CN107540493A - Method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene - Google Patents
Method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene Download PDFInfo
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- CN107540493A CN107540493A CN201610495186.1A CN201610495186A CN107540493A CN 107540493 A CN107540493 A CN 107540493A CN 201610495186 A CN201610495186 A CN 201610495186A CN 107540493 A CN107540493 A CN 107540493A
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- aromatic hydrocarbons
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 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 66
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 160
- 238000011069 regeneration method Methods 0.000 claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 230000003134 recirculating effect Effects 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 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
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims description 72
- 230000008929 regeneration Effects 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 56
- 229910052760 oxygen Inorganic materials 0.000 claims description 56
- 239000001301 oxygen Substances 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 239000012530 fluid Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000003546 flue gas Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000005243 fluidization Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 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 55
- 238000010521 absorption reaction Methods 0.000 description 41
- -1 hydrocarbon.1985 Chemical class 0.000 description 18
- 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 14
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 241000209094 Oryza Species 0.000 description 9
- 235000007164 Oryza sativa Nutrition 0.000 description 9
- 235000009566 rice Nutrition 0.000 description 9
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002808 molecular sieve Substances 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
- 230000001172 regenerating effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 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
- 241001120493 Arene Species 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
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 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
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 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
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 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
- 229910001845 yogo sapphire Inorganic materials 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
- 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 by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene, 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 metal supported catalysts；The reclaimable catalyst of inactivation first passes through first fluidized bed regenerator (8), control lower temperature mainly completes annealing in hydrogen atmosphere process, then fast bed (16) is sequentially entered again, second fluidized bed regenerator (15) controls higher temperature to complete the technical scheme made charcoal, during methanol or dimethyl ether are preferably resolved for aromatic hydrocarbons and low-carbon alkene the problem of catalyst hydrothermal deactivation, continuous and steady operation, available for by methanol or dimethyl ether in the industrial production of aromatic hydrocarbons and low-carbon alkene.
Description
Technical field
The present invention relates to a kind of method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene.Specifically, it is related to one
Kind is by methanol or dimethyl ether for aromatic hydrocarbons and the recirculating fluidized bed reaction-regeneration system of low-carbon alkene.
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 standby fragrant 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 metal supported catalysts.It is it is characterized in that used
Recirculating fluidized bed reaction-regeneration system include fluidized-bed reactor (1), reactor cyclone (4), reactor heat collector
(5), stripper (6), inclined tube (7) to be generated, first fluidized bed regenerator (8), the first regenerator cyclone separator (11), first again
Raw device heat collector (12), semi-regeneration stand pipe (13), semi regeneration inclined tube (14), second fluidized bed regenerator (15), fast bed (16),
Fast bed external warmer (21), outer circulating tube (22), Second reactivator cyclone separator (20), degassing tank (23), regenerator sloped tube
And macroporous plate (17) (24)；Decaying catalyst first passes through first fluidized bed regenerator (8), and control lower temperature completes annealing in hydrogen atmosphere mistake
Journey, then sequentially enters fast bed (16), second fluidized bed regenerator (15) controls higher temperature to complete to make charcoal again, obtains height
The regenerated catalyst of 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 Bi；It is furthermore preferred that Zn and Bi 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 (2) and dilute-phase zone (3) are included, methanol or dimethyl ether enter emulsion zone (2) and catalyst from fluidized-bed reactor (1) bottom
Contact carries out the reaction generation product such as aromatic hydrocarbons and low-carbon alkene, the reactor that the product gas of entrained catalyst passes through dilute-phase zone (3)
Fluidized-bed reactor (1) is left after cyclone separator (4) progress gas solid separation and enters subsequent separation system, and the catalyst of recovery returns
Return emulsion zone (2).
In above-mentioned technical proposal, it is preferable that fluidized-bed reactor (1) is by setting interior heat collector (5) or external warmer (5)
Or set interior heat collector (5) and external warmer (5) to remove heat caused by reaction simultaneously, while control fluidized-bed reactor (1)
Reaction temperature.The reclaimable catalyst of fluidized-bed reactor (1) interior carbon deposit is after stripper (6) removes micro hydro carbons, through treating
Raw inclined tube (7) enters the emulsion zone (9) of first fluidized bed regenerator (8).
In above-mentioned technical proposal, it is preferable that catalyst regeneration is regenerated using two device fast beds, first fluidized bed regenerator
(8) emulsion zone (9), dilute-phase zone (10), regenerator cyclone separator (11), the first regenerator heat collector (12), semi regeneration are included
Standpipe (13), semi regeneration inclined tube (14)；Second fluidized bed regenerator (15) includes emulsion zone (18), dilute-phase zone (19), regenerator
Cyclone separator (20), degassing tank (23), regenerator sloped tube (24) and fast bed (16), macroporous plate (17), fast bed outside heat removing
Device (21), outer circulating tube (22)；It is highly preferred that regenerator cyclone separator (11) and (20) are 1-5 levels, generally 2 or 3 grades.
In above-mentioned technical proposal, it is preferable that first fluidized bed regenerator (8) is arranged in juxtaposition with fast bed (16), first-class
Change bed regenerator (8) to be connected by semi-regeneration stand pipe (13) and semi regeneration inclined tube (14) with fast bed (16)；Second fluidized bed is again
In fast bed (16) above, insertion second fluidized bed regenerator (15) bottom at the top of fast bed (16), both pass through raw device (15)
Fast bed heat collector (21), outer circulating tube (22) connect with macroporous plate (17).
In above-mentioned technical proposal, it is preferable that reclaimable catalyst is in first fluidized bed regenerator (8) emulsion zone (9) with coming from
The air contact of first fluidized bed regenerator (8) bottom carries out catalyst regeneration.First fluidized bed regenerator (8) using annealing in hydrogen atmosphere as
It is main, incomplete regen-eration is carried out using relatively low regeneration temperature and appropriate oxygen content, controls oxygen content in flue gas to be less than
1%；Flue gas of the oxygen content less than 1% carries out gas solid separation by the first regenerator cyclone separator (11) of dilute-phase zone (10)
After leave first fluidized bed regenerator (8) and enter subsequent power recovery system；Semi regeneration in first fluidized bed regenerator (8) is urged
Agent enters fast bed (16) bottom by semi-regeneration stand pipe (13) and semi regeneration inclined tube (14).
In above-mentioned technical proposal, it is preferable that the excessive main wind of oxygen content enters from fast bed (16) bottom and semi regeneration is urged
Agent contacts under the high temperature conditions, carries out the complete regeneration based on making charcoal；Oxygen content more than 1% fast bed (16) flue gas and
The reclaimable catalyst for remaining a small amount of carbon deposit enters second fluidized bed regenerator (15) by macroporous plate (17) at the top of fast bed (16)
Emulsion zone (18) with two again main wind mix, further coke burning regeneration.Flue gas of the oxygen content more than 1% passes through dilute-phase zone (19)
Second reactivator cyclone separator (20) leaves second fluidized bed regenerator (15) into subsequent power time after carrying out gas solid separation
Receipts system.
In above-mentioned technical proposal, it is preferable that the high temperature catalyst in first fluidized bed regenerator (8) passes through in the first regeneration
Device external warmer (12) returns to first fluidized bed regenerator (8) emulsion zone (9) after reducing temperature, by controlling catalyst internal circulating load
To adjust the regeneration temperature of first fluidized bed regenerator.
In above-mentioned technical proposal, it is preferable that the high temperature catalyst in second fluidized bed regenerator (15) emulsion zone (18) leads to
Enter fast bed (16) bottom after crossing fast bed external warmer (21) reduction temperature, burnt by controlling catalyst internal circulating load to adjust
Burnt temperature.The catalyst of second fluidized bed regenerator (15) emulsion zone (18) enters fast bed device by outer circulating tube (22)
(16) to ensure the density of fast bed device (16) interior catalyst.
In above-mentioned technical proposal, it is preferable that the catalyst in fast bed device (16) passes through macroporous plate with flue gas is burnt
(17) second fluidized bed regenerator (15) emulsion zone (18), the catalyst regenerated completely in second fluidized bed regenerator (15) are entered
After micro non-hydrocarbon gases by the entrainment of degassing tank (23) Removal of catalyst, into fluidized-bed reactor (1) emulsion zone (2).
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 (2) catalyst averag density3, it is empty in fluidized-bed reactor (1)
The meter per second of 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 regeneration temperature, regeneration pressure 0~
1.0MPa, 200~550 kgs/m of first fluidized bed reactor emulsion zone (2) catalyst averag density3, first fluidized bed regeneration
The average meter per second of void tower linear speed 0.1~1.0 in device emulsion zone (9).
In above-mentioned technical proposal, it is preferable that 600~720 DEG C, 0~1.2MPa of regeneration pressure of fast bed (16) regeneration temperature,
30~150 kgs/m of catalyst averag density3, the average meter per second of void tower linear speed 1.0~3.0 in fast bed (16).Second fluidisation
600~720 DEG C, 0~1.0MPa of regeneration pressure of regenerator (15) regeneration temperature of bed, 200~550 kilograms of catalyst averag density/
Rice3, the average meter per second of void tower linear speed 0.1~1.0 in second fluidized bed regenerator (15).
For the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene, it is proposed that recirculating fluidized bed reaction-regeneration
System includes fluidized-bed reactor (1), reactor cyclone (4), reactor heat collector (5), stripper (6), it is to be generated tiltedly
Manage (7), first fluidized bed regenerator (8), the first regenerator cyclone separator (11), the first external catalyst cooler for regenerator (12), half
Standpipe (13), semi regeneration inclined tube (14), second fluidized bed regenerator (15), Second reactivator cyclone separator (20), take off
Gas tank (23), regenerator sloped tube (24), fast bed (16), fast bed external warmer (21), semi regeneration outer circulating tube (22) and macropore
Sieve plate (17).It is higher regeneration temperature, oxygen-enriched by low regeneration temperature, incomplete regen-eration annealing in hydrogen atmosphere using technical scheme
Regeneration is made charcoal completely, is had the catalyst hydrothermal stability for keeping good simultaneously, the low-carbon regenerative agent of high quality is obtained, after regeneration
Carbon content is less than 0.1% on catalyst, maintains higher aromatics yield, and the carbon base absorption rate of its aromatic hydrocarbons obtains up to more than 60%
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 reactor emulsion zone；3 be reactor dilute-phase zone；4 be reactor
Cyclone separator；5 be reactor heat collector；6 be stripper；7 be inclined tube to be generated；8 be first fluidized bed regenerator；9 be first
Fluid bed regenerator emulsion zone；10 be first fluidized bed regenerator dilute-phase zone；11 be first fluidized bed regenerator cyclone separator；
12 be first fluidized bed external catalyst cooler for regenerator；13 be semi-regeneration stand pipe, and 14 be semi regeneration inclined tube, and 15 be that second fluidized bed regenerates
Device；16 be fast bed；17 macroporous plates；18 be second fluidized bed regenerator emulsion zone；19 be second fluidized bed regenerator dilute phase
Area；20 be second fluidized bed regenerator cyclone separator；21 be fast bed external warmer；22 be outer circulating tube；23 be degassing tank；
24 be regenerator sloped tube；25 be the main wind of first fluidized bed regenerator (main wind again and again)；26 be the main wind of fast bed；27 be second fluidized bed
The main wind of 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%Ag/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 470 DEG C, reaction pressure 0.2MPa, emulsion zone catalyst averag density 350
Kg/m3, the average meter per second of void tower linear speed 0.7.The technological condition of regeneration of fluid bed regenerator is：Again and again temperature be 550 DEG C, one
Pressure is 0.2MPa again, 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；
Quick bed tempertaure is 680 DEG C, and fast bed pressure is 0.21MPa, and quick bed catalyst averag density is 80 kgs/m, fast bed
The average meter per second of void tower linear speed 1.2：Two again temperature be 660 DEG C, two again pressure be 0.2MPa, two again emulsion zone catalyst be averaged it is close
450 kgs/m of degree3, two again be averaged the meter per second of void tower linear speed 0.5；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 4.1% (volumes) again, 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 61.8%, 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 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%Ag/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 450 DEG C, reaction pressure 0.3MPa, emulsion zone catalyst averag density 300
Kg/m3, the average meter per second of void tower linear speed 0.6.The technological condition of regeneration of fluid bed regenerator is：Again and again temperature be 540 DEG C, one
Pressure is 0.3MPa again, 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；
Quick bed tempertaure is 680 DEG C, and fast bed pressure is 0.31MPa, and quick bed catalyst averag density is 50 kgs/m, fast bed
The average meter per second of void tower linear speed 1.8：Two again temperature be 690 DEG C, two again pressure be 0.3MPa, two again emulsion zone catalyst be averaged it is close
400 kgs/m of degree3, two again be averaged the meter per second of void tower linear speed 0.6；Two main wind oxygen content 21% (volume) again, again and again exhanst gas outlet
Oxygen content 0.4% (volume), two exhanst gas outlet oxygen content 5.8% (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 60.86%, ethene carbon base absorption rate 7.89%, propylene carbon base absorption rate 5.42%.
【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 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%Ag/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 480 DEG C, reaction pressure 0.3MPa, emulsion zone catalyst averag density 380
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 0.3MPa again, 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；
Quick bed tempertaure is 690 DEG C, and fast bed pressure is 0.31MPa, and quick bed catalyst averag density is double centner/rice, fast bed
The average meter per second of void tower linear speed 1.1；Two again temperature be 680 DEG C, two again pressure be 0.3MPa；Two again emulsion zone catalyst it is average close
350 kgs/m of degree3, two again be averaged the meter per second of void tower linear speed 0.82；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 3.2% (volumes) again, carbon content 0.04% 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 62.51%, 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 2 reaction-again
Raw system, fluidized-bed reactor sets external warmer, using metal supported catalyst 1%Zn/3%Ag/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 490 DEG C, reaction pressure 0.2MPa, emulsion zone catalyst averag density 430
Kg/m3, the average meter per second of void tower linear speed 0.9.The technological condition of regeneration of fluid bed regenerator is：Again and again temperature be 560 DEG C, one
Pressure is 0.2MPa again, again and again 250 kgs/m of emulsion zone catalyst averag density3, the average meter per second of void tower linear speed 0.8 again and again；
Quick bed tempertaure is 680 DEG C, and fast bed pressure is 0.21MPa, and quick bed catalyst averag density is 75 kgs/m, fast bed
The average meter per second of void tower linear speed 1.5；Two again temperature be 680 DEG C, two again pressure be 0.2MPa, two again emulsion zone catalyst be averaged it is close
380 kgs/m of degree3, two again be averaged the meter per second of void tower linear speed 0.7；Two main wind oxygen content 21% (volume) again, again and again exhanst gas outlet
Oxygen content 0.9% (volume), two exhanst gas outlet oxygen content 5.1% (volumes) again, 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 61.4%, ethene carbon base absorption rate 8.32%, propylene carbon base absorption rate 6.01%.
【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%Ag/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 470 DEG C, reaction pressure 0.5MPa, emulsion zone catalyst averag density 300
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 550 DEG C, one
Pressure is 0.5MPa again, again and again 200 kgs/m of emulsion zone catalyst averag density3, the average meter per second of void tower linear speed 0.9 again and again；
Quick bed tempertaure is 670 DEG C, and fast bed pressure is 0.51MPa, and quick bed catalyst averag density is 67 kgs/m, average sky
The meter per second of tower linear speed 1.6；Two again temperature be 680 DEG C, two again pressure be 0.5MPa, two emulsion zone catalyst averag densities 350,000 again
Grams m3, two again be averaged the meter per second of void tower linear speed 0.8；Two main wind oxygen content 21% (volume) again, again and again exhanst gas outlet oxygen content
0.6% (volume), two exhanst gas outlet oxygen content 4.4% (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 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%Ag/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 580 again and again
DEG C, pressure is 0.15MPa again and again, again and again 320 kgs/m of emulsion zone catalyst averag density3, average void tower linear speed 0.7 again and again
Meter per second；Quick bed tempertaure is 660 DEG C, and pressure be 0.16MPa to fast bed two again, quick bed catalyst averag density for 92 kilograms/
Rice, the average meter per second of void tower linear speed 1.2；Two again temperature be 670 DEG C, two again pressure be 0.15MPa, two again emulsion zone catalyst put down
Equal 400 kgs/m of density3, the average meter per second of void tower linear speed 0.6 again and again；Two main wind oxygen content 21% (volume) again, again and again flue gas
Export oxygen content 0.8% (volume), 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 60.3%, ethene carbon base absorption rate 9.17%, propylene carbon base absorption rate 7.94%.
【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%Ag/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 0.9.The technological condition of regeneration of fluid bed regenerator is：Temperature is 550 again and again
DEG C, pressure is 0.05MPa again and again, again and again 360 kgs/m of emulsion zone catalyst averag density3, average void tower linear speed 0.62 again and again
Meter per second；Quick bed tempertaure is 689 DEG C, and pressure be 0.06MPa to fast bed two again, quick bed catalyst averag density for 84 kilograms/
Rice, the average meter per second of void tower linear speed 1.4；Two again temperature be 690 DEG C, two again pressure be 0.05MPa, two again emulsion zone catalyst put down
Equal 400 kgs/m of density3, the average meter per second of void tower linear speed 0.6 again and again；Two main wind oxygen content 21% (volume) again, again and again flue gas
Export oxygen content 0.7% (volume), two exhanst gas outlet oxygen content 3.9% (volumes) again, carbon content on regenerated catalyst
0.08%.
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 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%Ag/MCM-48.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 580 again and again
DEG C, pressure is 0.15MPa again and again, again and again 320 kgs/m of emulsion zone catalyst averag density3, average void tower linear speed 0.7 again and again
Meter per second；Quick bed tempertaure is 660 DEG C, and pressure be 0.16MPa to fast bed two again, quick bed catalyst averag density for 92 kilograms/
Rice, the average meter per second of void tower linear speed 1.2；Two again temperature be 670 DEG C, two again pressure be 0.15MPa, two again emulsion zone catalyst put down
Equal 400 kgs/m of density3, the average meter per second of void tower linear speed 0.6 again and again；Two main wind oxygen content 21% (volume) again, again and again flue gas
Export oxygen content 0.8% (volume), 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 60.0%, ethene carbon base absorption rate 9.20%, propylene carbon base absorption rate 7.5%.
【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 1 reaction-again
Raw system, fluidized-bed reactor sets interior heat collector, using metal supported catalyst 1%Zn/3%Rb/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 580 again and again
DEG C, pressure is 0.15MPa again and again, again and again 320 kgs/m of emulsion zone catalyst averag density3, average void tower linear speed 0.7 again and again
Meter per second；Quick bed tempertaure is 660 DEG C, and pressure be 0.16MPa to fast bed two again, quick bed catalyst averag density for 92 kilograms/
Rice, the average meter per second of void tower linear speed 1.2；Two again temperature be 670 DEG C, two again pressure be 0.15MPa, two again emulsion zone catalyst put down
Equal 400 kgs/m of density3, the average meter per second of void tower linear speed 0.6 again and again；Two main wind oxygen content 21% (volume) again, again and again flue gas
Export oxygen content 0.8% (volume), 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 60.4%, ethene carbon base absorption rate 9.0%, propylene carbon base absorption rate 7.6%.
【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%Bi/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 0.9.The technological condition of regeneration of fluid bed regenerator is：Temperature is 550 again and again
DEG C, pressure is 0.05MPa again and again, again and again 360 kgs/m of emulsion zone catalyst averag density3, average void tower linear speed 0.62 again and again
Meter per second；Quick bed tempertaure is 689 DEG C, and pressure be 0.06MPa to fast bed two again, quick bed catalyst averag density for 84 kilograms/
Rice, the average meter per second of void tower linear speed 1.4；Two again temperature be 690 DEG C, two again pressure be 0.05MPa, two again emulsion zone catalyst put down
Equal 400 kgs/m of density3, the average meter per second of void tower linear speed 0.6 again and again；Two main wind oxygen content 21% (volume) again, again and again flue gas
Export oxygen content 0.7% (volume), two exhanst gas outlet oxygen content 3.9% (volumes) again, carbon content on regenerated catalyst
0.08%.
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 60.1%, ethene carbon base absorption rate 12.1%, propylene carbon base absorption rate 9.5%.
【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%Bi/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 0.9.The technological condition of regeneration of fluid bed regenerator is：Temperature is 550 again and again
DEG C, pressure is 0.05MPa again and again, again and again 360 kgs/m of emulsion zone catalyst averag density3, average void tower linear speed 0.62 again and again
Meter per second；Quick bed tempertaure is 689 DEG C, and pressure be 0.06MPa to fast bed two again, quick bed catalyst averag density for 84 kilograms/
Rice, the average meter per second of void tower linear speed 1.4；Two again temperature be 690 DEG C, two again pressure be 0.05MPa, two again emulsion zone catalyst put down
Equal 400 kgs/m of density3, the average meter per second of void tower linear speed 0.6 again and again；Two main wind oxygen content 21% (volume) again, again and again flue gas
Export oxygen content 0.7% (volume), two exhanst gas outlet oxygen content 3.9% (volumes) again, carbon content on regenerated catalyst
0.08%.
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 64.0%, ethene carbon base absorption rate 10.0%, propylene carbon base absorption rate 7.2%.
【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 1%Zn/3%Bi/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 0.9.The technological condition of regeneration of fluid bed regenerator is：Temperature is 550 again and again
DEG C, pressure is 0.05MPa again and again, again and again 360 kgs/m of emulsion zone catalyst averag density3, average void tower linear speed 0.62 again and again
Meter per second；Quick bed tempertaure is 689 DEG C, and pressure be 0.06MPa to fast bed two again, quick bed catalyst averag density for 84 kilograms/
Rice, the average meter per second of void tower linear speed 1.4；Two again temperature be 690 DEG C, two again pressure be 0.05MPa, two again emulsion zone catalyst put down
Equal 400 kgs/m of density3, the average meter per second of void tower linear speed 0.6 again and again；Two main wind oxygen content 21% (volume) again, again and again flue gas
Export oxygen content 0.7% (volume), two exhanst gas outlet oxygen content 3.9% (volumes) again, carbon content on regenerated catalyst
0.08%.
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 64.2%, ethene carbon base absorption rate 9.5%, propylene carbon base absorption rate 7.8%.
【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%Ag/ZSM-5.Fluid bed is anti-
The reaction process condition for answering device is：Reaction temperature is 470 DEG C, reaction pressure 0.5MPa, emulsion zone catalyst averag density 330
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 680 DEG C, one
Pressure is 0.5MPa again, 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 again temperature be 680 DEG C, two again pressure be 0.51MPa, two 310 kgs/m of emulsion zone catalyst averag density again3, put down again and again
The equal 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
Exhanst gas outlet oxygen content 4.1% (volume) again, 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%Ag/ZSM-5.The reaction work of fluidized-bed reactor
Skill condition is：Reaction temperature is 470 DEG C, reaction pressure 0.5MPa, 300 kgs/m of emulsion zone catalyst averag density3, put down
The equal 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,
380 kgs/m of regenerator 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 by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene, using recirculating fluidized bed reaction-regeneration system,
Methanol and/or dimethyl ether contact generation low-carbon alkene and richness by fluidized-bed reactor with one or more metal supported catalysts
Effluent containing aromatic hydrocarbons.It is characterized in that recirculating fluidized bed reaction-regeneration system used includes fluidized-bed reactor (1), instead
Answer device cyclone separator (4), reactor heat collector (5), stripper (6), inclined tube (7) to be generated, first fluidized bed regenerator (8),
First regenerator cyclone separator (11), the first regenerator heat collector (12), semi-regeneration stand pipe (13), semi regeneration inclined tube (14),
Second fluidized bed regenerator (15), fast bed (16), fast bed external warmer (21), outer circulating tube (22), Second reactivator rotation
Wind separator (20), degassing tank (23), regenerator sloped tube (24) and macroporous plate (17)；Decaying catalyst first passes through the first fluidized bed
Regenerator (8), control lower temperature complete annealing in hydrogen atmosphere process, then sequentially enter fast bed (16), second fluidized bed regenerator again
(15) control higher temperature to complete to make charcoal, obtain the regenerated catalyst of high quality.
2. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that methanol
Or dimethyl ether conversion reaction uses turbulent fluid bed reactor (1), including emulsion zone (2) and dilute-phase zone (3), methanol or dimethyl ether
Enter emulsion zone (2) from fluidized-bed reactor (1) bottom and catalyst contact carries out the reaction generation production such as aromatic hydrocarbons and low-carbon alkene
Thing, the product gas of entrained catalyst pass through dilute-phase zone (3) reactor cyclone (4) carry out gas solid separation after leave fluidisation
Bed reactor (1) enters subsequent separation system, and the catalyst of recovery returns to emulsion zone (2).
3. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that fluidisation
Bed reactor (1) is by setting interior heat collector (5) or external warmer (5) or setting interior heat collector (5) and external warmer (5) simultaneously
Heat caused by reaction is removed, while controls the reaction temperature of fluidized-bed reactor (1)；Fluidized-bed reactor (1) interior carbon deposit
Reclaimable catalyst enters first fluidized bed regenerator (8) after stripper (6) removes micro hydro carbons, through inclined tube to be generated (7)
Emulsion zone (9).
4. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that catalysis
Agent regeneration is regenerated using two device fast beds, and first fluidized bed regenerator (8) includes emulsion zone (9), dilute-phase zone (10), regenerator rotation
Wind separator (11), the first regenerator heat collector (12), semi-regeneration stand pipe (13), semi regeneration inclined tube (14)；Second fluidized bed is again
Raw device (15) includes emulsion zone (18), dilute-phase zone (19), regenerator cyclone separator (20), degassing tank (23), regenerator sloped tube
(24) and fast bed (16), macroporous plate (17), fast bed external warmer (21), outer circulating tube (22).
5. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that first
Fluid bed regenerator (8) is arranged in juxtaposition with fast bed (16), and first fluidized bed regenerator (8) passes through semi regeneration with fast bed (16)
Standpipe (13) and semi regeneration inclined tube (14) connection；Second fluidized bed regenerator (15) in fast bed (16) above, fast bed (16)
Second fluidized bed regenerator (15) bottom is inserted at top, and both pass through fast bed heat collector (21), outer circulating tube (22) and macropore
Sieve plate (17) connects.
6. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that to be generated
Catalyst enters in first fluidized bed regenerator (8) emulsion zone (9) and the air contact from first fluidized bed regenerator (8) bottom
Row catalyst regenerates；First fluidized bed regenerator (8) is based on annealing in hydrogen atmosphere, using relatively low regeneration temperature and appropriate oxygen content
Incomplete regen-eration is carried out, controls oxygen content in flue gas to be less than 1%；Flue gas of the oxygen content less than 1% passes through dilute-phase zone (10)
The first regenerator cyclone separator (11) carry out gas solid separation after leave first fluidized bed regenerator (8) into subsequent power return
Receipts system；Semi regeneration catalyst in first fluidized bed regenerator (8) passes through semi-regeneration stand pipe (13) and semi regeneration inclined tube (14)
Into fast bed (16) bottom.
7. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that oxygen-containing
Measure excessive main wind to contact under the high temperature conditions from fast bed (16) bottom into semi regeneration catalyst, carry out based on making charcoal
Complete regeneration；The reclaimable catalyst of fast bed (16) flue gas of the oxygen content more than 1% and surplus a small amount of carbon deposit passes through fast bed
(16) top macroporous plate (17) enter second fluidized bed regenerator (15) emulsion zone (18) with two again main wind mix, further burning
Jiao's regeneration；Flue gas of the oxygen content more than 1% carries out gas-solid by the Second reactivator cyclone separator (20) of dilute-phase zone (19)
Second fluidized bed regenerator (15) is left after separation and enters subsequent power recovery system.
8. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that first
High temperature catalyst in fluid bed regenerator (8) is first-class by being returned after the first external catalyst cooler for regenerator (12) reduces temperature
Change bed regenerator (8) emulsion zone (9), the regeneration temperature of first fluidized bed regenerator is adjusted by controlling catalyst internal circulating load.
9. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that second
High temperature catalyst in fluid bed regenerator (15) emulsion zone (18) enters after reducing temperature by fast bed external warmer (21)
Fast bed (16) bottom, the temperature burnt is adjusted by controlling catalyst internal circulating load；Second fluidized bed regenerator (15) close phase
The catalyst in area (18) enters fast bed device (16) to ensure the close of fast bed device (16) interior catalyst by outer circulating tube (22)
Degree.
10. the method by methanol or dimethyl ether for aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that quick
Catalyst in bed device (16) enters second fluidized bed regenerator (15) emulsion zone with flue gas is burnt by macroporous plate (17)
(18) catalyst, regenerated completely in second fluidized bed regenerator (15) is micro by the entrainment of degassing tank (23) Removal of catalyst
After non-hydrocarbon gases, into fluidized-bed reactor (1) emulsion zone (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056901A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Reaction system and reaction method for preparing aromatic hydrocarbon through catalytic conversion of methanol |
| CN111111749A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Fluidized bed reaction-regeneration method for preparing aromatic hydrocarbon |
| WO2021185168A1 (en) * | 2020-03-19 | 2021-09-23 | 中国石油化工股份有限公司 | Methanol-to-olefin conversion method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557365A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Coaxial fluidized bed reaction system and reaction method for preparing ethylene, propylene and arene by converting methanol and/ or dimethyl ether |
| CN105457569A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Double regenerator reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for double regenerator reaction device |
| CN105457568A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Double regenerator reaction device for preparing ethylene and aromatic hydrocarbon by catalytic conversion of methanol and/or dimethyl ether and reaction method for double regenerator reaction device |
| CN105457570A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Coaxial two-stage regenerative reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for coaxial two-stage regenerative reaction device |
| US20160102032A1 (en) * | 2014-10-10 | 2016-04-14 | Exxonmobil Research And Engineering Company | Apparatus and process for producing gasoline, olefins and aromatics from oxygenates |
-
2016
- 2016-06-29 CN CN201610495186.1A patent/CN107540493A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557365A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Coaxial fluidized bed reaction system and reaction method for preparing ethylene, propylene and arene by converting methanol and/ or dimethyl ether |
| CN105457569A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Double regenerator reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for double regenerator reaction device |
| CN105457568A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Double regenerator reaction device for preparing ethylene and aromatic hydrocarbon by catalytic conversion of methanol and/or dimethyl ether and reaction method for double regenerator reaction device |
| CN105457570A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Coaxial two-stage regenerative reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for coaxial two-stage regenerative reaction device |
| US20160102032A1 (en) * | 2014-10-10 | 2016-04-14 | Exxonmobil Research And Engineering Company | Apparatus and process for producing gasoline, olefins and aromatics from oxygenates |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056901A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Reaction system and reaction method for preparing aromatic hydrocarbon through catalytic conversion of methanol |
| CN111056901B (en) * | 2018-10-17 | 2022-10-11 | 中国石油化工股份有限公司 | Reaction system and reaction method for preparing aromatic hydrocarbon through catalytic conversion of methanol |
| CN111111749A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Fluidized bed reaction-regeneration method for preparing aromatic hydrocarbon |
| CN111111749B (en) * | 2018-10-30 | 2023-04-07 | 中国石油化工股份有限公司 | Fluidized bed reaction-regeneration method for preparing aromatic hydrocarbon |
| WO2021185168A1 (en) * | 2020-03-19 | 2021-09-23 | 中国石油化工股份有限公司 | Methanol-to-olefin conversion method |
| CN115244025A (en) * | 2020-03-19 | 2022-10-25 | 中国石油化工股份有限公司 | Methanol to olefin conversion process |
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