CN105693447B - A kind of method and apparatus of methanol production aromatic hydrocarbons and by-product MTBE - Google Patents
A kind of method and apparatus of methanol production aromatic hydrocarbons and by-product MTBE Download PDFInfo
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Abstract
The invention provides methanol production aromatic hydrocarbons and by-product MTBE method to include：Methanol oxidation aromatisation obtains primary product, and primary product refrigerated separation is obtained into one-level gas phase and one-level oil phase；One-level gas phase is reacted to obtain MTBE and tail gas product with methanol, and MTBE is directly collected, and tail gas product catalytic aromatization obtains secondary products, and secondary products refrigerated separation obtains secondary gas phase and two level oil phase；One-level oil phase merges collection with two level oil phase, and secondary gas phase is expelled directly out carrying out vent gas treatment recovery.Additionally provide supporting equipment, including one-level aromatization reactor, aromatization of methanol product separator, MTBE reactors, two level aromatization reactor, one-level gas phase pipeline, one-level oil phase pipeline, tail gas product pipeline, secondary gas phase pipeline, two level oil phase pipeline.The method reaction condition of the embodiment of the present invention is gentle, by utilizing the yield and selectivity that improve target product low-carbon aromatic hydrocarbons to the effective of accessory substance.
Description
Technical field
The present invention relates to methanol production low-carbon aromatic hydrocarbons field, in particular to a kind of methanol production aromatic hydrocarbons and by-product
MTBE method and apparatus.
Background technology
Low-carbon aromatic hydrocarbons mainly includes benzene,toluene,xylene, and general abbreviation BTX is important basic chemical industry raw material, wherein right
Dimethylbenzene (PX) accounts for 45% or so of BTX total quantity consumeds, and industrial aromatics production about 95% or so comes from petrochemical industry, on a small quantity
From coal tar processing, about 14,200,000 tons of China's BTX yield in 2010, Apparent con- sumption is up to 19,000,000 tons, insufficiency of supply-demand about 480
Ten thousand tons, wherein the PX degrees of self-sufficiency only 61.6%, 3,320,000 tons of net importation.In order to fill up the breach in aromatic hydrocarbons market, aromatic hydrocarbons is reduced to oil
The dependence of resource, it from resourceful coal resources conversion for preparing arene, can not only alleviate the shortage of aromatic hydrocarbon resource, improve coal
The added value of downstream product, extend Chemical Industry chain, there is important value.In view of the growing aromatic hydrocarbons in China needs at present
Ask and increasingly the coal-based methanol of production capacity surplus the problems such as, the exploitation for actively developing coal-based methanol aromatic hydrocarbons technology not only alleviates city
An achievable road have found to the demand of low-carbon aromatic hydrocarbons, the also comprehensive utilization for coal-based methanol.
Methanol aromatic hydrocarbons theory appears in the MTG technologies of Mobil companies exploitation earliest, and the 1970s, Mobil was public
Department develops ZSM-5 zeolite molecular sieve, and high-knock rating gasoline can be effectively converted methanol into using this zeolite molecular sieve, its
Middle arene content is more than 35%.The subsequent Mobil companies patent USP4590321 in U. S. application, discloses methanol aromatic hydrocarbons
Experimental result, the patent introduction use the ZSM-5 zeolite molecular sieve that P is modified as catalyst, P content 2.7wt%, reaction temperature
Between 400-450 DEG C, methanol Feed space velocities are 1.3h-1, the ZSM-5 molecular sieve catalyst that experimental result display P is modified is in height
Level hydrocarbon, it is well more many than unmodified ZSM-5 molecular sieve in the selectivity of aromatic hydrocarbons, but arene content is not very high.Then,
Mobil companies have applied for United States Patent (USP) USP4686312 again, disclose and the low-carbon oxygen-containing compound such as methanol is converted into rich in virtue
The multistage reaction process of the product of hydrocarbon.Low-carbon alkanes and alkene are converted into first paragraph methanol, subsequently enter second segment reactor,
Aromatization further occurs in the presence of catalyst, obtains the product rich in low-carbon aromatic hydrocarbons.
At present, the country has a lot of scientific research institutions all in exploitation MTA catalysis and its technology, wherein Chinese Academy of Sciences Shanxi coalification
The fixed bed methanol aromatic hydrocarbons technology cooperated with Sai Ding engineering companies, the recirculating fluidized bed methanol aromatic hydrocarbons of Tsing-Hua University
(FMTA) technology is all being actively pushed forward the pilot scale stage, and Henan research institute of coalification group is with Beijing University of Chemical Technology also in cooperation development first
Alcohol aromatic hydrocarbons technology.
Shanxi coalification patent CN1880288A disclose a kind of process of methanol conversion for preparing arene and catalyst and catalysis
Agent preparation method, modified ZSM-5 is used as catalyst, two sections of fixed bed reactors, operating pressure 0.1-5.0Mpa, operation
Temperature is 300-460 DEG C, and raw material liq air speed is 0.1-6.0h-1Under the conditions of be catalytically conveted to product based on aromatic hydrocarbons.Use
Ga, La be modified ZSM-5 molecular sieve with small crystal grains be catalyst, wherein the main function of second segment reactor is first paragraph reactor
The aromatisation of caused non-aromatic and lower carbon number hydrocarbons again, oil phase yield are more than 40%, and wherein arene content is more than 80%, have total virtue
The advantages of hydrocarbon-selective is high, and technological operation is flexible.A kind of continuous aromatization is disclosed in Tsing-Hua University patent CN101244969A
With the devices and methods therefor of catalyst regeneration, aromatic hydrocarbons is converted methanol into using fluidization, having can regulating catalyst work
Property and selectivity, can make reaction operate continuously and it is not parking.Tianji Coal Chemical Industry Group Co., Ltd.'s patent
A kind of preparation side for the technique and its catalyst for improving aromatization of methanol preparing aromatic hydrocarbon selectivity is disclosed in CN101550051A
Method, the patent is using methanol as raw material, and with the Ga of various concentrations, Zn, Cu, the composite modified HZSM-5 molecular sieves of Ag isoreactivity ions are urged
Agent, catalysis methanol aromatization, using fixed bed continuity method or floating bed continuity method, reaction pressure 0.1-3.5Mpa,
380-500 DEG C of reaction temperature, raw material liq air speed are 0.1-10.0h-1, the advantage is that using hybrid ionic modified ZSM-5 point
Son sieve.China National Offshore Oil Corporation patent CN101602646A disclose a kind of methanol/dimethyl ether production aromatic hydrocarbons method and
Its special reaction device, described reaction unit is the fluid bed of successive reaction regeneration, the methanol in the method that the patent provides
Conversion ratio is more than 80%, and arene content is in 50-60wt% in product.CN101823929A discloses a kind of methanol or dimethyl ether and turned
Change the system and technique of preparing aromatic hydrocarbon, material benzenemethanol or dimethyl ether are reacted in aromatization reactor first, reacted
Product is after separation, hydrogen, methane, mixing C8Aromatic hydrocarbons and part C9 +Aromatic hydrocarbons is as output of products, and C2 +Non-aromatics and except mixed
Close C8Aromatic hydrocarbons and part C9 +Aromatic hydrocarbons outside aromatic hydrocarbons then returns to corresponding reactor as circulation logistics and carries out further aromatization
Change reaction, it is possible to achieve the accessory substance in aromatization of methanol is recycled, improves the yield and selectivity of aromatic hydrocarbons, and work
Skill is flexible, can be according to market demand variation targets product at any time.Above technology is improving methanol conversion and catalyst modification
Aspect has good research, but without reference to the research in terms of the recycling of byproduct of reaction, the selection of overall aromatics
Property is not very high, generally maintains 40-60% or so.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of methanol production aromatic hydrocarbons and by-product MTBE method, methods described carry
Go out and thoroughly solve the technical problem appeared above, reaction condition is gentle, by improving target to effective utilize of accessory substance
The yield and selectivity of product low-carbon aromatic hydrocarbons, and a certain amount of MTBE of by-product is gone back, create certain economic benefit.
The second object of the present invention is to provide a kind of equipment for preparing methanol production MTBE simultaneously used in by-product MTBE, described
Each component of equipment is usual means, and source is wide, and floor space is small, and equipment investment is few, easy to operate and green non-pollution etc.
Advantage.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
The embodiments of the invention provide a kind of method of methanol production aromatic hydrocarbons and by-product MTBE, comprise the following steps：(A) first
Alcohol catalysis aromatisation obtains primary product, and the primary product refrigerated separation is obtained into one-level gas phase and one-level oil phase；(B) one-level
Gas phase is reacted to obtain MTBE and tail gas product with methanol, and the MTBE is directly collected, and the tail gas product catalytic aromatization obtains
Secondary products, the secondary products refrigerated separation obtain secondary gas phase and two level oil phase；(C) one-level oil phase merges with two level oil phase
Collect, secondary gas phase is expelled directly out carrying out vent gas treatment recovery.
In the prior art, the technology of methanol production aromatic hydrocarbons is highly developed, with Mobil companies exploitation the 1970s
MTG technologies be the beginning, the research history for also having decades, in order to improve the conversion ratio of methanol, improve aromatic hydrocarbons selectivity with
And yield, reactor, reaction condition, catalyst and the various conditional parameters closely bound up with reaction are optimized, still
The focus of research is only limited in the index of raw material and target product, in the application for not relating to byproduct of reaction.Ability
Domain personnel know to generate with the non-aromatic material of some low-carbons during methanol aromatization, and this is also Main By product, but
It is that accessory substance is not used well for existing process, causes the waste of resource, the present invention is in order to fill up this technology
Blank, a kind of method of methanol production aromatic hydrocarbons and by-product MTBE and supporting process equipment are developed, exactly well will be this
Non-aromatic accessory substance simultaneously realizes recycling, has not only produced valuable chemical products, additionally creates certain economic effect
Benefit, it is thus also avoided that the wasting of resources.
Wherein, the one-level gas-phase product of methanol oxidation aromatisation typically can directly carry out Secondary aromatization to improve product virtue
The selectivity of hydrocarbon, but one-level gas phase is not carried out aromatization again directly by the present invention, but first given birth to methanol feedstock
MTBE is produced, then goes aromatisation using producing the tail gas after MTBE, this not only increases the selectivity of aromatic hydrocarbons, moreover it is possible to reaches secondary
Produce the purpose of valuable chemical products, the design of this process route is in the prior art that still category is pioneering from being not directed to.
In order to improve the selectivity of aromatic hydrocarbons, yield, the one-level oil phase obtained in step of the invention (A) is further separated into non-aromatics and mixed
Compound and low-carbon BTX aromatics, low-carbon BTX aromatics are directly collected, non-aromatic hydrocarbon mixture enter step (B) in tail gas product
Mixing, that is to say, that the non-aromatic material in oil phase is further used, not only make it that oil phase is purer, improves pure virtue
The content of hydrocarbon, moreover it is possible to which non-aromatic material is further utilized into the overall selectivity and total recovery for improving follow-up aromatic hydrocarbons.Likewise, step
(B) the two level oil phase obtained in also mixes with primary oil is further separated into non-aromatic hydrocarbon mixture and low-carbon BTX aromatics,
One-level oil phase with non-aromatic material contained in two level oil phase rationally effectively use to realize.The technique of the present invention
Can not only by-product MTBE, the selectivity of overall aromatics may also reach up 85% or so, compare for universal virtue in the prior art
Hydrocarbon-selective rests on 50-60%, and highest also can only achieve 80%.
It can be seen that it is simple two sections of aromatizations step in the past that inventor has abandoned when planning whole process route
Suddenly, although conventional two-stage process has totally improved the selectivity of aromatic hydrocarbons compared with a segment process, it is again without by oil
Non-aromatic material in phase sufficiently uses, and the primary raw material for synthesizing MTBE in addition is isobutene and methanol, and just fragrant
Due to that containing the low-carbon hydrocarbon materials such as isobutene, can be synthesized, synthesized as MTBE raw material in gas phase after structureization reaction
Major part or C in MTBE tail gas3-C4Material, so enter after two sections of aromatizations the low-carbon that can equally obtain in high yield
Aromatic hydrocarbons, the selectivity of aromatic hydrocarbons is also improved, be to kill two birds with one stone.This process route of the present invention is that inventor passes through largely in fact
Trample and grope what is obtained, improve MTBE added value, provide a kind of novel synthesis mode for MTBE production, be advantageous to
Widely research in terms of MTBE synthesis.
In addition, the optimization of operating condition of the present invention is：In step (A), methanol is with air speed 0.5-3h-1, temperature 300-450
Catalytic aromatization is carried out under conditions of DEG C, catalyst is to be urged with the modified ZSM-5 of the one or more in Zn, P, Ag, Ga element
Agent, in step (B), the tail gas product is with air speed 0.5-5h-1, temperature be 300-450 DEG C under conditions of carry out catalysis aromatization
Change, catalyst be with the modified ZSM-5 catalyst of the one or more in Zn, P, Ag, Ga element, first time aromatization of methanol with
Catalyst used in second of aromatization of low carbon hydrocarbon is preferably selected ZSM-5 molecular sieve, and using one in Zn, P, Ag, Ga element
Kind or it is several be modified, this catalyst best results, pass through metallic element introducing improve molecular sieve aromatisation
The stability of activity, enhancing molecular sieve, and have adjusted the Acidity of molecular sieve.Wherein, it is element modified using Zn, P, Ag, Ga
ZSM-5 catalyst, each metallic element, which preferably matches, is：Zn accounts for the 1-6% of total catalyst weight,；P accounts for total catalyst weight
2-10%, Ag account for the 1-4% of total catalyst weight, and Ga accounts for the 0.5-5% of total catalyst weight.It is more excellent to account for overall catalyst weight for Zn
The 2-4% of amount,；P accounts for the 3-6% of total catalyst weight, and Ag accounts for the 2-3% of total catalyst weight, and Ga accounts for total catalyst weight
2-4%.Reactions steps, by methanol preparing aromatic hydrocarbon, can make the overall selectivity of aromatic hydrocarbons increase, enter by using two-stage process
The conditional parameter such as doses and temperature has strict control, operates more standardized.
A kind of method of the embodiment of the present invention except providing methanol production aromatic hydrocarbons and by-product MTBE, is additionally provided matched
Equipment, including：One-level aromatization reactor, aromatization of methanol product separator, MTBE reactors, two level aromatization
Device, one-level gas phase pipeline, one-level oil phase pipeline, tail gas product pipeline, secondary gas phase pipeline, two level oil phase pipeline；
The one-level aromatization reactor is connected with the sidepiece of aromatization of methanol product separator by pipeline, methanol aromatization
The top for changing product separator is connected by one-level gas phase pipeline with the sidepiece of MTBE reactors, the two level aromatization reactor
Sidepiece be connected by sidepiece of the tail gas product pipeline also with the MTBE reactors, the one-level oil phase pipeline is arranged at described
The bottom of aromatization of methanol product separator, the secondary gas phase pipeline, the two level oil phase pipeline are respectively arranged at described two
The top and bottom of level aromatization reactor.
Further, in addition to Aromatics Extractive Project device, low-carbon BTX aromatics conveyance conduit, non-aromatic hydrocarbon mixture conveyance conduit；
The non-aromatic hydrocarbon mixture conveyance conduit is arranged at the top of the Aromatics Extractive Project device and connects the side of two level aromatization reactor
Portion, the one-level oil phase pipeline are connected with the sidepiece of the Aromatics Extractive Project device, and the low-carbon BTX aromatics conveyance conduit is arranged at
The bottom of the Aromatics Extractive Project device.
Further, the two level oil phase pipeline is connected with the sidepiece of the Aromatics Extractive Project device.
Each component of the equipment provided in an embodiment of the present invention is usual means, and source is wide, and floor space is small, equipment
Small investment, easy to operate and green non-pollution, reactor used can be fixed bed reactors, moving-burden bed reactor or fluid bed
Reactor, it is adjusted according to being actually needed.Each part belongs to common chemical mechanical equipment in equipment, can be obtained by commercially available
, preparation method realizes the pollution-free operation of pure green, the mouth of pipe and pipeline connection and reasonable arrangement, and the achievable Automated condtrol of whole process need not
People guards, and saves manpower, reduces cost of investment, and Automated condtrol can take PLC, DCS system to be controlled.
Compared with prior art, beneficial effects of the present invention are as follows：
(1) methanol production aromatic hydrocarbons of the invention and by-product MTBE method, by being improved to effective utilize of accessory substance
The yield and selectivity of target product low-carbon aromatic hydrocarbons, and a certain amount of MTBE of by-product is gone back, create certain economic benefit；
(2) reaction condition of the invention is gentle, easy to operate, after the creative non-aromatic material by oil phase extracts
It is used, not only increases the purity of aromatic hydrocarbon substance, and reliable utilization ways have been found for non-aromatic material so that this hair
Bright technique can not only by-product MTBE, the selectivity of overall aromatics can reach 85% or so, but universal in the prior art
Arenes selectivity also can only achieve 80% in 50-60%, highest；
(3) the whole preparation method Process Route Planning of the present invention is reasonable, and technological process short operation is convenient, save operation into
This and human cost, each part of supporting process equipment belong to common chemical mechanical equipment, can be accounted for by commercially available acquisition
Ground area is small, and equipment investment is few, easy to operate and green non-pollution.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described.
Fig. 1 is the methanol production aromatic hydrocarbons of the embodiment of the present invention one and by-product MTBE equipment structure chart；
Fig. 2 is the methanol production aromatic hydrocarbons of the embodiment of the present invention two and by-product MTBE equipment structure chart；
Fig. 3 is the methanol production aromatic hydrocarbons of the embodiment of the present invention three and by-product MTBE equipment structure chart；
Reference：
101- one-level aromatization reactors；102- aromatization of methanol product separators；
103-MTBE reactors；104- two level aromatization reactors；
105- one-level gas phase pipelines；106- one-level oil phase pipelines；
107- tail gas product pipelines；108- secondary gas phase pipelines；
109- two level oil phase pipelines；110- Aromatics Extractive Project devices；
111- non-aromatics conveyance conduits；112- low-carbon BTX aromatics conveyance conduits.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
Methanol is with air speed 0.5-3.0h-1, temperature be 300-450 DEG C, normal pressure, in one-level aromatization under catalyst action
Aromatisation is carried out in device 101, catalyst is the ZSM-5 catalyst being modified with Zn, P, Ag, Ga, and wherein ZSM-5 silica alumina ratio exists
36-100, the product of aromatisation, which enters in aromatization of methanol product separator 102, to be separated, and obtains one-level oil-phase product, and one
Level gas phase separation gas and water, water are expelled directly out device, and primary oil is mutually discharged by primary oil phase pipeline 106 and collected, one-level
Gas phase enters MTBE reactors 103 by one-level gas phase pipeline 105, and the MTBE of reaction generation is fed as product with MTBE methanol
Discharger, tail gas product enter two level aromatization reactor 104 by tail gas product pipeline 107, in ZSM-5 points that Zn is modified
Under sub- sieve catalyst effect, 300-450 DEG C of reaction temperature, Feed space velocities 0.5-5.0h-1Reaction condition under, react generation
Secondary gas phase dry gas product passes through the carrying device of secondary gas phase pipeline 108, a part of carrying devices of LPG of generation, and a part is made
Two level aromatization reactor 104 is returned for freshening gas and enters aromatization of low carbon hydrocarbon unit, and two level oil phase passes through two level oil phase pipeline
109 discharges are collected, and specific equipment structure chart is as shown in Figure 1.
Embodiment 2
Methanol is with air speed 0.5-3.0h-1, temperature be 300-450 DEG C, normal pressure, in one-level aromatization under catalyst action
Aromatisation is carried out in device 101, catalyst is the ZSM-5 catalyst being modified with Zn, P, Ag, Ga, and wherein ZSM-5 silica alumina ratio exists
36-100, the product of aromatisation, which enters in aromatization of methanol product separator 102, to be separated, and obtains one-level oil-phase product, and one
Level gas phase separation gas and water, water are expelled directly out device, and primary oil mutually enters Aromatics Extractive Project device by primary oil phase pipeline 106
110 carry out Aromatics Extractive Project, and oil-phase product is separated into non-aromatic hydrocarbon mixture and low-carbon BTX aromatics, low-carbon mixing virtue after extracting
Hydrocarbon is discharged by low-carbon BTX aromatics conveyance conduit 112, and non-aromatic hydrocarbon mixture enters two level virtue by non-aromatics conveyance conduit 111
In structure reactor 104, one-level gas phase enters MTBE reactors 103 by one-level gas phase pipeline 105, anti-with the charging of MTBE methanol
The MTBE that should be generated enters two level aromatization reactor as product discharger, tail gas product by tail gas product pipeline 107
104, using under the element modified ZSM-5 molecular sieve catalyst action of Zn, P, Ag, Ga, wherein Zn accounts for the 1- of total catalyst weight
6%, P account for the 2-10% of total catalyst weight, and Ag accounts for the 1-4% of total catalyst weight, and Ga accounts for the 0.5- of total catalyst weight
5%, 300-450 DEG C of reaction temperature, Feed space velocities 0.5-5.0h-1Reaction condition under, react the secondary gas phase dry gas of generation
Product passes through the carrying device of secondary gas phase pipeline 108, a part of carrying devices of LPG of generation, and a part returns as freshening gas
Two level aromatization reactor 104 enters aromatization of low carbon hydrocarbon unit, and two level oil phase is collected by the discharge of two level oil phase pipeline 109,
Specific equipment structure chart is as shown in Figure 2.
Embodiment 3
Methanol is with air speed 0.5-3.0h-1, temperature be 300-450 DEG C, normal pressure, in one-level aromatization under catalyst action
Aromatisation is carried out in device 101, catalyst is the ZSM-5 catalyst being modified with Zn, P, Ag, Ga, and wherein ZSM-5 silica alumina ratio exists
36-100, the product of aromatisation, which enters in aromatization of methanol product separator 102, to be separated, and obtains one-level oil-phase product, and one
Level gas phase separation gas and water, water are expelled directly out device, and primary oil mutually enters Aromatics Extractive Project device by primary oil phase pipeline 106
110 carry out Aromatics Extractive Project, and oil-phase product is separated into non-aromatic hydrocarbon mixture and low-carbon BTX aromatics, low-carbon mixing virtue after extracting
Hydrocarbon is discharged by low-carbon BTX aromatics conveyance conduit 112, and non-aromatic hydrocarbon mixture enters two level virtue by non-aromatics conveyance conduit 111
In structure reactor 104, one-level gas phase enters MTBE reactors 103 by one-level gas phase pipeline 105, anti-with the charging of MTBE methanol
The MTBE that should be generated enters two level aromatization reactor as product discharger, tail gas product by tail gas product pipeline 107
104, using under the element modified ZSM-5 molecular sieve catalyst action of Zn, P, Ag, Ga, wherein Zn accounts for the 2- of total catalyst weight
4%, P account for the 3-6% of total catalyst weight, and Ag accounts for the 2-3% of total catalyst weight, and Ga accounts for the 2-4% of total catalyst weight, instead
Answer 300-450 DEG C of temperature, Feed space velocities 0.5-5.0h-1Reaction condition under, react generation secondary gas phase dry gas product warp
The carrying device of secondary gas phase pipeline 108, a part of carrying devices of LPG of generation are crossed, a part returns to two level virtue as freshening gas
Structure reactor 104 enters aromatization of low carbon hydrocarbon unit, and two level oil phase enters Aromatics Extractive Project device by two level oil phase pipeline 109
110 carry out Aromatics Extractive Project, and specific equipment structure chart is as shown in Figure 3.
Experimental example 1
1-3 of embodiment of the present invention product composition is as shown in table 1 below after testing：
The product of table 1 forms
From table 1 it follows that the arenes selectivity of the embodiment of the present invention is good, high income, and can also by-product it is a certain amount of
MTBE, create certain economic value.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (6)
1. a kind of method of methanol production aromatic hydrocarbons and by-product MTBE, it is characterised in that comprise the following steps：
(A) methanol oxidation aromatisation obtains primary product, and the primary product refrigerated separation is obtained into one-level gas phase and primary oil
Phase, the temperature control of catalytic aromatization is at 300-450 DEG C；
(B) one-level gas phase is reacted to obtain MTBE and tail gas product with methanol, and the MTBE is directly collected, the tail gas product catalysis
Aromatisation obtains secondary products, and the secondary products refrigerated separation obtains secondary gas phase and two level oil phase, the temperature of catalytic aromatization
Degree control is at 300-450 DEG C；
(C) one-level oil phase merges collection with two level oil phase, and secondary gas phase is expelled directly out carrying out vent gas treatment recovery；
Wherein, in the step (A), obtained one-level oil phase is further separated into non-aromatic hydrocarbon mixture and low-carbon mixing virtue
Hydrocarbon, the low-carbon BTX aromatics are directly collected, and the non-aromatic hydrocarbon mixture enters in the step (B) to be mixed with the tail gas product
Close；
In the step (B), two level oil phase, which returns to mix with primary oil, is further separated into non-aromatic hydrocarbon mixture and low-carbon
BTX aromatics.
2. the method for a kind of methanol production aromatic hydrocarbons according to claim 1 and by-product MTBE, it is characterised in that the step
(A) in, methanol is with air speed 0.5-3h-1, catalyst is to be catalyzed with the modified ZSM-5 of the one or more in Zn, P, Ag, Ga element
Agent.
3. the method for a kind of methanol production aromatic hydrocarbons according to claim 1 and by-product MTBE, it is characterised in that the step
(B) in, for the tail gas product with air speed 0.5-5h-1, catalyst is modified with the one or more in Zn, P, Ag, Ga element
ZSM-5 catalyst.
4. the method for a kind of methanol production aromatic hydrocarbons according to claim 3 and by-product MTBE, it is characterised in that the step
(B) in, using the element modified ZSM-5 catalyst of Zn, P, Ag, Ga, wherein Zn accounts for the 1-6% of total catalyst weight,；P accounts for catalysis
The 2-10% of agent gross weight, Ag account for the 1-4% of total catalyst weight, and Ga accounts for the 0.5-5% of total catalyst weight.
5. the method for a kind of methanol production aromatic hydrocarbons according to claim 4 and by-product MTBE, it is characterised in that the step
(B) in, Zn accounts for the 2-4% of total catalyst weight,；P accounts for the 3-6% of total catalyst weight, and Ag accounts for the 2- of total catalyst weight
3%, Ga account for the 2-4% of total catalyst weight.
6. a kind of equipment for implementing any one of the claim 1-5 methanol production aromatic hydrocarbons and by-product MTBE method, its feature
It is, including：One-level aromatization reactor, aromatization of methanol product separator, MTBE reactors, two level aromatization reactor,
One-level gas phase pipeline, one-level oil phase pipeline, tail gas product pipeline, secondary gas phase pipeline, two level oil phase pipeline；
The one-level aromatization reactor is connected with the sidepiece of aromatization of methanol product separator by pipeline, aromatization of methanol production
The top of thing separator is connected by one-level gas phase pipeline with the sidepiece of MTBE reactors, the side of the two level aromatization reactor
Portion is connected by sidepiece of the tail gas product pipeline also with the MTBE reactors, and the one-level oil phase pipeline is arranged at the methanol
The bottom of aromatization products separator, the secondary gas phase pipeline, the two level oil phase pipeline are respectively arranged at the two level virtue
The top and bottom of structure reactor；
Also include Aromatics Extractive Project device, low-carbon BTX aromatics conveyance conduit, non-aromatic hydrocarbon mixture conveyance conduit；The non-aromatics mixing
Thing conveyance conduit is arranged at the top of the Aromatics Extractive Project device and connects the sidepiece of two level aromatization reactor, the one-level oil phase
Pipeline is connected with the sidepiece of the Aromatics Extractive Project device, and the low-carbon BTX aromatics conveyance conduit is arranged at the Aromatics Extractive Project device
Bottom, the two level oil phase pipeline are connected with the sidepiece of the Aromatics Extractive Project device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610010120.9A CN105693447B (en) | 2016-01-07 | 2016-01-07 | A kind of method and apparatus of methanol production aromatic hydrocarbons and by-product MTBE |
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| CN201610010120.9A CN105693447B (en) | 2016-01-07 | 2016-01-07 | A kind of method and apparatus of methanol production aromatic hydrocarbons and by-product MTBE |
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| Publication Number | Publication Date |
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| CN105693447A CN105693447A (en) | 2016-06-22 |
| CN105693447B true CN105693447B (en) | 2018-02-16 |
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