propylene, acrylonitrile, expoxy propane, isopropanol etc..Nearly in the world 67% propylene comes from steam cracking production ethene at present
Byproduct, about 30% product, which comes from, produces vapour, the byproduct of diesel oil in catalytic cracking oil refining process, also a small amount of propylene production
Product come from dehydrogenating propane and Ethylene/Butylene metathesis reaction.
And in the last few years, the demand Continued of ethene and propylene, and in the case of petroleum resources scarcity increasingly, non-petroleum
Resource production ethene, the coal chemical technology of propylene, can greatly alleviate China's oil situation in short supply, promote China to change again
The great-leap-forward development of work and the structural adjustment of raw material route, with important strategic importance and social and economic benefits.
Currently, MTO technology all possesses basis and the bar of industrial applications from technology or economically
Part, current MTO technology flow is similar to catalytic cracking unit, uses successive reaction-regeneration.To methanol
The analysis and research of the engineering technology feature of olefin process processed show that the SAPO catalyst used in MTO technology is different from urging
Change the molecular sieve catalyst of cracking, there is its unique requirement to engineering technology.It is in particular in the state of reaction raw materials, enters
Expect distribution mode, catalyst fluidization, catalyst circulation, agent alcohol ratio, reaction temperature, coking yield etc..
Document CN1723262 discloses a kind of multiple riser reactor with central catalyst return and converted for hydrocarbon
Apparatus and method.The device includes multiple riser reactors, the Disengagement zone of multiple entrances, multiple offset components etc..For passing
System the height for reactor higher large-scale heavy separator of top (especially) cause costliness supporting construction and maintenance on it is tired
It is difficult, it is proposed that the multiple complete and independent reactor assembly with stand-alone separator, effectively reduce whole hydrocarbon conversion unit
Height.But this method is to sacrifice floor space as cost, while pipeline arrangement is complex, energy consumption is also higher, the method
It is particularly well suited to weather more severe area (the larger area of such as wind-force).
Document CN101164685A discloses a kind of for the combined quickly fluidized bed of methanol or second diether catalytic reaction
Reactor.Proposition is external by the separator of settling section, effectively reduces the space of settler, improves catalyst sedimentation speed,
Reduce the alkene residence time, efficiently solve ethene and Propylene Selectivity is low, yield is low technical problem.Relative to tradition sedimentation
For the external fast fluidized bed reactor of device, yield of ethene can be improved more than 4%, and propene yield can be improved more than 3%.
In summary, main using traditional block form methanol to olefins reaction regenerating unit in above-mentioned document, reactor is
Legacy upstream fast fluidized bed reactor, this reactor has that particle radial direction concentration distribution is very uneven, particle radially expands
Dissipate more acutely, the features such as particle axial backmixing is serious, catalyst activity of reactor upper semisection is weaker, additionally due to methanol system
Alkene is exothermic reaction, higher in the temperature of inside reactor, especially too high in the terminal temperature of reactor, easily occurs temperature runaway
Phenomenon, is easily caused the destruction of normal operation, produces accessory substance, or even burns catalyst, and the present invention is targetedly solved
These problems.
The content of the invention
Present invention mainly solves one of technical problem be that methanol-to-olefins fluidized-bed reactor has in the prior art
Particle diameter is to concentration distribution is very uneven, particle radial diffusion more acutely, particle axial backmixing it is serious, reactor upper semisection
Catalyst activity is weaker and terminal temperature of reactor is too high, and there is provided a kind of new first for the problem of easily occurring temperature runaway phenomenon etc.
The reaction-regenerative device of alcohol ethene.Fluidized-bed reactor has particle radial direction uniform concentration distribution in the combination unit, radially
Diffusion is small, the characteristics of axial backmixing is small, simultaneously because the particularity of this reactor so that its can catalyst activity compared with
Weak, the temperature of a relatively high easy reactor second half section for occurring temperature runaway phenomenon injects the catalyst of fresh low temperature, it is ensured that reaction
Efficiently with stably.
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 reaction
Method.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：It is a kind of for methanol-to-olefins
Down-flow fluidized bed using ECT reaction-regenerative device, mainly includes：Settler 5, descending-bed reactor 7, regenerator 11, low temperature catalyst storage tank
14th, supplement catalyst inclined tube 16, riser 17, with the supplement phase of catalyst inclined tube 16 wherein at the posterior segment of descending-bed reactor 7
Even, its outlet at bottom is connected with settler 5, and the upper end of settler 5 is provided with product gas outlet pipeline 6, and bottom connects stripper 2,
Stripper 2 is connected with riser 17 by inclined tube 18 to be generated, and the top of riser 17 is regenerator 11, the bottom point of regenerator 11
It is not connected with gas-solid distributor 8, low temperature catalyst storage tank 14, the bottom of gas-solid distributor 8 is descending-bed reactor 7.
In above-mentioned technical proposal, distance of the posterior segment of descending-bed reactor 7 at the top of down-flow fluidized bed using ECT is down-flow fluidized bed using ECT bed
High 0.5-0.75 positions are provided with 2-10 supplement catalyst inclined tube 16.Compensation regeneration inclined tube 16 is sharp with descending-bed reactor 7
Angle angle is 5-75 °.The section of compensation regeneration inclined tube 16 is circular, semicircle or fan-shaped, and its sectional area is descending-bed reactor 7
0.05-0.5 times of sectional area.Low temperature catalyst storage tank 14 is adiabatic heat-insulation storage tank, and heat insulation layer is set between shell and inner bag,
Outside is provided with external heat exchanger 15.The gas-solid mixing mode of gas-solid distributor 8 is pre-dispersed using first catalyst granules is carried out, after
Unstripped gas is introduced among catalyst flow by way of nozzle, and the residence time is less than or equal to 0.5 s wherein.Down-flow fluidized bed using ECT
The outlet of reactor 7 is thick rotation or one kind of fast separating device.
For solve the above problems two, the technical solution adopted by the present invention is as follows：A kind of method of methanol-to-olefins, is used
Above-mentioned reaction unit, reaction method includes following several steps：
(a) gas raw material enters in inlet of downer gas-solid distributor 8 from gas raw material feeding line 9, with catalyst particles
After grain mixing, reacted into descending-bed reactor 7, generate olefin product, while forming carbon deposited catalyst.In down-flow fluidized bed using ECT
Enough low-temp recovery catalyst from regenerator 11 are supplemented near 7 posterior segment position, it is complete with unreacted in down-flow fluidized bed using ECT 7
Raw material proceed high-efficient contact reaction；
(b) reacted product carries reclaimable catalyst after thick rotation 3 is separated with gas-solid cyclone separator 4 into sedimentation
In device 5, wherein, product gas enters later separation workshop section by product gas outlet pipeline；Reclaimable catalyst particle is by stripping
It is parallel upwards by riser 17 by inclined tube 18 to be generated and the regenerating medium from regenerating medium feeding line 19 after device 2, enter
Enter in regenerator 11；
(c) fresh catalyst after the completion of regenerating is partly into low temperature catalyst storage tank 14, and another part enters gas-solid
Distributor 8 mixes cocurrent with the low temperature catalyst in low temperature catalyst storage tank 14 downwards, is relayed into descending-bed reactor 7
Continuous reaction.
In above-mentioned technical proposal, the regenerating medium is air, and the catalyst is in SAPO-34, descending-bed reactor
Reaction condition is：Reaction pressure is calculated as that 0-0.4MPa, mean temperature are 380-550 DEG C, gas phase linear speed is 1.0-10.0 using gauge pressure
Regeneration condition is in m/s, regenerator：Regeneration temperature is 600-700 DEG C.
Descending-bed reactor of the present invention refers to the top-down type of reactor in Gas-particle Flows direction.
Due in the course of reaction of methanol-to-olefins, it is desirable to which gas-solid carries out quick mixing contact, the reaction time requires short.And
It is known in the art, typically used in the prior art is up fluidized-bed reactor, its feature is solid catalyst particle
Concentration distribution it is more uneven, be radially middle dilute, four careful distribution characteristics；Axle looks up, and bottom is at the top of close phase
For dilute phase, radially the back-mixing with axial direction is more serious, totally unfavorable to reacting.With the progress of reaction, bottom catalyst is gradually
Coking, cause top catalyst coke content it is higher, catalyst inactivation phenomenon is more serious.Because this course of reaction is heat release
Reaction, it is higher in the temperature of the second half section of reactor, easily occur temperature runaway phenomenon, this is to reacting more unfavorable.Therefore using this
Down-flow fluidized bed using ECT pattern in the reaction regeneration device of invention, it is similar to the gas-solid fluidised form of laminar flow it is possible to prevente effectively from solid back-mixing
With the radial diffusion of gas, while the pattern of the top-down flowing just because of down-flow fluidized bed using ECT so that in the reactor section mend
Fill catalyst to become possible to, will so effectively improve the control of the catalyzer coke content of reaction second half section, and then improve alkene and receive
Rate.Concurrently injected low temperature catalyst can effectively reduce the temperature of reactor second half section, so as to avoid temperature runaway phenomenon, contribute to
The stable progress of reaction.
Using technical scheme：The top of the descending-bed reactor 7 is provided with gas-solid distributor 8, and posterior segment is set
There is supplement catalyst inclined tube 16, bottom is provided with thick rotation or fast sub-export；The gas-solid mixing mode of the gas-solid distributor 8 is first will
Catalyst granules carry out it is pre-dispersed, after the mode that is introduced unstripped gas among catalyst flow by way of nozzle, and gas-solid
Residence time of the mixed phase in gas-solid distributor 8 is controlled within 0.5s；The supplement catalyst inclined tube 16 is located under distance
Distance at the top of row bed for the 0.5-0.75 positions of the down-flow fluidized bed using ECT height of bed at, and the acute angle of its angle and descending-bed reactor 7
, can be uniform 2-10 in the surrounding of descending-bed reactor 7 for 5-75 °；The peripheral hardware external heat exchanger 15 of low temperature catalyst storage tank 14, point
It is not connected with regenerator 11, gas-solid distributor 8, supplement catalyst inclined tube 16；The catalyst granules is SAPO-34 molecules
Sieve, the unevenness (standard deviation) than the axial concentration distribution in reactor in the prior art reduces 43.6%, and reaction
Device internal temperature is preferably controlled, it is to avoid the generation of temperature runaway phenomenon, achieves preferable technique effect.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the method for the invention：
In Fig. 1,1 is stripping fluid feeding line；2 be stripper；3 be thick rotation；4 be gas-solid cyclone separator；5 be sedimentation
Device；6 be product gas outlet pipeline；7 be descending-bed reactor；8 be gas-solid distributor；9 be gas raw material feeding line；10 be cigarette
Gas outlet line；11 be regenerator；12 be gas-solid cyclone separator；13 be external catalyst cooler for regenerator；14 be that low temperature catalyst is stored up
Tank；15 be external heat exchanger；16 be supplement catalyst inclined tube；17 be riser；18 be inclined tube to be generated；19 be that regenerating medium is fed
Pipeline.
Gas raw material enters in gas-solid distributor 8 from gas raw material feeding line 9, after being mixed with catalyst granules, enters
Reacted in descending-bed reactor 7, generate olefin product, while forming carbon deposited catalyst.In the posterior segment position of down-flow fluidized bed using ECT 7
Nearby supplement enough low-temp recovery catalyst from regenerator 11, with the complete raw material of unreacted in down-flow fluidized bed using ECT 7 continue into
Row high-efficient contact reacts.Reacted product carries reclaimable catalyst and entered after thick rotation 3 is separated with gas-solid cyclone separator 4
In settler 5, wherein, product gas enters later separation workshop section by product gas outlet pipeline；Reclaimable catalyst particle passes through
After stripper 2, by inclined tube 18 to be generated and the regenerating medium from regenerating medium feeding line 19 by riser 17 it is parallel to
On, into regenerator 11.Fresh catalyst after the completion of regeneration is partly into low temperature catalyst storage tank 14, another part
Cocurrent is mixed with the low temperature catalyst in low temperature catalyst storage tank 14 downwards into gas-solid distributor 8, it is anti-into down-flow fluidized bed using ECT
Answer and continue to react in device 7.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
The overall structure for the small-sized hot-die experimental provision that reaction-regenerative device as shown in Figure 1 is used by the present embodiment
Figure, experiment purpose is that improvement of the new device of the checking present invention to the Axial and radial concentration distribution in methanol to olefins reaction device is made
With, and temperature controlled ability.Experiment used fluidized-bed reactor internal diameter 50mm, height of bed 1.2m, set 2 internal diameters as
10mm supplement catalyst inclined tube position at away from descending tube inlet 0.6m, supplement catalyst inclined tube and the angle of ascending tube are
30 °, catalyst granules uses SAPO-34, and linear speed is 1.8m/s.
Because temperature of reactor is higher, average particle concentration is measured using resistant to elevated temperatures pressure sensor in fluid bed, is led to
Overpressure difference method calculates gained；Temperature is measured by thermocouple.Measurement result as shown in table 1, contains admittedly in descending-bed reactor
Rate scope is 0.045-0.120, and standard deviation is 0.031, and averga cross section concentration distribution is more uniform, and temperature control is 500
DEG C or so.
Table 1
【Embodiment 2】
The overall structure for the small-sized hot-die experimental provision that reaction-regenerative device as shown in Figure 1 is used by the present embodiment
Figure, experiment purpose is that improvement of the new device of the checking present invention to the Axial and radial concentration distribution in methanol to olefins reaction device is made
With, and temperature controlled ability.Experiment fluidized-bed reactor internal diameter 50mm, height of bed 1.2m used, set 2 internal diameters as 5mm
Supplement catalyst inclined tube at away from descending tube inlet 0.6m position, supplement catalyst inclined tube and ascending tube angle be 30 °, urge
Catalyst particles use SAPO-34, and linear speed is 1.5m/s.
Because temperature of reactor is higher, average particle concentration is measured using resistant to elevated temperatures pressure sensor in fluid bed, is led to
Overpressure difference method calculates gained；Temperature is measured by thermocouple.Measurement result as shown in table 1, contains admittedly in descending-bed reactor
Rate scope is 0.050-0.125, and standard deviation is 0.030, and averga cross section concentration distribution is more uniform, and temperature control is 500
DEG C or so.
【Embodiment 3】
The overall structure for the small-sized hot-die experimental provision that reaction-regenerative device as shown in Figure 1 is used by the present embodiment
Figure, experiment purpose is that improvement of the new device of the checking present invention to the Axial and radial concentration distribution in methanol to olefins reaction device is made
With, and temperature controlled ability.Experiment fluidized-bed reactor internal diameter 50mm, height of bed 1.2m used, set 4 internal diameters as 5mm
Supplement catalyst inclined tube at away from descending tube inlet 0.8m position, supplement catalyst inclined tube and ascending tube angle be 30 °, urge
Catalyst particles use SAPO-34, and linear speed is 1.8m/s.
Because temperature of reactor is higher, average particle concentration is measured using resistant to elevated temperatures pressure sensor in fluid bed, is led to
Overpressure difference method calculates gained；Temperature is measured by thermocouple.Measurement result as shown in table 1, contains admittedly in descending-bed reactor
Rate scope is 0.058-0.130, and standard deviation is 0.028, and averga cross section concentration distribution is more uniform, and temperature control is 500
DEG C or so.
【Comparative example 1】
According in the reaction-regenerative device shown in Fig. 1, entered using traditional up fluid bed without supplement catalyst inclined tube
Row experiment, experiment fluidized-bed reactor internal diameter 50mm used, height of bed 1.2m, catalyst granules uses SAPO-34, and linear speed is
1.8m/s。
Because temperature of reactor is higher, average particle concentration is measured using resistant to elevated temperatures pressure sensor in fluid bed, is led to
Overpressure difference method calculates gained；Temperature passes through thermocouple measurement.Measurement result is as shown in table 1, averga cross section in up bed reactor
Solid holdup scope is 0.058-0.200, and standard deviation is 0.055, compared with the concentration distribution of descending-bed reactor in embodiment 1,2,3
It is uneven；In addition, the temperature of reactor posterior segment is uncontrollable, temperature fluctuation is larger, is fluctuated in the range of 370-565 DEG C.
Claims (10)
1. a kind of down-flow fluidized bed using ECT reaction-regenerative device for methanol-to-olefins, capital equipment includes：Settler (5), down-flow fluidized bed using ECT are anti-
Device (7), regenerator (11), low temperature catalyst storage tank (14), supplement catalyst inclined tube (16), riser (17) are answered, wherein descending
It is connected at the posterior segment of bed reactor (7) with supplement catalyst inclined tube (16), its outlet at bottom is connected with settler (5),
The upper end of settler (5) is provided with product gas outlet pipeline (6), bottom connection stripper (2), stripper (2) and riser (17)
Be connected by inclined tube to be generated (18), the top of riser (17) is regenerator (11), the bottom of regenerator (11) respectively with gas
Gu distributor (8), low temperature catalyst storage tank (14) are connected, the bottom of gas-solid distributor (8) is descending-bed reactor (7).
2. the down-flow fluidized bed using ECT reaction-regenerative device of methanol-to-olefins according to claim 1, it is characterised in that descending-bed reactor
(7) posterior segment, the distance at the top of down-flow fluidized bed using ECT is at the 0.5-0.75 positions of the down-flow fluidized bed using ECT height of bed, provided with 2-10 supplement catalysis
Agent inclined tube (16).
3. the down-flow fluidized bed using ECT reaction-regenerative device of methanol-to-olefins according to claim 2, it is characterised in that compensation regeneration inclined tube
(16) it is 5-75 ° with the acute angle of descending-bed reactor (7).
4. the down-flow fluidized bed using ECT reaction-regenerative device of methanol-to-olefins according to claim 2, it is characterised in that compensation regeneration inclined tube
(16) section is circular, semicircle or fan-shaped, and sectional area is 0.05-0.5 times of descending-bed reactor (7) sectional area.
5. the down-flow fluidized bed using ECT reaction-regenerative device of methanol-to-olefins according to claim 1, it is characterised in that low temperature catalyst is stored up
External heat exchanger (15) is provided with outside tank (14).
6. the down-flow fluidized bed using ECT reaction-regenerative device of methanol-to-olefins according to claim 1, it is characterised in that low temperature catalyst is stored up
Tank (14) is adiabatic heat-insulation storage tank, and heat insulation layer is set between shell and inner bag.
7. the down-flow fluidized bed using ECT reaction-regenerative device of methanol-to-olefins according to claim 1, it is characterised in that the gas-solid distribution
The gas-solid mixing mode of device (8) is pre-dispersed using first catalyst granules is carried out, after unstripped gas introduced by way of nozzle
Among catalyst flow.
8. the down-flow fluidized bed using ECT reaction-regenerative device of methanol-to-olefins according to claim 1, it is characterised in that descending-bed reactor
(7) outlet is thick rotation or fast separating device.
9. a kind of method of methanol-to-olefins, using the reaction-regenerative device of claim 1~8, reaction method includes following several
Individual step：
(a) gas raw material enters in inlet of downer gas-solid distributor (8) from gas raw material feeding line (9), with catalyst particles
After grain mixing, reacted into descending-bed reactor (7), generate olefin product, while forming carbon deposited catalyst；Descending
The posterior segment position of bed (7) supplements enough low-temp recovery catalyst from regenerator (11), with unreacted in down-flow fluidized bed using ECT (7)
Complete raw material proceeds high-efficient contact reaction；
(b) reacted product carries reclaimable catalyst after slightly rotation (3) is separated with gas-solid cyclone separator (4) into sedimentation
In device (5), wherein, product gas enters later separation workshop section by product gas outlet pipeline；Reclaimable catalyst particle passes through vapour
Carry after device (2), it is parallel by riser (17) by the regenerating medium of inclined tube to be generated (18) and regenerating medium feeding line (19)
Upwards, into regenerator (11)；
(c) fresh catalyst after the completion of regenerating is partly into low temperature catalyst storage tank (14), and another part divides into gas-solid
Orchestration (8) mixes cocurrent with the low temperature catalyst in low temperature catalyst storage tank (14) downwards, into descending-bed reactor (7)
It is middle to continue to react.
10. the method for methanol-to-olefins according to claim 9, it is characterised in that the regenerating medium is air, described
Catalyst is that reaction condition is in SAPO-34, descending-bed reactor：Reaction pressure is calculated as 0-0.4MPa, mean temperature with gauge pressure
It is that regeneration condition is in 1.0-10.0m/s, regenerator for 380-550 DEG C, gas phase linear speed：Regeneration temperature is 600-700 DEG C.
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