CN105985209A - Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides - Google Patents
Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides Download PDFInfo
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- CN105985209A CN105985209A CN201510041825.2A CN201510041825A CN105985209A CN 105985209 A CN105985209 A CN 105985209A CN 201510041825 A CN201510041825 A CN 201510041825A CN 105985209 A CN105985209 A CN 105985209A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method of producing aromatic hydrocarbon through catalytic conversion of organic oxides. The method includes the steps of: a) contacting the organic oxides in a dense-phase bed reaction section with a regenerated catalyst from a second regenerator to perform an aromatization reaction; b) discharging the reaction product from a reactor dilute-phase section, wherein to-be-regenerated catalyst successively passes through a first regenerator and the regenerator and then is fed back to the reactor for the reaction. The method has safe and stable process, achieves continuous operation, reduces usage amount of oxygen-containing gas for coking, catalyst loss and hydrothermal deactivation, is low in operation cost and has low environment pollution.
Description
Technical field
The present invention relates to a kind of method of organic oxygen compound catalytic cracking aromatic hydrocarbons.
Background technology
Aromatic hydrocarbons is a kind of important organic chemical industry's basic material, and wherein benzene, toluene and dimethylbenzene (include neighbour
Dimethylbenzene, meta-xylene and paraxylene) purposes is quite varied, its end product for synthetic resin,
Synthetic fibers, synthetic rubber, coating, dyestuff and medicine and other fields.With China's socio-economic development,
Also growing to the demand of aromatic hydrocarbons, the consumption of the annual aromatic hydrocarbons of current China more than 20,000,000 tons, but
It is to have the half need to be from external import.
Benzene, toluene and dimethylbenzene are mainly derived from petrochemical industry, and domestic petroleum chemical industry route produces
Aromatic hydrocarbons accounts for aromatics production total amount more than 85%, and production technology specifically includes that naphtha catalytic reforming, second
The hydrogenation extracting of alkene cracking naphtha and low-carbon (LC) aromatization of hydrocarbons etc., wherein naphtha catalytic reforming aromatic production
Accounting for the 80% of petrochemical industry route aromatic production, cracking of ethylene petroleum naphtha hydrogenation extracting aromatic production accounts for
16%.With the exhaustion day by day of petroleum resources, crude oil price remains high, and produces to petrochemical industry route
Aromatic hydrocarbons brings bigger cost pressure.The Energy Situation of China is many coals few oil deficency, 20th century 90
With economic sustainable growth since age, China's external oil dependency degree is continuously increased, and 1993 extremely
1996, China's external oil dependency degree was substantially within 10%, by 2000 first more than 30%,
Within 2007, reach 50.5%, within 2013, reach 57.39%, exceed well over 30% warning line generally acknowledged in the world.
Then, rich coal resources in China, in recent years national policy support under, ammonia from coal, dimethyl ether and
The industries such as ethylene glycol develop rapidly, according to statistics nearly 29,000,000 tons of China's methanol output in 2013.Therefore,
Development organic oxygen compound catalytic cracking aromatic hydrocarbons technology, to substitute traditional petrochemical industry route, can reduce
The dependency degree to petroleum for the aromatic hydrocarbons, has important work to Chinese energy safety and aromatics production industry
With.
Utilize the technology of organic oxygen compound catalytic cracking aromatic hydrocarbons, carried by Mobil Oil Corporation of the U.S. the earliest
Going out, the patent US4156698 A of application in its 1979 discloses the composite catalyzing utilizing containing molecular sieve
Agent is by C1-C4Alcohols or ether compound are converted into the method for low-carbon alkene and aromatic hydrocarbons；Application in 1985
Patent US4590321 A discloses and utilizes ZSM-5 or ZSM-11 equimolecular sieve catalyst by C2-C12
Alkane, C2-C12Alkene, C1-C5Alcohols and C2-C12The non-aromatics compounds such as ethers are converted into aromatic hydrocarbons
Technique；United States Patent (USP) US4686312 A, US4724270 A, US4822939 A, US4822939 A
Also disclose that the side of methyl alcohol or dimethyl ether aromatic hydrocarbons under different catalysts effect with US4049573 A etc.
Method.But the emphasis of these United States Patent (USP)s essentially consists in Study of Catalyst composition and operation condition to virtue
Hydrocarbon conversion rate and selective impact, indivedual patents propose the reaction process of methyl alcohol or dimethyl ether aromatic hydrocarbons,
But all clearly do not propose the reaction-regeneration system of organic oxygen compound aromatic hydrocarbons technology, reaction regeneration method with
And reactor and regenerator pattern.
At present, organic oxygen compound aromatic hydrocarbons technology is researched and developed by domestic Ye Youduojia institute, mainly
Including Tsing-Hua University, Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences, Sinopec Shanghai petrochemical industry are ground
Study carefully institute and Dalian Inst of Chemicophysics, Chinese Academy of Sciences etc..Chinese patent CN 1880288A discloses
The technique being raw material aromatic hydrocarbons processed under ZSM-5 Type Zeolites agent effect with methyl alcohol, this patent will
Isolating low-carbon (LC) hydro carbons and liquid product after the cooling of first stage reactor aromatization of methanol gas-phase product, liquid phase is produced
Thing obtains aromatic hydrocarbons and non-aromatics through extract and separate, and low-carbon (LC) hydro carbons enters the further aromatisation of second stage reactor,
Thus improve the overall selectivity of aromatic hydrocarbons.Chinese patent CN 101823929 B proposes a kind of methyl alcohol or two
The system of methyl ether preparing aromatic hydrocarbon and technique, methyl alcohol or dimethyl ether are first in aromatization reactor reaction, and reaction is produced
Hydrogen, methane, mixing C in thing8Aromatic hydrocarbons and part C9+Hydro carbons is as product, C2+Non-aromatics and except mixed
Close C8Aromatic hydrocarbons and part C9+Aromatic hydrocarbons outside hydro carbons then can be recycled to another reactor and carry out further virtue
Structure, improves yield and the selectivity of aromatic hydrocarbons.Chinese patent CN 101607858 B, CN 102190546
B, CN 102371176 B and CN 102371177 B etc. also individually disclose organic oxygen compound catalysis and turn
Change aromatics process processed and organic oxygen compound catalytic cracking arenes catalytic agent and preparation method.Above-mentioned patent is same
Sample focus on investigate different catalysts composition and rare metal, rare-earth metal modified to aromatization process
Impact, CN 1880288A and CN 101823929 B mainly proposes product circulation aromatisation to virtue
The impact of hydrocarbon yield, but these patents do not relate to the reaction-regeneration system of organic oxygen compound aromatic hydrocarbons yet.
Chinese patent CN 101244969 A discloses the device of a kind of continuous aromatization and catalyst regeneration
And method, this device include an aromatisation fluid bed and a continuous catalyst regenerating fluid bed and
It is arranged on the pipeline for catalyst transport between two fluid beds and solids delivery device, but this patent
Do not suggest that the concrete form of regenerative system, and there are some problems: regenerator only sets one-level gas-solid and divides
From system, catalyst recovery yield is low, and the catalyst stack less causing costliness is serious；Regenerator pattern is single hop
Bed regenerates, and for ensureing catalyst regeneration efficiency, regeneration temperature reaches as high as 750 DEG C, due to catalyst
The coke carried secretly contains part hydrogen, after burning, generates water, catalyst water under high temperature and water vapor acting
Heat inactivation is serious, causes catalyst activity to reduce；It is the interior heat that takes that regenerator takes hot mode, and only arranges
A piece heat production coil pipe, takes thermal medium and scurries into regenerator in a large number, can cause regenerator pressure when coil pipe bursts
Raise rapidly, even can set off an explosion when serious.
Content of the invention
It is an object of the invention to provide a kind of method of organic oxygen compound catalytic cracking aromatic hydrocarbons, the method was both
Can meet and improve aromatic hydrocarbon product yield and optionally require, be suitable for again organic oxygen compound catalytic cracking
Arene industrialization produces continuously, and catalyst stack less and hydrothermal deactivation can be greatly lowered simultaneously, reduces work
The cost of industry organic oxygen compound catalytic cracking aromatic hydrocarbons.
To achieve these goals, the present invention provides the side of a kind of organic oxygen compound catalytic cracking aromatic hydrocarbons
Method, the method includes:
Organic oxygen compound is sent into from the bottom of the dense-phase bed conversion zone of fluidized-bed reactor bottom fluidisation
In bed reactor, contact with aromatized catalyst at this dense-phase bed conversion zone and aromatization occurs；
Described fluidisation will be sent at the reacted oil gas being entrained with a small amount of catalyst of dense-phase bed conversion zone
The reactor dilute phase section on bed reactor top, and carry out product in this reactor dilute phase section and urge with to be generated
The product separating is sent into subsequent product and is reclaimed piece-rate system by the separation of agent；
The inclined tube to be generated from described dense-phase bed conversion zone top for the reacted reclaimable catalyst is drawn institute
State fluidized-bed reactor and be delivered to the first regenerator and contain with from the first of described first regenerator bottoms
Carrier of oxygen contacts and carries out the first regeneration under the regeneration temperature of 500-650 DEG C, obtains semi regeneration catalyst
With the first regenerated flue gas；The protium weight wherein controlling coke contained by described semi regeneration catalyst is described
The 0-40 weight % of the protium weight of coke contained by reclaimable catalyst, controls contained by described semi regeneration catalyst
The carbon weight of coke is the 10-50 weight % of the carbon weight of coke contained by described reclaimable catalyst；
Described semi regeneration catalyst is sent into Second reactivator and the second oxygen-containing gas contact and
Carry out the second regeneration under the regeneration temperature of 600-750 DEG C, obtain regenerated catalyst and the second regenerated flue gas；
Described regenerated catalyst is sent back to the bottom of described dense-phase bed conversion zone, and from dense-phase bed
Described organic oxygen compound haptoreaction bottom conversion zone.
Preferably, wherein, described organic oxygen compound is for selected from C1-C10Alcohols, C2-C12Ethers and C3-C12
At least one in ketone；Described catalyst is the microspherical catalyst containing molecular sieve and carrier.
Preferably, wherein, it is re-fed into described stream after first described organic oxygen compound being preheated to 150-250 DEG C
Fluidized bed reactor reacts.
Preferably, wherein, by described organic oxygen compound by being positioned at bottom described dense-phase bed conversion zone
Feed distributing plate is sent in described fluid bed regenerator, and with by being positioned above described feed distributing plate
The described regenerated catalyst contact that regenerative agent distributor pipe is sent into.
Preferably, wherein, the condition of described aromatization is: the reaction temperature of dense-phase bed conversion zone
For 400-600 DEG C, the reaction pressure of reactor dilute phase section is 0.05-0.6MPa, dense-phase bed conversion zone matter
Amount air speed is 0.1-10 hour-1, organic oxygen compound is the 5-30 second in the time of staying of dense-phase bed conversion zone.
Preferably, wherein, by weight and on the basis of the gross weight of catalyst, control is from described fluidisation
The coke content of the described reclaimable catalyst that bed reactor is drawn is 0.1-2.0 weight %.
Preferably, wherein, by least one set two stage cyclone separator carry out described product with to be generated
The separation of catalyst.
Preferably, wherein, take out a part of catalyst from the top of described dense-phase bed conversion zone and enter anti-
Answer external warmer to take heat, then send the catalyst after this outside heat removing back to described dense-phase bed conversion zone upper
Portion.
Preferably, wherein, described fluid bed is adjusted by the heat that takes of control described reaction external warmer
The reaction temperature of reactor.
Preferably, wherein, by described reacted reclaimable catalyst from described dense-phase bed conversion zone top
Inclined tube to be generated draw fluidized-bed reactor, through stripping after be delivered to the first regenerator.
Preferably, wherein, described reclaimable catalyst by deadweight and/or is promoted wind feeding described first
In regenerator.
Preferably, wherein, described first oxygen-containing gas is for selected from air, flue gas, oxygen, air+nitrogen
At least one in gas and oxygen+nitrogen, described second oxygen-containing gas for selected from air, flue gas, oxygen,
At least one in air+nitrogen and oxygen+nitrogen；Wherein said flue gas is for selected from described first regeneration cigarette
The mixture of gas, described second regenerated flue gas and the first regenerated flue gas and the second regenerated flue gas is through further
After burning gained gas at least one.
Preferably, wherein, it is used for sending in described first regenerator after described first oxygen-containing gas preheating
Regeneration, and/or be used for regenerating by sending in Second reactivator after described second oxygen-containing gas preheating.
Preferably, wherein, described first oxygen-containing gas is divided by oxygen-containing gas distribution rings or oxygen-containing gas
Stringing is sent in described first regenerator and is used for regenerating, and/or passes through oxygenous by described second oxygen-containing gas
Body distribution rings or oxygen-containing gas distributor pipe are sent in Second reactivator and are used for regenerating.
Preferably, wherein, from described first regenerator, take out a part of catalyst enter regeneration outside heat removing
Device takes heat, then sends into the catalyst after this outside heat removing in described Second reactivator and carries out described second again
Give birth to or send back in the dense bed of described first regenerator.
Preferably, wherein, described first is adjusted again by the heat that takes of control described regeneration external warmer
The regeneration temperature of raw device and/or the regeneration temperature of described Second reactivator.
Preferably, wherein, by weight and on the basis of the gross weight of catalyst, control described regeneration and urge
In agent, the content of coke is 0.01-0.1 weight %.
Preferably, wherein, it is arranged in juxtaposition described first regenerator and described Second reactivator；By at least
Described semi regeneration catalyst is separated and by institute by one group of two stage cyclone separator with described first regenerated flue gas
State the first regenerated flue gas and send described first regenerator；By least one set two stage cyclone separator by described
Regenerated catalyst separates with described second regenerated flue gas and described second regenerated flue gas is sent described second
Regenerator.
Preferably, wherein, by described first regenerated flue gas sent from described first regenerator with from described
Burn after the described second regenerated flue gas mixing that Second reactivator is sent, obtain combustion product gases and carry out
Energy regenerating.
Preferably, wherein, the first regenerator described in upper and lower arranged superposed and described Second reactivator and first
Regenerator is arranged on above Second reactivator, and the first regenerator is arranged with the junction of Second reactivator
For only allowing the gas carrying a small amount of catalyst secretly to pass through；Described second regenerated flue gas is fed to described first
The bottom of regenerator, together with described first oxygen-containing gas for described first regenerator described first again
Raw.
Preferably, wherein, described first regenerated flue gas is passed through least one set two stage cyclone separator and institute
State after semi regeneration catalyst separates and send the first regenerator.
Preferably, wherein, described first regenerator oxygen deprivation operation, the oxygen-enriched operation of described Second reactivator,
By volume, the ratio controlling carbon monoxide and carbon dioxide in described first regenerated flue gas is 0.2-3,
The content controlling oxygen in described second regenerated flue gas is 0.5-15 body %.
Preferably, wherein, it is re-fed into institute after described semi regeneration catalyst being sent into the degassing of semi regeneration deaeration pipe
State in Second reactivator.
Preferably, wherein, control described by the catalyst discharge of the described semi regeneration deaeration pipe of control
The catalyst material position of the first regenerator.
Preferably, wherein, after degassed for described regenerated catalyst, described dense-phase bed conversion zone is sent back to
Bottom, contact with the described organic oxygen compound bottom dense-phase bed conversion zone.
Preferably, wherein, it is regenerated catalyst through deadweight by described and/or promote the described fluidisation of wind feeding
In bed reactor.
The method of the organic oxygen compound catalytic cracking aromatic hydrocarbons that the present invention provides has the advantage that
1st, the reaction of organic oxygen compound catalytic cracking aromatic hydrocarbons and catalyst regenerate respectively in reactor and regeneration
Carrying out in device, between two devices, inclined tube is respectively provided with degassing facility, reaction raw materials and product with burn with oxygenous
Body does not contacts substantially, and process safety is steady, can realize continuous operation；
2nd, the first regenerator low temperature oxygen deprivation operation, the high-temperature oxygen-enriched operation of Second reactivator, at utmost
While upper reduction catalyst hydrothermal deactivation, can reduce to burn and use oxygen-containing gas consumption, thus reduce and have
The running cost of machine oxide catalyst conversion for preparing arene；
3rd, reactor arranges outside heat removing system, takes organic oxygen compound aromatization liberated heat away,
Control reaction temperature, in optimum range, can reach good aromatization effect；
4th, regenerator arranges outside heat removing system, takes away and burns liberated heat, control the first regenerator and
The temperature of Second reactivator, maintains heat endurance and the activity of catalyst；
5th, reactor and regenerator are respectively provided with two-stage efficient cyclone separator, reclaim product as far as possible
With the catalyst carried secretly in flue gas, catalyst attrition and running cost can be reduced, reaction can also be reduced
The environmental pollution that the pipeline of the follow-up cooling separation of product and equipment attrition and fume emission bring.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of specification, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
The organic oxygen compound catalytic cracking aromatic hydrocarbons that Fig. 1 is used by the first detailed description of the invention of the present invention
System (i.e. eclipsed form two-stage regeneration, reclaimable catalyst conveying circuit uses and promotes wind lifting)；
The organic oxygen compound catalytic cracking aromatic hydrocarbons that Fig. 2 is used by the second detailed description of the invention of the present invention
System (i.e. eclipsed form two-stage regeneration, regenerated catalyst conveying circuit uses and promotes wind lifting)；
The organic oxygen compound catalytic cracking aromatic hydrocarbons that Fig. 3 is used by the third detailed description of the invention of the present invention
(i.e. eclipsed form two-stage regeneration, reclaimable catalyst and regenerated catalyst conveying circuit all use lifting wind to system
Promote)；
The organic oxygen compound catalytic cracking aromatic hydrocarbons that Fig. 4 is used by the 4th kind of detailed description of the invention of the present invention
System (i.e. block form two-stage regeneration, semi regeneration catalyst transport circuit uses and promotes wind lifting).
Description of reference numerals
1 reactor 2 regenerator 3 dense-phase bed conversion zone 4 reactor dilute phase section
5 first regenerator 6 Second reactivator 7 spent agent stripper 8 regenerative agent degassing tanks
9 semi regeneration deaeration pipe 10 feed distributing plate 11 reactor primary cyclones
Inclined tube on 12 reactor secondary cyclone 13 reactor collection chamber 14 spent agents
15 stripping fluid distributor pipe 16 spent agent lower oblique tube 17 guiding valves to be generated
18 spent agent riser 19 oxygen-containing gas distributor pipe 20 oxygen-containing gas distribution rings
21 first regenerator primary cyclone 22 first regenerator secondary cyclones
Inclined tube 25 regenerative agent degassing dielectric distribution ring on 23 first regenerator collection chamber 24 regenerative agents
26 regenerative agent lower oblique tubes 27 regenerate inclined tube on guiding valve 28 semi regeneration
29 semi regeneration agent degassing dielectric distribution ring 30 semi regeneration lower oblique tube 31 semi regeneration guiding valves
32 regenerative agent riser 33 semi regeneration agent riser 34 Second reactivator primary cyclones
35 Second reactivator secondary cyclone 36 Second reactivator collection chambers
Detailed description of the invention
It is described in detail below in conjunction with the detailed description of the invention to the present invention for the accompanying drawing.It should be appreciated that
Detailed description of the invention described herein is merely to illustrate and explains the present invention, is not limited to this
Bright.
The present invention provides a kind of method of organic oxygen compound catalytic cracking aromatic hydrocarbons, and the method includes: will have
Machine oxide sends into fluidized-bed reactor from the bottom of the dense-phase bed conversion zone of fluidized-bed reactor bottom
In, contact with aromatized catalyst at this dense-phase bed conversion zone and aromatization occurs；Will be in close phase
The reacted oil gas being entrained with a small amount of catalyst of bed conversion zone sends into described fluidized-bed reactor top
Reactor dilute phase section, and carry out product in this reactor dilute phase section and separate with reclaimable catalyst,
The product separating is sent into subsequent product and reclaims piece-rate system；By reacted reclaimable catalyst from institute
The inclined tube to be generated stating dense-phase bed conversion zone top is drawn described fluidized-bed reactor and is delivered to first again
Raw device contacts with the first oxygen-containing gas from described first regenerator bottoms and the regeneration of 500-650 DEG C
At a temperature of carry out the first regeneration, obtain semi regeneration catalyst and the first regenerated flue gas；Wherein control described half
The protium weight of coke contained by regenerated catalyst is the protium weight of coke contained by described reclaimable catalyst
The 0-40 weight % of amount, controlling the carbon weight of coke contained by described semi regeneration catalyst is described to be generated urge
The 10-50 weight % of the carbon weight of coke contained by agent；Described semi regeneration catalyst is sent into second again
Raw device and the second oxygen-containing gas contact and carry out the second regeneration under the regeneration temperature of 600-750 DEG C, obtain
Regenerated catalyst and the second regenerated flue gas；Described regenerated catalyst is sent back to described dense-phase bed conversion zone
Bottom, with the described organic oxygen compound haptoreaction bottom dense-phase bed conversion zone.
According to the present invention, described dense-phase bed conversion zone is dense bed section, and reactor dilute phase section is dilute phase
Bed section, arranges the time of staying that dense bed section is to control organic oxygen compound at reaction bed, protects
Abundant high-efficient contact between card organic oxidation raw material and catalyst, suppression air pocket and catalyst agglomeration thing
Generate, thus maintain higher reaction conversion ratio and arenes selectivity；Arranging dilute-phase leanphase fluidized bed section is to make
The catalyst that reactor product gas is carried secretly by gravity initial gross separation under compared with low flow velocity, and have enough spaces
Arrange two stage cyclone separator for further separation catalyst, reduce catalyst stack less and catalyst sets to follow-up
The standby abrasion with pipeline.
According to the present invention, described organic oxygen compound and the catalysis for organic oxygen compound catalytic cracking aromatic hydrocarbons
Agent is well known to the skilled person, and for example, described organic oxygen compound can be for selected from C1-C10
Alcohols, C2-C12Ethers and C3-C12At least one in ketone；Described catalyst can be for containing molecule
Sieve and the microspherical catalyst of carrier, described molecular sieve is preferably ZSM-5 molecular sieve.The present invention's is described
The condition of aromatization is not specifically limited, for example, can be: the reaction temperature of dense-phase bed conversion zone
Degree is 400-600 DEG C, and the reaction pressure of reactor dilute phase section is 0.05-0.6MPa, dense-phase bed conversion zone
Mass space velocity is 0.1-10 hour-1, organic oxygen compound is 5-30 in the time of staying of dense-phase bed conversion zone
Second.
According to the present invention it is possible to be re-fed into described after first described organic oxygen compound being preheated to 150-250 DEG C
Fluidized-bed reactor reacts, and the organic oxygen compound after preheating is preferably gas phase state.Described preheating
Method is well-known to those skilled in the art, and the present invention repeats no more.
According to the present invention, in order to strengthen the main reaction of organic oxygen compound catalytic cracking aromatic hydrocarbons, it is thus achieved that higher
BTX (benzene, toluene and dimethylbenzene) selectivity, it is necessary to assure filling between organic oxygen compound and catalyst
Tap is touched, and can be divided described organic oxygen compound by the charging being positioned at bottom described dense-phase bed conversion zone
Fabric swatch is sent in described fluid bed regenerator, and with by being positioned at the regenerative agent above described feed distributing plate
The described regenerated catalyst contact that distributor pipe is sent into.Described feed distributing plate is that those skilled in the art institute is ripe
Knowing, for example, can being cone structure, upper surface be cambered surface, and arc sizes can react than dense-phase bed
The section little 10-200mm of internal diameter, to meet thermal expansion and the equally distributed requirement of organic oxygen compound；In cambered surface
Should be uniformly distributed at least 1 wear resistant short tube, wear resistant short tube bore can be Φ 5-Φ 200mm, gas phase
Organic oxygen compound enter after feed distributing plate can rapidly from each wear resistant short tube high velocity jet out,
It is uniformly distributed on the cross section of dense-phase bed conversion zone.Described regenerative agent distributor pipe is also those skilled in the art
Known, the inside and outside of such as regenerative agent distributor pipe can all serve as a contrast wear resistance lining, to reduce catalyst abrasion,
The catalyst distribution hole of at least 1 polygon or circle should be set at the bottom of pipe, to ensure that regenerated catalyst exists
It is uniformly distributed on the cross section of dense-phase bed conversion zone, and be fully contacted with gas phase organic oxygen compound.
According to the present invention, by weight and on the basis of the gross weight of catalyst, can control from described stream
The coke content of the described reclaimable catalyst that fluidized bed reactor is drawn is 0.1-2.0 weight %, it is ensured that conversion zone end
End catalyst still retains certain activity, so that the activity of the catalyst in reactor meets reaction and wants
Ask.
According to the present invention it is possible to carried out described product by least one set two stage cyclone separator and treat
The separation of raw catalyst.Described cyclone separator is well-known to those skilled in the art, and the present invention is no longer
Repeat.General one group of two stage cyclone separator include series connection a primary cyclone and one two grades
Cyclone separator；When arranging many group two stage cyclone separators, primary cyclone and two grades of whirlwind divide
Typically identical from the quantity of device, between can be connected one to one by riser, it is also possible to by multiple one-levels
It after the riser of cyclone separator merges into a concetrated pipe, then is connected with multiple secondary cyclones,
The riser of secondary cyclone is all connected with collection chamber, and described collection chamber can be located at the interior of regenerator
Portion, it is also possible to be located at the outside of regenerator.
Owing to organic oxygen compound catalytic cracking aromatic hydrocarbons is an exothermic reaction, for taking the heat that reaction produces away
Amount, controls reaction temperature, can take out at least a portion catalysis from the top of described dense-phase bed conversion zone
Agent enters reaction external warmer and takes heat, then sends the catalyst after this outside heat removing back to described dense-phase bed anti-
The top of the section of answering.According to a kind of detailed description of the invention of the present invention, catalyst can react from dense-phase bed
Section top enters reaction external warmer by inclined tube on reaction external warmer and cools down, the catalysis after cooling
Agent reacted external warmer lower oblique tube and reaction external warmer riser return to dense-phase bed conversion zone top.
At least 1 group heat removing tube bundle can be set in reaction external warmer, often organize tube bank and can individually excise, when wherein
Reaction external warmer and the reaction of organic oxygen compound catalytic cracking aromatic hydrocarbons is not interfered with during one group of tube bank booster
The operation of system.In addition, the bottom of described reaction external warmer can also arrange and take outside at least 1 reaction
Hot device fluidizing agent distributor pipe, fluidizing agent is including but not limited to selected from steam, nitrogen, methane, dry gas
With at least one gas in fuel gas.Described reaction external warmer fluidizing agent distributor pipe can use tree
Dendritic distributor pipe, it is ensured that fluidizing agent is evenly distributed at reaction external warmer, it is ensured that in reaction external warmer
Catalyst fluidization state and heat transfer efficiency.Further, it will be appreciated by persons skilled in the art that
Can by control described reaction external warmer take the reaction that heat adjusts described fluidized-bed reactor
Temperature.The i.e. temperature of dense-phase bed conversion zone can be controlled by reacting the heat that takes of external warmer, more
Specifically can be controlled catalyst internal circulating load by guiding valve under reaction external warmer or be fluidized by adjustment
Medium amount, it is achieved take the regulation of thermic load 0-100%.
According to the present invention it is possible to by described reacted reclaimable catalyst from described dense-phase bed conversion zone
The inclined tube to be generated in portion draws fluidized-bed reactor, is delivered to the first regenerator after stripping.Preferably, root
Different according to the catalyst outlet of dense-phase bed conversion zone and the height of the first regenerator catalyst entrance, to be generated
Catalyst is had two kinds by dense-phase bed reactor to the mode of movement of the first regenerator: when dense-phase bed reaction
Section catalyst outlet than first regenerator catalyst entrance high more when, reclaimable catalyst can pass through oneself
Weight flow in the first regenerator certainly；When the catalyst outlet of dense-phase bed conversion zone is catalyzed than the first regenerator
When agent entrance is low, identical or exceeds few, reclaimable catalyst can send into the first regenerator by promoting wind
In, i.e. described reclaimable catalyst by deadweight and/or can be promoted in described first regenerator of wind feeding；
It is equally possible that be regenerated catalyst through deadweight by described and/or promote the described fluidized-bed reaction of wind feeding
In device, just repeat no more here；Described lifting wind can including but not limited to be selected from oxygen-containing gas, nitrogen
With at least one in steam.According to a kind of detailed description of the invention of the present invention, reclaimable catalyst is from close phase
Bed conversion zone top enters spent agent stripper by inclined tube on spent agent, will under stripping fluid effect
The product of catalyst entrainment is stripped off, and the product being stripped off is by spent agent stripper top
Returning reactor dilute phase section；Reclaimable catalyst then flows downward, by spent agent lower oblique tube, by or not
Enter regenerator by spent agent riser；The material position of dense-phase bed conversion zone is controlled by guiding valve to be generated.Its
In, the effect of described spent agent stripper is that the partial reaction of reclaimable catalyst entrained with after stripping reacts produces
Thing, to reduce product loss.One or more stripping fluid distributor pipes are set in described spent agent stripper
Being used for being distributed stripping fluid, stripping fluid can including but not limited to be selected from steam, nitrogen, methane, do
At least one in gas and fuel gas.
According to the present invention, described first oxygen-containing gas and described second oxygen-containing gas are oxygen-containing gas, this
Invention limits to its oxygen content, gas composition and source be not concrete, as long as can reach described lean
Oxygen operation and the purpose of described oxygen-enriched operation.For example, described first oxygen-containing gas can be for selected from sky
At least one in gas, flue gas, oxygen, air+nitrogen and oxygen+nitrogen, described second oxygen-containing gas
Also at least one in air, air+nitrogen and oxygen+nitrogen can be；Wherein said flue gas can
Think selected from described first regenerated flue gas, described second regenerated flue gas and the first regenerated flue gas and second again
At least one in the gas of mixture gained after burning further of raw flue gas.
According to the present invention, during normal operating, described first oxygen-containing gas is sent directly into the described first regeneration
Device is used for regenerate, is sent directly into described second oxygen-containing gas in described Second reactivator and is used for regenerating；
When going into operation or when two regenerator temperature decline, can be by by after described first oxygen-containing gas preheating
Send in described first regenerator for regenerating, and/or send into second after described second oxygen-containing gas preheating
Regenerator is used for regenerate, thus improves the temperature of regenerator.The mode of described preheating is art technology
Known to personnel, for example, can will be used for the gas of regeneration at the equipment such as auxiliary combustion chamber or electric heater
In preheat.
According to the present invention, for ensureing to be distributed in the first regenerator and Second reactivator for the gas of regeneration
It uniformly and is fully contacted with catalyst, burn effect and fluidized state to reach good, can be by described
First oxygen-containing gas passes through oxygen-containing gas distribution rings or oxygen-containing gas distributor pipe sends into described first regenerator
In be used for regenerating, and/or can by described second oxygen-containing gas pass through oxygen-containing gas distribution rings or oxygen-containing gas
Distributor pipe is sent in Second reactivator and is used for regenerating.Wherein, should be at least in described oxygen-containing gas distribution rings
1 wear resistant short tube is set；Described oxygen-containing gas distributor pipe typically uses dendroid distributor pipe, each branch
Also should be at least provided with 1 wear resistant short tube on the branched pipe of shape, therefore oxygen-containing gas distributor pipe is to gas
Distributed effect is typically better than oxygen-containing gas distribution rings.In the present invention, owing to being mostly used in the gas of regeneration
Body enters bottom Second reactivator, so Second reactivator is preferably provided with oxygen-containing gas distributor pipe, it is considered to
Second regenerated flue gas flow resistance, the first regenerator is preferably provided with oxygen-containing gas distribution rings.
According to the present invention, owing to the temperature control of the first regenerator and Second reactivator is steady to the heat of catalyst
Qualitative and active play an important role, and regenerate to burn and can release big calorimetric, for maintaining regenerator temperature,
A part of catalyst entrance regeneration external warmer can be taken out from described first regenerator, take heat, then will
Catalyst after this outside heat removing is sent into and is carried out the described second regeneration in described Second reactivator or send back to described
In the dense bed of the first regenerator.Regeneration external warmer of the present invention is well known to those skilled in the art
, similar with reaction external warmer noted earlier, repeat no more here.Further, the present invention is also
Can by control described regeneration external warmer take the regeneration temperature that heat adjusts described first regenerator
Degree and/or the regeneration temperature of described Second reactivator, i.e. by guiding valve control catalyst under regeneration external warmer
Internal circulating load or by adjusting fluidizing agent flow, it is achieved take the regulation of thermic load 0-100%, thus realize the
The temperature control of one regenerator and/or Second reactivator.
According to the present invention, after described reclaimable catalyst carries out the second regeneration, by weight and with catalyst
Gross weight on the basis of, can control the content of coke in described regenerated catalyst is 0.01-0.1 weight %.
According to a kind of detailed description of the invention of the present invention, can be arranged in juxtaposition described first regenerator with described
Second reactivator (as shown in Figure 4)；Wherein it is possible to by least one set two stage cyclone separator by institute
State semi regeneration catalyst and separate with described first regenerated flue gas and described first regenerated flue gas is sent described
First regenerator；Can also be by least one set two stage cyclone separator also by described regenerated catalyst and institute
State the second regenerated flue gas separate and described second regenerated flue gas is sent described Second reactivator.Described first
The described first regeneration carrying out in regenerator refers to carry out oxygen deprivation operation, controls in the first regenerated flue gas and does not contains
There is oxygen, and contain a certain proportion of carbon monoxide；Described second carrying out in described Second reactivator is again
Life refers to oxygen-enriched operation, controls containing superfluous oxygen in the second regenerated flue gas, and carbon monoxide is totally converted
For carbon dioxide.Owing to the second regenerated flue gas containing superfluous oxygen, the first regenerated flue gas contains an oxygen
Change carbon, therefore can be by described first regenerated flue gas sent from described first regenerator and from described second
Burn after the described second regenerated flue gas mixing that regenerator is sent, obtain combustion product gases and carry out energy
Reclaim.This is possible not only to improve the temperature of mixed flue gas, and beneficially follow-up system reclaims heat, reduces
Oxygen-containing gas consumption and oxygen-containing gas blower fan wasted work, CO excessive concentration band when can avoid fume emission simultaneously
The environmental pollution coming.
According to the another kind of detailed description of the invention of the present invention, can the first regenerator described in arranged superposed up and down
Be arranged on above Second reactivator with described Second reactivator and the first regenerator, and the first regenerator with
The junction of Second reactivator is configured to only allow the gas carrying a small amount of catalyst secretly by (such as Fig. 1-3
Shown in)；Wherein, described second regenerated flue gas can be fed to the bottom of described first regenerator, with
Described first oxygen-containing gas, simultaneously can also be by together for the described first regeneration of described first regenerator
In first regenerator, described first regenerated flue gas of gained passes through least one set two stage cyclone separator and institute
State after semi regeneration catalyst separates and send the first regenerator.
Due to organic oxygen compound catalytic cracking arenes catalytic agent hydro-thermal when high temperature and high steam partial pressure
Inactivation is more obvious, therefore described first regenerator is for using the oxygen deprivation operation of the first oxygen-containing gas, can control
The temperature making the described first regeneration is 500-650 DEG C, and owing to the burning velocity of Hydrogen In The Coke is big far away
In the burning velocity of carbon, reclaimable catalyst, under the regeneration condition that the first regenerator more relaxes, can be burnt
In coke, the carbon and 60 of 50 weight %-90 weight % weighs the protium of %-100 weight %, although major part hydrogen
Element is burnt in the first regenerator and is become water vapour, but relatively low owing to burning temperature, can effectively reduce
The hydrothermal deactivation of catalyst.Second reactivator, for using the oxygen-enriched operation of the second oxygen-containing gas, can control
The temperature of described second regeneration is 600-750 DEG C, and regeneration condition is harsher than the first regenerator, due to coke
The basic burning in the first regenerator of middle protium is complete, and Second reactivator can divide at the low water vapour of high temperature
The protium that the carbon and 0 of 10 weight %-50 weight % on catalyst weighs under conditions of pressure %-40 weight % is complete
Full burning, to reduce the hydrothermal deactivation of catalyst, i.e. can control coke contained by described semi regeneration catalyst
Protium weight be coke contained by described reclaimable catalyst protium weight 0-40 weight %, can control
The carbon weight making coke contained by described semi regeneration catalyst is coke contained by described reclaimable catalyst
The 10-50 weight % of carbon weight；And the content preferably controlling coke in described regenerated catalyst is
0.01-0.1 weight %.
According to the present invention, anyway arranging described first regenerator and Second reactivator, described first again
The described first regeneration carrying out in raw device refers to carry out oxygen deprivation operation, i.e. can control in the first regenerated flue gas
Do not contain oxygen, and contain a certain proportion of carbon monoxide；Described carrying out in described Second reactivator
Two regeneration refer to oxygen-enriched operation, i.e. can control in the second regenerated flue gas containing superfluous oxygen, an oxidation
Carbon is completely converted into carbon dioxide.Preferably, by volume, can control in described first regenerated flue gas
The ratio of carbon monoxide and carbon dioxide is 0.2-3；Oxygen in described second regenerated flue gas can be controlled
Content is 0.5-15 body %.
According to the present invention it is possible to be re-fed into after described semi regeneration catalyst is sent into the degassing of semi regeneration deaeration pipe
In described Second reactivator, may then pass through the catalyst discharge controlling described semi regeneration deaeration pipe
Control the catalyst material position of described first regenerator.According to a kind of detailed description of the invention of the present invention, permissible
By described semi regeneration catalyst from the first regenerator by inclined tube on semi regeneration, semi regeneration deaeration pipe and partly again
Giving birth to inclined tube and entering the bottom of Second reactivator, the first regenerator material position can be controlled by semi regeneration guiding valve.
Described semi regeneration deaeration pipe is well known to those skilled in the art, and its effect is to reduce semi regeneration catalyst folder
The flue gas of band, increases semi regeneration lower oblique tube inner catalyst density to improve the pressure reduction of semi regeneration guiding valve, it is ensured that
The quiet run of semi regeneration guiding valve.Semi regeneration deaeration pipe can arrange at least 1 semi regeneration agent degassing medium
Distribution rings, degassing medium can including but not limited to be selected from steam, nitrogen, air and other inert gases
In at least one.
According to the present invention it is possible to send back to the reaction of described dense-phase bed after degassed for described regenerated catalyst
The bottom of section, contacts with the described organic oxygen compound bottom dense-phase bed conversion zone.According to the present invention
A kind of detailed description of the invention, regenerated catalyst from Second reactivator dense bed top by regenerative agent tiltedly
Pipe enters regenerative agent degassing tank, and the regenerated catalyst after degassing is delivered to reaction by regenerative agent lower oblique tube
Device, regenerated catalyst internal circulating load is by regenerating guiding valve control.For ensureing degasifying effect, reduce and enter reactor
In non-hydrocarbon component to reduce product energy consumption of compressor, regenerative agent degassing tank can arrange at least 1
Regenerative agent degassing dielectric distribution ring；Degassing medium can including but not limited to be selected from steam, nitrogen and other
At least one in inert gas.
The following examples will illustrate the present invention further in conjunction with accompanying drawing, but the present invention is not therefore
And it is any way limited.
In the present embodiment, the SRIPT-3 method of Sinopec research institute exploitation is used to measure catalysis to be generated
Coke content in agent and regenerated catalyst, methanol conversion, aromatic hydrocarbons carbon base absorption rate and BTX carbon back are received
Rate is calculated according to product slates after reaction and methyl alcohol inlet amount.
Embodiment 1
The system of organic oxygen compound catalytic cracking aromatic hydrocarbons as shown in Figure 1, organic oxygen compound of the present invention is urged
Technical process and the operating condition of changing the first detailed description of the invention of conversion for preparing arene method are as follows:
Setting up the catalyst circulation between reactor and regenerator according to the inventive method, catalyst is warp
Cross the ZSM-5 molecular sieve catalyst (research institute is synthetically produced by Sinopec, lower same) of modification, former
Material is industrial methanol, and feeding preheating temperature is 180 DEG C；Reaction temperature 490 DEG C, reactor dilute phase section and
First regenerator overhead pressure 0.2MPa (g).Gas-phase methanol is entered dense-phase bed reaction by feed distributing plate
It bottom Duan, is fully contacted with the regenerated catalyst come from Second reactivator and reacts, gas and catalysis
Agent following current is upwards moved and reacts in whole dense-phase bed conversion zone, methanol quality air speed 1.5h-1。
Product enters reactor dilute phase section, by reactor primary cyclone and reactor two grades rotation
The catalyst that major part is carried secretly isolated by wind separator, and the catalyst separated flows downward and enters close phase
Bed conversion zone；The product isolating major part catalyst enters reactor collection chamber, finally enters
Follow-up system carries out refrigerated separation and obtains target product aromatic hydrocarbons and corresponding byproduct.
Reclaimable catalyst enters spent agent stripping from dense-phase bed conversion zone top by inclined tube on spent agent
Device, arranges 1 stripping fluid distributor pipe, will urge under stripping fluid vapor action in spent agent stripper
The product that agent is carried secretly is stripped off and Returning reactor dilute phase section；Reclaimable catalyst passes through spent agent
Lower oblique tube and spent agent riser, enter the top of the first regenerator under promoting vapor action.
First regenerator oxygen deprivation operation, burns and is entered first with the first oxygen-containing gas by oxygen-containing gas distribution rings
Regenerator bottoms, burns with reclaimable catalyst adverse current, burns the carbon and 90 of 60 weight %-70 weight % in coke
The hydrogen of weight %-100 weight %.Semi regeneration catalyst is entered by inclined tube on semi regeneration from the bottom of the first regenerator
Enter semi regeneration deaeration pipe, under nitrogen effect, remove the flue gas of semi regeneration catalyst entrainment, then by semi regeneration
Lower oblique tube enters Second reactivator bottom.The oxygen-enriched operation of Second reactivator, most of second oxygen-containing gas by
Oxygen-containing gas distributor pipe enters, and burns carbon remaining on catalyst and hydrogen completely at a higher temperature and carries out
Catalyst regenerates.Oxygen content 1 body %-2 body % in second regenerated flue gas, is upwards moved into first again
Raw device, mixes with the first oxygen-containing gas that oxygen-containing gas distribution rings is come and burns；CO in second regenerated flue gas
With CO2Volume ratio is about 0.4-0.5.First regenerated flue gas enter the first regenerator primary cyclone and
The catalyst that major part is carried secretly isolated by first regenerator secondary cyclone, the catalyst separated
Entering the bottom of the first regenerator, the first regenerated flue gas enters the first regenerator collection chamber, subsequently into energy
Amount recovery system carries out energy regenerating and is finally discharged by chimney.
Regenerated catalyst after burning is discharged from Second reactivator top, is entered regeneration by inclined tube on regenerative agent
Agent degassing tank, is removed, under degassing medium nitrogen effect, the flue gas carried secretly, then is entered by regenerative agent lower oblique tube
Enter dense-phase bed conversion zone to react with methyl alcohol.
The method using above-mentioned organic oxygen compound catalytic cracking aromatic hydrocarbons prepares aromatic hydrocarbons, and continuous and stable runs
After, methanol conversion 99.6 weight %, aromatic hydrocarbons carbon base absorption rate 51.0 weight %, BTX (benzene, toluene, diformazan
Benzene) carbon base absorption rate 40.0 weight %.
Embodiment 2
The system of organic oxygen compound catalytic cracking aromatic hydrocarbons as shown in Figure 2, organic oxygen compound of the present invention is urged
Technical process and the operating condition of changing the second detailed description of the invention of conversion for preparing arene method are as follows:
Setting up the catalyst circulation between reactor and regenerator according to the inventive method, catalyst is
ZSM-5 molecular sieve catalyst, raw material is industrial methanol, and feeding preheating temperature is 160 DEG C；Reaction temperature
470 DEG C, reactor dilute phase section and the first regenerator overhead pressure 0.15MPa (g).Gas-phase methanol is by feeding
Distribution grid enters bottom dense-phase bed conversion zone, is fully contacted with the regenerated catalyst come from Second reactivator
And react, gas and catalyst following current are upwards moved and react in whole dense-phase bed conversion zone,
Methanol quality air speed is 0.5h-1。
Product enters reactor dilute phase section, by reactor primary cyclone and reactor two grades rotation
The catalyst that major part is carried secretly isolated by wind separator, and the catalyst separated flows downward and enters close phase
Bed conversion zone；The product isolating major part catalyst enters reactor collection chamber, finally enters
Follow-up system carries out refrigerated separation and obtains target product aromatic hydrocarbons and corresponding byproduct.
Reclaimable catalyst enters spent agent stripping from dense-phase bed conversion zone top by inclined tube on spent agent
Device, arranges 1 stripping fluid distributor pipe, will urge under stripping fluid vapor action in spent agent stripper
The product that agent is carried secretly is stripped off and Returning reactor dilute phase section；Reclaimable catalyst passes through spent agent
Lower oblique tube enters the first regenerator top.
First regenerator oxygen deprivation operation, burns and is entered first with the first oxygen-containing gas by oxygen-containing gas distribution rings
Regenerator bottoms, burns with reclaimable catalyst adverse current, burns the carbon and 90 of 60 weight %-70 weight % in coke
The hydrogen of weight %-100 weight %.Semi regeneration catalyst is entered by inclined tube on semi regeneration from the bottom of the first regenerator
Enter semi regeneration deaeration pipe, under nitrogen effect, remove the flue gas of semi regeneration catalyst entrainment, then by semi regeneration
Lower oblique tube enters the bottom of Second reactivator.The oxygen-enriched operation of Second reactivator, most of second oxygen-containing gas
Entered by oxygen-containing gas distributor pipe, at a higher temperature carbon remaining on catalyst and hydrogen are burnt completely into
Row catalyst regenerates.In second regenerated flue gas, oxygen content 1 body %-2 body %, is upwards moved into first
Regenerator, mixes with the first oxygen-containing gas that oxygen-containing gas distribution rings is come and burns；In first regenerated flue gas
CO and CO2Volume ratio is 0.4-0.5.First regenerated flue gas enters the first regenerator primary cyclone
Isolate the catalyst that major part is carried secretly with the first regenerator secondary cyclone, the catalysis separated
Agent enters the first regenerator bottom, and flue gas enters the first regenerator collection chamber, subsequently into energy regenerating system
System carries out energy regenerating and is finally discharged by chimney.
Regenerated catalyst after burning is discharged from the top of Second reactivator, is entered by inclined tube on regenerative agent again
Raw agent degassing tank, removes the flue gas carried secretly under degassing medium nitrogen effect, then passes through regenerative agent lower oblique tube
Enter dense-phase bed conversion zone with regenerative agent riser to react with methyl alcohol.
The method using above-mentioned organic oxygen compound catalytic cracking aromatic hydrocarbons prepares aromatic hydrocarbons, and continuous and stable runs
After, methanol conversion 99.1 weight %, aromatic hydrocarbons carbon base absorption rate 52.7 weight %, BTX carbon base absorption rate 41.6 weight %.
Embodiment 3
The system of organic oxygen compound catalytic cracking aromatic hydrocarbons as shown in Figure 3, organic oxygen compound of the present invention is urged
Technical process and the operating condition of changing the third detailed description of the invention of conversion for preparing arene method are as follows:
Setting up the catalyst circulation between reactor and regenerator according to the inventive method, catalyst is
ZSM-5 molecular sieve catalyst, raw material is industrial methanol, and feeding preheating temperature is 200 DEG C；Reaction temperature
490 DEG C, reactor dilute phase section and the first regenerator overhead pressure 0.3MPa (g).Gas-phase methanol is by feeding point
Fabric swatch enters bottom dense-phase bed conversion zone, is fully contacted simultaneously with the regenerated catalyst come from Second reactivator
Reacting, gas and catalyst following current are upwards moved and react in whole dense-phase bed conversion zone, first
Alcohol mass space velocity 2.0h-1。
Product enters reactor dilute phase section, by reactor primary cyclone and reactor two grades rotation
The catalyst that major part is carried secretly isolated by wind separator, and the catalyst separated flows downward and enters close phase
Bed conversion zone；The product isolating major part catalyst enters reactor collection chamber, finally enters
Follow-up system carries out refrigerated separation and obtains target product aromatic hydrocarbons and corresponding byproduct.
Reclaimable catalyst enters spent agent stripping from dense-phase bed conversion zone top by inclined tube on spent agent
Device, arranges 1 stripping fluid distributor pipe, will urge under stripping fluid vapor action in spent agent stripper
The product that agent is carried secretly is stripped off and Returning reactor dilute phase section；Reclaimable catalyst flows downward logical
Cross spent agent lower oblique tube and enter the first regenerator top through spent agent riser.
First regenerator oxygen deprivation operation, burns and is entered first with the first oxygen-containing gas by oxygen-containing gas distribution rings
Regenerator bottoms, burns with reclaimable catalyst adverse current, burns the carbon and 90 of 60 weight %-70 weight % in coke
The hydrogen of weight %-100 weight %.Semi regeneration catalyst is entered by inclined tube on semi regeneration from the first regenerator bottom
Semi regeneration deaeration pipe, removes the flue gas of semi regeneration catalyst entrainment under nitrogen effect, then by under semi regeneration
Inclined tube enters Second reactivator bottom.The oxygen-enriched operation of Second reactivator, most of second oxygen-containing gas is by containing
Carrier of oxygen distributor pipe enters, and burns carbon remaining on catalyst and hydrogen completely at a higher temperature and urges
Agent regenerates.In second regenerated flue gas, oxygen content 1 body %-2 body %, is upwards moved into the first regeneration
Device, mixes with the first oxygen-containing gas that oxygen-containing gas distribution rings is come and burns；In first regenerated flue gas CO with
CO2Volume ratio is 0.4-0.5.First regenerated flue gas enters the first regenerator primary cyclone and first
The catalyst that major part is carried secretly isolated by regenerator secondary cyclone, and the catalyst separated enters
First regenerator bottom, flue gas enters the first regenerator collection chamber, carries out subsequently into energy-recuperation system
Energy regenerating is simultaneously finally discharged by chimney.
Regenerated catalyst after burning is discharged from Second reactivator top, is entered regeneration by inclined tube on regenerative agent
Agent degassing tank, removes, under degassing medium nitrogen effect, the flue gas carried secretly, then by regenerative agent lower oblique tube and
Regenerative agent riser enters dense-phase bed conversion zone and reacts with methyl alcohol.
The method using above-mentioned organic oxygen compound catalytic cracking aromatic hydrocarbons prepares aromatic hydrocarbons, and continuous and stable runs
After, methanol conversion 99.5w%, aromatic hydrocarbons carbon base absorption rate 51.1w%, BTX carbon base absorption rate 41.0w%.
By the result of embodiment 1-3 it can be seen that the method for the employing present invention is prepared aromatic hydrocarbons, not only
Methyl alcohol conversion is complete, and aromatic hydrocarbons carbon base absorption rate and BTX carbon base absorption rate all reach higher level.
Claims (26)
1. a method for organic oxygen compound catalytic cracking aromatic hydrocarbons, the method includes:
Organic oxygen compound is sent into from the bottom of the dense-phase bed conversion zone of fluidized-bed reactor bottom fluidisation
In bed reactor, contact with aromatized catalyst at this dense-phase bed conversion zone and aromatization occurs；
Described fluidisation will be sent at the reacted oil gas being entrained with a small amount of catalyst of dense-phase bed conversion zone
The reactor dilute phase section on bed reactor top, and carry out product in this reactor dilute phase section and urge with to be generated
The product separating is sent into subsequent product and is reclaimed piece-rate system by the separation of agent；
The inclined tube to be generated from described dense-phase bed conversion zone top for the reacted reclaimable catalyst is drawn institute
State fluidized-bed reactor and be delivered to the first regenerator and contain with from the first of described first regenerator bottoms
Carrier of oxygen contacts and carries out the first regeneration under the regeneration temperature of 500-650 DEG C, obtains semi regeneration catalyst
With the first regenerated flue gas；The protium weight wherein controlling coke contained by described semi regeneration catalyst is described
The 0-40 weight % of the protium weight of coke contained by reclaimable catalyst, controls contained by described semi regeneration catalyst
The carbon weight of coke is the 10-50 weight % of the carbon weight of coke contained by described reclaimable catalyst；
Described semi regeneration catalyst is sent into Second reactivator and the second oxygen-containing gas contact and
Carry out the second regeneration under the regeneration temperature of 600-750 DEG C, obtain regenerated catalyst and the second regenerated flue gas；
Described regenerated catalyst is sent back to the bottom of described dense-phase bed conversion zone, and from dense-phase bed
Described organic oxygen compound haptoreaction bottom conversion zone.
2. method according to claim 1, wherein, described organic oxygen compound is for selected from C1-C10Alcohols,
C2-C12Ethers and C3-C12At least one in ketone；Described catalyst is containing molecular sieve and carrier
Microspherical catalyst.
3. described organic oxygen compound wherein, is first preheated to 150-250 DEG C by method according to claim 1
After be re-fed into described fluidized-bed reactor and react.
4. method according to claim 1, wherein, described organic oxygen compound is described close by being positioned at
Feed distributing plate bottom phase bed conversion zone is sent in described fluid bed regenerator, and with by being positioned at
State the described regenerated catalyst contact that the regenerative agent distributor pipe above feed distributing plate is sent into.
5. method according to claim 1, wherein, the condition of described aromatization is: dense bed
The reaction temperature of layer conversion zone is 400-600 DEG C, and the reaction pressure of reactor dilute phase section is
0.05-0.6MPa, dense-phase bed conversion zone mass space velocity is 0.1-10 hour-1, organic oxygen compound is in close phase
The time of staying of bed conversion zone is the 5-30 second.
6. method according to claim 1, wherein, by weight and with the gross weight of catalyst as base
Standard, control is 0.1-2.0 from the coke content of the described reclaimable catalyst that described fluidized-bed reactor is drawn
Weight %.
7. method according to claim 1, wherein, is carried out by least one set two stage cyclone separator
Described product separates with reclaimable catalyst.
8. method according to claim 1, wherein, takes out from the top of described dense-phase bed conversion zone
A part of catalyst enters reaction external warmer and takes heat, then sends the catalyst after this outside heat removing back to described
The top of dense-phase bed conversion zone.
9. method according to claim 8, wherein, by control described reaction external warmer take heat
Amount adjusts the reaction temperature of described fluidized-bed reactor.
10. method according to claim 1, wherein, by described reacted reclaimable catalyst from described
The inclined tube to be generated on dense-phase bed conversion zone top draws fluidized-bed reactor, is delivered to first again after stripping
Raw device.
11. according to the method for claim 1 or 10, wherein, by described reclaimable catalyst by deadweight
And/or promote in described first regenerator of wind feeding.
12. methods according to claim 1, wherein, described first oxygen-containing gas is for selected from air, cigarette
At least one in gas, oxygen, air+nitrogen and oxygen+nitrogen, described second oxygen-containing gas for selected from
At least one in air, flue gas, oxygen, air+nitrogen and oxygen+nitrogen；Wherein said flue gas is
Selected from described first regenerated flue gas, described second regenerated flue gas and the first regenerated flue gas and the second regeneration cigarette
At least one in the gas of the mixture of gas gained after burning further.
13. methods according to claim 1, wherein, send into institute after described first oxygen-containing gas preheating
State in the first regenerator for regenerating, and/or send into Second reactivator after described second oxygen-containing gas preheating
In be used for regenerating.
Described first oxygen-containing gas wherein, is passed through oxygen-containing gas by 14. methods according to claim 1
Distribution rings or oxygen-containing gas distributor pipe are sent in described first regenerator and are used for regenerating, and/or by described second
Oxygen-containing gas passes through oxygen-containing gas distribution rings or oxygen-containing gas distributor pipe is sent in Second reactivator for again
Raw.
15. methods according to claim 1, wherein, take out a part from described first regenerator and urge
Agent enters regeneration external warmer and takes heat, and then the catalyst after this outside heat removing is sent into the described second regeneration
Device carries out described second regenerate or send back in the dense bed of described first regenerator.
16. methods according to claim 15, wherein, by taking of control described regeneration external warmer
Heat adjusts the regeneration temperature of described first regenerator and/or the regeneration temperature of described Second reactivator.
17. methods according to claim 1, wherein, by weight and with the gross weight of catalyst as base
Standard, the content controlling coke in described regenerated catalyst is 0.01-0.1 weight %.
18. methods according to claim 1, wherein, are arranged in juxtaposition described first regenerator and described the
Two regenerators；By least one set two stage cyclone separator by described semi regeneration catalyst with described first again
Raw flue gas separates and described first regenerated flue gas is sent described first regenerator；By least one set two-stage
Described regenerated catalyst is separated and by described second regeneration by cyclone separator with described second regenerated flue gas
Flue gas sends described Second reactivator.
19. methods according to claim 18, wherein, described in sending from described first regenerator
First regenerated flue gas fires after mixing with described second regenerated flue gas sent from described Second reactivator
Burn, obtain combustion product gases and carry out energy regenerating.
20. methods according to claim 1, wherein, the first regenerator described in upper and lower arranged superposed and institute
State Second reactivator and the first regenerator is arranged on above Second reactivator, and the first regenerator and second
The gas that the junction of regenerator is set to only allow to carry secretly a small amount of catalyst passes through；Described second regeneration cigarette
Gas is fed to the bottom of described first regenerator, is used for described first together with described first oxygen-containing gas
Described first regeneration of regenerator.
Described first regenerated flue gas wherein, is passed through at least one by 21. methods according to claim 20
Group two stage cyclone separator sends the first regenerator after separating with described semi regeneration catalyst.
22. according to claim the 1st, 18 or 20 method, wherein, described first regenerator oxygen deprivation behaviour
Make, the oxygen-enriched operation of described Second reactivator, by volume, control an oxidation in described first regenerated flue gas
The ratio of carbon and carbon dioxide is 0.2-3, and the content controlling oxygen in described second regenerated flue gas is 0.5-15
Body %.
Described semi regeneration catalyst feeding semi regeneration wherein, is taken off by 23. methods according to claim 1
It is re-fed in described Second reactivator after tracheae degassing.
24. methods according to claim 23, wherein, by controlling urging of described semi regeneration deaeration pipe
Agent discharge controls the catalyst material position of described first regenerator.
25. methods according to claim 1, wherein, send back to after degassed for described regenerated catalyst
The bottom of described dense-phase bed conversion zone, with the described organic oxygen compound bottom dense-phase bed conversion zone
Contact.
26. methods according to claim 1, wherein, by described be regenerated catalyst through deadweight and/or
Promote wind to send in described fluidized-bed reactor.
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| CN106732822A (en) * | 2017-01-22 | 2017-05-31 | 清华大学 | A kind of catalyst regeneration device, method and system |
| CN108017484A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | The method of high arenes selectivity during maintenance methanol aromatic hydrocarbons |
| CN109694297A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The method for maintaining high arenes selectivity during methanol aromatic hydrocarbons |
| EP3616784A4 (en) * | 2017-04-27 | 2020-04-01 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Apparatus and method for preparing para-xylene co-producing low-carbon olefin from methanol and/or dimethyl ether and benzene |
| CN111056902A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Reaction system for recycling byproduct oxide in methanol-to-aromatics process |
| US11180431B2 (en) | 2017-04-27 | 2021-11-23 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Fluidized bed device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and toluene |
| US11311852B2 (en) | 2017-04-27 | 2022-04-26 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and toluene |
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| CN108017484A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | The method of high arenes selectivity during maintenance methanol aromatic hydrocarbons |
| CN108017484B (en) * | 2016-11-04 | 2020-09-04 | 中国石油化工股份有限公司 | Method for maintaining high aromatic selectivity in process of preparing aromatic hydrocarbon from methanol |
| CN106732822A (en) * | 2017-01-22 | 2017-05-31 | 清华大学 | A kind of catalyst regeneration device, method and system |
| EP3616784A4 (en) * | 2017-04-27 | 2020-04-01 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Apparatus and method for preparing para-xylene co-producing low-carbon olefin from methanol and/or dimethyl ether and benzene |
| US11084765B2 (en) | 2017-04-27 | 2021-08-10 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and benzene |
| US11180431B2 (en) | 2017-04-27 | 2021-11-23 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Fluidized bed device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and toluene |
| US11311852B2 (en) | 2017-04-27 | 2022-04-26 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and toluene |
| CN109694297A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The method for maintaining high arenes selectivity during methanol aromatic hydrocarbons |
| CN109694297B (en) * | 2017-10-20 | 2022-02-01 | 中国石油化工股份有限公司 | Method for maintaining high aromatic selectivity in process of preparing aromatic hydrocarbon from methanol |
| CN111056902A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Reaction system for recycling byproduct oxide in methanol-to-aromatics process |
| CN114870909A (en) * | 2022-05-05 | 2022-08-09 | 中国石油化工股份有限公司 | Method for regenerating catalytic cracking spent catalyst |
| CN114870909B (en) * | 2022-05-05 | 2023-10-20 | 中国石油化工股份有限公司 | Method for regenerating catalytic cracking spent catalyst |
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