CN108325477A - A kind of tandem moving bed reaction system and methods for using them for oxygenate conversion - Google Patents
A kind of tandem moving bed reaction system and methods for using them for oxygenate conversion Download PDFInfo
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- CN108325477A CN108325477A CN201710037778.3A CN201710037778A CN108325477A CN 108325477 A CN108325477 A CN 108325477A CN 201710037778 A CN201710037778 A CN 201710037778A CN 108325477 A CN108325477 A CN 108325477A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
A kind of tandem moving bed reaction system for oxygenate conversion, including n moving-burden bed reactor, 1 catalyst devator of n, regenerator, catalyst mixer, fresh catalyst storage tank, three phase separator, optional Tuo Fangta, optional dethanizer and optional C4 knockout towers, wherein n >=2.Reaction system provided by the invention is used for the conversion of oxygenatedchemicals, promote catalyst to the conversion of oxygenatedchemicals the reaction of carbon deposited catalyst containing arene stream and improves the selectivity of purpose product, it avoids using process water as diluent return oxygenate conversion reactor increase energy consumption and catalyst poisoning, the stability of product distribution is also ensured while reducing energy consumption.
Description
Technical field
The present invention relates to a kind of reaction systems for oxygenate conversion, more particularly to will be contained using moving bed technique
The tandem reaction system of oxygen compound conversion.
Background technology
Propylene is a kind of important petrochemical industry base stock for being only second to ethylene, be mainly derived from oil catalytic pyrolysis,
Steam cracking and propane (butane) dehydrogenation of naphtha etc..In recent years, because of the pulling of propylene downstream industry, global propylene demand
The trend of rapid growth, propylene resource provisioning anxiety is aggravated year by year.
China's coal resource is abundant, and ammonia from coal large industrialized technology is increasingly mature, with the MTP by methanol production propylene
The industrialization of technology, to open a feasible approach to clean Coal Chemical Industry Route production propylene.
The process route of preparing propylene from methanol (MTP) technology generally uses " two-stage method " reaction process, i.e. first segment methanol system
Dimethyl ether (MTD) reactor converts methanol fractions to dimethyl ether (DME), and first segment reaction product enters after being mixed with diluent
Second segment MTP reactors carry out Synthin reaction, and second segment reaction product is by detaching, compressing, being refining to obtain qualified products.
In " one-step method " MTP techniques also, methanol enters MTP reactors progress Synthin and reacts after directly being mixed with diluent,
Reaction product is by detaching, compressing, being refining to obtain qualified products.
U.S. Patent application US2003/0139635A1 discloses the method from methanol production propylene.Methanol is first via first
Reactor is partially converted into dimethyl ether, then passes through the second fixed bed reactors of filling Pentasil type shape-selective zeolite catalysts
Generate the product containing propylene.The catalyst has 300~600m2The specific surface area of/g, the Kong Rong of 0.3~0.8mL/g, is less than
The alkali metal content of 380ppm and be less than 0.1% ZnO and CdO contents.One anti-outlet material of which part and steam are direct
Into second reactor, it is partially separated out the intermediate product after propylene and recycles freshening to second reactor.Second reactor it is anti-
It is 350-500 DEG C to answer temperature.
Also some technologies are distributed in such a way that methanol and petroleum hydrocarbon are co-feeding come the product of modulation product light olefin
And selectivity.It is co-feeding with aromatic compounds that Chinese patent application 99806355.X proposition will contain methanol and/or dimethyl ether, in α
Under zeolite catalyst effect of the value less than 10,350~480 DEG C of reaction temperature and the partial pressure of methanol and/dimethyl ether are more than 70kPa's
Under the conditions of, the conversion ratio for controlling methanol and/or dimethyl ether is less than 90%, obtains Light olefin products, especially improves feed aromatics
The selectivity to ethylene can be improved in ratio.The co-feeding organic charging for being more than 10% (weight) including arene content of aromatics, including but
It is not limited to benzene,toluene,xylene, C9+Reforming material, lightweight reformate, full range reformate or any straight-run, coking
Aromatic hydrocarbons derived from gasoline fraction, FCC naphtha and coal may also comprise the fraction that methanol feeds the generation of itself aromatization.First
The molar ratio of alcohol and/or dimethyl ether and aromatic feed is generally higher than 5：1, avoid the excessive concentration of aromatic compounds from causing excessively to tie
Burnt, separated volume and circular flow increase and selectivity of product added value is reduced.
Chinese patent application 200710180086.0 proposes self-produced C in preparing propylene from methanol device7+ aromatic hydrocarbons material freshening
Extremely aromatic compounds and light alkene are produced simultaneously to realize with the co-feeding oxygenatedchemicals olefin hydrocarbon reactor of oxygenatedchemicals material
Hydrocarbon.
Chinese patent application 201010607910.8 is disclosed using activation ZSM-5 molecular sieve catalyst coupling between methanol
The method of naphtha catalytic cracking reaction.ZSM-5 molecular sieve catalyst of this method containing lanthanum and phosphorus, reaction temperature 550-670
DEG C, methanol and naphtha are simultaneously by catalyst bed, and wherein methanol and naphtha mass ratio are 0.05-0.8, combined feed air speed
For 1.0-5h-1Reaction condition under haptoreaction.
The method that Chinese patent application 201310512646.3 discloses methanol or dimethyl ether aromatic hydrocarbons, in reaction temperature
350-650 DEG C, under the conditions of pressure 0.1-2.0MPa, methanol or dimethyl ether and dry gas, rich gas, liquefied gas, direct steaming gasoline, pumice brain
One or more mixing in oil and catalyst haptoreaction.
U.S. Patent application US6680418B2 discloses the multi-methyl benzene of methanol and/or dimethyl ether and at least 10% (weight)
The co-feeding technique that production light olefin is contacted with porous crystalline material catalyst.250-500 DEG C of reaction temperature, methanol and/or two
Methyl ether divides 35-1725kPa.
In the fixed-bed process of these methanol production alkene, catalyst runs initial stage can make methanol conversion close to 100%,
But extend with the duration of runs, catalyst surface carbon deposit causes methanol conversion to be gradually reduced with olefine selective.Typical MTP techniques
In, general single pass life averagely about 667h or so of shape-selective catalyst, terminal life about 8000h [Chemical Industry in Guangzhou, 2013,41
(17)：192].MTP reactions are a typical acid catalyzed reactions, and the alkene generated in reaction is very active, are easy further contracting
Symphysis causes the covering of catalyst surface acid centre and duct to block, under keeping catalyst activity and selectivity gradual at carbon deposit
Drop.Therefore, the MTP catalyst runs period is relatively short, needs frequent regeneration.To ensure that production is carried out continuously, MTP reactors are logical
Often it is standby to open one for selection two.
Moving bed technique can make the regeneration of catalyst successive reaction to the attention of researcher.CN101023047B discloses one
Alcoholic oxygenate is the method for propylene using moving bed technique and etherification step by kind.The process is in the first reaction zone
Methanol is first converted into dimethyl ether using γ-Al2O3 catalyst, then second reaction zone using moving-burden bed reactor,
ZSM-5 or SAPO-34 molecular sieve catalysts, by the outflow mixture of the first reaction zone, part by-product water, ethylene, part C4+
The return hydrocarbon of alkene composition is converted into the product rich in propylene, and catalyst residence times are shorter than 300h in this reaction zone.
CN101367701A discloses a kind of method converting oxygenate compounds to propylene using moving bed technique, uses
Oxygen-containing compound material is generated product by two-stage reaction area in first segment reaction zone, then by the C in product5The above component is passed through
Second reaction zone carries out the pre- carbon deposit of regenerated catalyst, then the catalyst circulation of the pre- carbon deposit in second reaction zone is used for the first reaction zone
Reaction, is finally passed through regenerator by catalyst.
CN102344328A discloses a kind of semicontinuous method converting methanol into propylene using moving bed technique, packet
It includes：The first reaction zone is passed through after molecular sieve catalyst is mixed with diluent, methanol feedstock is passed through the first reaction zone and molecular sieve
Catalyst haptoreaction generates first burst of logistics；First burst of logistics is passed through second reaction zone and molecular sieve catalyst haptoreaction,
Generate second burst of logistics；After second burst of logistics methanol feedstock heat exchange, through being dehydrated and being detached after oxide removal, it is anti-to obtain second
It answers area to return to material, second reaction zone discharging and third reaction zone feeds, second reaction zone to return to material and be incorporated to first burst of logistics；Third
Reaction zone feeds are passed through third reaction zone and contact generation third stock logistics with molecular sieve catalyst；Molecular sieve catalyst is using catalysis
Agent collector is periodically transported to after being regenerated in regenerating unit, is intermittently incorporated in molecular sieve catalyst and recycles.
CN102942435A discloses a kind of reaction process converting methanol into propylene using moving bed technique, including with
Lower step：(1) it will be passed into pre-reaction zone together after methanol feedstock and return hydrocarbon Hybrid Heating and contacts progress with regenerated catalyst
Etherification reaction generates a product stream；(2) main reaction region and carbon deposit will be passed through after product stream and diluent heat exchange
Catalyst carries out olefine reaction processed, and the secondary product stream rich in propylene is obtained from reactor outlet；(3) secondary product streaming is gone
Disengagement zone obtains product propylene and other by-products after dehydration and oxide removal, by the ethylene in other by-products, portion
Divide C4Alkene, C4Alkane, C5Hydrocarbon, C6Hydrocarbon is used as return hydrocarbon to be back to pre-reaction zone after merging.
This utilization regenerated process of successive reaction-is related to catalyst between reaction zone and reaction regeneration area is defeated
It send, needs special air-lift device, this needs prodigious conveying power, energy consumption excessively high；In addition, the work being converted into using methanol
Skill water contains the technological deficiency that impurity makes catalyst poisoning as return diluent increase energy consumption and process water.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of tandem moving bed reaction systems and use should
Reaction system, oxygenate conversion efficiency can be improved, extend the catalyst stabilization duration of runs oxygenate conversion side
Method.
Provided by the present invention for the tandem moving bed reaction system of oxygenate conversion, including n moving bed reaction
Device, n-1 catalyst devator, regenerator, catalyst mixer, fresh catalyst storage tank, three phase separator, optional de- virtue
Tower, optional dethanizer and optional C4 knockout towers, wherein n >=2；
In the system, urged with first movement bed reactor, the first catalyst devator, the second moving-burden bed reactor, second
Agent lifter, until (n-1)th moving-burden bed reactor, (n-1)th catalyst devator and n-th moving-burden bed reactor it is suitable
Sequence is in series；N-th of moving-burden bed reactor is connected with regenerator, and carbon deposition catalyst connects with oxygen flow in a regenerator
It touches to burn and be regenerated；
The catalyst mixer is connected with regenerator, fresh catalyst storage tank, catalyst devator respectively, receives and
It is urged from the regenerated catalyst of regenerator, the fresh catalyst from fresh catalyst storage tank, the activation from catalyst devator
Agent, the catalyst mixer and first movement bed reactor or with including first movement bed reactor at least
Two moving-burden bed reactors are connected, and the catalyst in catalyst mixer is sent into first movement bed reactor, or are sent into
In at least two moving-burden bed reactors including first movement bed reactor；
The n moving-burden bed reactor is equipped with reaction raw materials entrance, for input oxygen-containing compound material logistics or
The logistics of person's oxygen-containing compound material with by optionally from dethanizer C2 logistics, optionally from the C4 logistics of C4 knockout towers
With the mixture flow for returning to hydrocarbon and being formed of the C5C6 logistics composition optionally from Tuo Fangta；
The n-1 catalyst devator is both provided with entrance containing aromatic hydrocarbon substance and mixed fragrant product exit；
The n moving-burden bed reactor, n-1 catalyst devator are connected with three phase separator, the three-phase
Separator produces the reaction product stream from n moving-burden bed reactor and the mixed virtue from n-1 catalyst devator outlet
The mixture flow of object logistics is separated into gas phase, water phase and oil phase logistics；
The optional dethanizer is connected with three phase separator, and optional dethanizer will be from three phase separator
Gaseous stream isolates the C2 logistics；
The optional Tuo Fangta is connected with three phase separator, and optional Tuo Fangta is by the oil phase from three phase separator
Arene stream and the C5C6 logistics are isolated in logistics；
The optional C4 knockout towers are connected with dethanizer, and it is isolated will to come from deethanizer bottoms stream progress
The C4 logistics.
The present invention also provides the oxygenate conversion process for using above-mentioned tandem moving bed reaction system.
The conversion of oxygenatedchemicals is used for using reaction system provided by the invention, containing arene stream to carbon deposited catalyst
Reaction promotes catalyst to the conversion of oxygenatedchemicals and improves the selectivity of purpose product, avoids using process water as dilute
It releases agent and returns to oxygenate conversion reactor increase energy consumption and catalyst poisoning, product point is also ensured while reducing energy consumption
The stability of cloth.
Description of the drawings
Fig. 1 be 2 moving-burden bed reactors of the present invention, 1 catalyst devator combining form tandem moving bed reaction
System schematic.
Fig. 2 be 3 moving-burden bed reactors of the present invention, 2 catalyst devator combining forms tandem moving bed reaction
System schematic.
Specific implementation mode
In reaction system provided by the invention, n moving-burden bed reactor, n-1 catalyst devator, institute have been included at least
The n stated is preferably 2,3,4 or 5.It is the combination of " 2 moving-burden bed reactors, 1 catalyst devator " for example, when n is 2；N is
When 2, it is the combination of " 3 moving-burden bed reactors, 2 catalyst devators "；N be 4 when, be " 4 moving-burden bed reactors, 3 urge
The combination, etc. of agent lifter ".
The reaction system of the present invention is described further below in conjunction with attached drawing and specific embodiment.In order to simplify this hair
Bright description, unless to understand the present invention it is necessary to equipment, in attached drawing include heater, heat exchanger, cooler, valve,
The diagram of control device and conventional equipment well-known to those skilled in the art.
Fig. 1 is that n is 2, i.e. 2 moving-burden bed reactors, 1 catalyst devator combining form tandem moving bed reaction system
System schematic diagram.Including 2 moving-burden bed reactors, 1 catalyst devator, regenerator, catalyst mixer, fresh catalyst storage
Tank, three phase separator, Tuo Fangta, dethanizer and C4 knockout towers；
In the system, with first movement bed reactor, the first catalyst devator, the second moving-burden bed reactor, sequence
It is in series；2nd moving-burden bed reactor is connected with regenerator, and carbon deposition catalyst is contacted with oxygen flow in a regenerator
It burns and is regenerated；The catalyst mixer is connected with regenerator, fresh catalyst storage tank, catalyst devator respectively,
Receive the regenerated catalyst from regenerator, the fresh catalyst from fresh catalyst storage tank, from catalyst devator
Activated catalyst, the catalyst mixer are same with first movement bed reactor or with the first, second moving-burden bed reactor
Catalyst in catalyst mixer is sent into first movement bed reactor by Shi Xianglian, or is sent into the first, second moving bed
In reactor；Two moving-burden bed reactors are equipped with reaction raw materials entrance, for inputting oxygen-containing compound material logistics
Or oxygen-containing compound material logistics with by the C2 logistics from dethanizer, the C4 logistics from C4 knockout towers and come autospasy virtue
The mixture flow for returning to hydrocarbon and being formed of the C5C6 logistics composition of tower；The catalyst devator is both provided with to be entered containing aromatic hydrocarbon substance
Mouthful；Two moving-burden bed reactors, the catalyst devators are connected with three phase separator, and the three phase separator is in the future
It is separated into from the reaction product stream of two moving-burden bed reactors with the mixture flow of the logistics from catalyst devator outlet
Gas phase, water phase and oil phase logistics；The dethanizer is connected with three phase separator, and dethanizer will be from three phase separator
Gaseous stream isolates the C2 logistics；The Tuo Fangta is connected with three phase separator, and Tuo Fangta will come from three phase separation
The oil phase thing flow point of device separates out arene stream and the C5C6 logistics；The C4 knockout towers are connected with dethanizer, in the future
The isolated C4 logistics is carried out from deethanizer bottoms stream.
The procedure declaration of the reaction system of service chart 1 is as follows：
The return hydrocarbon of oxygenatedchemicals material 10 and the three strands of materials from this system subsequent separation system by preheating
Mixing, including the C for coming from dethanizer 172Logistics 174 goes out autospasy C4The C of tower 184Logistics 184 and go out autospasy virtue tower 19
C5C6Logistics 194 obtains mixed feeding and heats, and a part of mixed feeding logistics 111 enters first movement bed reactor 11
It is contacted with catalyst, converts oxygenate compounds to the first product stream 113 and flowed out from the top of first movement bed reactor 11, come
The catalyst 113 of self-catalysis agent mixer 14 enters from 11 top of first movement bed reactor, table after being contacted with feed stream 111
Area charcoal is flowed out from the bottom of first movement bed reactor 11 into carbon deposited catalyst 114, and the carbon deposited catalyst 114 is in catalyst
Promoted containing 196 contact activation of arene stream via what de- fragrant tower 19 flowed out in lifter 21, catalyst devator 21 export the
One mixed fragrant product stream 212 is mixed with from the first product stream 113, the activated catalyst logistics 213 that catalyst devator 21 exports
Be divided into two strands, one activated catalyst logistics 141 enter catalyst mixer 14 with from the fresh of fresh catalyst storage tank 09
The regenerated catalyst 132 that catalyst 140, catalyst regenerator 13 export mixes, another burst of activated catalyst logistics 123 from second
12 top of moving-burden bed reactor enters, 121 haptoreaction of another part feed stream separated with mixed feeding, oxygenatedchemicals
It is converted into the top outflow of 122 autoreactor 12 of the second product stream rich in propylene, this second product stream 122 and the first product stream
113, the first mixed fragrant product stream 212 is mixed into mix products stream 151, the carbon deposited catalyst of the second moving-burden bed reactor bottom outflow
Logistics 124, which is contacted into regenerator 13 with oxygen flow, burns, and the regenerated catalyst logistics 132 after burning is recycled into catalyst
Mixer 14.
Mix products stream 151 is separated into water phase, oil phase and gas phase, wherein water-phase product stream 153 into cooling separator 15
Outflow is recycled as sewage；Oil-phase product stream 191 is detached via de- fragrant tower 19, top C5C6Fraction logistics 192, part are made
For C5C6Product stream 195, remaining is as C5C6Hydrocarbon stream 194 is returned to mix with oxygenatedchemicals material 10；19 bottoms Tuo Fangta contain
Arene stream 193, partly be used as product aromatics logistics 197, remaining containing arene stream 196 as lifter 21 catalyst promotion
Medium and carbon deposited catalyst contact activation；The vapor phase product stream 152 that three phase separator 15 exports is obtained via the boosting of compressor 16
Boosting logistics 171, detaches into dethanizer 17, and tower top flows out C2Fuel gas stream 172 is partly used as fuel gas product
173, remaining is as C2Hydrocarbon stream 174 is returned to mix with oxygenatedchemicals material 10；17 tower base stream 181 of dethanizer enters C4
Knockout tower 18, tower top enter propylene separation system, bottom of tower C rich in propylene product stream 1834182 part of logistics is as C4Product stream
185, remaining is as C4Hydrocarbon stream 184 is returned to mix with oxygenatedchemicals material 10.
Fig. 2 is that n is 3, i.e. 3 moving-burden bed reactors, 2 catalyst devator combining forms tandem moving bed reaction system
System schematic diagram.Including three moving-burden bed reactors, 2 catalyst devators, regenerator, catalyst mixer, fresh catalyst
Storage tank, three phase separator, Tuo Fangta, dethanizer and C4 knockout towers；
In the system, urged with first movement bed reactor, the first catalyst devator, the second moving-burden bed reactor, second
Agent lifter, third moving-burden bed reactor sequence be in series；The third moving-burden bed reactor is connected with regenerator, product
C catalyst contacts to burn with oxygen flow in a regenerator to be regenerated；The catalyst mixer respectively with regenerator,
Fresh catalyst storage tank, catalyst devator are connected, and receive the regenerated catalyst from regenerator, come from fresh catalyst storage tank
Fresh catalyst, the activated catalyst from catalyst devator, the catalyst mixer reacts with first movement bed
Device is connected at least two moving-burden bed reactors including first movement bed reactor, will be in catalyst mixer
Catalyst is sent into first movement bed reactor, or is sent at least two moving beds including first movement bed reactor
In reactor；Three moving-burden bed reactors are equipped with reaction raw materials entrance, for inputting oxygen-containing compound material logistics
Or oxygen-containing compound material logistics with by the C2 logistics from dethanizer, the C4 logistics from C4 knockout towers and come autospasy virtue
The mixture flow for returning to hydrocarbon and being formed of the C5C6 logistics composition of tower；Two catalyst devators are both provided with object containing aromatic hydrocarbons
Matter entrance；Three moving-burden bed reactors, two catalyst devators are connected with three phase separator, the three-phase separate
From device by the mixed of the reaction product stream from three moving-burden bed reactors and the logistics from the outlet of two catalyst devators
It closes logistics and is separated into gas phase, water phase and oil phase logistics；The dethanizer is connected with three phase separator, and dethanizer will come from
The gaseous stream of three phase separator isolates the C2 logistics；The Tuo Fangta is connected with three phase separator, and Tuo Fangta will
Oil phase thing flow point from three phase separator separates out arene stream and the C5C6 logistics；The optional C4 knockout towers with
Dethanizer is connected, and will carry out the isolated C4 logistics from deethanizer bottoms stream.
The procedure declaration of the reaction system of service chart 2 is as follows：
Oxygenatedchemicals material 10 by preheating is mixed with the three strands of materials from this system subsequent separation system, wherein
C including coming from dethanizer 172Logistics 174 goes out autospasy C4The C of tower 184Logistics 184 and the C for going out autospasy virtue tower 195C6Logistics
194, obtain mixed feeding and heat after, in a part of logistics 111 of the mixed feeding enter first movement bed reactor 11 with
Pellet catalyst contact containing shape-selective molecular sieve converts oxygenate compounds to the first product stream 112 rich in propylene from the
The top of one moving-burden bed reactor 11 is flowed out, and the pellet catalyst material 113 from catalyst mixer 14 is from first movement bed
The top of reactor 11 enters, and rear surface carbon deposit is contacted with feed stream 111, from the outflow of the bottom of first movement bed reactor 11 at
Carbon deposited catalyst 114, the object containing aromatic hydrocarbons which flows out in the first catalyst devator 21 via de- fragrant tower 19
The promotion of 196 contact activations is flowed, the first 212 and first product stream 112 of mixed fragrant product stream of the first catalyst devator 21 outlet is mixed
It closes, it is two strands that the activated catalyst logistics 123 of the first catalyst devator 21 outlet, which is divided to, one activated catalyst 141, which enters, urges
Agent mixer 14, another strand of activated catalyst 123 enter from 12 top of the second moving-burden bed reactor, are separated with mixed feeding
121 haptoreaction of another part feed stream converts oxygenate compounds to the second product stream 122 rich in propylene and is moved from second
The top outflow of dynamic bed reactor 12, this second product stream 122 mix fragrant product stream 212 with the first product stream 112, first and mix,
The carbon deposited catalyst 124 of second moving-burden bed reactor bottom outflow, the carbon deposited catalyst 124 is in the second catalyst devator 22
It is promoted containing 198 contact activation of arene stream via what de- fragrant tower 19 flowed out, the second mixed virtue of the second catalyst devator 22 outlet
Product stream 222 is mixed with mixed fragrant 212 and second product stream 122 of product stream of the first product stream 112, first, and the second catalyst is promoted
It is two strands that the activated catalyst 133 that device 22 exports, which is divided to, one activated catalyst 142 enters catalyst mixer 14, and another stock swashs
Catalyst 133 living enters from 13 top of third moving-burden bed reactor, and another part feed stream 131 separated with mixed feeding connects
Reaction is touched, oxygenate conversion is that the third product logistics 132 rich in propylene is flowed from the top of third moving-burden bed reactor 13
Go out, the miscarriage 132 of this third product and the mixed fragrant product stream 212 of the first product stream 112, first, the mixed virtue of the second product stream 122 and second
Logistics 222 is mixed into mix products stream 151, and the carbon deposited catalyst 134 of third moving-burden bed reactor bottom outflow enters regenerator
23 contact with oxygen flow and burn, and the regenerated catalyst 143 after burning enters catalyst mixer 14 and comes from fresh catalyst
The fresh catalyst 140 of storage tank 09, the activated catalyst logistics 141 of the first catalyst devator 21 outlet and the second catalyst carry
Rise device 22 export activated catalyst logistics 142 mix, catalyst mixer 14 export mixed catalyst logistics 113 recycle into
Enter 11 top of first movement bed reactor.
Mix products stream 151 is separated into water phase, oil phase and gas phase into three phase separator 15；Wherein, water-phase product stream 153
Outflow is recycled as sewage；Oil-phase product logistics 191 is detached via de- fragrant tower 19, top C5C6Fraction logistics 192, part
As C5C6Product stream 195, remaining is as C5C6Hydrocarbon stream 194 is returned to mix with oxygenatedchemicals material 10；19 bottoms Tuo Fangta
Containing arene stream 193, it is partly used as product aromatics logistics 197, partly contains arene stream 196 and is used as the first catalyst devator 21
Catalyst promoted medium contacted with carbon deposited catalyst, remaining urging as the second catalyst devator 22 containing arene stream 198
Agent promotes medium and is contacted with carbon deposited catalyst；The vapor phase product stream 152 that separator 15 exports is obtained via the boosting of compressor 16
Boosting logistics 171, detaches into dethanizer 17, and tower top flows out C2Fuel gas stream 172 is partly used as fuel gas product
173, remaining is as C2Hydrocarbon stream 174 is returned to mix with oxygenatedchemicals material 10；17 tower base stream 181 of dethanizer enters C4
Knockout tower 18, tower top enter propylene separation system, bottom of tower C rich in propylene product stream 1834182 part of logistics is as C4Product stream
185, remaining is as C4Hydrocarbon stream 184 is returned to mix with oxygenatedchemicals material 10.
Oxygenatedchemicals of the present invention includes methanol, dimethyl ether or the mixture containing methanol and dimethyl ether.
The conversion for the oxygenatedchemicals that tandem moving bed reaction system using the present invention carries out is, it is preferable to use containing shape-selective
The pellet catalyst of molecular sieve converts oxygenatedchemicals and return hydrocarbon to the hydrocarbon product rich in propylene.Reaction item used
Part is that reaction temperature is 300~550 DEG C, 0.01~1.0MPa of reaction pressure, oxygen compound feedstock mass space velocity 0.01~
100h-1, the mass ratio for returning to hydrocarbon and oxygenatedchemicals is 0~10.0, residence time of the catalyst in reactor be 1~
1000h.450~500 DEG C, 0.05~0.3MPa of reaction pressure of preferable reaction temperature, multiple oxygen compound feedstock mass space velocity 0.1
~10h-1, the mass ratio for returning to hydrocarbon and oxygenatedchemicals is 0.2~2.0, residence time of the catalyst in reactor be 50~
500h。
The shape-selective molecular sieve pellet catalyst includes the molecular sieve that aperture is more than the cut off diameter of aromatic compounds
Porous crystalline material, this kind of material can be reacted with catalysis methanol gas-phase dehydration generates the hydrocarbon products such as ethylene, propylene.It is this kind of shape-selective
Molecular sieve includes but not limited to ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, IM-
5, MOR, Beta, SAPO-11, SAPO-5, SAPO-31 etc., preferably ZSM-5 and ZSM-11.
The shape-selective molecular sieve pellet catalyst can be above-mentioned molecular sieve porous crystalline material and various binders
Or filling substrate material is prepared by mixing into diameter 1.0~3.0mm diameter beads, to meet the need of moving bed MTP reactors filling
It wants.The binder includes one or more mixed in silica, aluminium oxide, amorphous silica-alumina, titanium oxide, zirconium oxide, magnesia
Close object.The filling substrate material includes one or more mixtures such as clay, diatomite, attapulgite, hydrotalcite.
In the present invention, the entrance containing aromatic hydrocarbon substance of catalyst devator setting receives the aromatic hydrocarbons object from the Tuo Fangta
Stream.The effect of catalyst devator is using being contacted with carbon deposited catalyst containing aromatic fraction, containing aromatic fraction in catalyst table
The reactions such as disproportionation, the modulation composition of the active intermediate of catalyst surface, to continue moving bed reaction after entering occur for face
After device, conversion rate of oxygenated compound and selectivity of product are greatly improved；Another effect of catalyst devator be by
Carbon deposited catalyst is promoted from moving-burden bed reactor bottom to more than moving-burden bed reactor top height, to meet in secondary reactor
The movement of catalyst.Catalyst devator interior reaction temperature is 250~550 DEG C, 0.05~1MPa of reaction pressure, contains aromatic fraction
0.01~10h of mass space velocity-1, 0.01~100h of time of contact.350~500 DEG C of preferable reaction temperature, reaction pressure 0.1~
0.5MPa, the 0.03~3h of mass space velocity containing aromatic fraction-1, 0.1~50h of time of contact.
In the present invention, regenerator is that carbonaceous material is removed from catalyst, is to make to urge at enough temperature and oxygen concentration
Charcoal in agent burns to remove.Its condition used is the technical conditions known to the researcher of this field.
In the present invention, catalyst mixer is to mix regenerated catalyst, fresh catalyst and the catalyst of resurrection,
To adjust the activity of catalyst, medium atmosphere is nitrogen in mixer, is conducive to catalyst transport.The described catalyst that enters mixes
The catalyst of the resurrection of device accounts for 0~90%, preferably the 10~50% of the catalyst total flow that catalyst devator outlet is brought back to life.Institute
Say that fresh catalyst addition accounts for the 0~90% of regenerated catalyst flow, preferably 1~20%.Its mixing condition used is this
Technical conditions known to area research personnel.
The oxygenate conversion containing methanol that tandem moving bed reaction system using the present invention carries out is the side of propylene
Method, with n for 2, i.e. 2 moving-burden bed reactors, 1 catalyst devator combination for illustrate, include the following steps：
(1) oxygen-containing compound material is passed into first movement bed reactor and regenerated catalyst with hydrocarbon Hybrid Heating rear portion is returned
Contact is reacted, and the first product stream rich in propylene is generated, and carbon deposited catalyst flows out moving-burden bed reactor bottom；(2) it utilizes
The part of product Tuo Fangta separation containing arene stream in catalyst devator with carbon deposited catalyst contact activation and be promoted to the
At the top of two moving-burden bed reactors, the catalyst stream of mixed fragrant product stream and activation is generated；(3) by the oxygenatedchemicals containing methanol
Raw material is passed into the second moving-burden bed reactor with the remaining part after return hydrocarbon Hybrid Heating and contacts progress with the catalyst of activation
Reaction, generates the second product stream rich in propylene, and carbon deposited catalyst outflow moving-burden bed reactor bottom enters regenerator and burns again
It is raw, obtain regenerated catalyst；(4) the activation catalysis that the fresh catalyst of regenerated catalyst and supplement, catalyst devator export
After agent logistics mixes in catalyst mixer, it is recycled back to first movement bed reactor head；(5) by the first product stream, second
Three phase separator is sent in product stream and mixed fragrant product stream mixing, is detached through three phase separator, wherein water phase is as sewage logistics
Recycling；Oil phase thing Liu Jin Ru Tuo Fangta separation, takes off virtue column overhead C5And C6Hydrocarbon stream part is used as and returns as product, remaining part
The part for returning hydrocarbon returns, and mix with the oxygen compound feedstock containing methanol, takes off fragrant bottom of tower part containing arene stream as product,
Remaining part promotes medium as catalyst devator；Gaseous stream enters dethanizer, deethanization overhead stream after compression
Part is used as fuel gas product, remaining part to be mixed with the oxygen compound feedstock containing methanol as the part for returning to hydrocarbon, takes off
Ethane tower base stream, which enters, takes off C4Tower takes off C4Tower top enters propylene product piece-rate system rich in propylene stream, and tower base stream part is made
For C4Hydrocarbon products, remaining part are mixed as the part for returning to hydrocarbon with the oxygen compound feedstock containing methanol.
In tandem moving bed reaction system as above, in first movement bed reactor, the oxygenatedchemicals containing methanol
Charging is converted into the hydrocarbon product rich in propylene, while catalyst surface area under the catalyst action containing shape-selective molecular sieve
Charcoal；It in catalyst devator, is contacted with carbon deposited catalyst using containing arene stream, disproportionation, alkylation occur for aromatic compound
Equal reactions generate mixed fragrant product, and change catalyst surface property, improve oxygenate conversion ability, while catalyst being carried
It rises at the top of moving-burden bed reactor；The carbon deposited catalyst progress coke burning regeneration of second moving-burden bed reactor outlet is obtained regeneration to urge
Agent；A part in the catalyst for the activation that the fresh catalyst of regenerated catalyst and supplement, catalyst devator export exists
After being mixed in catalyst mixer, it is recycled back to first movement bed reactor head；By the outlet of the first, second moving-burden bed reactor
The mixed fragrant product stream mixing of reaction product material and catalyst devator outlet, is detached in three phase separator, obtain by
Water phase sewage product stream, the product stream rich in propylene, C2Fuel gas stream, C4Hydrocarbon stream, C5C6Mixture flow and object containing aromatic hydrocarbons
Stream, and by part C2Fuel gas stream, C4Hydrocarbon stream, C5C6Mixture flow mixing is as return hydrocarbon and the oxygen-containing chemical combination containing methanol
Object charging mixing is fed as moving-burden bed reactor, while part being fed containing arene stream as catalyst devator.
Freshening logistics includes generating after oxygenate conversion in moving bed MTP reactor mixed feedings of the present invention
C2-、C4、C5And C6Product, but not including that water that oxygenate conversion generates or additional.This is because the vaporization of water
Cycle energy consumption is big, and is possible to make catalyst permanently be poisoned containing objectionable impurities in recirculated water, it is often more important that in the present invention
Reaction in lifter improves the activity and selectivity of catalyst, so as to avoid remaining to obtain using steam diluent
High propylene yield.
Moving bed methanol to propylene reaction system of the present invention is recycled using continuous reaction regeneration, can keep urging
Agent is activity stabilized and reaction product composition is stablized so that device stable operation, and save energy consumption.
It below will be to giving further with the embodiment of the oxygenate conversion process of reaction system using the present invention
Explanation, but it is not thereby limiting the invention.
Comparative example
This comparative example explanation simulates a moving-burden bed reactor on small atmospheric fixed-bed micro-devices and carries out methanol system
The experimental result of propylene reaction.
Atmospheric fixed bed micro anti-evaluation device is made of sampling system, reactor, product collection system and temperature control system.Instead
It is 5 grams to answer loaded catalyst in device, and catalyst is purged with High Purity Nitrogen to reaction temperature, methanol in reaction evaluating pre-heating temperature elevation
Raw material is injected into Micro-metering Pumps in reactor, and reactor outlet product cools down laggard promoting the circulation of qi liquid product separation, gaseous products
Chromatography is measured and carried out through wet flow indicator, and liquid-phase product carries out chromatography after collecting；It, will be anti-after the completion of evaluation response
Device purging cooling is answered, carbon deposited catalyst roasting regeneration in Muffle furnace is drawn off.Methanol used is that analysis is pure.Simulate lifter operation
Methanol feedstock is changed into feed containing aroamtic hydrocarbon raw material when processing and is reacted with carbon deposited catalyst, after the completion of reaction, switches back into methanol charging
Carry out methanol to propylene reaction.The segmentation statistics duration of runs and methanol actual treatment amount (gram methanol/gram catalyst), calculate average
Propylene/ethylene (P/E) mass ratio and propylene carbon base absorption rate.
Methanol conversion is calculated according to formula (1), formula (2) calculates the carbon-based yield of propylene：
Methanol conversion=(methanol quality in charging methanol quality-product)/charging quantity of methyl alcohol × 100% ... (1)
In the carbon-based yield=propylene of propylene in quality/charging methanol of carbon carbon quality × 100% ... ... (2)
MTP catalyst used is that ZSM-5 molecular sieve catalyst (is produced containing 80% Hunan Jianchang Petrochemical Co., Ltd
ZRP-5 molecular sieves, remainder be silica, use roll the method for forming be shaped to 1~1.2mm beads by binder of Ludox).
Catalyst sieves 20-40 mesh, first in 480 DEG C of temperature, normal pressure, 100% water vapour feedstock quality air speed 2h-1Lower processing 12h.
The MTP reactions of first movement bed are simulated, evaluation test, reaction pressure is normal pressure, and control MTP reactor die temperatures are
480±5℃.According to methanol feedstock quality air speed 1h-1, add up operation 144h, methanol conversion is down to from initial 100%
95.03%, it is out of service.It is considered as MTP catalyst coking deactivation, moving-burden bed reactor should be removed and carry out coke burning regeneration.First
138 grams of methanol/gram catalysts of alcohol treating capacity, average propylene/ethylene (P/E) mass ratio 7.76, propylene carbon base absorption rate 39.54%.
Embodiment 1
This example demonstrates that simulating two moving-burden bed reactors on small atmospheric fixed-bed micro-devices carries out methanol system
The experimental result of propylene reaction.
Small atmospheric fixed-bed micro-devices and MTP catalyst used are the same as comparative example 1.Catalyst sieves 20-40 mesh, first
In 480 DEG C of temperature, normal pressure, 100% water vapour feedstock quality air speed 2h-1Lower processing 12h.
The MTP reactions of first movement bed are simulated, evaluation test, reaction pressure is normal pressure, and control MTP reactor die temperatures are
480±5℃.According to methanol feedstock quality air speed 0.96h-1, add up operation 144h, methanol conversion is down to from initial 100%
95.03%, it is out of service.It is considered as MTP catalyst coking deactivation, moving-burden bed reactor should be removed.138 grams of methyl alcohol process amount
Methanol/gram catalyst, average propylene/ethylene (P/E) mass ratio 7.76, propylene carbon base absorption rate 39.54%.
Catalyst devator reaction is simulated, is contained with toluene (analyzing pure, Tianjin Ke Miou chemical reagent Co., Ltd) simulation
Aromatic hydrocarbons material carries out evaluation test, and reaction pressure is normal pressure, and control MTP reactor die temperatures are 470 ± 5 DEG C.Switch to first
Benzene feedstock quality air speed 1h-1, add up to run 14h, it is out of service.
The experiment of the second moving bed MTP reaction evaluatings is simulated, reaction pressure is normal pressure, and control MTP reactor die temperatures are
480±5℃.According to methanol feedstock quality air speed 0.91h-1, add up operation 96h, methanol conversion is down to from initial 100%
94.53%, it is out of service.It is considered as MTP catalyst coking deactivation, moving-burden bed reactor should be removed and send coke burning regeneration.Methanol
87 grams of methanol/gram catalysts for the treatment of capacity, average P/E mass ratioes 9.37, propylene carbon base absorption rate 42.34%.Continuous two simulations move
Dynamic bed reaction is total, 225 grams of methanol/gram catalysts of methyl alcohol process amount, average P/E mass ratioes 8.38, propylene carbon base absorption rate
40.62%.
Embodiment 2
This example demonstrates that simulating three moving-burden bed reactors on small atmospheric fixed-bed micro-devices carries out methanol system
The experimental result of propylene reaction.
The evaluation of embodiment 1 is connect, simulation catalyst devator reaction carries out evaluation test with toluene simulation material containing aromatic hydrocarbons,
Reaction pressure is normal pressure, and control MTP reactor die temperatures are 475 ± 5 DEG C.Switch to toluene feed mass space velocity 0.5h-1, tire out
Meter runs 16h, out of service.
The experiment of third moving bed MTP reaction evaluatings is simulated, reaction pressure is normal pressure, and control MTP reactor die temperatures are
480±5℃.According to methanol feedstock quality air speed 0.85h-1, add up operation 82h, methanol conversion is down to from initial 100%
93.54%, it is out of service.It is considered as MTP catalyst coking deactivation, moving-burden bed reactor should be removed and send coke burning regeneration.Methanol
70 grams of methanol/gram catalysts for the treatment of capacity, average P/E mass ratioes 9.33, propylene carbon base absorption rate 42.55%.
Continuous three Simulation moving beds reaction is total, 295 grams of methanol/gram catalysts of methyl alcohol process amount, average P/E mass ratioes
8.61, propylene carbon base absorption rate 41.08%.
Embodiment 3
This example demonstrates that carrying out preparing propylene from methanol on two moving beds of middle- scale device of successive reaction regenerative operation
Experimental result.
Using identical pellet catalyst is formed in embodiment 1, screening 1.6~1.8mm particles are evaluated.First movement
Bed methanol to propylene reaction device, inlet temperature are 450 DEG C, reaction pressure 0.15MPa, oxygen compound feedstock mass space velocity
1.0h-1, C2-、C4Hydrocarbon, C5C6It is 0.9 that hydrocarbon, which always returns to hydrocarbon and the mass ratio of oxygen compound feedstock, and catalyst is in reactor
Residence time is 100h.
The operating condition of lifter is as follows, and reaction temperature is 460 DEG C, reaction pressure 0.17MPa, and quality containing aromatic fraction is empty
Fast 0.5h-1, time of contact 8h.The 20% of the catalyst of lifter outlet enters catalyst mixer.
Second moving bed methanol to propylene reaction device, inlet temperature are 455 DEG C, reaction pressure 0.15MPa, oxygenatedchemicals
Feedstock quality air speed 0.8h-1, C2-、C4Hydrocarbon, C5C6It is 0.9 that hydrocarbon, which always returns to hydrocarbon and the mass ratio of oxygen compound feedstock, catalyst
Residence time in reactor is 80h.
Regenerator operation condition is that oxygen content is that the mixing nitrogen inlet temperature of 3% volume is 435 DEG C, regeneration pressure
0.4MPa, mixing nitrogen feed GHSV are 1000h-1.Regenerated catalyst all returns to catalyst mixer.
Collect product from device, methanol content analyzed from water phase, calculate methanol conversion ratio be 99.6%, and
It is propylene 73.75% to the hydrocarbon product yield percentage composition in terms of butt, liquefied gas 8.23%, C5+ gasoline 15.3%, C2-
Fuel gas 2.72%.
Embodiment 4
This example demonstrates that carrying out preparing propylene from methanol on three moving beds of middle- scale device of successive reaction regenerative operation
Experimental result.
Using identical pellet catalyst is formed in embodiment 1, screening 1.6~1.8mm particles are evaluated.First movement
Bed methanol to propylene reaction device, inlet temperature are 450 DEG C, reaction pressure 0.13MPa, oxygen compound feedstock mass space velocity
1.0h-1, C2-、C4Hydrocarbon, C5C6It is 0.9 that hydrocarbon, which always returns to hydrocarbon and the mass ratio of oxygen compound feedstock, and catalyst is in reactor
Residence time is 96h.
The operating condition of first lifter is as follows, and reaction temperature is 460 DEG C, reaction pressure 0.16MPa, matter containing aromatic fraction
Measure air speed 0.5h-1, time of contact 8h.The 20% of the catalyst of lifter outlet enters catalyst mixer.
Second moving bed methanol to propylene reaction device, inlet temperature are 455 DEG C, reaction pressure 0.13MPa, oxygenatedchemicals
Feedstock quality air speed 0.8h-1, C2-、C4Hydrocarbon, C5C6It is 0.9 that hydrocarbon, which always returns to hydrocarbon and the mass ratio of oxygen compound feedstock, catalyst
Residence time in reactor is 72h.
The operating condition of second lifter is as follows, and reaction temperature is 460 DEG C, reaction pressure 0.16MPa, matter containing aromatic fraction
Measure air speed 1.0h-1, time of contact 4h.The 10% of the catalyst of lifter outlet enters catalyst mixer.
Third moving bed methanol to propylene reaction device, inlet temperature are 460 DEG C, reaction pressure 0.13MPa, oxygenatedchemicals
Feedstock quality air speed 0.75h-1, C2-、C4Hydrocarbon, C5C6It is 0.9 that hydrocarbon, which always returns to hydrocarbon and the mass ratio of oxygen compound feedstock, catalyst
Residence time in reactor is 48h.
Regenerator operation condition is that oxygen content is that the mixing nitrogen inlet temperature of 3% volume is 435 DEG C, regeneration pressure
0.4MPa, mixing nitrogen feed GHSV are 1000h-1.Regenerated catalyst all returns to catalyst mixer.It is mixed to catalyst simultaneously
Supplement accounts for fresh dose of bead of regenerated catalyst quality 3% in clutch.
Collect product from device, methanol content analyzed from water phase, calculate methanol conversion ratio be 99.7%, and
It is propylene 74.05% to the hydrocarbon product yield percentage composition in terms of butt, liquefied gas 8.63%, C5+ gasoline 13.7%, C2-
Fuel gas 3.32%.
Claims (16)
1. a kind of tandem moving bed reaction system for oxygenate conversion, including n moving-burden bed reactor, n-1 are urged
It is agent lifter, regenerator, catalyst mixer, fresh catalyst storage tank, three phase separator, optional Tuo Fangta, optional
Dethanizer and optional C4 knockout towers, wherein n >=2；
In the system, with first movement bed reactor, the first catalyst devator, the second moving-burden bed reactor, the second catalyst
Lifter, until the sequence phase of (n-1)th moving-burden bed reactor, (n-1)th catalyst devator and n-th of moving-burden bed reactor
Series connection；N-th of moving-burden bed reactor is connected with regenerator, and carbon deposition catalyst contacts burning with oxygen flow in a regenerator
Coke is regenerated；
The catalyst mixer is connected with regenerator, fresh catalyst storage tank, catalyst devator respectively, receives from again
The regenerated catalyst of raw device, the fresh catalyst from fresh catalyst storage tank, the activated catalyst from catalyst devator,
The catalyst mixer with first movement bed reactor or at least two including first movement bed reactor
Moving-burden bed reactor is connected, and the catalyst in catalyst mixer is sent into first movement bed reactor, or is sent into and includes
In at least two moving-burden bed reactors including first movement bed reactor；
The n moving-burden bed reactor is equipped with reaction raw materials entrance, for inputting oxygen-containing compound material logistics or containing
Oxygenate feedstock logistics with by optionally from dethanizer C2 logistics, optionally from C4 knockout towers C4 logistics and can
The mixture flow for returning to hydrocarbon and being formed of the C5C6 logistics composition for carrying out autospasy virtue tower of choosing；
The n-1 catalyst devator is both provided with entrance containing aromatic hydrocarbon substance；
The n moving-burden bed reactor, n-1 catalyst devator are connected with three phase separator, the three phase separation
Device is by the mixing of the reaction product stream from n moving-burden bed reactor and the logistics from the outlet of n-1 catalyst devator
Logistics is separated into gas phase, water phase and oil phase logistics；
The optional dethanizer is connected with three phase separator, and optional dethanizer is by the gas phase from three phase separator
The C2 logistics is isolated in logistics；
The optional Tuo Fangta is connected with three phase separator, and optional Tuo Fangta is by the oil phase logistics from three phase separator
Isolate arene stream and the C5C6 logistics；
The optional C4 knockout towers are connected with dethanizer, and it is isolated described will to come from deethanizer bottoms stream progress
C4 logistics.
2. according to the reaction system of claim 1, wherein the n is 2,3,4 or 5.
3. according to the reaction system of claim 1, including 2 moving-burden bed reactors, 1 catalyst devator, regenerator, catalysis
Agent mixer, fresh catalyst storage tank, three phase separator, Tuo Fangta, dethanizer and C4 knockout towers；
In the system, mutually gone here and there with first movement bed reactor, the first catalyst devator, the second moving-burden bed reactor, sequence
Connection；2nd moving-burden bed reactor is connected with regenerator, and carbon deposition catalyst is contacted with oxygen flow in a regenerator to be burnt
It is regenerated；The catalyst mixer is connected with regenerator, fresh catalyst storage tank, catalyst devator respectively, receives
Regenerated catalyst from regenerator, the fresh catalyst from fresh catalyst storage tank, the activation from catalyst devator
Catalyst, the catalyst mixer and first movement bed reactor or with the same phase of the first, second moving-burden bed reactor
Catalyst in catalyst mixer is sent into first movement bed reactor by connection, or is sent into the first, second moving bed reaction
In device；Two moving-burden bed reactors are equipped with reaction raw materials entrance, for input oxygen-containing compound material logistics or
Oxygen-containing compound material logistics with by the C2 logistics from dethanizer, the C4 logistics from C4 knockout towers and come autospasy virtue tower
The mixture flow for returning to hydrocarbon and being formed of C5C6 logistics composition；The catalyst devator is both provided with entrance containing aromatic hydrocarbon substance；
Two moving-burden bed reactors, the catalyst devators are connected with three phase separator, and the three phase separator will come from
The reaction product stream of two moving-burden bed reactors and the mixture flow of logistics from catalyst devator outlet are separated into gas
Phase, water phase and oil phase logistics；The dethanizer is connected with three phase separator, and dethanizer is by the gas from three phase separator
The C2 logistics is isolated in phase logistics；The Tuo Fangta is connected with three phase separator, and Tuo Fangta will come from three phase separator
Oil phase thing flow point separate out arene stream and the C5C6 logistics；The C4 knockout towers are connected with dethanizer, will come from
Deethanizer bottoms stream carries out the isolated C4 logistics.
4. according to the reaction system of claim 1, including three moving-burden bed reactors, 2 catalyst devators, regenerator, urge
Agent mixer, fresh catalyst storage tank, three phase separator, Tuo Fangta, dethanizer and C4 knockout towers；
In the system, with first movement bed reactor, the first catalyst devator, the second moving-burden bed reactor, the second catalyst
Lifter, third moving-burden bed reactor sequence be in series；The third moving-burden bed reactor is connected with regenerator, and carbon distribution is urged
Agent contacts to burn with oxygen flow in a regenerator to be regenerated；The catalyst mixer respectively with regenerator, fresh
Catalyst storage tank, catalyst devator are connected, and receive regenerated catalyst from regenerator, from the new of fresh catalyst storage tank
Fresh catalyst, the activated catalyst from catalyst devator, the catalyst mixer and first movement bed reactor or
Person is connected at least two moving-burden bed reactors including first movement bed reactor, by the catalysis in catalyst mixer
Agent is sent into first movement bed reactor, or is sent at least two moving bed reactions including first movement bed reactor
In device；Three moving-burden bed reactors are equipped with reaction raw materials entrance, for input oxygen-containing compound material logistics or
Oxygen-containing compound material logistics with by the C2 logistics from dethanizer, the C4 logistics from C4 knockout towers and come autospasy virtue tower
The mixture flow for returning to hydrocarbon and being formed of C5C6 logistics composition；Two catalyst devators are both provided with to enter containing aromatic hydrocarbon substance
Mouthful；Three moving-burden bed reactors, two catalyst devators are connected with three phase separator, the three phase separator
By the mixture of reaction product stream and the logistics exported from two catalyst devators from three moving-burden bed reactors
Flow separation is gas phase, water phase and oil phase logistics；The dethanizer is connected with three phase separator, and dethanizer will come from three-phase
The gaseous stream of separator isolates the C2 logistics；The Tuo Fangta is connected with three phase separator, and Tuo Fangta will come from
The oil phase thing flow point of three phase separator separates out arene stream and the C5C6 logistics；The optional C4 knockout towers and de- second
Alkane tower is connected, and will carry out the isolated C4 logistics from deethanizer bottoms stream.
5. according to the reaction system of claim 1, wherein the entrance containing aromatic hydrocarbon substance of catalyst devator setting, which receives, comes from institute
State the arene stream of Tuo Fangta.
6. a kind of method for transformation of the oxygenatedchemicals of tandem moving bed reaction system using claim 1.
7. according to the method for transformation of claim 6, wherein the oxygenatedchemicals is methanol and/or dimethyl ether.
8. according to the method for transformation of claim 6, it is characterised in that in moving-burden bed reactor, reaction temperature is 300~550 DEG C,
0.01~1.0MPa of reaction pressure, 0.01~100h of oxygen compound feedstock mass space velocity-1, return to the matter of hydrocarbon and oxygenatedchemicals
For amount than being 0~10.0, residence time of the catalyst in moving-burden bed reactor is 1~1000h.
9. according to the method for transformation of claim 8, wherein 450~500 DEG C, 0.05~0.3MPa of reaction pressure of reaction temperature, it is multiple
0.1~10h of oxygen compound feedstock mass space velocity-1, the mass ratio for returning to hydrocarbon and oxygenatedchemicals is 0.2~2.0, and catalyst exists
Residence time in reactor is 50~500h.
10. according to the method for transformation of claim 6, which is characterized in that catalyst is shape-selective molecular sieve pellet catalyst, described
Shape-selective molecular sieve is the molecular sieve porous crystalline material for the cut off diameter that aperture is more than aromatic compounds.
11. according to the method for transformation of claim 6, wherein the shape-selective molecular sieve be selected from ZSM-5, ZSM-11, ZSM-12,
One in ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, IM-5, MOR, Beta, SAPO-11, SAPO-5, SAPO-31
Kind is a variety of.
12. according to the method for transformation of claim 6, wherein the shape-selective molecular sieve is ZSM-5 and/or ZSM-11.
13. according to the method for transformation of claim 6, catalyst devator interior reaction temperature is 250~550 DEG C, reaction pressure
0.05~1MPa, the 0.01~10h of mass space velocity containing aromatic fraction-1, 0.01~100h of time of contact.
14. according to the method for transformation of claim 6,350~500 DEG C of catalyst devator interior reaction temperature, reaction pressure 0.1~
0.5MPa, the 0.03~3h of mass space velocity containing aromatic fraction-1, 0.1~50h of time of contact.
15. according to the method for transformation of claim 6, wherein the catalyst into the activation of catalyst mixer accounts for catalyst and carries
Rise device outlet bring back to life catalyst total flow 0~90%, fresh catalyst addition account for regenerated catalyst flow 0~
90%.
16. according to the method for transformation of claim 15, wherein the catalyst into the activation of catalyst mixer accounts for catalyst and carries
Rise device outlet bring back to life catalyst total flow 10~50%, fresh catalyst addition account for regenerated catalyst flow 1~
20%.
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| CN112707777A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon by using oxygen-containing compound as raw material |
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