CN107540492A - By methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene - Google Patents
By methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene Download PDFInfo
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- CN107540492A CN107540492A CN201610495175.3A CN201610495175A CN107540492A CN 107540492 A CN107540492 A CN 107540492A CN 201610495175 A CN201610495175 A CN 201610495175A CN 107540492 A CN107540492 A CN 107540492A
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- regenerator
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- fluidized bed
- methanol
- aromatic hydrocarbons
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 86
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 67
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 133
- 238000011069 regeneration method Methods 0.000 claims abstract description 70
- 230000003134 recirculating effect Effects 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003610 charcoal Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000000839 emulsion Substances 0.000 claims description 60
- 230000008929 regeneration Effects 0.000 claims description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 55
- 229910052760 oxygen Inorganic materials 0.000 claims description 55
- 239000001301 oxygen Substances 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000012530 fluid Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 6
- 238000005243 fluidization Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000003780 insertion Methods 0.000 claims 1
- 230000037431 insertion Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 230000009849 deactivation Effects 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011800 void material Substances 0.000 description 44
- 238000010521 absorption reaction Methods 0.000 description 38
- -1 hydrocarbon.1985 Chemical class 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 229910052725 zinc Inorganic materials 0.000 description 17
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical compound [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 13
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 241001120493 Arene Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- XDLDASNSMGOEMX-UHFFFAOYSA-N benzene benzene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1 XDLDASNSMGOEMX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BHAROVLESINHSM-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1.CC1=CC=CC=C1 BHAROVLESINHSM-UHFFFAOYSA-N 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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)
Abstract
The present invention relates to a kind of method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether, mainly solve that regenerator temperature is higher in production process, make the gradual hydrothermal deactivation of catalyst, aromatics yield reduces, the problem of influenceing device continuous and steady operation.The present invention contacts generation low-carbon alkene and the effluent rich in aromatic hydrocarbons by using recirculating fluidized bed reaction-regeneration system, methanol and/or dimethyl ether by fluidized-bed reactor with one or more silicon metal supported catalysts；The reclaimable catalyst of inactivation first passes through first fluidized bed regenerator, control lower temperature mainly completes annealing in hydrogen atmosphere process, higher temperature is controlled to complete the technical scheme made charcoal subsequently into second fluidized bed regenerator, the problem of preferably resolving catalyst hydrothermal deactivation, continuous and steady operation during methanol or dimethyl ether production aromatic hydrocarbons and low-carbon alkene, available in the industrial production that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether.
Description
Technical field
The present invention relates to a kind of method for producing aromatic hydrocarbons and low-carbon alkene by methanol or dimethyl ether.Specifically, it is related to one
Kind is produced the recirculating fluidized bed reaction-regeneration system of aromatic hydrocarbons and low-carbon alkene by methanol or dimethyl ether.
Background technology
Ethene, propylene and aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX)
It is important basic organic synthesis raw material, at present, is mainly produced using petroleum path.In recent years, International Crude Oil is high always
Position operation, the production technology to petroleum path bring very big cost pressure.
All the time, coal or producing synthesis gas from natural gas, synthesising gas systeming carbinol and alkene, separation technologies for aromatics have rule
Modelling mature experience, but it is the breakpoint and difficult point of this industrial chain by the process of methanol to ethene, propylene and aromatic hydrocarbons, and be somebody's turn to do
The solution of key technology can provide a new original to produce basic organic ethene, propylene and aromatic hydrocarbons by non-oil resource
Expect route
In various existing methanol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons is simultaneously
Including ethene, propylene and aromatic hydrocarbons.The technology initially sees Chang of Mobil companies in 1977 et al. (Journal of
Catalysis, 1977,47,249) report methanol and its oxygenatedchemicals conversion preparation virtue on ZSM-5 molecular sieve catalyst
The method of the hydrocarbons such as hydrocarbon.1985, Mobil companies disclosed first in its United States Patent (USP) applied US1590321
The result of study of methanol, dimethyl ether conversion aromatic hydrocarbons, the research use the phosphorous ZSM-5 molecular sieve for 2.7% (weight) to urge
Agent, reaction temperature are 400~450 DEG C, methanol, dimethyl ether air speed 1.3 (Grams Per Hour)/gram catalyst.
The relevant report and patent in the field are more, but the purpose product of most of technologies is aromatic hydrocarbons, ethene, propylene category
It is low in accessory substance, yield.Such as the patent in terms of methanol arenes catalytic agent：Chinese patent CN102372535,
CN102371176、CN102371177、CN102372550、CN102372536、CN102371178、CN102416342、
CN101550051, United States Patent (USP) US4615995, US2002/0099249A1 etc..Such as in terms of methanol aromatics process
Patent：United States Patent (USP) US4686312, Chinese patent ZL101244969, ZL1880288, CN101602646,
CN101823929, CN101671226, CN102199069, CN102199446, CN1880288 etc..
In addition, while technology path disclosed in some patents is methanol aromatic hydrocarbons co-producing light olefins, gasoline etc. other
Product, such as patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537.
Wherein, Multi-function methanol processing method disclosed in patent CN102775261 and device utilize methanol production low-carbon alkene
Hydrocarbon, gasoline, aromatic hydrocarbons.This method uses two-step method production technology, and first step methanol feedstock produces low under the effect of special-purpose catalyst 1
Carbon olefin, second step by the reaction gas containing low-carbon alkene after heat exchange, chilling, carrying out washing treatment, in the presence of special-purpose catalyst 2
Synthesize aromatic hydrocarbons and/or gasoline.The reactor of two courses of reaction can be fixed bed or fluid bed.This method uses two-step method, technique
Flow is complicated.
Patent CN102146010 discloses the work that low-carbon alkene and arene parallel cogeneration gasoline are produced using methanol as raw material
Skill.Low-carbon alkene and aromatic hydrocarbons are produced using methanol as raw material and using molecular sieve catalyst through methanol alkylation reaction and aromatization
Co-production gasoline.The reactor of methanol alkylation reaction and aromatization is various types of fixed bed reactors, pressure 0.01
~0.5 MPa, 180~600 DEG C of temperature.Total liquid yield is more than 70 weight %, and triphen yield is more than 90% (weight).This method is also adopted
It is complicated with two reactors, technological process.
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 can be used
Or fluidized-bed reactor.Reaction temperature is 550~670 DEG C, air speed 1.0~5 (Grams Per Hour)/gram catalyst.The triolefin of this method
Yield 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 above-mentioned existing fluidization that aromatic hydrocarbons is produced using methanol and/or dimethyl ether as raw material all regenerates system using single
System carries 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,
0.5% (weight) below, therefore unavoidably needs high temperature regeneration, and general regeneration temperature is more than 650 DEG C.Jiao of reclaimable catalyst
Hydrogeneous in charcoal, hydrogen and oxygen reaction can produce vapor., can be because dividing under this high temperature, hydro-thermal atmosphere for molecular sieve catalyst
Son sieves framework dealumination and loses activity, and this inactivation is permanent and irreversible.For current regenerative system, in order to ensure
The reproduction quality of catalyst, residence time of the catalyst in regenerator is longer, causes catalyst hydrothermal deactivation serious, uses the longevity
Life reduces, and aromatics yield declines, production cost increase.
The content of the invention
The technical problems to be solved by the invention are that regenerator temperature is higher in the prior art, lose the gradual hydro-thermal of catalyst
Living, aromatics yield reduces, the problem of influenceing device continuous and steady operation, there is provided a kind of to produce aromatic hydrocarbons and low by methanol or dimethyl ether
The method of carbon olefin.This method is made charcoal using low temperature, incomplete regen-eration annealing in hydrogen atmosphere, higher temperature, oxygen-enriched regeneration completely, is had and protected
Hold good catalyst hydrothermal stability simultaneously, obtain the low-carbon regenerative agent of high quality, the advantages of improving aromatics yield.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：It is a kind of that virtue is produced by methanol or dimethyl ether
The method of hydrocarbon and low-carbon alkene, using recirculating fluidized bed reaction-regeneration system, methanol and/or dimethyl ether pass through fluidized-bed reaction
Device contacts generation low-carbon alkene and the effluent rich in aromatic hydrocarbons with one or more silicon metal supported catalysts；It is characterized in that institute
Recirculating fluidized bed reaction-regeneration system includes fluidized-bed reactor (1), reactor heat collector (3), and stripper (5) is to be generated
Inclined tube (7), riser (10) to be generated, reactor cyclone (11), first fluidized bed regenerator (2), regenerator outside heat removing
Device (4), regenerator cyclone separator (12), immediately formula direct coupled structure (19), thick cyclone separator (20), second fluidized bed regenerate
Device (15), degassing tank (6), regenerator sloped tube (8), semi regeneration outer circulating tube (9) and macroporous plate (18)；Decaying catalyst first passes through
First fluidized bed regenerator afterwards, control lower temperature are mainly completed annealing in hydrogen atmosphere process, controlled subsequently into second fluidized bed regenerator
Higher temperature is completed to make charcoal, the regenerated catalyst of obtained high quality.
In above-mentioned technical proposal, it is preferable that metal supported catalyst is silica alumina ratio SiO2/Al2O3At least 10~100
Crystal aluminosilicate.
In above-mentioned technical proposal, it is highly preferred that catalyst is loaded with least one of Zn, Ag, P, Ga, Cu, Mn and Mg member
Element or oxide.
In above-mentioned technical proposal, it is preferable that crystal aluminosilicate is ZSM-5 and/or ZSM-11.
In above-mentioned technical proposal, it is preferable that carried metal is preferably Zn and/or Sb；It is furthermore preferred that Zn and Sb weight ratio
For (1：9)~(1：4).
In technical scheme, carried metal mainly exists in the form of the oxide in the catalyst, works as catalyst
When being expressed as a%Zn/ZSM-5, the mass percentage content for illustrating Zn elements in catalyst is a%, except Zn or its oxide
Remaining is ZSM-5 outside, contains other trace elements in catalyst because raw material or other reasonses ultimately result in preparation process
The general component for being not counted in catalyst.
In above-mentioned technical proposal, it is preferable that the regenerated catalyst carbon content is less than 0.1%.
In above-mentioned technical proposal, it is preferable that methanol or dimethyl ether conversion reaction use turbulent fluid bed reactor (1), wrap
Emulsion zone (13) and dilute-phase zone (14) are included, methanol or dimethyl ether enter emulsion zone (13) from fluidized-bed reactor (1) bottom and urged
Agent contact carries out the reaction generation product such as aromatic hydrocarbons and low-carbon alkene, and the product gas of entrained catalyst passes through the anti-of dilute-phase zone (14)
Device cyclone separator (11) is answered to leave fluidized-bed reactor (1) after carrying out gas solid separation and enter subsequent separation system, recovery is urged
Agent returns to emulsion zone (13).
In above-mentioned technical proposal, it is preferable that fluidized-bed reactor (1) is by setting interior heat collector (3) or external warmer (3)
Or set interior heat collector (3) and external warmer (3) to remove heat caused by reaction simultaneously, while control fluidized-bed reactor (1)
Reaction temperature.
In above-mentioned technical proposal, it is preferable that catalyst regeneration is regenerated using two sections of turbulent fluidized bed regenerators, including first
Fluid bed regenerator (2), first fluidized bed regenerator emulsion zone (16), first fluidized bed regenerator dilute-phase zone (17), regenerator
Cyclone separator (12), immediately formula direct coupled structure (19), thick cyclone separator (20), second fluidized bed regenerator (15), partly again
Raw outer circulating tube (9) and macroporous plate (18)；It is highly preferred that regenerator cyclone separator (14) and (21) are 1-5 levels, typically
For 2 or 3 grades.
In above-mentioned technical proposal, it is preferable that fluidized-bed reactor (1) is put with first fluidized bed regenerator (2) tied portion, the
One fluid bed regenerator (2) above, below, at the top of second fluidized bed regenerator (15) insert by second fluidized bed regenerator (15)
Enter first fluidized bed regenerator (2) bottom, both are connected by macroporous plate (18) with semi regeneration outer circulating tube (9).
In above-mentioned technical proposal, it is preferable that reclaimable catalyst is in first fluidized bed regenerator (2) emulsion zone (16) and air
Contact carries out catalyst regeneration；First fluidized bed regenerator (2) is based on annealing in hydrogen atmosphere, using relatively low regeneration temperature and appropriate oxygen
Gas content carries out incomplete regen-eration, controls oxygen content in flue gas to be less than 1%.Semi regeneration in first fluidized bed regenerator (2)
Catalyst enters second fluidized bed regenerator (15) bottom, second fluidized bed regenerator (15) by semi regeneration outer circulating tube (9)
Based on making charcoal, the higher regeneration temperature of use, oxygen-enriched regeneration completely, the low-carbon regenerative agent of high quality is obtained.
In above-mentioned technical proposal, it is preferable that oxygen content excessive two again main wind (23) from second fluidized bed regenerator (15) bottom
Portion enters with semi regeneration catalyst under the high temperature conditions, is regenerated completely；Oxygen content more than 1% two again flue gas pass through it is big
Hole sizer plate (18) mixes into first fluidized bed regenerator (2) emulsion zone (16) with main wind (22) again and again, and anti-from fluid bed
The reclaimable catalyst of device (1) is answered to carry out incomplete regen-eration；The regenerator that flue gas of the oxygen content less than 1% passes through dilute-phase zone (17)
After cyclone separator (12) recovery catalyst, leave fluid bed regenerator (2) and enter subsequent power recovery system.
In above-mentioned technical proposal, it is preferable that by setting interior heat collector (4) or taking outside in first fluidized bed regenerator (2)
Hot device (4) sets interior heat collector (4) and external warmer (4) to control the regeneration temperature of first fluidized bed regenerator (2) simultaneously, the
The regeneration temperature of two fluid bed regenerators (15) is by controlling two devices to burn ratio control.
In above-mentioned technical proposal, it is preferable that the reclaimable catalyst of fluidized-bed reactor (1) interior carbon deposit passes through stripper (5)
After removing micro hydro carbons, first fluidized bed regenerator (2) top is sent into through inclined tube to be generated (7), riser to be generated (10), through thick rotation
Wind separator (20) enters first fluidized bed regenerator (2) emulsion zone (16) afterwards；Gas (21) is lifted through thick cyclone separator (20)
After separation, the overwhelming majority discharges regenerator by immediately formula direct coupled structure (19), regenerator cyclone separator (12) with flue gas；More
Preferably, it is high steam to lift gas (21).
In above-mentioned technical proposal, it is preferable that the catalyst regenerated completely in second fluidized bed regenerator (15) is by degassing
After the micro non-hydrocarbon gases of tank (6) Removal of catalyst entrainment, enter fluidized-bed reactor (1) emulsion zone through regenerator sloped tube (8)
(13)。
In above-mentioned technical proposal, it is preferable that methanol or 400~550 DEG C of the reaction temperature of dimethyl ether conversion reaction, reaction pressure
0~1.0MPa of power, 200~550 kgs/m of reactor emulsion zone (12) catalyst averag density3, in fluidized-bed reactor (1)
The meter per second of void tower linear speed 0.1~1.0.
In above-mentioned technical proposal, it is preferable that 500~600 DEG C of first fluidized bed regenerator (2) regeneration temperature, regeneration pressure 0
~1.0MPa, 150~550 kgs/m of emulsion zone (15) catalyst averag density3, first fluidized bed regenerator emulsion zone (16)
The interior meter per second of void tower linear speed 0.1~1.0.
In above-mentioned technical proposal, it is preferable that 600~720 DEG C of second fluidized bed regenerator (14) regeneration temperature, regeneration pressure
0~1.2MPa, 150~550 kgs/m of catalyst averag density3, the interior void tower linear speed 0.1 of second fluidized bed regenerator (15)~
1.0 meter per second.
Method for producing aromatic hydrocarbons and low-carbon alkene by methanol or dimethyl ether, it is proposed that recirculating fluidized bed reaction-regeneration
System includes fluidized-bed reactor (1), first fluidized bed regenerator (2), second fluidized bed regenerator (15), reactor heat collector
(3), regenerator heat collector (4), stripper (5), degassing tank (6), inclined tube (7) to be generated, regenerator sloped tube (8), semi regeneration outer circulation
Manage (9), riser (10) to be generated, reactor cyclone (11), regenerator cyclone separator (12), macroporous plate (18),
Connect formula direct coupled structure (19) and thick cyclone separator (20).Using technical scheme, by low regeneration temperature, not exclusively
Annealing in hydrogen atmosphere is regenerated, higher regeneration temperature, oxygen-enriched regeneration completely are made charcoal, has the catalyst hydrothermal stability for keeping good simultaneously, obtain
To the low-carbon regenerative agent of high quality, carbon content is less than 0.1% on regenerated catalyst, maintains higher aromatics yield, its aromatic hydrocarbons
Carbon base absorption rate up to more than 60%, achieve good technique effect.
Brief description of the drawings
Fig. 1 is recirculating fluidized bed reaction-regeneration system of the present invention (fluidized-bed reactor setting interior heat collector) schematic diagram；
Fig. 2 is recirculating fluidized bed reaction-regeneration system of the present invention (fluidized-bed reactor setting external warmer) schematic diagram；
In Fig. 1, Fig. 2,1 is fluidized-bed reactor；2 be first fluidized bed regenerator；3 be reactor heat collector；4 is again
Raw device heat collector；5 be stripper；6 be degassing tank；7 be inclined tube to be generated；8 be regenerator sloped tube；9 be semi regeneration outer circulating tube；10 are
Riser to be generated；11 be reactor cyclone；12 be regenerator cyclone separator；13 be reactor emulsion zone；14 be anti-
Answer device dilute-phase zone；15 be second fluidized bed regenerator；16 be first fluidized bed regenerator emulsion zone；17 be that the first fluidized bed regenerates
Device dilute-phase zone；18 be macroporous plate；19 be to connect formula direct coupled structure；20 be thick cyclone separator；21 be lifting gas；22 be first-class
Change the main wind of bed regenerator (main wind again and again)；23 be the main wind of second fluidized bed regenerator (two again main wind).
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 470 DEG C, reaction pressure 0.2MPa, emulsion zone catalyst averag density 350,000
Grams m3, the average meter per second of void tower linear speed 0.7.The technological condition of regeneration of fluid bed regenerator is：Temperature is 550 DEG C again and again, again and again
Pressure is 0.2MPa, again and again 300 kgs/m of emulsion zone catalyst averag density3, the average meter per second of void tower linear speed 0.8 again and again；Two
Temperature is 680 DEG C again, two again pressure be 0.21MPa, two 450 kgs/m of emulsion zone catalyst averag density again3, two is average again
The meter per second of void tower linear speed 0.5, two main wind oxygen content 21% (volume) again, exhanst gas outlet oxygen content 0.8% (volume) again and again, two again
Exhanst gas outlet oxygen content 5% (volume), carbon content 0.05% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 61.80%, ethene carbon base absorption rate 8.89%, propylene carbon base absorption rate 6.24%.
【Embodiment 2】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 450 DEG C, reaction pressure 0.3MPa, emulsion zone catalyst averag density 300,000
Grams m3, the average meter per second of void tower linear speed 0.6.The technological condition of regeneration of fluid bed regenerator is：Temperature is 540 DEG C again and again, again and again
Pressure is 0.3MPa, again and again 400 kgs/m of emulsion zone catalyst averag density3, the average meter per second of void tower linear speed 0.5 again and again；Two
Temperature is 680 DEG C again, two again pressure be 0.31MPa, two 400 kgs/m of emulsion zone catalyst averag density again3, two is average again
The meter per second of void tower linear speed 0.6, two main wind oxygen content 21% (volume) again, exhanst gas outlet oxygen content 0.4% (volume) again and again, two again
Exhanst gas outlet oxygen content 2.8% (volume), carbon content 0.06% on regenerated catalyst.
Under conditions above and structural parameters, aromatic hydrocarbons carbon base absorption rate 61.92%, ethene 7.31 rate % of carbon-based receipts, propylene carbon
Base yield 5.04%.
【Embodiment 3】
The device of 1200000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 480 DEG C, reaction pressure 0.3MPa, emulsion zone catalyst averag density 380,000
Grams m3, the average meter per second of void tower linear speed 0.8.The technological condition of regeneration of fluid bed regenerator is：Temperature is 530 DEG C again and again, again and again
Pressure is 0.3MPa, again and again 350 kgs/m of emulsion zone catalyst averag density3, the average meter per second of void tower linear speed 0.6 again and again；Two
Temperature is 690 DEG C again, two again pressure be 0.31MPa, two 350 kgs/m of emulsion zone catalyst averag density again3, two is average again
The meter per second of void tower linear speed 0.8, two main wind oxygen content 21% (volume) again, oxygen-containing generally 0.5% (volume) of exhanst gas outlet again and again,
Two exhanst gas outlet oxygen content 4.3% (volumes) again, carbon content 0.04% on regenerated catalyst.
Methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain more satisfactory result, aromatic hydrocarbons is carbon-based
Yield 65.51%, ethene carbon base absorption rate 8.07%, propylene carbon base absorption rate 6.38%.
【Embodiment 4】
The device of 600000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 490 DEG C, reaction pressure 0.2MPa, emulsion zone catalyst averag density 430,000
Grams m3, the average meter per second of void tower linear speed 0.9.The technological condition of regeneration of fluid bed regenerator is：Temperature is 560 DEG C again and again, again and again
Pressure is 0.2MPa, again and again 250 kgs/m of emulsion zone catalyst averag density3, 0.8 meter of the void tower linear speed that is averaged again and again/
Second；Two again temperature be 680 DEG C, two again pressure be 0.21MPa, two 380 kgs/m of emulsion zone catalyst averag density again3, two again
The average meter per second of void tower linear speed 0.7, two main wind oxygen content 21% (volume) again, exhanst gas outlet oxygen content 0.9% (volume) again and again,
Two exhanst gas outlet oxygen content 2% (volumes) again, carbon content 0.07% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 63.26%, ethene carbon base absorption rate 6.30%, propylene carbon base absorption rate 4.89%.
【Embodiment 5】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 470 DEG C, reaction pressure 0.5MPa, emulsion zone catalyst averag density 300,000
Grams m3, the average meter per second of void tower linear speed 0.5.The technological condition of regeneration of fluid bed regenerator is：Temperature is 550 DEG C again and again, again and again
Pressure is 0.5MPa, again and again 200 kgs/m of emulsion zone catalyst averag density3, 0.9 meter of the void tower linear speed that is averaged again and again/
Second；Two again temperature be 670 DEG C, two again pressure be 0.51MPa, two 350 kgs/m of emulsion zone catalyst averag density again3, again and again
The average meter per second of void tower linear speed 0.8, two main wind oxygen content 21% (volume) again, exhanst gas outlet oxygen content 0.6% (volume) again and again,
Two exhanst gas outlet oxygen content 3.6% (volumes) again, carbon content 0.06% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 63.3%, ethene carbon base absorption rate 6.17%, propylene carbon base absorption rate 4.94%.
【Embodiment 6】
The device of 1200000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 480 DEG C, reaction pressure 0.15MPa, emulsion zone catalyst averag density 480
Kg/m3, the average meter per second of void tower linear speed 0.5.The technological condition of regeneration of fluid bed regenerator is：Again and again temperature be 520 DEG C, one
Pressure is 0.15MPa again, again and again 320 kgs/m of emulsion zone catalyst averag density3, be averaged void tower linear speed 0.7 again and again
Meter per second；Two again temperature be 660 DEG C, two again pressure be 0.16MPa, two 400 kgs/m of emulsion zone catalyst averag density again3,
Two are averaged the meter per second of void tower linear speed 0.6 again, two main wind oxygen content 21% (volume) again, again and again (the body of exhanst gas outlet oxygen content 0.8%
Product), two exhanst gas outlet oxygen content 6% (volumes) again, carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 62.78%, ethene carbon base absorption rate 7.1%, propylene carbon base absorption rate 5.47%.
【Embodiment 7】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 500 DEG C, reaction pressure 0.05MPa, emulsion zone catalyst averag density 550
Kg/m3, the average meter per second of void tower linear speed 0.8.The technological condition of regeneration of fluid bed regenerator is：Again and again temperature be 530 DEG C, one
Pressure is 0.05MPa again, again and again 350 kgs/m of emulsion zone catalyst averag density3, be averaged void tower linear speed 0.6 again and again
Meter per second；Two again temperature be 690 DEG C, two again pressure be 0.06MPa, two 350 kgs/m of emulsion zone catalyst averag density again3,
Two are averaged the meter per second of void tower linear speed 0.8 again, two main wind oxygen content 21% (volume) again, again and again (the body of exhanst gas outlet oxygen content 0.5%
Product), two exhanst gas outlet oxygen content 4.3% (volumes) again, carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 53.83%, ethene carbon base absorption rate 14.02%, propylene carbon base absorption rate 10.17%.
【Embodiment 8】
The device of 1200000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%P/Al2O3.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 480 DEG C, reaction pressure 0.15MPa, emulsion zone catalyst averag density 480
Kg/m3, the average meter per second of void tower linear speed 0.5.The technological condition of regeneration of fluid bed regenerator is：Again and again temperature be 520 DEG C, one
Pressure is 0.15MPa again, again and again 320 kgs/m of emulsion zone catalyst averag density3, be averaged void tower linear speed 0.7 again and again
Meter per second；Two again temperature be 660 DEG C, two again pressure be 0.16MPa, two 400 kgs/m of emulsion zone catalyst averag density again3,
Two are averaged the meter per second of void tower linear speed 0.6 again, two main wind oxygen content 21% (volume) again, again and again (the body of exhanst gas outlet oxygen content 0.8%
Product), two exhanst gas outlet oxygen content 6% (volumes) again, carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 61.6%, ethene carbon base absorption rate 7.5%, propylene carbon base absorption rate 5.6%.
【Embodiment 9】
The device of 1200000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%Re/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 480 DEG C, reaction pressure 0.15MPa, emulsion zone catalyst averag density
480 kgs/m3, the average meter per second of void tower linear speed 0.5.The technological condition of regeneration of fluid bed regenerator is：Temperature is 520 again and again
DEG C, pressure is 0.15MPa again and again, again and again 320 kgs/m of emulsion zone catalyst averag density3, be averaged void tower linear speed again and again
0.7 meter per second；Two again temperature be 660 DEG C, two again pressure be 0.16MPa, two again 400 kilograms of emulsion zone catalyst averag density/
Rice3, two are averaged the meter per second of void tower linear speed 0.6 again, two main wind oxygen content 21% (volume) again, again and again exhanst gas outlet oxygen content 0.8%
(volume), two exhanst gas outlet oxygen content 6% (volumes) again, carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 63.0%, ethene carbon base absorption rate 7.0%, propylene carbon base absorption rate 5.4%.
【Embodiment 10】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%Sb/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 500 DEG C, reaction pressure 0.05MPa, emulsion zone catalyst averag density
550 kgs/m3, the average meter per second of void tower linear speed 0.8.The technological condition of regeneration of fluid bed regenerator is：Temperature is 530 again and again
DEG C, pressure is 0.05MPa again and again, again and again 350 kgs/m of emulsion zone catalyst averag density3, be averaged void tower linear speed again and again
0.6 meter per second；Two again temperature be 690 DEG C, two again pressure be 0.06MPa, two again 350 kilograms of emulsion zone catalyst averag density/
Rice3, two are averaged the meter per second of void tower linear speed 0.8 again, two main wind oxygen content 21% (volume) again, again and again exhanst gas outlet oxygen content 0.5%
(volume), two exhanst gas outlet oxygen content 4.3% (volumes) again, carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 60.5%, ethene carbon base absorption rate 10.2%, propylene carbon base absorption rate 8.6%.
【Embodiment 11】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 0.4%Zn/3.6%Sb/ZSM-5.Fluidisation
Bed reactor reaction process condition be：Reaction temperature is 500 DEG C, reaction pressure 0.05MPa, and emulsion zone catalyst is average close
550 kgs/m of degree3, the average meter per second of void tower linear speed 0.8.The technological condition of regeneration of fluid bed regenerator is：Temperature is 530 again and again
DEG C, pressure is 0.05MPa again and again, again and again 350 kgs/m of emulsion zone catalyst averag density3, be averaged void tower linear speed again and again
0.6 meter per second；Two again temperature be 690 DEG C, two again pressure be 0.06MPa, two again 350 kilograms of emulsion zone catalyst averag density/
Rice3, two are averaged the meter per second of void tower linear speed 0.8 again, two main wind oxygen content 21% (volume) again, again and again exhanst gas outlet oxygen content 0.5%
(volume), two exhanst gas outlet oxygen content 4.3% (volumes) again, carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 64.5%, ethene carbon base absorption rate 8.2%, propylene carbon base absorption rate 7.4%.
【Embodiment 12】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 0.8%Zn/3.2%Sb/ZSM-5.Fluidisation
Bed reactor reaction process condition be：Reaction temperature is 500 DEG C, reaction pressure 0.05MPa, and emulsion zone catalyst is average close
550 kgs/m of degree3, the average meter per second of void tower linear speed 0.8.The technological condition of regeneration of fluid bed regenerator is：Temperature is 530 again and again
DEG C, pressure is 0.05MPa again and again, again and again 350 kgs/m of emulsion zone catalyst averag density3, be averaged void tower linear speed again and again
0.6 meter per second；Two again temperature be 690 DEG C, two again pressure be 0.06MPa, two again 350 kilograms of emulsion zone catalyst averag density/
Rice3, two are averaged the meter per second of void tower linear speed 0.8 again, two main wind oxygen content 21% (volume) again, again and again exhanst gas outlet oxygen content 0.5%
(volume), two exhanst gas outlet oxygen content 4.3% (volumes) again, carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, methanol aromatic hydrocarbons and alkene are carried out by method of the present invention, can obtain
More satisfactory result, aromatic hydrocarbons carbon base absorption rate 64.8%, ethene carbon base absorption rate 8.0%, propylene carbon base absorption rate 7.2%.
【Comparative example 1】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene using recirculating fluidized bed as shown in Figure 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%P/ZSM-5.Fluidized-bed reaction
The reaction process condition of device is：Reaction temperature is 470 DEG C, reaction pressure 0.5MPa, emulsion zone catalyst averag density 330,000
Grams m3, the average meter per second of void tower linear speed 0.5.The technological condition of regeneration of fluid bed regenerator is：Temperature is 680 DEG C again and again, again and again
Pressure is 0.5MPa, again and again 280 kgs/m of emulsion zone catalyst averag density3, the average meter per second of void tower linear speed 0.7 again and again；Two
Temperature is 680 DEG C again, two again pressure be 0.51MPa, two 310 kgs/m of emulsion zone catalyst averag density again3, it is average again and again
The meter per second of void tower linear speed 0.8, two main wind oxygen content 21% (volume) again, exhanst gas outlet oxygen content 1.8% (volume) again and again, two again
Exhanst gas outlet oxygen content 4.1% (volume), carbon content 0.08% on regenerated catalyst.
Under conditions above and structural parameters, available operation result, aromatic hydrocarbons carbon base absorption rate 50.95%, the carbon-based receipts of ethene
Rate 13.21%, propylene carbon base absorption rate 9.52%.
【Comparative example 2】
The device of 1800000 tons/year of methanol production aromatic hydrocarbons and low-carbon alkene uses regular circulation fluidized-bed reaction-regeneration system
System, regenerator is one section of regeneration, using metal supported catalyst 1%Zn/3%P/ZSM-5.The reaction process of fluidized-bed reactor
Condition is：Reaction temperature is 470 DEG C, reaction pressure 0.5MPa, 300 kgs/m of emulsion zone catalyst averag density3, it is average
The meter per second of void tower linear speed 0.5.The technological condition of regeneration of fluid bed regenerator is：Temperature is 550 DEG C, regeneration pressure 0.5MPa, then
Raw 380 kgs/m of device emulsion zone catalyst averag density3, the average meter per second of void tower linear speed 0.6 of regenerator；Main wind oxygen content 21%
(volume), exhanst gas outlet oxygen content 0.4% (volume), carbon content 1.8% on regenerated catalyst.
Under conditions above and structural parameters, available operation result, aromatic hydrocarbons carbon base absorption rate 47.71%, the carbon-based receipts of ethene
Rate 16.63%, propylene carbon base absorption rate 11.82%.
Claims (10)
1. a kind of method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether, using recirculating fluidized bed reaction-regeneration system,
Methanol and/or dimethyl ether contacted by fluidized-bed reactor with one or more silicon metal supported catalysts generation low-carbon alkene and
Effluent rich in aromatic hydrocarbons；It is characterized in that recirculating fluidized bed reaction-regeneration system used includes fluidized-bed reactor (1),
Reactor heat collector (3), stripper (5), inclined tube (7) to be generated, riser (10) to be generated, reactor cyclone (11), the
One fluid bed regenerator (2), external catalyst cooler for regenerator (4), regenerator cyclone separator (12), immediately formula direct coupled structure (19),
Thick cyclone separator (20), second fluidized bed regenerator (15), degassing tank (6), regenerator sloped tube (8), semi regeneration outer circulating tube (9)
With macroporous plate (18)；Decaying catalyst first passes through rear first fluidized bed regenerator, and control lower temperature mainly completes annealing in hydrogen atmosphere mistake
Journey, higher temperature is controlled to complete to make charcoal subsequently into second fluidized bed regenerator, the regenerated catalyst of obtained high quality.
2. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that methanol
Or dimethyl ether conversion reaction uses turbulent fluid bed reactor (1), including emulsion zone (13) and dilute-phase zone (14), methanol or diformazan
Ether enters emulsion zone (13) from fluidized-bed reactor (1) bottom and catalyst contact carries out reaction generation aromatic hydrocarbons and low-carbon alkene etc.
Product, the product gas of entrained catalyst pass through dilute-phase zone (14) reactor cyclone (11) carry out gas solid separation after leave
Fluidized-bed reactor (1) enters subsequent separation system, and the catalyst of recovery returns to emulsion zone (13).
3. methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that fluid bed
Reactor (1) is by setting interior heat collector (3) or external warmer (3) or setting interior heat collector (3) and external warmer (3) to move simultaneously
Heat caused by reaction is walked, while controls the reaction temperature of fluidized-bed reactor (1).
4. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that catalysis
Agent regeneration is regenerated using two sections of turbulent fluidized bed regenerators, including first fluidized bed regenerator (2), first fluidized bed regenerator are close
Phase region (16), first fluidized bed regenerator dilute-phase zone (17), regenerator cyclone separator (12), immediately formula direct coupled structure (19),
Thick cyclone separator (20), second fluidized bed regenerator (15), semi regeneration outer circulating tube (9) and macroporous plate (18).
5. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that fluidisation
Bed reactor (1) is put with first fluidized bed regenerator (2) tied portion, and first fluidized bed regenerator (2) is above, second fluidized bed
Below, insertion first fluidized bed regenerator (2) bottom at the top of second fluidized bed regenerator (15), both pass through regenerator (15)
Macroporous plate (18) connects with semi regeneration outer circulating tube (9).
6. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that to be generated
Catalyst carries out catalyst regeneration in first fluidized bed regenerator (2) emulsion zone (16) and air contact.The first fluidized bed regenerates
Device (2) carries out incomplete regen-eration based on annealing in hydrogen atmosphere, using relatively low regeneration temperature and appropriate oxygen content, controls oxygen in flue gas
Gas content is less than 1%；Semi regeneration catalyst in first fluidized bed regenerator (2) enters the by semi regeneration outer circulating tube (9)
Two fluid bed regenerators (15) bottom, second fluidized bed regenerator (15) is based on making charcoal, and the higher regeneration temperature of use is oxygen-enriched
Regeneration completely, obtains the low-carbon regenerative agent of high quality.
7. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that oxygen-containing
Main wind (23) enters with semi regeneration catalyst under the high temperature conditions amount excessive two from second fluidized bed regenerator (15) bottom again, enters
Row regeneration completely；Flue gas is close into first fluidized bed regenerator (2) by macroporous plate (18) again by two of oxygen content more than 1%
Phase region (16) is mixed with main wind (22) again and again, and incomplete regen-eration is carried out with the reclaimable catalyst from fluidized-bed reactor (1)；Oxygen
After flue gas of the Gas content less than 1% reclaims catalyst by the regenerator cyclone separator (12) of dilute-phase zone (17), fluidisation is left
Bed regenerator (2) enters subsequent power recovery system.
8. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that first
By setting interior heat collector (4) or external warmer (4) or setting interior heat collector (4) simultaneously and take outside in fluid bed regenerator (2)
The regeneration temperature of hot device (4) control first fluidized bed regenerator (2), the regeneration temperature of second fluidized bed regenerator (15) pass through control
Make two devices and burn ratio control.
9. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that fluidisation
The reclaimable catalyst of bed reactor (1) interior carbon deposit through inclined tube to be generated (7), to be generated carries after the micro hydro carbons of stripper (5) removing
Riser (10) is sent into first fluidized bed regenerator (2) top, and first fluidized bed regenerator is entered after thick cyclone separator (20)
(2) emulsion zone (16)；Gas (21) is lifted after thick cyclone separator (20) separation, the overwhelming majority passes through immediately formula direct coupled structure
(19), regenerator cyclone separator (12) discharges regenerator with flue gas.
10. the method that aromatic hydrocarbons and low-carbon alkene are produced by methanol or dimethyl ether according to claim 1, it is characterised in that second
The catalyst regenerated completely in fluid bed regenerator (15) passes through the micro non-hydrocarbon gases of degassing tank (6) Removal of catalyst entrainment
Afterwards, fluidized-bed reactor (1) emulsion zone (13) is entered through regenerator sloped tube (8).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022077460A1 (en) * | 2020-10-16 | 2022-04-21 | 中国科学院大连化学物理研究所 | Fluidised bed regenerator, apparatus for preparing low carbon olefin, and application thereof |
| CN114377730A (en) * | 2020-10-16 | 2022-04-22 | 中国科学院大连化学物理研究所 | Regeneration device, device for preparing light olefin and its application |
| RU2807509C1 (en) * | 2020-10-16 | 2023-11-15 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайенсез | Fluidized bed regenerator, device for producing low-carbon olefins and their application |
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| CN114377730B (en) * | 2020-10-16 | 2023-11-21 | 中国科学院大连化学物理研究所 | Regeneration device, device for preparing low-carbon olefin and application thereof |
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