CN104557401B - Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons - Google Patents

Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons Download PDF

Info

Publication number
CN104557401B
CN104557401B CN201510033499.0A CN201510033499A CN104557401B CN 104557401 B CN104557401 B CN 104557401B CN 201510033499 A CN201510033499 A CN 201510033499A CN 104557401 B CN104557401 B CN 104557401B
Authority
CN
China
Prior art keywords
reaction zone
zone
reaction
molecular sieve
disengagement
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510033499.0A
Other languages
Chinese (zh)
Other versions
CN104557401A (en
Inventor
蒋斌波
陆飞鹏
廖祖维
王靖岱
黄正梁
阳永荣
严丽霞
蒋云涛
王中仁
周冰洁
许彩霞
孟嘉辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201510033499.0A priority Critical patent/CN104557401B/en
Publication of CN104557401A publication Critical patent/CN104557401A/en
Application granted granted Critical
Publication of CN104557401B publication Critical patent/CN104557401B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of method of use moving bed technique propylene enhancing and aromatic hydrocarbons.(1)First reaction zone raw material and diluent are passed through into the first reaction zone and A molecular sieve catalyst haptoreactions;First reaction zone logistics includes hydrogen, C1~C5 hydrocarbon, aromatic component and more than C5 non-aromatic components;(2)By the first reaction zone logistics Jing after processing, then it is passed through Disengagement zone 1 and is separated, a part is incorporated to the first reaction zone raw material to the return material of Disengagement zone 1 in proportion, and the charging of Disengagement zone 2 is passed through Disengagement zone 2 and is separated;(3)Second reaction zone raw material and diluent and step(2)In remainder Disengagement zone 1 return material be passed through together second reaction zone contact with molecular sieve catalyst B occur aromatization, generation second reaction zone logistics, be incorporated to step(2)In the first reaction zone logistics.On the one hand the method improves catalyst stability, is on the other hand regulated and controled by multi-reaction-area and recycle hydrocarbons selective reprocessing realizes flexible propylene enhancing and aromatic hydrocarbons.

Description

Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons
Technical field
The present invention relates to a kind of method for preparing propylene and aromatic hydrocarbons, more particularly to it is a kind of using moving bed technique propylene enhancing With the reaction method of aromatic hydrocarbons.
Background technology
Propylene and aromatic hydrocarbons, especially light aromatics BTX(Benzene,toluene,xylene)All it is important Organic Chemicals.With The shortage of petroleum resources, traditional petroleum path obtains propylene and BTX aromatic hydrocarbons is possible to substituted, therefore be badly in need of a kind of replacement Petroleum path produces the new technology of propylene and aromatic hydrocarbons, and such as coal base or natural gas base methyl alcohol prepares propylene or aromatic hydrocarbons technology.The technology The shortage problem of propylene and aromatic hydrocarbon resource demand is alleviated not only, also the added value to raising Downstream Products of Methanol, is coal and day New path is opened up in so industrial chain development of gasification work.
The existing mature industry technology of preparing propylene from methanol technology, such as the MTP technologies of LURGI, which adopts fixed-bed process Obtain the product based on propylene.The research origin of aromatization of methanol is developed in 20 Mobil oil companies of the century 70 U.S. Methyl alcohol is converted into the MTG routes of gasoline.Using ZSM-5 zeolite molecular sieve shape-selective catalyst, it is totally converted can methyl alcohol, generates rich Rich hydro carbons, especially has excellent selectivity, while also obtain a small amount of aromatic product to high-knock rating gasoline.With stone The oily energy it is day by day in short supply, original work become well sold and in short supply for the aromatic hydrocarbons of petrochemical industry product, so as to the methanol feedstock aromatisation system that has been born Aromatic hydrocarbons (MTA) this concept.
U.S. patent Nos USP 4686312 discloses a kind of multistage reaction work converted methanol into rich in aromatic hydrocarbon product Skill.In first paragraph reactor, methyl alcohol is first converted into the product based on low-carbon (LC) hydro carbons, and first paragraph product is in second segment There is catalytic aromatization reaction in reactor, generate the product rich in aromatic hydrocarbons.
CN 100548945C describe a kind of preparation method of the technique and catalyst of methanol conversion for preparing arene.The method With modified zsm-5 zeolite as catalyst, it is 0.1~5.0MPa, 300~460 DEG C of operation temperature, material liquid in operating pressure Body air speed is 0.1~6.0h-1Under the conditions of be catalytically conveted to based on aromatic hydrocarbons product, Jing refrigerated separations are by gas-phase product low-carbon (LC) Hydrocarbon is separated with liquid product C5+ hydrocarbon, and lower carbon number hydrocarbons component enters second stage reactor and continues to produce virtue;Liquid product C5+ hydrocarbon Jing is extracted Separate, obtain aromatic hydrocarbons and non-aromatics.The invention can improve aromatic hydrocarbons overall selectivity.
Moving bed process is to solve the not enough effective ways of catalyst stability, as patent CN101195762A is announced A kind of catalysis conversion method that gasoline and liquefied gas are carried out on moving bed, the method are compared with fixed-bed process and significantly can be carried The stability of high catalyst, and compared with fluid bed, the mechanical strength of catalyst is particularly abrasion index and significantly can decline.
CN 101823929A describe the system and technique of a kind of methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon.Material benzenemethanol Or dimethyl ether is reacted in aromatization reactor first, after reacted product is separated, H2, methane, mixing C8 aromatic hydrocarbons With part C9+ hydro carbons as output of products system, and C2+ non-aromaticss and the virtue in addition to mixing C8 aromatic hydrocarbons and part C9+ hydro carbons Hydrocarbon then returns respective reaction device as circulation logistics and carries out further aromatization.The technique uses multiple molecular sieve catalysts Aromatization is carried out, unfavorable industrialization catalyst development and reaction regeneration are controlled.
Secondly, it is also a kind of new technology for producing aromatic hydrocarbons to carry out aromatisation using light hydrocarbon component.101993320 B of CN are public Opened a kind of technology of aromatization for producing light aromatics, with mix carbon four and C9+ heavy arenes as raw material non-hydrogen condition Lower zeolite-catalyzed reaction productive aromatic hydrocarbon, CN 101607858B describe a kind of methanol/dimethyl ether and prepare aromatic hydrocarbons and propylene simultaneously Method, which is isolated remaining component after propylene from fixed bed reaction product and carries out second step aromatization, and the method can be with Productive aromatic hydrocarbon is particularly xylene components, but the method propylene and aromatics yield are wayward.
In existing methanol conversion technology, not yet have can the selective flexible technique of propylene enhancing and aromatic hydrocarbons one of which, Using the characteristic and selectivity of product freshening of ZSM-5 molecular sieve catalyst, it is possible to achieve the maximization of product economic benefit.
The content of the invention
It is to overcome the deficiencies in the prior art that the present invention is purpose, there is provided a kind of to use moving bed technique propylene enhancing and virtue The reaction method of hydrocarbon, the technique can improve the stability of catalyst operation using moving bed technique, while in product Component carry out it is selective recycle, such that it is able to control and realize propylene enhancing and aromatics yield.
Technical scheme is mainly as described below:
The reaction method of a kind of use moving bed technique propylene enhancing and aromatic hydrocarbons, comprises the following steps:
(1)Molecular sieve catalyst A is passed through into the first reaction zone, the first reaction zone raw material and diluent are passed through into the first reaction Area and A molecular sieve catalyst haptoreactions, produce the first reaction zone logistics;
The first described reaction zone raw material includes methyl alcohol, dimethyl ether;
The first described reaction zone logistics includes hydrogen, C1~C5 hydrocarbon, aromatic component and more than C5 non-aromatic components;
The first described reaction zone includes at least one moving-burden bed reactor;
(2)By step(1)In the first reaction zone logistics Jing after processing, then be passed through Disengagement zone 1 and separated, separated Area 1 returns material, Disengagement zone 1 discharges and Disengagement zone 2 feeds, and a part is incorporated to the first reaction zone to the return material of Disengagement zone 1 in proportion Raw material, the charging of Disengagement zone 2 are passed through Disengagement zone 2 and are separated, and obtain 2 cycle stock of Disengagement zone and Disengagement zone 2 discharges;
(3)Molecular sieve catalyst B is continuously passed through into second reaction zone, second reaction zone raw material and diluent and step (2)In remainder Disengagement zone 1 return material be passed through together second reaction zone contact with molecular sieve catalyst B occur aromatisation it is anti- Should, second reaction zone logistics is produced, step is incorporated to(2)Described in the first reaction zone logistics;
Described second reaction zone includes at least one moving-burden bed reactor.
The reaction method of a kind of use moving bed technique propylene enhancing and aromatic hydrocarbons, comprises the following steps:
(1)Molecular sieve catalyst A is passed through into the first reaction zone, the first reaction zone raw material and diluent are passed through into the first reaction Area and A molecular sieve catalyst haptoreactions, produce the first reaction zone logistics;
The first described reaction zone raw material includes methyl alcohol, dimethyl ether;
The first described reaction zone logistics includes hydrogen, C1~C5 hydrocarbon, aromatic component and more than C5 non-aromatic components;
The first described reaction zone includes at least one moving-burden bed reactor;
(2)By step(1)In the first reaction zone logistics Jing after processing, then be passed through Disengagement zone 1 and separated, separated Area 1 returns material, Disengagement zone 1 discharges and Disengagement zone 2 feeds, and a part is incorporated to the first reaction zone to the return material of Disengagement zone 1 in proportion Raw material, the charging of Disengagement zone 2 are passed through Disengagement zone 2 and are separated, and obtain 2 cycle stock of Disengagement zone and Disengagement zone 2 discharges;
(3)Molecular sieve catalyst B is continuously passed through into second reaction zone, second reaction zone raw material and diluent and step (2)In remainder Disengagement zone 1 return material be passed through together second reaction zone contact with molecular sieve catalyst B occur aromatisation it is anti- Should, second reaction zone logistics is produced, step is incorporated to(2)Described in the first reaction zone logistics;
Described second reaction zone includes at least one moving-burden bed reactor.
(4)The discharging of Disengagement zone 2 is further fed into Disengagement zone 3 and is separated, isolated benzene and toluene recycle stream stock, and C8 is mixed Aromatic hydrocarbons stream stock and C8+ aromatic hydrocarbons recycle stream stocks are closed, wherein benzene and toluene recycle stream stock is reacted as the 3rd with C8+ aromatic hydrocarbons recycle stream stocks Area's charging is contacted with the B molecular sieve catalysts flowed out from second reaction zone and is reacted, and is produced the 3rd reaction zone logistics, is incorporated to step Suddenly(2)Described in the first reaction zone logistics.
The 3rd described reaction zone includes at least one moving-burden bed reactor.
Step(2)Described in Disengagement zone 1 return material and include C2 ~ C5 hydrocarbon component except propylene in addition to, Disengagement zone 1 discharges includes hydrogen Gas, methane and propylene, the charging of Disengagement zone 2 include more than C5 components, and 2 cycle stock of Disengagement zone includes more than C5 non-aromatic components, point The discharging from area 2 includes more than C5 aromatic components;Step(3)Described in second reaction zone logistics include hydrogen, C1~C5 hydrocarbon, virtue Hydrocarbon component and more than C5 non-aromatic components.
Step(1)Described in the first reaction zone raw material come from pre-reaction zone outlet streams, molecular sieve catalyst A is successively By pre-reaction zone, the first reaction zone, pre-reaction zone raw material is methyl alcohol, dimethyl ether.
Step(2)Described in the return material of Disengagement zone 1 be incorporated to the first reaction zone or pre-reaction zone raw material.
Described diluent is vapor, and described methyl alcohol and diluent mass ratio are 0.1~10:1.
The return material of described Disengagement zone 1 is incorporated to the ratio that the part of the first reaction zone or pre-reaction zone raw material accounts for gross mass Example is 0 ~ 100%.
Described molecular sieve catalyst A is ZSM-5 molecular sieve catalyst, and molecular sieve catalyst B is metal-modified ZSM-5 Molecular sieve catalyst.
In described molecular sieve catalyst A and each reaction zones of molecular sieve catalyst B, the time of staying is 30 ~ 400h.
Described pre-reaction zone reaction condition is 220~350 DEG C, 0.1MPa~1MPa, and the first reaction zone reaction condition is 350 DEG C~490 DEG C, 0.08MPa~0.8MPa, second reaction zone reaction condition be 380~550 DEG C, 0.06MPa~0.5MPa, 3rd reaction zone reaction condition is 400~580 DEG C, 0.04MPa~0.3MPa, the weight (hourly) space velocity (WHSV) of each reaction zone is 0.1~ 15h-1
The present invention uses the reaction process of moving bed technique propylene enhancing and aromatic hydrocarbons, with existing preparing propylene from methanol and methyl alcohol Aromatization technology is compared and is had the advantage that:
The cyclic regeneration of molecular sieve catalyst can be realized using moving bed technique, it is ensured that catalyst be always maintained at compared with High activity so that propylene and the output of aromatic hydrocarbon product efficient stable;
The average temperature rising of reactor is reduced using constituent part freshening in diluent and product, on the one hand Be conducive to the control of catalytic reaction temperature, propylene enhancing and virtue are realized by non-targeted product component selective reprocessing on the other hand Hydrocarbon yield;
Convert methanol into propylene and aromatic hydrocarbons process is divided into four reaction areas, each reaction zone realizes different reactions Function, by the selective reprocessing of separation product to differential responses area, and controls its freshening path and ratio, is capable of achieving propylene The flexible modulation of C8 aromatics yields is particularly with aromatic product, realizes that product benefit is maximum.
Description of the drawings
The use moving bed technique propylene enhancing and the reaction method of aromatic hydrocarbons of the 1st kind of embodiment that Fig. 1 is provided for the present invention Flow chart;
The use moving bed technique propylene enhancing and the reaction method of aromatic hydrocarbons of the 2nd kind of embodiment that Fig. 2 is provided for the present invention Flow chart;
The use moving bed technique propylene enhancing and the reaction method of aromatic hydrocarbons of the 3rd kind of embodiment that Fig. 3 is provided for the present invention Flow chart;
The use moving bed technique propylene enhancing of the 4-9 kind embodiments that Fig. 4 is provided for the present invention and the reaction side of aromatic hydrocarbons Method flow chart.
Specific embodiment
Below in conjunction with accompanying drawing, the present invention is described further.
As shown in figure 4, be the reaction process flow chart using moving bed technique propylene enhancing and aromatic hydrocarbons, including pre-reaction zone P-R, the first reaction zone R1, second reaction zone R2 and the 3rd reaction zone R3, two catalyst regeneration devices 1 and 2, and three points From area Sep1, Sep2 and Sep3.Pre-reaction zone P-R, the first reaction zone R1, second reaction zone R2 and the 3rd reaction zone R3 are respectively extremely A moving-burden bed reactor is included less, and the heat transmission equipment between each stream stock is not marked.
In Fig. 4, molecular sieve catalyst A is delivered continuously to pre-reaction zone, and the slow movements of molecular sieve catalyst A flow through pre- successively Reaction zone, the first reaction zone, carry out regenerate Posterior circle to pre- into regenerator 1 through the molecular sieve catalyst A of the first reaction zone Reaction zone.Molecular sieve catalyst B is delivered continuously to second reaction zone, and it is anti-that the slow movements of molecular sieve catalyst B flow through second successively Area, the 3rd reaction zone are answered, carries out regenerate Posterior circle to second into regenerator 1 through the molecular sieve catalyst B of the 3rd reaction zone Reaction zone.
In Fig. 4, pre-reaction zone raw material and thinner composition enter pre-reaction zone and react, and pre-reaction zone outlet is flowed stock and enters the One reaction zone reacts, and the first reaction zone logistics is separated into Sep1, the isolated top H of Sep12, methane and product third Olefinic constituent, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, and a portion is recycled into pre-reaction zone, and remainder sends into second Reaction zone reacts, and bottom C5+ components are separated into Sep2;The isolated top components of Sep2 are also recycled back to pre-reaction zone, Bottom component is sent into Sep3 and is separated, and the C8+ aromatic components of the benzene, toluene component and bottom at isolated top close input 3rd reaction zone reacts, and middle part C8 BTX aromatics are used as product output system;Second reaction zone logistics and the 3rd reaction zone logistics It is recycled to Sep1 to be separated.
In order to better illustrate the present invention, below it is further elaborated:
Pre-reaction zone raw material is preferably the mixture of methyl alcohol, dimethyl ether or both with second reaction zone raw material, when pre- anti- Answer area's raw material for dimethyl ether or it is most of for dimethyl ether component when, can now be not provided with pre-reaction zone, i.e. pre-reaction zone raw material with Recycle stream stock is directly entered the reaction that the first reaction zone occurs preparing propylene from methanol, so as to simplify the reaction process.And pre-reaction zone Setting cause raw material first to carry out pre-reaction in pre-reaction zone, compared to raw material be directly entered the first reaction zone reaction, its catalysis Agent carries out segmentation reaction causes catalytic reaction course different, and products therefrom distribution also has different, this is because carrying out pre- The catalyst of reaction carbon deposit flows into the first reaction zone, compares and fresh catalyst, and its catalysis activity reaches stationary phase, can be certain Degree improves the yield of target product.
In order to further improve the yield of dimethylbenzene in aromatic product, two bottom component of Disengagement zone is further separated, is obtained The target product dimethylbenzene transmitting system for arriving, and benzene, toluene and C8+ aromatic hydrocarbons merge the 3rd reaction zone of feeding and molecular sieve catalytic Agent contact is converted into xylene products, and the product for obtaining is recycled to Disengagement zone 1, can be effectively improved two in product by the method The yield of toluene, so as to further improve product value.
The exothermic heat of reaction that methyl alcohol is converted directly into hydro carbons is larger, and diluent is passed through in reactant can reduce raw material Partial pressure and serve as heat carrier, which is simultaneously not involved in aromatization, so as to reach the effect of control reaction temperature rising, typically using inertia Gas, can be vapor, methane, nitrogen etc., and in methanol molecules sieve catalytic conversion process, catalyst is also easy to produce a large amount of carbon deposits, and Vapor can also effectively suppress catalyst carbon deposit, therefore the present invention preferably vapor as diluent as diluent.Institute The methyl alcohol stated is 0.1~10 with diluent mass ratio:1.
For the freshening and the selective yield for improving propylene and aromatic hydrocarbons of effective control non-targeted product, step of the present invention (3)Disengagement zone 1 returns material and 2 cycle stock a portion of Disengagement zone is recycled to pre-reaction zone or the first reaction zone and carries out subsequently Preparing propylene from methanol reaction, remainder returns to second reaction zone and carries out aromatization, and on the one hand the recycle stock can reduce On the other hand reactant partial pressure can increase corresponding propylene and aromatic product as hydrocarbon stream is returned so as to control reaction heat effect Yield.The return material and 2 cycle stock of Disengagement zone of described Disengagement zone 1 is incorporated to pre-reaction zone feedstock circulation to pre-reaction zone or The part of one reaction zone accounts for the ratio of total amount and is preferably 0 ~ 100%.The ratio can be adjusted according to the market demand, when production third During alkene high efficiency, which is back to the large percentage of pre-reaction zone, and when aromatic hydrocarbons high efficiency is produced, which is back to second reaction zone Large percentage.
Described four reaction areas use two kinds of molecular sieve catalysts.Described molecular sieve catalyst A and molecular sieve catalytic Preferably with ZSM-5 molecular sieve of different nature, further preferred molecular sieve-4 A catalyst is ZSM-5 molecular sieve to agent B, molecule Sieve B catalyst is metal-modified ZSM-5 molecular sieve.Realize that pre-reaction zone is reacted by molecular sieve catalyst A loopy movings(Methyl alcohol It is converted into dimethyl ether reaction)React with the first reaction zone(Predominantly methyl alcohol and dimethyl ether conversion are propylene), urged by molecular sieve Agent B loopy moving realizes second reaction zone(Predominantly methyl alcohol and aromatization of low carbon hydrocarbon reaction)With the 3rd reaction zone(Predominantly The non-product aromatics of C5+ are converted into dimethylbenzene reaction), so as at utmost fecund mixes C8 aromatic hydrocarbons, especially paraxylene.
The described molecular sieve catalyst A and molecular sieve catalyst B time of staying in each reaction zone is preferably 30 ~ 400h. Control molecular sieve catalyst is in the time of staying of each reaction zone, so that catalyst is always in the range of higher activity stability Operation, to ensure the high selectivity of product.
Described pre-reaction zone reaction condition is 220~350 DEG C, 0.1MPa~1MPa, and the first reaction zone reaction condition is 350 DEG C~490 DEG C, 0.08MPa~0.8MPa, under this temperature, pressure scope, methyl alcohol or dimethyl ether component can be efficiently converted into Alkene is particularly propylene component, and second reaction zone reaction condition is 380~550 DEG C, 0.06MPa~0.5MPa, in this temperature pressure Under power scope, lower carbon number hydrocarbons component can effectively be converted into aromatic hydrocarbons and be particularly xylene components, and the 3rd reaction zone reaction condition is 400~580 DEG C, 0.04MPa~0.3MPa, under this temperature, pressure scope, benzene and toluene recycle stream stock can have with C8+ aromatic hydrocarbons What is imitated is converted into xylene components.
Reactant generally represents with weight (hourly) space velocity (WHSV) that with catalyst contact time reaction is former during weight (hourly) space velocity (WHSV) refers to charging per hour The quality of material and the ratio of catalyst in reactor quality, weight (hourly) space velocity (WHSV) is bigger, and to represent the time of staying shorter, each anti-in the present invention The weight (hourly) space velocity (WHSV) in area is answered to be 0.1~15h-1
Illustrate with reference to specific embodiment the present invention relates to content, but following specific embodiment is not right The restriction of the present invention, the scope of the present invention are defined by the claim applied.
Embodiment 1
According to the technological process shown in Fig. 1, specific implementation process is as follows:
1)The first reaction zone and ZSM-5 molecular sieve haptoreaction, wherein methyl alcohol are entered after material benzenemethanol and vapor preheating Mass ratio with water is 1:10,420 DEG C of controlling reaction temperature, reaction pressure are 0.4Mpa, and weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 molecules Sieve catalyst stops 70h in pre-reaction zone, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
2)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 440 DEG C of temperature, pressure 0.3Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are in second reaction zone 60h is stopped, now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
3)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, wherein 20% the first reaction zone of input, remaining 80% is input into Second reaction zone is reacted, and bottom C5+ components are separated into Sep2, the isolated top C5+ non-aromatic components circulations of Sep2 Return the first reaction zone, bottom C5+ aromatic component output systems.
First reaction zone bottom and second reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively and carry out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, the first reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Embodiment 2
According to the technological process shown in Fig. 2, specific implementation process is as follows:
1)Enter pre-reaction zone and ZSM-5 molecular sieve haptoreaction after the preheating of material benzenemethanol and vapor, wherein methyl alcohol with The mass ratio of water is 1:1, it is 300 DEG C of temperature, pressure 0.5MPa to control reaction condition, and methyl alcohol weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 point Sub- sieve catalyst stops 70h in pre-reaction zone, and now pre-reaction zone methanol conversion is 85%, and dimethyl ether selectivity is 100%.
Pre-reaction zone is a moving-burden bed reactor;
2)Pre-reaction zone product dimethyl ether is connect into the first reaction zone and ZSM-5 molecular sieve with unreacted methanol and water Reaction is touched, 420 DEG C of controlling reaction temperature, reaction pressure are 0.4Mpa, and weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 molecular sieve catalyst is pre- Reaction zone stops 70h, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
3)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 440 DEG C of temperature, pressure 0.3Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are in second reaction zone 60h is stopped, now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
4)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, wherein 20% input pre-reaction zone, remaining 80% input the Two reaction zones react, and bottom C5+ components are separated into Sep2.The isolated top C5+ non-aromatic components of Sep2 are looped back First reaction zone, bottom C5+ aromatic component output systems.
First reaction zone bottom and second reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively and carry out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, the first reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Embodiment 3
According to the technological process shown in Fig. 3, specific implementation process is as follows:
1)The first reaction zone and ZSM-5 molecular sieve haptoreaction, wherein methyl alcohol are entered after material benzenemethanol and vapor preheating Mass ratio with water is 1:10,420 DEG C of controlling reaction temperature, reaction pressure are 0.4Mpa, and weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 molecules Sieve catalyst stops 70h in pre-reaction zone, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
2)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 440 DEG C of temperature, pressure 0.3Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are in second reaction zone 60h is stopped, now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
3)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, wherein 20% the first reaction zone of input, remaining 80% is input into Second reaction zone is reacted, and bottom C5+ components are separated into Sep2;
5)The isolated top components of Sep2 loop back pre-reaction zone, and bottom component is separated into Sep3, is separated The benzene at the top arrived, toluene component merge the 3rd reaction zone of input and Zn-ZSM-5 haptoreactions with the C8+ aromatic components of bottom, It is 480 DEG C of temperature, pressure 0.1Mpa to control reaction condition, and weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are anti-second Area is answered to stop 60h, middle part C8 BTX aromatics are used as product output system.Second reaction zone logistics is merged with the 3rd reaction zone logistics It is recycled to Sep1 to be separated.
3rd reaction zone is a moving-burden bed reactor;
First reaction zone bottom and the 3rd reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively to be carried out Regeneration activity recovery, and be continuously recycled back at the top of the first reaction zone and second reaction zone.
Wherein, pre-reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Embodiment 4
According to the technological process shown in Fig. 4, specific implementation process is as follows:
1)Enter pre-reaction zone and ZSM-5 molecular sieve haptoreaction after the preheating of material benzenemethanol and vapor, wherein methyl alcohol with The mass ratio of water is 1:10, it is 220 DEG C of temperature, pressure 0.1MPa to control reaction condition, and methyl alcohol weight (hourly) space velocity (WHSV) is 0.1h-1, ZSM-5 Molecular sieve catalyst stops 30h in pre-reaction zone, and now pre-reaction zone methanol conversion is 80%, and dimethyl ether selectivity is 100%.
Pre-reaction zone is a moving-burden bed reactor;
2)Pre-reaction zone product dimethyl ether is connect into the first reaction zone and ZSM-5 molecular sieve with unreacted methanol and water Reaction is touched, 350 DEG C of controlling reaction temperature, reaction pressure are 0.08Mpa, and weight (hourly) space velocity (WHSV) is 0.1h-1, ZSM-5 molecular sieve catalyst 30h is stopped in pre-reaction zone, now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
3)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 380 DEG C of temperature, pressure 0.06Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 0.1h-1, Zn-ZSM-5 molecular sieve catalysts are anti-second Area is answered to stop 30h, now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
4)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, wherein 20% input pre-reaction zone, remaining 80% input the Two reaction zones react, and bottom C5+ components are separated into Sep2;
5)The isolated top components of Sep2 are also recycled back to pre-reaction zone, and bottom component is separated into Sep3, separate The benzene at the top for obtaining, toluene component are merged with the C8+ aromatic components of bottom and the 3rd reaction zone of input is contacted with Zn-ZSM-5 Reaction, it is 400 DEG C of temperature, pressure 0.04Mpa to control reaction condition, and weight (hourly) space velocity (WHSV) is 0.1h-1, Zn-ZSM-5 molecular sieve catalysts 30h is stopped in second reaction zone, middle part C8 BTX aromatics are used as product output system.Second reaction zone logistics and the 3rd reaction zone Logistics merging is recycled to Sep1 and is separated.
3rd reaction zone is a moving-burden bed reactor;
First reaction zone bottom and the 3rd reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively to be carried out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, pre-reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Product distribution when catalyst stabilization runs under the technique is as shown in table 1.
Embodiment 5
According to the technological process shown in Fig. 4, specific implementation process is as follows:
1)Enter pre-reaction zone and ZSM-5 molecular sieve haptoreaction after the preheating of material benzenemethanol and vapor, wherein methyl alcohol with The mass ratio of water is 1:1, it is 300 DEG C of temperature, pressure 0.5MPa to control reaction condition, and methyl alcohol weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 point Sub- sieve catalyst stops 70h in pre-reaction zone, and now pre-reaction zone methanol conversion is 85%, and dimethyl ether selectivity is 100%.
Pre-reaction zone is a moving-burden bed reactor;
2)Pre-reaction zone product dimethyl ether is connect into the first reaction zone and ZSM-5 molecular sieve with unreacted methanol and water Reaction is touched, 420 DEG C of controlling reaction temperature, reaction pressure are 0.4Mpa, and weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 molecular sieve catalyst is pre- Reaction zone stops 70h, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
3)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 440 DEG C of temperature, pressure 0.3Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are in second reaction zone 60h is stopped, now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
4)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, wherein 20% input pre-reaction zone, remaining 80% input the Two reaction zones react, and bottom C5+ components are separated into Sep2;
5)The isolated top components of Sep2 loop back pre-reaction zone, and bottom component is separated into Sep3, is separated The benzene at the top arrived, toluene component merge the 3rd reaction zone of input and Zn-ZSM-5 haptoreactions with the C8+ aromatic components of bottom, It is 480 DEG C of temperature, pressure 0.1Mpa to control reaction condition, and weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are anti-second Area is answered to stop 60h, middle part C8 BTX aromatics are used as product output system.Second reaction zone logistics is merged with the 3rd reaction zone logistics It is recycled to Sep1 to be separated.
3rd reaction zone is a moving-burden bed reactor;
First reaction zone bottom and the 3rd reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively to be carried out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, pre-reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Embodiment 6
According to the technological process shown in Fig. 4, specific implementation process is as follows:
1)Enter pre-reaction zone and ZSM-5 molecular sieve haptoreaction after the preheating of material benzenemethanol and vapor, wherein methyl alcohol with The mass ratio of water is 10:1, it is 350 DEG C of temperature, pressure 1MPa to control reaction condition, and methyl alcohol weight (hourly) space velocity (WHSV) is 15h-1, ZSM-5 point Sub- sieve catalyst stops 100h in pre-reaction zone, and now pre-reaction zone methanol conversion is 95%, and dimethyl ether selectivity is 100%.
Pre-reaction zone is a moving-burden bed reactor;
2)Pre-reaction zone product dimethyl ether is connect into the first reaction zone and ZSM-5 molecular sieve with unreacted methanol and water Reaction is touched, 490 DEG C of controlling reaction temperature, reaction pressure are 0.8Mpa, and weight (hourly) space velocity (WHSV) is 15h-1, ZSM-5 molecular sieve catalyst exists Pre-reaction zone stops 100h, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
3)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 550 DEG C of temperature, pressure 0.5Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 15h-1, Zn-ZSM-5 molecular sieve catalysts are in the second reaction Area stops 100h, and now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
4)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, wherein 20% enters pre-reaction zone, remaining 80% input second Reaction zone reacts, and bottom C5+ components are separated into Sep2;
5)The isolated top components of Sep2 loop back pre-reaction zone, and bottom component is separated into Sep3, separate The benzene at the top for obtaining, toluene component are merged the 3rd reaction zone of input with the C8+ aromatic components of bottom and are contacted instead with Zn-ZSM-5 Should, it is 580 DEG C of temperature, pressure 0.3Mpa to control reaction condition, and weight (hourly) space velocity (WHSV) is 15h-1, Zn-ZSM-5 molecular sieve catalysts are Two reaction zones stop 100h, and middle part C8 BTX aromatics are used as product output system.Second reaction zone logistics and the 3rd reaction zone thing Stream merging is recycled to Sep1 and is separated.
3rd reaction zone is a moving-burden bed reactor;
First reaction zone bottom and the 3rd reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively to be carried out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, pre-reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Embodiment 7
According to the technological process shown in Fig. 4, specific implementation process is as follows:
1)Material benzenemethanol enters pre-reaction zone and ZSM-5 molecular sieve haptoreaction, wherein methyl alcohol through pipeline 1 with vapor Mass ratio with water is 1:1, it is 300 DEG C of temperature, pressure 0.5MPa to control reaction condition, and methyl alcohol weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 Molecular sieve catalyst stops 70h in pre-reaction zone, and now pre-reaction zone methanol conversion is 85%, and dimethyl ether selectivity is 100%.
Pre-reaction zone is a moving-burden bed reactor;
2)Pre-reaction zone product dimethyl ether is connect into the first reaction zone and ZSM-5 molecular sieve with unreacted methanol and water Reaction is touched, 420 DEG C of controlling reaction temperature, reaction pressure are 0.4Mpa, and weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 molecular sieve catalyst is pre- Reaction zone stops 70h, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
3)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 440 DEG C of temperature, pressure 0.3Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are in second reaction zone 60h is stopped, now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
4)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, fully enter pre-reaction zone, and bottom C5+ components are by pipe Road 7 is separated into Sep2;
5)The isolated top components of Sep2 loop back pre-reaction zone, and bottom component is separated into Sep3, is separated The benzene at the top arrived, toluene component merge the 3rd reaction zone of input and Zn-ZSM-5 haptoreactions with the C8+ aromatic components of bottom, It is 480 DEG C of temperature, pressure 0.1Mpa to control reaction condition, and weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are anti-second Area is answered to stop 60h, middle part C8 BTX aromatics are used as product output system.Second reaction zone logistics is merged with the 3rd reaction zone logistics It is recycled to Sep1 to be separated.
3rd reaction zone is a moving-burden bed reactor;
First reaction zone bottom and the 3rd reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively to be carried out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, pre-reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Embodiment 8
According to the technological process shown in Fig. 4, specific implementation process is as follows:
1)Pre-reaction zone and ZSM-5 molecular sieve haptoreaction, wherein methyl alcohol are entered after material benzenemethanol is preheated with vapor Mass ratio with water is 1:1, it is 300 DEG C of temperature, pressure 0.5MPa to control reaction condition, and methyl alcohol weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 Molecular sieve catalyst stops 70h in pre-reaction zone, and now pre-reaction zone methanol conversion is 85%, and dimethyl ether selectivity is 100%.
Pre-reaction zone is a moving-burden bed reactor;
2)Pre-reaction zone product dimethyl ether is connect into the first reaction zone and ZSM-5 molecular sieve with unreacted methanol and water Reaction is touched, 420 DEG C of controlling reaction temperature, reaction pressure are 0.4Mpa, and weight (hourly) space velocity (WHSV) is 6h-1, ZSM-5 molecular sieve catalyst is pre- Reaction zone stops 70h, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
3)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 440 DEG C of temperature, pressure 0.3Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are in second reaction zone 60h is stopped, now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
4)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent loops back reaction zone by output system, middle part C2 ~ C5 hydrocarbon components, wherein 50% input pre-reaction zone, remaining 50% is defeated Enter second reaction zone reaction, bottom C5+ components are separated into Sep2;
5)The isolated top components of Sep2 loop back pre-reaction zone, and bottom component is separated into Sep3, is separated The benzene at the top arrived, toluene component merge the 3rd reaction zone of input and Zn-ZSM-5 haptoreactions with the C8+ aromatic components of bottom, It is 480 DEG C of temperature, pressure 0.1Mpa to control reaction condition, and weight (hourly) space velocity (WHSV) is 7h-1, Zn-ZSM-5 molecular sieve catalysts are anti-second Area is answered to stop 60h, middle part C8 BTX aromatics are used as product output system.Second reaction zone logistics is distinguished with the 3rd reaction zone logistics Merging is recycled to Sep1 and is separated.
3rd reaction zone is a moving-burden bed reactor;
First reaction zone bottom and the 3rd reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively to be carried out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, pre-reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.、
Embodiment 9
According to the technological process shown in Fig. 4, specific implementation process is as follows:
1)Material benzenemethanol and the preheated entrance pre-reaction zone of vapor and ZSM-5 molecular sieve haptoreaction, wherein methyl alcohol with The mass ratio of water is 10:1, it is 350 DEG C of temperature, pressure 1MPa to control reaction condition, and methyl alcohol weight (hourly) space velocity (WHSV) is 15h-1, ZSM-5 point Sub- sieve catalyst stops 100h in pre-reaction zone, and now pre-reaction zone methanol conversion is 95%, and dimethyl ether selectivity is 100%.
Pre-reaction zone is a moving-burden bed reactor;
2)Pre-reaction zone product dimethyl ether is connect into the first reaction zone and ZSM-5 molecular sieve with unreacted methanol and water Reaction is touched, 470 DEG C of controlling reaction temperature, reaction pressure are 0.8Mpa, and weight (hourly) space velocity (WHSV) is 15h-1, ZSM-5 molecular sieve catalyst exists Pre-reaction zone stops 100h, and now methyl alcohol and dimethyl ether conversion rate are 100%.
First reaction zone is a moving-burden bed reactor;
3)Material benzenemethanol is contacted with Zn-ZSM-5 into second reaction zone with vapor and carries out aromatization, control reaction Condition is 550 DEG C of temperature, pressure 0.5Mpa, and methyl alcohol weight (hourly) space velocity (WHSV) is 15h-1, Zn-ZSM-5 molecular sieve catalysts are in the second reaction Area stops 100h, and now second reaction zone occurs aromatization, and wherein methanol conversion is 100%.
Second reaction zone is a moving-burden bed reactor;
4)Separated from the first reaction zone product out into Sep1, the isolated top H of Sep12, methane and third Olefinic constituent output system, middle part C2 ~ C5 hydrocarbon components loop back reaction zone, fully enter second reaction zone reaction, bottom C5+ components Separated into Sep2;
5)The isolated top components of Sep2 loop back pre-reaction zone, and bottom component is separated into Sep3, is separated The benzene at the top arrived, toluene component merge the 3rd reaction zone of input and Zn-ZSM-5 haptoreactions with the C8+ aromatic components of bottom, It is 580 DEG C of temperature, pressure 0.3Mpa to control reaction condition, and weight (hourly) space velocity (WHSV) is 15h-1, Zn-ZSM-5 molecular sieve catalysts are second Reaction zone stops 100h, and middle part C8 BTX aromatics are used as product output system.Second reaction zone logistics and the 3rd reaction zone logistics Merging is recycled to Sep1 and is separated.
3rd reaction zone is a moving-burden bed reactor;
First reaction zone bottom and the 3rd reaction zone bottom molecular sieve catalyst are delivered to regenerating unit 1 and 2 respectively to be carried out Regeneration activity recovery, and be continuously recycled back at the top of pre-reaction zone and second reaction zone.
Wherein, pre-reaction zone material benzenemethanol and second reaction zone material benzenemethanol mass ratio are 1:1.
Output system product distribution when catalyst stabilization runs under the technique is as shown in table 1.
1 aromatization of methanol product of table is distributed, wt%(Butt)
Table 1 continues

Claims (6)

1. the reaction method of a kind of use moving bed technique propylene enhancing and aromatic hydrocarbons, comprises the following steps:
(1)Molecular sieve catalyst A is passed through into the first reaction zone, by the first reaction zone raw material and diluent be passed through the first reaction zone with A molecular sieve catalyst haptoreactions, produce the first reaction zone logistics;
The first described reaction zone raw material includes methyl alcohol, dimethyl ether;
The first described reaction zone logistics includes hydrogen, C1~C5 hydrocarbon, aromatic component and more than C5 non-aromatic components;
The first described reaction zone includes at least one moving-burden bed reactor;
(2)By step(1)In the first reaction zone logistics Jing after processing, then be passed through Disengagement zone 1 and separated, obtain Disengagement zone 1 Return material, Disengagement zone 1 discharges and Disengagement zone 2 feeds, a part is incorporated to the first reaction zone original to the return material of Disengagement zone 1 in proportion Material, the charging of Disengagement zone 2 are passed through Disengagement zone 2 and are separated, and obtain 2 cycle stock of Disengagement zone and Disengagement zone 2 discharges;Described Disengagement zone It is 0 ~ 100% that 1 return material is incorporated to the part of the first reaction zone or pre-reaction zone raw material and accounts for the ratio of gross mass;
(3)By molecular sieve catalyst
B is continuously passed through second reaction zone, second reaction zone raw material and diluent and step(2)In remainder Disengagement zone 1 Return material and be passed through second reaction zone together and contact with molecular sieve catalyst B and aromatization occurs, produce second reaction zone logistics, It is incorporated to step(2)Described in the first reaction zone logistics;
Described second reaction zone includes at least one moving-burden bed reactor;
Described molecular sieve catalyst A is ZSM-5 molecular sieve catalyst, and molecular sieve catalyst B is metal-modified ZSM-5 molecules Sieve catalyst;In described molecular sieve catalyst A and each reaction zones of molecular sieve catalyst B, the time of staying is 30 ~ 400h;
Step(2)Described in Disengagement zone 1 return material and include C2 ~ C5 hydrocarbon component except propylene in addition to, Disengagement zone 1 discharge include hydrogen, Methane and propylene, the charging of Disengagement zone 2 include more than C5 components, and 2 cycle stock of Disengagement zone includes more than C5 non-aromatic components, Disengagement zone 2 dischargings include more than C5 aromatic components;Step(3)Described in second reaction zone logistics include hydrogen, C1~C5 hydrocarbon, aromatic hydrocarbons group Divide and more than C5 non-aromatic components.
2. the reaction method of a kind of use moving bed technique propylene enhancing and aromatic hydrocarbons, comprises the following steps:
(1)Molecular sieve catalyst A is passed through into the first reaction zone, by the first reaction zone raw material and diluent be passed through the first reaction zone with A molecular sieve catalyst haptoreactions, produce the first reaction zone logistics;
The first described reaction zone raw material includes methyl alcohol, dimethyl ether;
The first described reaction zone logistics includes hydrogen, C1~C5 hydrocarbon, aromatic component and more than C5 non-aromatic components;
The first described reaction zone includes at least one moving-burden bed reactor;
(2)By step(1)In the first reaction zone logistics Jing after processing, then be passed through Disengagement zone 1 and separated, obtain Disengagement zone 1 Return material, Disengagement zone 1 discharges and Disengagement zone 2 feeds, a part is incorporated to the first reaction zone original to the return material of Disengagement zone 1 in proportion Material, the charging of Disengagement zone 2 are passed through Disengagement zone 2 and are separated, and obtain 2 cycle stock of Disengagement zone and Disengagement zone 2 discharges;Described Disengagement zone It is 0 ~ 100% that 1 return material is incorporated to the part of the first reaction zone or pre-reaction zone raw material and accounts for the ratio of gross mass;
(3)Molecular sieve catalyst B is continuously passed through into second reaction zone, second reaction zone raw material and diluent and step(2)In Remainder Disengagement zone 1 return material be passed through together second reaction zone contact with molecular sieve catalyst B occur aromatization, product Raw second reaction zone logistics, is incorporated to step(2)Described in the first reaction zone logistics;
Described second reaction zone includes at least one moving-burden bed reactor;
(4)The discharging of Disengagement zone 2 is further fed into Disengagement zone 3 and is separated, isolated benzene and toluene recycle stream stock, C8 mixing virtues Hydrocarbon stream stock and C8+ aromatic hydrocarbons recycle stream stocks, wherein benzene and toluene recycle stream stock are entered as the 3rd reaction zone with C8+ aromatic hydrocarbons recycle stream stocks Material is contacted with the B molecular sieve catalysts flowed out from second reaction zone and is reacted, and is produced the 3rd reaction zone logistics, is incorporated to step (2)Described in the first reaction zone logistics;
The 3rd described reaction zone includes at least one moving-burden bed reactor;Described molecular sieve catalyst A is ZSM-5 molecular sieve Catalyst, molecular sieve catalyst B are metal-modified ZSM-5 molecular sieve catalyst;Described molecular sieve catalyst A and molecular sieve In each reaction zones of catalyst B, the time of staying is 30 ~ 400h;
Step(2)Described in Disengagement zone 1 return material and include C2 ~ C5 hydrocarbon component except propylene in addition to, Disengagement zone 1 discharge include hydrogen, Methane and propylene, the charging of Disengagement zone 2 include more than C5 components, and 2 cycle stock of Disengagement zone includes more than C5 non-aromatic components, Disengagement zone 2 dischargings include more than C5 aromatic components;Step(3)Described in second reaction zone logistics include hydrogen, C1~C5 hydrocarbon, aromatic hydrocarbons group Divide and more than C5 non-aromatic components.
3. method according to claim 1 and 2, it is characterised in that step(1)Described in the first reaction zone raw material from In pre-reaction zone outlet streams, molecular sieve catalyst A passes sequentially through pre-reaction zone, the first reaction zone, and pre-reaction zone raw material is first Alcohol, dimethyl ether.
4. method according to claim 1 and 2, it is characterised in that step(2)Described in Disengagement zone 1 return material simultaneously Enter the first reaction zone or pre-reaction zone raw material.
5. method according to claim 1, it is characterised in that described diluent is vapor, described methyl alcohol with it is dilute Agent mass ratio is released for 0.1~10:1.
6. method according to claim 4, it is characterised in that described pre-reaction zone reaction condition is 220~350 DEG C, 0.1MPa~1MPa, the first reaction zone reaction condition are 350 DEG C~490 DEG C, 0.08MPa~0.8MPa, and second reaction zone is reacted Condition be 380~550 DEG C, 0.06MPa~0.5MPa, the 3rd reaction zone reaction condition be 400~580 DEG C, 0.04MPa~ 0.3MPa, the weight (hourly) space velocity (WHSV) of each reaction zone are 0.1~15h-1
CN201510033499.0A 2015-01-23 2015-01-23 Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons Active CN104557401B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510033499.0A CN104557401B (en) 2015-01-23 2015-01-23 Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510033499.0A CN104557401B (en) 2015-01-23 2015-01-23 Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons

Publications (2)

Publication Number Publication Date
CN104557401A CN104557401A (en) 2015-04-29
CN104557401B true CN104557401B (en) 2017-03-29

Family

ID=53074587

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510033499.0A Active CN104557401B (en) 2015-01-23 2015-01-23 Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons

Country Status (1)

Country Link
CN (1) CN104557401B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10513478B2 (en) * 2016-01-04 2019-12-24 Blue Cube Ip Llc Processes for preparing halogenated alkanes
CN107586244B (en) * 2016-07-08 2020-03-27 中国石油化工股份有限公司 Process for producing aromatic hydrocarbon
CN107586243B (en) * 2016-07-08 2020-03-27 中国石油化工股份有限公司 Process for producing aromatic hydrocarbon
WO2018197471A1 (en) * 2017-04-24 2018-11-01 Basf Se Process for the conversion of methanol to p-xylene
CN114057532B (en) * 2020-07-31 2023-12-12 中国石油化工股份有限公司 Method for producing light aromatic hydrocarbon and propylene
CN114057533B (en) * 2020-07-31 2023-12-12 中国石油化工股份有限公司 Method for producing light aromatic hydrocarbon and low-carbon olefin

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102076639B (en) * 2008-06-25 2014-04-16 道达尔石油化学产品研究弗吕公司 Process to make olefins and aromatics from organics
CN101671226B (en) * 2009-09-28 2013-07-17 清华大学 Process for preparing dimethylbenzene by aromatization of methanol
CN102190546B (en) * 2010-03-03 2013-09-18 中国石油化工股份有限公司 Method for preparing propylene and aromatic hydrocarbon by virtue of conversion of methanol
US20130165725A1 (en) * 2011-12-27 2013-06-27 Shell Oil Company Process for the preparation of an aromatic product
CN103464193B (en) * 2013-08-09 2015-06-17 华电煤业集团有限公司 Fluidized catalyst for alcohol ether and hydrocarbon aromatization, and preparation method and application method thereof
CN104177210B (en) * 2014-07-30 2016-05-18 清华大学 The method of alcohol ether compound coproduction alkene and aromatic hydrocarbons

Also Published As

Publication number Publication date
CN104557401A (en) 2015-04-29

Similar Documents

Publication Publication Date Title
CN104557401B (en) Using moving bed technique propylene enhancing and the method for aromatic hydrocarbons
CN103664482B (en) A kind of reaction process using moving bed technique oxygenatedchemicals to be converted into aromatic hydrocarbons
CN102320912B (en) Method for maximizing total ethylene and propylene yield in process of preparing low-carbon olefin by oxygen compound conversion
CN103131464B (en) A kind of hydrocarbons catalytic conversion method producing low-carbon alkene and light aromatic hydrocarbons
CN104334515A (en) Combined heavy reformate dealkylation-transalkylation process for maximizing xylenes production
CN103121894A (en) Combined method for producing low-carbon olefin
CN103864561B (en) Technical method for preparing aromatic hydrocarbon through methanol aromatization
CN111423302A (en) Method and device for preparing olefin from methanol
CN100567460C (en) Utilize catalyzing and cracking light-hydrocarbon material to prepare the method and the device of low-carbon alkene
CN107827691A (en) A kind of method of synthesis gas preparing low-carbon olefins
CN104447176A (en) Method for high-selectivity preparation of p-xylene
CN103509601B (en) A kind of processing method of C_4 hydrocarbon aromizing coproduction propane
CN100457857C (en) Method for producing olefin through catalytic cracking
CN101596461A (en) A kind of aromatizing catalyst for light hydrocarbon and preparation method thereof
CN108017490B (en) Method for preparing aromatic hydrocarbon by catalytic conversion of oxygen-containing compound-containing raw material
CN103509600B (en) A kind of mixed c 4 hydrocarbon aromatizing produces the method for stop bracket gasoline blend component
CN109321268A (en) A kind of Fischer-Tropsch process exhaust prepares the method and device thereof of gasoline and aromatic hydrocarbons
CN101585747B (en) Method for transforming oxygenates into propylene
CN110201609B (en) Equipment and method for co-producing olefin and aromatic hydrocarbon by using synthesis gas through hydrogenation
CN101165020B (en) Method for increasing yield of propylene
CN103864564A (en) Technique for processing methanol-to-propylene by-products
CN207347425U (en) Prepare the device of ethene
CN207347428U (en) The process units of ethene
CN106608786B (en) The method of alcohol ether dimethylbenzene coproduction ethylbenzene
CN102899084B (en) Method for co-production of pyrolysis raw material for ethylene through C4 hydrocarbon aromatization

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant