CN104557362B - Methanol and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the system and method for propylene - Google Patents

Abstract

The present invention relates to a kind of methanol and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the system and method for propylene, mainly solve process route complexity, the low problem of ethylene, propylene and aromatics yield in prior art.The present invention is by including aromatization reactor（1）, chilling tower（2）, knockout tower（3）, separative element（4）System, aromatization reactor（1）The product of generation sequentially enters chilling tower（2）And knockout tower（3）, knockout tower（3）The gaseous products for obtaining are through compressor（5）Enter separative element（4）, knockout tower（3）And separative element（4）The part C5 and C6 for obtaining is non-aromatic（24）, ethane（17）, propane（18）, C4 and C5 and C6 non-aromatic（19）Aromatization reactor is returned as recycle stock（1）Technical scheme, preferably solve the problem, can be used in the commercial production of ethylene, propylene and aromatic hydrocarbons.

Description

Methanol and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the system and method for propylene

Technical field

The present invention relates to a kind of methanol and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the system and method for propylene.

Background technology

Ethylene, propylene and aromatic hydrocarbons（Especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX） It is important basic organic synthesis raw material.Driven by downstream derivative thing demand, the market demand of ethylene, propylene and aromatic hydrocarbons continues Increase.

With liquid hydrocarbon（Such as Petroleum, diesel oil, secondary operations oil）Steam cracking process for raw material is ethylene, propylene and virtue The main production of hydrocarbon.The technique belongs to petroleum path production technology, in recent years, due to the limited supply of petroleum resources and Higher price, cost of material are continuously increased.By factor, alternative materials prepare ethylene, propylene and aromatic hydrocarbons technology cause more next More widely pay close attention to.Wherein, for coal-based methanol, dimethyl ether raw material, due to rich coal resources in China, one kind is increasingly becoming Important Chemical Manufacture raw material, becomes the important supplement of petroleum.Accordingly, it is considered to methanol and/or dimethyl ether as raw material system Standby ethylene, propylene and aromatic hydrocarbons.

In various existing methanol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons is simultaneously Including ethylene, propylene and aromatic hydrocarbons.The technology initially sees Chang of Mobil companies in 1977 et al.（Journal of Catalysis, 1977,47,249）Report methanol and its oxygenatedchemicalss conversion on ZSM-5 molecular sieve catalyst and prepare virtue The method of the Hydrocarbon such as hydrocarbon.1985, Mobil companies were disclosed in its United States Patent (USP) US1590321 that applies first Methanol, the result of study of dimethyl ether conversion aromatic hydrocarbons, the research adopt the phosphorous ZSM-5 molecular sieve for 2.7 weight % for catalysis Agent, reaction temperature are 400 ~ 450 DEG C, methanol, dimethyl ether air speed 1.3 (Grams Per Hour)/gram catalyst.

The relevant report and patent in the field is more, but the purpose product of most of technology is aromatic hydrocarbons, and ethylene, propylene belong to In by-product, yield is low.Such as, the patent in terms of methanol arenes catalytic agent：Chinese patent CN102372535, CN102371176、CN102371177、CN102372550、CN102372536、CN102371178、CN102416342、 CN101550051, United States Patent (USP) US4615995, US2002/0099249A1 etc..Such as, in terms of methanol aromatics process Patent：United States Patent (USP) US4686312, Chinese patent ZL101244969, ZL1880288, CN101602646, CN101823929, CN101671226, CN102199069, CN102199446, CN1880288 etc..

In addition, while technology path disclosed in some patents is methanol aromatic hydrocarbons co-producing light olefins, gasoline etc. other Product, such as patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537 etc..

Wherein, Multi-function methanol processing method disclosed in patent CN102775261 and device utilize methanol production low-carbon (LC) alkene Hydrocarbon, gasoline, aromatic hydrocarbons.The method adopts two-step method production technology, first step methanol feedstock to produce low under the effect of special-purpose catalyst 1 Carbon olefin, second step by containing low-carbon alkene reaction gas through heat exchange, chilling, carrying out washing treatment after, in the presence of special-purpose catalyst 2 Synthesis aromatic hydrocarbons and/or gasoline.The reactor of two courses of reaction can be fixed bed or fluid bed.The method adopts two-step method, technique Flow process is complicated.

Patent CN102146010 is disclosed with methanol as raw material production low-carbon alkene and the work of arene parallel cogeneration gasoline Skill.Low-carbon alkene and aromatic hydrocarbons is produced with methanol as raw material and using molecular sieve catalyst through methanol alkylation reaction and aromatization Co-production gasoline.The reactor of methanol alkylation reaction and aromatization is various types of fixed bed reactors, pressure 0.01 ~ 0.5 MPa, 180 ~ 600 DEG C of temperature.Total liquid yield is more than 70 weight %, and triphen yield is more than 90 weight %.The method is also adopted by two Reactor, technological process are complicated.

The method that patent CN102531821 discloses methanol and the co-feeding production low-carbon alkene of Petroleum and/or aromatic hydrocarbons, Using 2.2 ~ 6.0 weight %La of load and the ZSM-5 catalyst of 1.0 ~ 2.8 weight %P, fixed bed reactors or fluid bed can be adopted Reactor.Reaction temperature is 550 ~ 670 DEG C, air speed 1.0 ~ 5 (Grams Per Hour)/gram catalyst.The triolefin yield of the method is higher, But BTX yields are low, only 5 ~ 17 weight %.

The method that patent CN102372537 and CN102190546 disclose preparing propylene by methanol transformation and aromatic hydrocarbons.This two specially Profit is developed on the basis of preparing propylene by methanol transformation technology, and propylene is main purpose product, and aromatics yield is relatively low.

In above-mentioned patented technology or technological process is complicated, there are two reactors；Or ethylene, propene yield are low；Or Aromatics yield is low.The present invention pointedly proposes technical scheme, solves the problems referred to above.

Content of the invention

One of the technical problem to be solved is that the process route of existing process is complicated, ethylene, propylene and aromatic hydrocarbons The low technical problem of yield, there is provided a kind of methanol and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the system of propylene.The system Have technological process simple, the high advantage of ethylene, propylene and aromatics yield.

The two of the technical problem to be solved are to provide a kind of method corresponding with one of technical problem is solved.

For one of solving the above problems, the technical solution used in the present invention is as follows：A kind of methanol and/dimethyl ether conversion system virtue Hydrocarbon coproduction ethylene, the system of propylene, including aromatization reactor 1, chilling tower 2, knockout tower 3, separative element 4, aromatization The product that device 1 is generated sequentially enters chilling tower 2 and knockout tower 3, and the gaseous products that knockout tower 3 is obtained are entered through compressor 5 and separated Part C5 and C6 that unit 4, knockout tower 3 and separative element 4 are obtained are non-aromatic 24, ethane 17, propane 18, C4 and C5 and C6 non-aromatic 19 Aromatization reactor 1 is returned as recycle stock.

In said system, methanol and/or dimethyl ether and recycle stock be converted in aromatization reactor 1 ethylene, third Product based on alkene and aromatic hydrocarbons；The product that aromatization reactor 1 is generated is cooled down in chilling tower 2；The product out of chilling tower 2 exists It is separated in knockout tower 3 that water, gaseous hydrocarbon, C5 and C6 be non-aromatic, BTX aromatics；Gaseous hydrocarbon is separated into hydrogen, first in separative element 4 Alkane, ethylene, ethane, propylene, propane, C4 and C5 and C6 are non-aromatic.

In said system, aromatization reactor 1, for by methanol and/or dimethyl ether and recycle stock be converted into ethylene, Product based on propylene and aromatic hydrocarbons；Chilling tower 2, cools down the product that aromatization reactor 1 is generated；Knockout tower 3, chilling tower 2 is gone out The product for coming is separated into that water, gaseous hydrocarbon, C5 and C6 be non-aromatic, BTX aromatics；Separative element 4, by product be separated into hydrogen, methane, Ethylene, ethane, propylene, propane, C4 and C5 and C6 are non-aromatic.

For solve the above problems two, the technical solution used in the present invention is as follows：A kind of methanol and/dimethyl ether conversion system virtue Hydrocarbon coproduction ethylene, the method for propylene, using above-mentioned system, described method includes following step：

a）Methanol and/or dimethyl ether and recycle stock in 1 catalyst neutralisation haptoreaction of aromatization reactor, generate with Product based on ethylene, propylene and aromatic hydrocarbons；

b）The product that aromatization reactor 1 is obtained enters chilling tower 2 and cools down；

c）Knockout tower 3 is entered through chilling tower 2 after cooling down, and tower top is isolated gaseous hydrocarbon, isolates C5 and C6 is non-aromatic in the middle part of tower 23, bottom of towe is isolated product and enters oil water separator 6, is separated into BTX aromatics 8 and water 9, and BTX aromatics 8 are used as output of products system System；

d）After gaseous hydrocarbon is through the pressurization of compressor 5, separative element 4 is entered；

e）Separative element 4 by product be separated into hydrogen 10, methane 11, ethylene 12, ethane 14, propylene 13, propane 15, C4 and C5 and C6 non-aromatic 16, wherein hydrogen 10, methane 11, ethylene 12, propylene 13 are used as output of products system；

f）C5 and non-aromatic 24 conducts of C6 that part ethane 17, propane 18, C4 and C5 and C6 non-aromatic 19 and knockout tower 3 are obtained Recycle stock return aromatization reactor 1, remaining ethane 20, propane 21, C4 and C5 and C6 non-aromatic 22 and knockout tower 3 are obtained C5 and C6 non-aromatic 23 that C5 and C6 non-aromatic 25 or whole ethane 14, propane 15, C4 and C5 and C6 non-aromatic 16 and knockout tower 3 are obtained As output of products system.

In above-mentioned technical proposal, aromatization reactor 1 adopts fixed bed reactors, moving-burden bed reactor, fluidized-bed reaction Device or the circulating fluid bed reactor with regenerator, preferably fluidized-bed reactor or the circulating fluid bed reactor with regenerator.

In above-mentioned technical proposal, the reaction temperature of aromatization reactor 1 is 400 ~ 550 DEG C, counts reaction pressure as 0 with gauge pressure ~ 0.5 MPa, weight space velocity is 0.1 ~ 15 (Grams Per Hour)/gram catalyst, and preferable reaction temperature is 440 ~ 500 DEG C, in terms of gauge pressure Reaction pressure is 0.1 ~ 0.4 MPa, and weight space velocity is 0.15 ~ 8 (Grams Per Hour)/gram catalyst.

In above-mentioned technical proposal, catalyst activity component is ZSM-5, ZSM-23, ZSM-11, β, Y or is formed each other Composite molecular screen, preferably ZSM-5；Carrier is Kaolin, aluminium oxide, silicon dioxide；The mass ratio of active component and carrier is（10 ~50）∶（50~90）, preferably（20~40）∶（60~80）.

In above-mentioned technical proposal, catalyst is loaded with one or more element or oxidation in Zn, Ag, P, Ga, Cu, Mn, Mg Thing, preferably Zn, P；In terms of the mass percent of catalyst, the element of load content on a catalyst is 0.01 ~ 15 weight %, It is preferred that 0.02 ~ 8 weight %.

In above-mentioned technical proposal, the active component of catalyst is selected from ZSM-5 molecular sieve, with the percentage by weight of catalyst Meter, loads the Zn elements or oxide, the P element of 0.1 ~ 8 weight % or oxide of 0.01 ~ 5 weight % on catalyst.

In above-mentioned technical proposal, the raw material of aromatization reactor 1 can be the mixture of methanol or dimethyl ether or both；Raw material The weight/mass percentage composition of middle water be 0 ~ 30 weight %, preferably shorter than 10 weight %.

In above-mentioned technical proposal, the system of separative element 4 include domethanizing column 26, dethanizer 27, ethylene rectifying column 28, Depropanizing tower 29, propylene rectification tower 30；26 tower top of domethanizing column isolates hydrogen 10, methane 11；28 tower top of ethylene rectifying column point Ethylene 12 is separated out, bottom of towe isolates ethane 14；30 tower top of propylene rectification tower isolates propylene 13, and bottom of towe isolates propane 15；De- 29 bottom of towe of propane tower isolates C4 and C5 and C6 non-aromatic 16.

Separative element of the present invention 4 using the technical scheme of order separation process is：Methanol and/or dimethyl ether and recycle Material generates the product based on ethylene, propylene and aromatic hydrocarbons in 1 catalyst neutralisation haptoreaction of aromatization reactor；Aromatisation is anti- The product for answering device 1 to obtain enters chilling tower 2 and cools down；Knockout tower 3 is entered through chilling tower 2 after cooling down, and tower top isolates gaseous hydrocarbon, tower C5 and C6 non-aromatic 23 is isolated at middle part, and bottom of towe is isolated product and enters oil water separator 6, is separated into BTX aromatics 8 and water 9, mixes Aromatic hydrocarbons 8 is closed as output of products system；Gaseous hydrocarbon through compressor 5 pressurization after, enter separative element 4 in domethanizing column 26, tower Hydrogen 10, methane 11 are isolated in top, and tower bottom product enters dethanizer 27；The C2 products of 27 tower top of dethanizer enter ethylene essence Tower 28 is evaporated, the carbon number of bottom of towe is higher than more than 2 hydrocarbon entrance depropanizing tower 29；28 tower top of ethylene rectifying column isolates ethylene 12, tower Isolate ethane 14 in bottom；The C3 that 29 tower top of depropanizing tower is isolated enters propylene rectification tower 30, and the carbon number that bottom of towe is isolated is higher than 3 Hydrocarbon, i.e. C4 and C5 and C6 non-aromatic 16；30 tower top of propylene rectification tower isolates propylene 13, and bottom of towe isolates propane 15；Wherein hydrogen Gas 10, methane 11, ethylene 12, propylene 13 are used as output of products system；Part ethane 17, propane 18, C4 and C5 and C6 non-aromatic 19 And knockout tower 3 C5 that obtains and C6 non-aromatic 24 return aromatization reactor 1 as recycle stock, remaining ethane 20, propane 21, The C5 and C6 non-aromatic 25 or whole ethane 14, propane 15, C4 and C5 and C6 that C4 and C5 and C6 non-aromatic 22 and knockout tower 3 are obtained is non- Virtue 16 and knockout tower 3 C5 that obtains and C6 non-aromatic 23 are used as output of products system.

Separative element of the present invention 4 using the technical scheme of front-end deethanization flow process is：Methanol and/or dimethyl ether and recycle Material generates the product based on ethylene, propylene and aromatic hydrocarbons in 1 catalyst neutralisation haptoreaction of aromatization reactor；Aromatisation is anti- The product for answering device 1 to obtain enters chilling tower 2 and cools down；Knockout tower 3 is entered through chilling tower 2 after cooling down, and tower top isolates gaseous hydrocarbon, tower C5 and C6 non-aromatic 23 is isolated at middle part, and bottom of towe is isolated product and enters oil water separator 6, is separated into BTX aromatics 8 and water 9, mixes Aromatic hydrocarbons 8 is closed as output of products system；Gaseous hydrocarbon through compressor 5 pressurization after, enter separative element 4 in dethanizer 27, tower The product on top enters domethanizing column 26, and bottom product enters depropanizing tower 29；28 tower top of domethanizing column isolates hydrogen 15, methane 16, tower bottom product enters ethylene rectifying column 28；28 tower top of ethylene rectifying column isolates ethylene 12, and bottom of towe isolates ethane 14；De- The C3 that 29 tower top of propane tower is isolated enters propylene rectification tower 30, hydrocarbon of the carbon number that bottom of towe is isolated higher than 3, i.e. C4 and C5 and C6 Non-aromatic 16；30 tower top of propylene rectification tower isolates propylene 13, and bottom of towe isolates propane 15；Wherein hydrogen 10, methane 11, ethylene 12nd, propylene 13 is used as output of products system；Part ethane 17, propane 18, C4 and C5 and C6 non-aromatic 19 and knockout tower 3 are obtained C5 and C6 non-aromatic 24 returns aromatization reactor 1, remaining ethane 20, propane 21, C4 and C5 and C6 non-aromatic 22 as recycle stock And knockout tower 3 C5 that obtains and C6 non-aromatic 25 or all ethane 14, propane 15, C4 and C5 and C6 non-aromatic 16 and knockout tower 3 The C5 and C6 non-aromatic 23 for obtaining is used as output of products system.

Separative element of the present invention 4 using the technical scheme of predepropanization process is：Methanol and/or dimethyl ether and recycle Material generates the product based on ethylene, propylene and aromatic hydrocarbons in 1 catalyst neutralisation haptoreaction of aromatization reactor；Aromatisation is anti- The product for answering device 1 to obtain enters chilling tower 2 and cools down；Knockout tower 3 is entered through chilling tower 2 after cooling down, and tower top isolates gaseous hydrocarbon, tower C5 and C6 non-aromatic 23 is isolated at middle part, and bottom of towe is isolated product and enters oil water separator 6, is separated into BTX aromatics 8 and water 9, mixes Aromatic hydrocarbons 8 is closed as output of products system；Gaseous hydrocarbon through compressor 5 pressurization after, enter separative element 4 in depropanizing tower 29, tower The product on top enters domethanizing column 26, hydrocarbon of the carbon number that bottom of towe is isolated higher than 3, i.e. C4 and C5 and C6 non-aromatic 16；Domethanizing column 26 tower tops isolate hydrogen 10, methane 11, and tower bottom product enters dethanizer 27；The C2 products of 27 tower top of dethanizer enter second Alkene rectifying column 28, the carbon number of bottom of towe are higher than 2 hydrocarbon entrance propylene rectification tower 30；28 tower top of ethylene rectifying column isolates ethylene 12, Bottom of towe isolates ethane 14；30 tower top of propylene rectification tower isolates propylene 13, and bottom of towe isolates propane 15；Wherein hydrogen 10, first Alkane 11, ethylene 12, propylene 13 are used as output of products system；Part ethane 17, propane 18, C4 and C5 and C6 non-aromatic 19 and separation The C5 and C6 non-aromatic 24 that tower 3 is obtained as recycle stock return aromatization reactor 1, remaining ethane 20, propane 21, C4 and C5 and C5 that C6 non-aromatic 22 and knockout tower 3 are obtained and C6 non-aromatic 25 or all ethane 14, propane 15, C4 and C5 and C6 non-aromatic 16 and The C5 and C6 non-aromatic 23 that knockout tower 3 is obtained is used as output of products system.

The present invention is by the separation of product during methanol and/or dimethyl ether catalysis conversion reaction and by-product circulation profit With realization improves yield and the selective purpose of ethylene, propylene and aromatic hydrocarbons；By selecting different Reaction conditions ranges, real Existing maximum ethylene and propylene, maximum aromatic hydrocarbons, ethylene, three kinds of operator schemes of propylene and aromatic hydrocarbons coproduction.In addition, methanol and/or Dimethyl ether is reacted in a reactor, and integrated artistic flow process is relatively easy, and cost of investment is low.

Using the technical scheme of order separation process of the present invention, the aromatization reactor is adopted with regenerator Circulating fluid bed reactor；Reaction temperature is 480 DEG C, counts reaction pressure as 0.25 MPa with gauge pressure, and weight space velocity is 0.6 (Grams Per Hour)/gram catalyst；Using Zn-P-ZSM-5 catalyst；Methanol feeds；Ethylene carbon base absorption rate is 14.1 weight %, propylene Carbon base absorption rate is 11.5 weight %, aromatic hydrocarbons carbon base absorption rate is 66.4 weight %, and BTX carbon base absorption rates are 46.5 weight %.

Description of the drawings

Fig. 1 is the schematic flow sheet of technical scheme of the present invention；Fig. 2 is order separation process technical side of the present invention The schematic flow sheet of piece-rate system 4 in case；Fig. 3 is the stream of piece-rate system 4 in front-end deethanization flow technologies scheme of the present invention Journey schematic diagram；Fig. 4 is the schematic flow sheet of piece-rate system 4 in predepropanization process technical scheme of the present invention.

In 1 ~ 4 in figure, 1 is aromatization reactor；2 is chilling tower；3 is knockout tower；4 is separative element；5 is compressor；6 For oil water separator；7 is methanol and/or dimethyl ether；8 is BTX aromatics；9 water obtained for oil water separator；10 is hydrogen；11 For methane；12 is ethylene；13 is propylene；14 is ethane；15 is propane；16 is that C4 and C5 and C6 is non-aromatic；17 are return aromatisation The ethane of reactor；18 is the propane for returning aromatization reactor；19 is non-aromatic for returning the C4 and C5 and C6 of aromatization reactor； 20 is the ethane of output system；21 is the propane of output system；22 is non-aromatic for the C4 and C5 and C6 of output system；23 is C5 and C6 Non-aromatic；24 is non-aromatic for returning the C5 and C6 of aromatization reactor；25 is non-aromatic for the C5 and C6 of output system；26 is domethanizing column； 27 is dethanizer；28 is ethylene rectifying column；29 is depropanizing tower；30 is propylene rectification tower.

In Fig. 1, methanol and/or dimethyl ether and recycle stock are in 1 catalyst neutralisation haptoreaction of aromatization reactor, raw Into the product based on ethylene, propylene and aromatic hydrocarbons；The product that aromatization reactor 1 is obtained enters chilling tower 2 and cools down；Through chilling tower Knockout tower 3 is entered after 2 coolings, and tower top is isolated gaseous hydrocarbon, C5 and C6 non-aromatic 23 is isolated in the middle part of tower, and bottom of towe is isolated product and entered Enter oil water separator 6, be separated into BTX aromatics 8 and water 9, BTX aromatics 8 are used as output of products system；Gaseous hydrocarbon is through compressor 5 After pressurization, separative element 4 is entered；Separative element 4 by product be separated into hydrogen 10, methane 11, ethylene 12, ethane 14, propylene 13, Propane 15, C4 and C5 and C6 non-aromatic 16, wherein hydrogen 10, methane 11, ethylene 12, propylene 13 are used as output of products system；Part The C5 and C6 non-aromatic 24 that ethane 17, propane 18, C4 and C5 and C6 non-aromatic 19 and knockout tower 3 are obtained returns virtue as recycle stock Structure reactor 1, C5 that remaining ethane 20, propane 21, C4 and C5 and C6 non-aromatic 22 and knockout tower 3 are obtained and C6 non-aromatic 25 or C5 that all ethane 14, propane 15, C4 and C5 and C6 non-aromatic 16 and knockout tower 3 are obtained and C6 non-aromatic 23 are used as output of products system System.

Domethanizing column 26 is entered through the product that compressor 5 pressurizes in Fig. 2, tower top isolates hydrogen 10, methane 11, and bottom of towe is produced Thing enters dethanizer 27；The C2 products of 27 tower top of dethanizer enter ethylene rectifying column 28, and the carbon number of bottom of towe is higher than more than 2 Hydrocarbon enters depropanizing tower 29；28 tower top of ethylene rectifying column isolates ethylene 12, and bottom of towe isolates ethane 14；29 tower top of depropanizing tower The C3 for isolating enters propylene rectification tower 30, hydrocarbon of the carbon number that bottom of towe is isolated higher than 3, i.e. C4 and C5 and C6 non-aromatic 16；Propylene 30 tower top of rectifying column isolates propylene 13, and bottom of towe isolates propane 15.

Dethanizer 27 is entered through the product that compressor 5 pressurizes in Fig. 3, the product of tower top enters domethanizing column 26, bottom of towe Product enters depropanizing tower 29；28 tower top of domethanizing column isolates hydrogen 15, methane 16, and tower bottom product enters ethylene rectifying column 28；28 tower top of ethylene rectifying column isolates ethylene 12, and bottom of towe isolates ethane 14；The C3 that 29 tower top of depropanizing tower is isolated is entered Propylene rectification tower 30, hydrocarbon of the carbon number that bottom of towe is isolated higher than 3, i.e. C4 and C5 and C6 non-aromatic 16；30 tower top of propylene rectification tower point Propylene 13 is separated out, bottom of towe isolates propane 15.

Depropanizing tower 29 is entered through the product that compressor 5 pressurizes in Fig. 4, the product of tower top enters domethanizing column 26, bottom of towe Hydrocarbon of the carbon number that isolates higher than 3, i.e. C4 and C5 and C6 non-aromatic 16；26 tower top of domethanizing column isolates hydrogen 10, methane 11, tower Bottom product enters dethanizer 27；The C2 products of 27 tower top of dethanizer enter ethylene rectifying column 28, and the carbon number of bottom of towe is higher than 2 Hydrocarbon enters propylene rectification tower 30；28 tower top of ethylene rectifying column isolates ethylene 12, and bottom of towe isolates ethane 14；Propylene rectification tower 30 Tower top isolates propylene 13, and bottom of towe isolates propane 15.

Below by specific embodiment, the invention will be further elaborated.

Specific embodiment

【Embodiment 1】

Using order separation process technical scheme.

Aromatization reactor adopts circulating fluid bed reactor.The operating procedure of the device includes：（1）Raw material enters aromatization Change in reactor, with regenerated catalyst haptoreaction, generate the product containing low-carbon alkene, reclaimable catalyst is carried through gas-solid Quick disconnector enters settler；（2）Most of catalyst entrance settler that cyclone separator is separated, and gaseous products And part is not entered next stage cyclone separator by the detached catalyst of cyclone separator and is separated again；（3）Gas phase is produced Product enter follow-up separate section through outlet line；（4）In settler reclaimable catalyst after stripping section stripping through to be generated tiltedly Pipe and guiding valve to be generated, enter coke-burning regeneration in regenerator, and the flue gas that coke burning is generated is discharged through regenerator internal cyclone separators System；（5）The catalyst that regeneration is completed is entered.

Reaction condition is：480 DEG C of temperature, 0.3 MPa of reaction pressure in terms of gauge pressure, weight space velocity 2 (Grams Per Hour)/gram urge Agent.With methanol as raw material, using Cu-ZSM-5 catalyst.Return the ethane 17 of aromatization reactor and the ethane of output system 20 mass ratio is 3:7, the mass ratio for returning the propane 21 of the propane 18 and output system of aromatization reactor is 2:8, return The mass ratio of the C4 and C5 and C6 non-aromatic 22 of the C4 and C5 of aromatization reactor and C6 non-aromatic 19 and output system is 9:1, return The mass ratio of the C5 and C6 non-aromatic 25 of the C5 and C6 non-aromatic 24 of aromatization reactor and output system is 8:2

The preparation process of Cu-ZSM-5 catalyst：By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add appropriate Water, HCl, control pH value are not less than 3, and serosity stirs spray shaping at 500 DEG C, and the ZSM-5 for making 60 ~ 300 mesh is urged Agent intermediate.The mass ratio of ZSM-5 molecular sieve and substrate is 4:6；The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25；Substrate is Kaolin and the mixture of aluminium sesquioxide, both mass ratioes are 7:3.By the solution that Cu mass of ion percentage compositions are 5%, Weight ratio with solution and catalyst is as 1.74:1 is impregnated, and dries 5 hours, place into Muffle furnace in 550 DEG C at 120 DEG C Lower roasting is prepared into the Cu-ZSM-5 catalyst that Cu constituent contents are 8 weight % for 6 hours.

【Embodiment 2】

Using the aromatization reactor in front-end deethanization separation process technical scheme and embodiment 1.

Reaction condition is：550 DEG C of temperature, 0.5 MPa of reaction pressure in terms of gauge pressure, weight space velocity 15 (Grams Per Hour)/gram urge Agent.With dimethyl ether as raw material, using Ag-Y-ZSM-23 catalyst.

The preparation process of Ag-Y-ZSM-23 catalyst：Will be mixed for Y molecular sieve, ZSM-23 molecular screen, carrier and binding agent machinery Close, add suitable quantity of water, HCl, control pH value to be not less than 3, serosity stirs spray shaping at 500 DEG C, makes 60 ~ 300 Purpose Y-ZSM-23 catalyst intermediate.The mass ratio of molecular sieve and substrate is 1:9；Y molecular sieve and ZSM-23 molecular screen quality Than for 3:7；The silicoaluminophosphate molecular ratio of Y molecular sieve is 10；The silicoaluminophosphate molecular ratio of ZSM-23 molecular screen is 60；Substrate is Kaolin and three The mixture of Al 2 O, both mass ratioes are 8:2.By the solution that Ag mass of ion percentage compositions are 1%, with solution and urge Agent weight ratio is 0.1:1 is impregnated, and is dried 5 hours at 120 DEG C, is placed into Muffle furnace roasting at 550 DEG C and is made for 6 hours For into the Ag-Y-ZSM-23 catalyst that Ag constituent contents are 0.1 weight %.

【Embodiment 3】

Using the aromatization reactor in predepropanization separation process technical scheme and embodiment 1.

Reaction condition is：400 DEG C of temperature, 0 MPa of reaction pressure in terms of gauge pressure, weight space velocity 0.1 (Grams Per Hour)/gram urge Agent.With dimethyl ether as raw material, using Ga- beta catalysts.

The preparation process of Ga- beta catalysts：By beta-molecular sieve, carrier and binding agent mechanical mixture, suitable quantity of water, HCl, control is added PH value processed is not less than 4, and serosity stirs spray shaping at 500 DEG C, makes the beta catalyst intermediate of 60 ~ 300 mesh.β point The mass ratio of son sieve and substrate is 5:5；The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20；Substrate is Kaolin, silicon dioxide and three oxidations The mixture of two aluminum, the mass ratio of three is 7:1:2.By the solution that Ga mass of ion percentage compositions are 2%, with solution and catalysis Agent weight ratio is 0.4:1 is impregnated, and is dried 5 hours at 120 DEG C, is placed into Muffle furnace roasting at 550 DEG C and is prepared for 6 hours Into the Ga- beta catalysts that Ga constituent contents are 0.8 weight %.

【Embodiment 4】

Using order separation process technical scheme.

Aromatization reactor is fixed bed reactors.Beds are located in the middle part of reactor, and reaction raw materials are from top to bottom Enter and reacted in reactor.

Reaction condition is：500 DEG C of temperature, 0.25 MPa of reaction pressure in terms of gauge pressure, weight space velocity 1 (Grams Per Hour)/gram urge Agent.With methanol as raw material, using Mn-ZSM-11 catalyst.

The preparation process of Mn-ZSM-11 catalyst：By ZSM-11 molecular sieves, carrier and binding agent mechanical mixture, add suitable Amount water, HCl, control pH value are not less than 3, and serosity stirs spray shaping at 500 DEG C, makes the ZSM-11 of 60 ~ 300 mesh Catalyst intermediate.The mass ratio of ZSM-11 molecular sieves and substrate is 3:7；The silicoaluminophosphate molecular ratio of ZSM-11 molecular sieves is 50；Base Matter is the mixture of Kaolin and aluminium sesquioxide, and both mass ratioes are 7:3.It is 10% by Mn mass of ion percentage compositions Solution, the weight ratio with solution and catalyst is as 1:1 is impregnated, and dries 5 hours, place into Muffle furnace in 550 at 120 DEG C At DEG C, roasting is prepared into the Mn-ZSM-11 catalyst that Mn constituent contents are 9.09 weight % for 6 hours.

【Embodiment 5】

Using the aromatization reactor in front-end deethanization separation process technical scheme and embodiment 1.

Reaction condition is：480 DEG C of temperature, 0.25 MPa of reaction pressure in terms of gauge pressure, weight space velocity 0.6 (Grams Per Hour)/gram Catalyst.With methanol as raw material, using Zn-P-ZSM-5 catalyst.

The preparation process of Zn-P-ZSM-5 catalyst：By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add suitable Amount water, H₃PO₄, control pH value is not less than 3, and serosity stirs spray shaping at 500 DEG C, makes the P- of 60 ~ 300 mesh ZSM-5 catalyst intermediates.H₃PO₄The concentration of solution is 1.53 for the weight ratio of 1 weight %, solution and molecular sieve:1.ZSM-5 point The mass ratio of son sieve and substrate is 3.5:6.5；The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25；Substrate is Kaolin and three oxidations The mixture of two aluminum, both mass ratioes are 7:3.By the solution that Zn mass of ion percentage compositions are 5%, with solution and P-ZSM-5 Catalyst weight ratio is 0.6:1 is impregnated, and dries 5 hours, place into Muffle furnace roasting 6 at 550 DEG C little at 120 DEG C When, Zn constituent contents are prepared into for 2.87 weight %, P element content is the Zn-P-ZSM-5 catalyst of 1.48 weight %.

【Embodiment 6】

Using the aromatization reactor in predepropanization separation process technical scheme and embodiment 4.

Reaction condition is：470 DEG C of temperature, 0.4 MPa of reaction pressure in terms of gauge pressure, weight space velocity 5 (Grams Per Hour)/gram urge Agent.With methanol as raw material, using ZSM-5- beta catalysts.

The preparation process of ZSM-5- beta catalysts：By ZSM-5 molecular sieve, beta-molecular sieve, carrier and binding agent mechanical mixture, plus Enter suitable quantity of water, HCl, control pH value is not less than 3, serosity stirs spray shaping at 500 DEG C, makes 60 ~ 300 purposes ZSM-5- beta catalysts.The mass ratio of ZSM-5 and beta-molecular sieve and substrate is 3.5: 6.5.The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 38；The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20；The mass ratio of ZSM-5 and beta-molecular sieve is 9:1.Substrate is Kaolin, silicon dioxide With the mixture of aluminium sesquioxide, the mass ratio of three is 5:2:3.

【Embodiment 7】

Using the aromatization reactor in order separation process technical scheme and embodiment 1.

Reaction condition is：500 DEG C of temperature, 0.3 MPa of reaction pressure in terms of gauge pressure, weight space velocity 3 (Grams Per Hour)/gram urge Agent.With methanol as raw material, using Zn-Ag-P-ZSM-5 catalyst.

The preparation process of Zn-Ag-P-ZSM-5 catalyst：By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add Suitable quantity of water, H₃PO₄, control pH value is not less than 3, and serosity stirs spray shaping at 500 DEG C, makes the P- of 60 ~ 300 mesh ZSM-5 catalyst intermediates.H₃PO₄The concentration of solution is 2 for the weight ratio of 2.5 weight %, solution and molecular sieve:1.ZSM-5 point The mass ratio of son sieve and substrate is 3.5:6.5；The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 28；Substrate is Kaolin and three oxidations The mixture of two aluminum, both mass ratioes are 8:2.It is that 1%, Zn mass of ion percentage compositions are by Ag mass of ions percentage composition 3% solution, with solution and P-ZSM-5 catalyst weights ratio as 0.8:1 is impregnated, and dries 5 hours, place at 120 DEG C Muffle furnace roasting 6 hours at 550 DEG C, are prepared into Zn constituent contents for 2.32 weight %, and Ag constituent contents are 0.78 weight %, P Constituent content is the Zn-Ag-P-ZSM-5 catalyst of 1.51 weight %.

【Embodiment 8】

Using the aromatization reactor in front-end deethanization separation process technical scheme and embodiment 1.

Reaction condition is：470 DEG C of temperature, 0.25 MPa of reaction pressure in terms of gauge pressure, weight space velocity 0.5 (Grams Per Hour)/gram Catalyst.With methanol as raw material, using Zn-Mg-P-ZSM-5 catalyst.

The preparation process of Zn-Mg-P-ZSM-5 catalyst：By ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, add Suitable quantity of water, H₃PO₄, control pH value is not less than 3, and serosity stirs spray shaping at 500 DEG C, makes the P- of 60 ~ 300 mesh ZSM-5 catalyst intermediates.H₃PO₄The concentration of solution is 2 for the weight ratio of 4 weight %, solution and molecular sieve:1.ZSM-5 molecules The mass ratio of sieve and substrate is 3:7；The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 32；Substrate is Kaolin and aluminium sesquioxide Mixture, both mass ratioes are 7:3.By Mg mass of ion percentage compositions be 2%, Zn mass of ion percentage compositions be 3% molten Liquid, with solution and P-ZSM-5 catalyst weights ratio as 1:1 is impregnated, at 120 DEG C dry 5 hours, place into Muffle furnace in Roasting 6 hours at 550 DEG C, are prepared into Zn constituent contents for 2.86 weight %, and Mg constituent contents are 1.9 weight %, and P element content is The Zn-Mg-P-ZSM-5 catalyst of 2.35 weight %.

Table 1

	Yield of ethene, weight %	Propene yield, weight %	Aromatics yield, weight %
				Embodiment 1	13.3	10.4	64.9
Embodiment 2	18.6	12.2	60.7
				Embodiment 3	9.2	15.4	56.9
Embodiment 4	15.0	10.2	63.4
				Embodiment 5	14.1	11.5	66.4
Embodiment 6	14.8	16.5	60.1
				Embodiment 7	15.7	13.1	62.6
Embodiment 8	14.4	12.7	65.3

Claims (9)

1. a kind of methanol and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, are turned using methanol and/or dimethyl ether Change aromatic hydrocarbons coproduction ethylene processed, the system of propylene, described method includes following step：

A) methanol and/or dimethyl ether and recycle stock are generated in aromatization reactor (1) catalyst neutralisation haptoreaction with second Product based on alkene, propylene and aromatic hydrocarbons；

B) product that aromatization reactor (1) is obtained enters chilling tower (2) cooling；

C) knockout tower (3) is entered after chilling tower (2) cooling, tower top is isolated gaseous hydrocarbon, isolates C5 and C6 is non-aromatic in the middle part of tower (23), bottom of towe is isolated product and enters oil water separator (6), is separated into BTX aromatics (8) and water (9), BTX aromatics (8) conduct Output of products system；

D), after gaseous hydrocarbon is through compressor (5) pressurization, separative element (4) is entered；

E) separative element (4) by product be separated into hydrogen (10), methane (11), ethylene (12), ethane (14), propylene (13), third Alkane (15), C4 and C5 and C6 non-aromatic (16), wherein hydrogen (10), methane (11), ethylene (12), propylene (13) are used as output of products System；

F) C5 and C6 that part ethane (17), propane (18), C4 and C5 and C6 non-aromatic (19) and knockout tower (3) are obtained is non-aromatic (24) aromatization reactor (1), remaining ethane (20), propane (21), C4 and C5 and C6 non-aromatic (22) are returned as recycle stock And knockout tower (3) C5 that obtains and C6 non-aromatic (25) or all ethane (14), propane (15), C4 and C5 and C6 non-aromatic (16) with And knockout tower (3) C5 that obtains and C6 non-aromatic (23) are used as output of products system；

Wherein, the system includes aromatization reactor (1), chilling tower (2), knockout tower (3), separative element (4), and aromatisation is anti- The product for answering device (1) to generate sequentially enters chilling tower (2) and knockout tower (3), and the gaseous products that knockout tower (3) is obtained are through compressor (5) enter separative element (4), part C5 and C6 non-aromatic (24) that knockout tower (3) and separative element (4) are obtained, ethane (17), third Alkane (18), C4 and C5 and C6 non-aromatic (19) return aromatization reactor (1) as recycle stock.

2. method according to claim 1, it is characterised in that the system includes：Methanol and/or dimethyl ether and circulation Material is converted into the product based on ethylene, propylene and aromatic hydrocarbons in aromatization reactor (1)；Aromatization reactor (1) is generated Product cooling in chilling tower (2)；Chilling tower (2) product out is separated into water, gaseous hydrocarbon, C5 and C6 in knockout tower (3) Non-aromatic, BTX aromatics；Gaseous hydrocarbon is separated into hydrogen, methane, ethylene, ethane, propylene, propane, C4 and C5 in separative element (4) Non-aromatic with C6.

3. methanol according to claim 1 and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, its feature It is, aromatization reactor (1) is using fixed bed reactors, moving-burden bed reactor, fluidized-bed reactor or following with regenerator Circulation fluidized bed reactor；The reaction temperature of aromatization reactor (1) is 400～550 DEG C, counts reaction pressure as 0～0.5 with gauge pressure MPa, weight space velocity is 0.1～15 (Grams Per Hour)/gram catalyst.

4. methanol according to claim 1 and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, its feature It is, the active component of catalyst is ZSM-5, ZSM-23, ZSM-11, β zeolite, Y zeolite or the compound molecule for being formed each other Sieve；Carrier is Kaolin, aluminium oxide, silicon dioxide；The mass ratio of active component and carrier is (10～50): (50～90)；Urge Agent is loaded with one or more element or oxide in Zn, Ag, P, Ga, Cu, Mn, Mg, in terms of the mass percent of catalyst, Its content is 0.01～15 weight %.

5. methanol according to claim 1 and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, its feature It is, the raw material of aromatization reactor (1) can be the mixture of methanol or dimethyl ether or both, and in raw material, the quality percentage of water contains Measure as 0～30 weight %.

6. methanol according to claim 1 and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, its feature It is, the system of separative element (4) includes domethanizing column (26), dethanizer (27), ethylene rectifying column (28), depropanizing tower (29), propylene rectification tower (30)；Domethanizing column (26) tower top isolates hydrogen (10), methane (11)；Ethylene rectifying column (28) tower Ethylene (12) is isolated on top, and bottom of towe isolates ethane (14)；Propylene rectification tower (30) tower top isolates propylene (13), and bottom of towe is separated Go out propane (15)；Depropanizing tower (29) bottom of towe isolates C4 and C5 and C6 non-aromatic (16).

7. methanol according to claim 6 and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, its feature It is, the separation method in separative element (4) includes following step：

A) domethanizing column (26) is entered through the product that compressor (5) compresses, tower top isolates hydrogen (10), methane (11), bottom of towe Product enters dethanizer (27)；

B) the C2 products of dethanizer (27) tower top enter ethylene rectifying column (28), and the carbon number of bottom of towe is higher than more than 2 hydrocarbon entrance Depropanizing tower (29)；

C) ethylene rectifying column (28) tower top isolates ethylene (12), and bottom of towe isolates ethane (14)；

D) C3 that depropanizing tower (29) tower top is isolated enters propylene rectification tower (30), and the carbon number that bottom of towe is isolated is higher than 3 hydrocarbon, That is C4 and C5 and C6 non-aromatic (16)；

E) propylene rectification tower (30) tower top isolates propylene (13), and bottom of towe isolates propane (15).

8. methanol according to claim 6 and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, its feature It is, the separation method in separative element (4) includes following step：

A) dethanizer (27) is entered through the product that compressor (5) compresses, the product of tower top enters domethanizing column (26), and bottom of towe is produced Product enter depropanizing tower (29)；

B) domethanizing column (28) tower top isolates hydrogen (15), methane (16), and tower bottom product enters ethylene rectifying column (28)；

C) ethylene rectifying column (28) tower top isolates ethylene (12), and bottom of towe isolates ethane (14)；

D) C3 that depropanizing tower (29) tower top is isolated enters propylene rectification tower (30), and the carbon number that bottom of towe is isolated is higher than 3 hydrocarbon, That is C4 and C5 and C6 non-aromatic (16)；

E) propylene rectification tower (30) tower top isolates propylene (13), and bottom of towe isolates propane (15).

9. methanol according to claim 6 and/or dimethyl ether conversion aromatic hydrocarbons coproduction ethylene, the method for propylene, its feature It is, the separation method in separative element (4) includes following step：

A) depropanizing tower (29) is entered through the product that compressor (5) compresses, the product of tower top enters domethanizing column (26), bottom of towe point Hydrocarbon of the carbon number for separating out higher than 3, i.e. C4 and C5 and C6 non-aromatic (16)；

B) domethanizing column (26) tower top isolates hydrogen (10), methane (11), and tower bottom product enters dethanizer (27)；

C) the C2 products of dethanizer (27) tower top enter ethylene rectifying column (28), and the carbon number of bottom of towe is higher than 2 hydrocarbon entrance propylene Rectifying column (30)；

D) ethylene rectifying column (28) tower top isolates ethylene (12), and bottom of towe isolates ethane (14)；

E) propylene rectification tower (30) tower top isolates propylene (13), and bottom of towe isolates propane (15).