CN105294374B - A kind of methanol and/or dimethyl ether for paraxylene and propylene method - Google Patents
A kind of methanol and/or dimethyl ether for paraxylene and propylene method Download PDFInfo
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- CN105294374B CN105294374B CN201410245420.6A CN201410245420A CN105294374B CN 105294374 B CN105294374 B CN 105294374B CN 201410245420 A CN201410245420 A CN 201410245420A CN 105294374 B CN105294374 B CN 105294374B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The present invention relates to a kind of methanol and/or dimethyl ether for the method for paraxylene and propylene, this method is including two courses of reaction of methanol and/or dimethyl ether aromatization, ethene and methanol and/or dimethyl ether alkylated reaction are coupled.The inventive method produces paraxylene and propylene with high selectivity by the way that the component Returning reacting system in methanol and/or dimethyl ether paraxylene byproduct of reaction rich in ethene is alkylated into reaction with methanol and/or dimethyl ether under catalyst.
Description
Technical field
The present invention relates to a kind of method that methanol and/or dimethyl ether react paraxylene processed and propylene, belong to chemical
Field.
Background technology
Paraxylene (PX) and propylene are important basic chemical raw materials.At present, paraxylene is mainly combined through aromatic hydrocarbons
Device is obtained, and naphtha is made into the reformed oil containing aromatic hydrocarbons by CONTINUOUS REFORMER first, then through Aromatics Extractive Project, aromatic hydrocarbons point
Evaporate, be disproportionated and the unit such as transalkylation, xylene isomerization and adsorbing separation obtains PX products to greatest extent.Due to two
Toluene three isomers content by balance controlled, paraxylene is in C823% or so is only accounted in BTX aromatics, so whole
Matter Transfer treating capacity is big in individual PX production processes, and equipment is huge, and operating cost is high.Particularly three isomers of dimethylbenzene
Boiling point difference very little, high-purity paraxylene can not be obtained using common distillation technique, and must be using expensive absorption
Separating technology.Propylene is mainly derived from petroleum refinery and naphtha steam cracking produces the byproduct of ethene, or with natural
The obtained propane of gas processing is that raw material is produced.Paraxylene is mainly for the production of polyester, and propylene is mainly for the preparation of poly- third
1,3-PD needed for alkene, acrylonitrile and production polyester, with the fast development of global economy, is used as chemical industry base stock
Paraxylene and propylene demand also cumulative year after year.
It is the new way that Non oil-based route produces aromatic hydrocarbons that methanol, which prepares aromatic hydrocarbons,.Chinese patent CN101244969 discloses one
Plant C1-C2The fluidized bed plant that hydro carbons or aromatization of methanol regenerate with catalyst, using the device and catalyst, can be adjusted at any time
The coking state of catalyst in aromatization reactor, so as to reach that continuous high-efficient converts C1-C2Hydro carbons or methanol and high selectivity
Generate the purpose of aromatic hydrocarbons.Chinese patent CN1880288 discloses a kind of process of methanol conversion for preparing arene, in modified ZSM-5 molecule
On sieve catalyst, methanol oxidation is converted into the product based on aromatic hydrocarbons, and the overall selectivity with aromatic hydrocarbons is high, and technological operation is flexible
Advantage.United States Patent (USP) US4615995 discloses a kind of ZSM-5 molecular sieve catalyst for having supported Zn and Mn, for methanol conversion
Alkene and aromatic hydrocarbons are prepared, low-carbon alkene/aromatic compound in product can be changed by Zn in regulating catalyst and Mn content
Ratio.
Methanol-to-olefins and preparing propylene from methanol are Non oil-based route production ethene, the new way of propylene.Mobil in 1976
Oil companies have carried out the reaction that methanol is converted into hydrocarbon on ZSM-5 molecular sieve catalyst.It is public in USP4,035,430
The process that methanol converts gasoline on ZSM-5 molecular sieve catalyst is opened；Methanol is disclosed in USP4,542,252 at ZSM-5 points
The technology of preparing low-carbon olefins on sub- sieve catalyst；USP3,911,041, USP4,049,573, USP4,100,219, JP60-
The ZSM-5 molecules being modified using phosphorus, magnesium, silicon or alkali metal are disclosed in 126233, JP61-97231 and JP62-70324
Sieve catalyst by preparing low carbon olefinic hydrocarbon with methanol reaction；Dalian Chemical Physics Research Institute is disclosed in USP5,367,100 and uses phosphorus
With lanthanum be modified ZSM-5 molecular sieve catalyst by methanol or methanol and/or dimethyl ether preparing low-carbon olefins reaction, its ethene and
Propylene overall selectivity is only 65wt% or so, and ethene, propylene and butylene overall selectivity are more than 85wt%.
CN101767038B and CN101780417B disclose a kind of methanol paraxylene co-producing light olefins catalyst
And method, it is indicated that realize in a course of reaction that three are directly produced by methanol is big on metal and silylating reagent catalyst
The purpose of basic chemical ethene, propylene and paraxylene.Selection of the paraxylene in aromatic hydrocarbons in reaction gained hydrocarbon product
Property be more than more than 80wt%, ethene and propylene are in C1-C5Selectively it is more than more than 80wt% in lower carbon number hydrocarbons.But the disadvantage of this method
End is that the ethylene product of high-purity to be obtained is had to by cold separation technology, and investment and energy consumption are larger, directly affects
The economy of the process.
In addition, CN101780417B is related to the side of preparing paraxylene by methyl alcohol conversion and low-carbon alkene (ethene and propylene)
Method, wherein not being directed to the difficulty that further propylene enhancing avoids ethylene separation, will be enriched in the C of ethene2 -Component freshening enters one
Step and the process of methanol alkylation propylene enhancing.CN102464550A discloses the side of a kind of co-producing light olefins and paraxylene
Method, methods described is to include carbon four, light dydrocarbon hydrocarbon into the first reaction zone alkene, and this is C4Or liquefied gas cracks alkene mistake processed
Journey, wherein not also being related to the process of ethene and methanol/dimethyl ether alkylation propylene processed.
The content of the invention
It is an object of the invention to provide a kind of method of methanol and/or dimethyl ether paraxylene and propylene.
Therefore, a kind of method that the present invention provides methanol and/or dimethyl ether paraxylene and propylene, including following step
Suddenly：
A) by the raw material containing methanol and/or dimethyl ether in reaction system with catalyst haptoreaction；By the reaction
The C rich in ethene that system comes out2 -Component returns to the reaction system, and continues reaction over the catalyst with raw material with life
Into propylene；
B) C come out from the reaction system6 +Component, is isolated to product paraxylene；With
C) C come out from the reaction system3Component is isolated to product propylene.
In a preferred embodiment, the reaction system includes the first reaction zone and second reaction zone, and described
Method comprises the following steps：
A) raw material containing methanol and/or dimethyl ether is contacted into generation aromatization with catalyst I by the first reaction zone first
Change reaction, generation alkylationization reaction is contacted with catalyst II subsequently into second reaction zone；Come out by the second reaction zone
The C rich in ethene2 -Component returns to the second reaction zone, and exists with the methanol and/or dimethyl ether in the second reaction zone
Alkylated reaction occurs on the catalyst II to generate propylene；
B) C come out from the second reaction zone6 +Component is through further isolated product paraxylene；With
C) C come out from the second reaction zone3Component is through further isolated propylene.
In a preferred embodiment, the reaction system includes the first reaction zone and second reaction zone, and described
Method comprises the following steps：
A) raw material containing methanol and/or dimethyl ether is contacted into generation aromatization with catalyst I by the first reaction zone first
Change reaction, obtain product A, after the product A is separated through piece-rate system, the C rich in ethene2 -Component returns to described second
Reaction zone, and alkylated reaction is carried out on catalyst II with the methanol and/or dimethyl ether that enter second reaction zone, given birth to
Into thing B；The C rich in ethene in product A and product B2 -Component continues back to second reaction zone, and and second reaction zone
In catalyst II contacts alkylated reaction to occur for interior methanol and/or dimethyl ether generate propylene；
B) C in the product A and product B6 +Component is through further isolated product paraxylene；With
C) C in the product A and product B3Component is through further isolated product propylene.
In a preferred embodiment, the catalyst, the catalyst I and catalyst II contain identical or different
Modified zeolite molecular sieve catalyst.
In a preferred embodiment, the modified zeolite molecular sieve catalyst is by ZSM-5 and/or ZSM-11 zeolites
Molecular sieve is modified what is obtained through noble metal and rare-earth metal modified and silicone-based compound.
In a preferred embodiment, in the modified zeolite molecular sieve catalyst, the content of the noble metal is institute
State the 0.1-10wt% of total catalyst weight.
In a preferred embodiment, the content of the rare earth metal is the 0.1-5wt% of the total catalyst weight.
In a preferred embodiment, it is the modified zeolite molecule that the Si amounts supported are modified by silicone-based compound
The 1-10wt% of the gross weight of sieve catalyst.
In a preferred embodiment, the noble metal is silver；The rare earth metal is lanthanum.
In a preferred embodiment, the silicone-based compound is modified used silicone-based compound, knot
Structure formula is shown below：
Wherein R1、R2、R3And R4It is C independently of one another1-10Alkyl.
In a preferred embodiment, the silicone-based compound is tetraethyl orthosilicate.
In a preferred embodiment, the reaction zone includes a reactor or multiple by series connection and/or in parallel
The reactor that mode is connected；And preferably, one in the optional self-retaining bed of the reactor, fluid bed and moving-burden bed reactor
Plant or a variety of.
In a preferred embodiment, first reaction zone and the second reaction zone are in same reactor；
And preferably, the one or more in the optional self-retaining bed of the reactor, fluid bed and moving-burden bed reactor.
In a preferred embodiment, first reaction zone include a reactor or it is multiple by series connection and/or
The reactor of parallel way connection；The second reaction zone includes a reactor or multiple by series connection and/or parallel way
The reactor of connection；And between first reaction zone and the second reaction zone, connected by way of serial or parallel connection；
And preferably, the one or more in the optional self-retaining bed of the reactor, fluid bed and moving-burden bed reactor.
Beneficial effects of the present invention include but is not limited to following aspect：The present invention provides one kind with methanol and/or dimethyl ether
The new method of paraxylene and propylene processed, wherein by by the C rich in ethene in reaction product2 -Component freshening and methanol and/
It is final to obtain high selectivity paraxylene and propylene or dimethyl ether occurs alkylated reaction and further generates propylene, on the one hand keep away
Exempt from the high expense of ethylene product separation, on the other hand can further increase production the propylene product with the bigger market demand,
So as to effectively improve the economy of the technology.
Brief description of the drawings
Fig. 1 is the flow chart of the method according to one embodiment of this invention.
Fig. 2 is the flow chart of the method according to another embodiment of the present invention.
Fig. 3 is the flow chart of the method according to another embodiment of the present invention.
Fig. 4 is the flow chart of the method according to another embodiment of the present invention.
Embodiment
In the method for the invention, by methanol and/or dimethyl ether aromatization, ethene and methanol and/or dimethyl ether alkane
Two course of reaction couplings of glycosylation reaction, while high selectivity production of para-xylene and propylene.Specifically, material benzenemethanol first
And/or dimethyl ether contacts progress aromatization, generation in reaction system with catalyst (catalyst is present in reactor)
Product into piece-rate system (such as fractionating column) separate；After being separated through piece-rate system, C is obtained6 +(carbon number is equal to and is more than component
6 aromatic hydrocarbons), C4-C5Component (carbon number is 4 and 5 hydro carbons), C3Component (carbon number be equal to 3 propylene and propane) and rich in ethene
C2 -(carbon number is less than or equal to 2 hydro carbons and CO, CO to component2And H2) and water (H2O), wherein, the C rich in ethene2 -Component is returned
Reaction system, C6 +Component obtains paraxylene, C through further separation (such as rectifying column, Crystallization Separation system)3Component is through entering
One step is separated obtains propylene (such as rectifying column), and a small amount of C4-C5Component and H2After O collections for other purposes.It is wherein described
Reaction system can be single reaction zone, or the combination of two or more reaction zone, and multiple reaction zones can be
In same reactor or respectively in the reactor of multiple serial or parallel connections.Preferably, the reactor is fixation
In bed, fluid bed or moving bed any one or it is any several.
In a preferred embodiment, a kind of reaction process of the method according to the invention is as shown in Figure 1.In Fig. 1,
Reaction system is made up of a reactor with a reaction zone, and wherein material benzenemethanol and/or dimethyl ether are in the reaction system
Reaction zone in catalyst haptoreaction therein, after the product of generation is separated through piece-rate system, obtain C6 +Component, C4-C5
Component, C3Component and C2 -Component (including the C rich in ethene2 -Component and periodic off-gases) and H2O, wherein, the C rich in ethene2 -Group
Divide Returning reacting system, C6 +Component is through further isolated paraxylene, C3Component is through further isolated propylene.
In a preferred embodiment, a kind of reaction process of the method according to the invention is as shown in Figure 2.In fig. 2,
Reaction system is made up of a reactor with two reaction zones, and the main reaction of the first reaction zone is methanol and/or dimethyl ether
Aromatization, the main reaction of second reaction zone is ethene (accessory substance of the first reaction zone) and methanol and/or dimethyl ether alkyl
Change reaction.Material benzenemethanol and/or dimethyl ether first by the first reaction zone and with catalyst I haptoreactions therein, Ran Houtong
Cross second reaction zone and with catalyst II haptoreactions therein, the product of generation separates into piece-rate system；Through piece-rate system
C is obtained after separation6 +Component, C4-C5Component, C3Component and C2 -Component (including the C rich in ethene2 -Component and periodic off-gases) and
H2O, wherein the C rich in ethene2 -Component returns to second reaction zone and and enters the methanol and/or dimethyl ether of second reaction zone with urging
Agent II contacts are alkylated reaction；C6 +Component is through further isolated paraxylene, C3Component is further isolated
Propylene.
In a preferred embodiment, a kind of reaction process of the method according to the invention is as shown in Figure 3.In figure 3, instead
Answer system to be made up of the two reaction zones respectively in two reactors in parallel, the main reaction of the first reaction zone for methanol and/
Or dimethyl ether aromatization, the main reaction of second reaction zone is ethene (accessory substance of the first reaction zone) and methanol and/or two
Methyl ether alkylated reaction.Methanol and/or dimethyl ether contact progress aromatisation generation product A, production with catalyst I in reaction zone first
Thing A is separated into piece-rate system；The C rich in ethene obtained after separation2 -Component returns to second reaction zone, with entering second
The methanol and/or dimethyl ether of reaction zone carry out alkylated reaction generation product B, product B on catalyst II and enter piece-rate system
Separation；After being separated through piece-rate system, wherein the C rich in ethene2 -Component returns to second reaction zone, and wherein described product A
The C obtained after being separated with product B through piece-rate system6 +Component is through further isolated paraxylene, C3Component is further separated
Obtain propylene.
In a preferred embodiment, a kind of reaction process of the method according to the invention is as shown in Figure 4.In Fig. 4,
Except reaction system is by addition to the two reaction zones respectively in same reactor are constituted, its course of reaction is with above-mentioned on figure
Process described by 3 is identical, repeats no more here, and such reaction system can be realized by multistage feeding.
In the present invention, used catalyst is ZSM-5 and/or ZSM-11 zeolite molecular sieves through noble metal and rare earth gold
Category modified ZSM-5 that is combined modified and being obtained through silicone-based compound surface modification and/or ZSM-11 zeolite molecular sieves are urged
Agent.When reaction zone is two, it can be identical or different to be respectively present in the catalyst I and catalyst II therein
Catalyst.For example, in a preferred embodiment, the catalyst I and catalyst II are same catalyst or identical
Catalyst.It is highly preferred that the catalyst used in the present invention, catalyst I or catalyst II are through silicone-based compound table
After the modification of face, Si loading is the 1-10wt% of the total catalyst weight.
In a preferred embodiment, the preparation process for the catalyst that the present invention is used is as follows：
(1) by the former powder of ZSM-5 and/or ZSM-11 zeolite molecular sieves through NH4 +Ion exchange, roasting are prepared into acid zeolite point
Son sieve.
(2) above-mentioned acidic zeolite is immersed in the soluble salt solutions of noble metal and rare earth metal, obtains gold
Belong to modified zeolite molecular sieve.
(3) surface modification, further modulation point are carried out to above-mentioned metal modified zeolites molecular sieve using Siloxane based agents
Son sieve outer surface acidity and pore structure, obtain modified zeolite molecular sieve catalyst.
Preferably, the catalyst, catalyst I or the catalyst II used in the present invention joins through noble metal and rare earth metal
Close modified, bullion content is the 0.1-10wt% of the total catalyst weight；Rare earth metal content is the total catalyst weight
0.1-5wt%.
Preferably, the noble metal used in the present invention is silver；Rare earth metal is lanthanum, and it is in the form of their soluble-salt
Use.
Preferably, the silicone-based compound used in the present invention is shown below：
Wherein R1、R2、R3And R4It is C independently of one another1-10Alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptan
Base and octyl group, and their isomeric forms.
Preferably, the silicone-based compound used is tetraethyl orthosilicate.
Preferably, in the present invention fixed bed reaction technique can be used in first reaction zone and second reaction zone,
It can be combined simultaneously with regenerator using fluid bed or moving bed reaction technique.First reaction zone and second reaction zone can be with
Respectively in a reactor or in the identical or different reactor of multiple serial or parallel connections, realized by multistage feeding.
In the methods of the invention, methanol and/or the alkylation of dimethyl ether aromatization, ethene and methanol and/or dimethyl ether
Reaction temperature is in the range of 300-600 DEG C, and methanol and/or the preferred reaction temperature of dimethyl ether aromatization are 450-
520 DEG C, ethene is 350-500 DEG C with methanol and/or dimethyl ether alkylated reaction preferable reaction temperature.
In the methods of the invention, methanol and/or dimethyl ether aromatization feedstock quality air speed are with methanol and/or dimethyl ether
It is calculated as 0.1-10h-1, preferably 1-5h-1.Wherein ethene is arbitrarily selected with methanol and/or dimethyl ether mol ratio in the range of 0.1-10
Select, it is generally preferable to be 0.5-5.
In the present invention, the C2 -Component refers to the component that carbon number in molecular formula is less than or equal to 2, including ethene and second
Alkane, methane, CO, CO2And H2Deng i.e. C2 -Component includes the C rich in ethene2 -Component and periodic off-gases.Periodic off-gases are mainly ethane, first
Alkane, CO, CO2And H2Deng.
In the present invention, the C3Component refers to the compound that carbon number in molecular formula is equal to 3, including propylene, propane etc..
In the present invention, the C4-C5Component refers to the component that carbon number in molecular formula is equal to 4,5, including iso-butane, isobutyl
Alkene, butane, 1- butylene, 2- butylene, isopentane, neopentane, pentane, 1- amylenes, 2- penta are dilute etc..
In the present invention, the C6 +Component refers to the component that carbon number in molecular formula is more than or equal to 6, including paraxylene and
Other virtue hydrocarbons and their derivates etc..
The present invention is described in detail below by embodiment, but the invention is not limited in these embodiments.
Gas chromatograph on-line analysis product is constituted, and analysis condition is：
Chromatogram model：Varian CP3800
Chromatographic column：CP Wax52CB capillary chromatographic columns
Carrier gas：Helium, 5ml/min
Post case temperature：60-220 DEG C, temperature programming, 15 DEG C/min
Injector temperature：260℃
Detector：Flame ionization ditector (FID)
Detector temperature：300℃
Embodiment 1
The preparation of catalyst：Silver-colored lanthanum and silane-modified HZSM-5 molecular sieve catalysts and HZSM-11 molecular sieve catalysts
1) by 500g ZSM-5 zeolites molecular screen primary powder (Fushun Petrochemical Company catalyst plant) (SiO2/Al2O3=68) and
500g ZSM-11 zeolite molecular sieves original powder (Catalyst Factory, Nankai Univ) (SiO2/Al2O3=50) be calcined and go at 550 DEG C respectively
Template agent removing, is swapped 4 times in 80 DEG C of water-baths with 0.5 molar equivalent ammonium nitrate solution, is dried after exchange in 120 DEG C of air
It is dry, it is calcined 3 hours at 550 DEG C, respectively obtains HZSM-5, HZSM-11 zeolite molecular sieve.
2) take step 1 respectively) prepare HZSM-5 and HZSM-11 zeolite molecular sieve 100g compression moldings, after crushing and screening
After obtain 40-60 mesh samples, with the silver nitrate (AgNO of 6% mass concentration3) solution normal temperature dipping 4 hours, pour out supernatant liquid
It is calcined 6 hours in 120 DEG C of drying afterwards, 550 DEG C of air, obtains the modified Ag-HZSM-5 and Ag-HZSM-11 zeolite molecular sieves of silver.
3) respectively by step 2) obtained Ag-HZSM-5 and Ag-HZSM-11 zeolite molecular sieve 5wt% lanthanum nitrate hexahydrates
(La(NO3)3·6H2O) normal temperature dipping 4 hours, pour out and are calcined 6 hours in 120 DEG C of drying, 550 DEG C of air after supernatant liquid, obtained
To silver and the combined modified Ag-La-HZSM-5 and Ag-La-HZSM-11 zeolite molecular sieves of lanthanum.
4) tetraethyl orthosilicate (TEOS) normal temperature dipping step 3 is respectively adopted) obtained Ag-La-HZSM-5 and Ag-La-
HZSM-11 zeolite molecular sieves 24 hours, pour out after supernatant liquid roasting in 120 DEG C of drying, 550 DEG C of air and obtain silver-colored lanthanum in 6 hours
With HZSM-5 the and HZSM-11 molecular sieve catalysts of silylating reagent, catalyst is respectively designated as MTPP-08 and MTPP-09.X
Ray fluorescence diffraction (XRF) analysis determines Ag on MTPP-08 and MTPP-09 catalyst each element loadings, MTPP-08 catalyst
Loading is 1.02wt%, and La loadings are 1.25wt%, and silanization Si loadings think 2.32wt%；MTPP-09 catalyst
Upper Ag loadings are 1.13wt%, and La loadings are 1.18wt%, and silanization Si loadings think 2.16wt%.
Embodiment 2
With methanol paraxylene and propylene
Reaction process according to Fig. 2, fixed reaction is respectively charged into by the MTPP-08 catalyst prepared in embodiment 1
In first reaction zone of device and second reaction zone (each reaction zone is 10 grams).It is anti-that first reaction zone is substantially carried out aromatization of methanol
Should, product enters second reaction zone after reaction, and methanol feedstock quality air speed is 2h-1, reaction temperature is 500 DEG C.Wherein reaction production
The C rich in ethene in thing distribution2 -Component enters second reaction zone with methanol and reacted jointly, wherein ethene/methanol (mol ratio)
For 1/1, reaction temperature is 400 DEG C, and second reaction zone carries out ethene and methanol alkylation reaction.
Constituted, removed after generation water using the reaction zone of gas chromatograph on-line analysis first and second reaction zone mix products
Product distribution it is as shown in table 1, then remove C2 -Return component after product distribution it is as shown in table 2.
From table 2 it can be seen that removing C in the first reaction zone and second reaction zone gross product2 -After component, propylene is selected in product
Selecting property is 42.52wt%, and Selectivity for paraxylene is 38.05wt%, and propylene and paraxylene overall selectivity are 80.57wt%.
Selectivity of the paraxylene in xylene isomer is 98.98wt%.
Table 1
* wt%, products weight percentage composition, similarly hereinafter.
Table 2
Embodiment 3
With methanol paraxylene and propylene
Reaction process according to Fig. 3 or 4, MTPP-08 the and MTPP-09 catalyst prepared in embodiment 1 is distinguished
Load the first reaction zone and second reaction zone (each reaction zone is 10 grams).First reaction zone carries out aromatization of methanol reaction, first
Alcohol feedstock quality air speed is 2h-1, reaction temperature is 500 DEG C.Second reaction zone carries out ethene and methanol alkylation reaction, according to right
The C of ethene is rich in ratio in the distribution of the reaction of methanol conversion product2 -Component enters second reaction zone with methanol and reacted jointly, wherein
Ethene/methanol (mol ratio) is 1/1, and reaction temperature is 400 DEG C.
Constituted, removed after generation water using the reaction zone of gas chromatograph on-line analysis first and second reaction zone mix products
Product distribution it is as shown in table 3, then remove C2 -Product distribution after component is as shown in table 4.
From table 4, it can be seen that removing C in the first reaction zone and second reaction zone gross product2 -After component, propylene is selected in product
Selecting property is 53.62wt%, and Selectivity for paraxylene is 30.59wt%, and propylene and paraxylene overall selectivity are 84.21wt%.
Selectivity of the paraxylene in xylene isomer is 99.32wt%.
Table 3
Table 4
Comparative example 1
With methanol paraxylene co-production propylene, but without C2 -The further reaction that component is returned
Take the MTPP-08 catalyst prepared in 10 grams of embodiments 1 to be fitted into reactor and carry out the reaction of methanol conversion, methanol matter
Amount air speed is 2h-1, reaction temperature is 500 DEG C.Constituted using gas chromatograph on-line analysis product, remove the product after generation water
Distribution is as shown in table 5.
When the independent methanol charging reaction of reactor, the selectivity of propylene is only 29.48wt% in product.
The reaction of methanol conversion result of table 5
Above to the present invention have been described in detail, but the invention is not limited in specific embodiment party described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes can be made and deformed.This hair
Bright scope is defined by the following claims.
Claims (12)
1. a kind of method of methanol and/or dimethyl ether paraxylene and propylene, the described method comprises the following steps：
A) by the raw material containing methanol and/or dimethyl ether in reaction system with catalyst I haptoreactions；From the reaction system
The C rich in ethene out2 -Component returns to the reaction system, and continues reaction to generate on catalyst II with the raw material
Propylene；
B) C come out from the reaction system6 +Component, is isolated to product paraxylene；With
C) C come out from the reaction system3Component is isolated to product propylene,
Wherein described catalyst I and the catalyst II contain identical or different modified zeolite molecular sieve catalyst, described to change
Property zeolite molecular sieve catalyst is through noble metal and rare-earth metal modified and silicon by ZSM-5 and/or ZSM-11 zeolite molecular sieves
Obtained from o-alkylation is polymer modified, the silicone-based compound is modified the structural formula of used silicone-based compound
It is as follows：
Wherein R1、R2、R3And R4It is C independently of one another1-10Alkyl.
2. according to the method described in claim 1, it is characterised in that the reaction system includes the first reaction zone and the second reaction
Area, and the described method comprises the following steps：
A) raw material containing methanol and/or dimethyl ether is contacted into generation aromatization with catalyst I by first reaction zone first
Change reaction, generation alkylated reaction is contacted with catalyst II subsequently into the second reaction zone；Go out from the second reaction zone
The C rich in ethene come2 -Component returns to the second reaction zone, and with the methanol and/or dimethyl ether in the second reaction zone
Alkylated reaction occurs on the catalyst II to generate propylene；
B) C come out from the second reaction zone6 +Component is through further isolated product paraxylene；With
C) C come out from the second reaction zone3Component is through further isolated propylene.
3. according to the method described in claim 1, it is characterised in that the reaction system includes the first reaction zone and the second reaction
Area, and the described method comprises the following steps：
A) raw material containing methanol and/or dimethyl ether is contacted into generation aromatization with catalyst I by first reaction zone first
Change reaction, obtain product A, after the product A is separated through piece-rate system, the C rich in ethene2 -Component returns to described second
Reaction zone, and alkylated reaction is carried out on catalyst II with the methanol and/or dimethyl ether that enter the second reaction zone, obtain
To product B；The C rich in ethene in the product A and product B2 -Component continues back to the second reaction zone, and
Occur alkylated reaction to generate propylene on the catalyst II with the methanol and/or dimethyl ether in the second reaction zone；
B) C in the product A and product B6 +Component is through further isolated product paraxylene；With
C) C in the product A and product B3Component is through further isolated product propylene.
4. according to the method described in claim 1, it is characterised in that in the modified zeolite molecular sieve catalyst, your gold
The content of category is the 0.1-10wt% of the total catalyst weight；The content of the rare earth metal is the total catalyst weight
0.1-5wt%；And the gross weight that the Si amounts supported are the modified zeolite molecular sieve catalyst is modified by silicone-based compound
The 1-10wt% of amount.
5. according to the method described in claim 1, it is characterised in that the noble metal is silver；The rare earth metal is lanthanum.
6. according to the method described in claim 1, it is characterised in that the silicone-based compound is tetraethyl orthosilicate.
7. according to the method described in claim 1, it is characterised in that the reaction system includes a reactor or multiple passed through
Series connection and/or the reactor of parallel way connection.
8. method according to claim 2, it is characterised in that first reaction zone and the second reaction zone are same
In individual reactor.
9. method according to claim 3, it is characterised in that first reaction zone includes a reactor or multiple logical
Cross the reactor of series connection and/or parallel way connection；The second reaction zone include a reactor or it is multiple by series connection and/
Or the reactor of parallel way connection；And pass through serial or parallel connection side between first reaction zone and the second reaction zone
Formula is connected.
10. method according to claim 7, it is characterised in that the reactor is to be selected from fixed bed, fluid bed and movement
One or more in bed reactor.
11. method according to claim 8, it is characterised in that the reactor is to be selected from fixed bed, fluid bed and movement
One or more in bed reactor.
12. method according to claim 9, it is characterised in that the reactor is to be selected from fixed bed, fluid bed and movement
One or more in bed reactor.
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| CN111187133B (en) * | 2018-11-15 | 2021-12-21 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing ethylbenzene and propylene from methanol and/or dimethyl ether and benzene |
| CN111187134A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing paraxylene and co-produced gasoline from methanol and/or dimethyl ether |
| CN111187132A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing gasoline and co-producing p-xylene from methanol and/or dimethyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177374A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Method for producing propylene by carbinol or dimethyl ether |
| CN101602643A (en) * | 2009-07-24 | 2009-12-16 | 中国海洋石油总公司 | A kind of methyl alcohol/dimethyl ether conversion is produced the method for ethylene and propylene and co-producing p-Xylol |
| CN101607858A (en) * | 2009-07-24 | 2009-12-23 | 中国海洋石油总公司 | The method of a kind of methyl alcohol/dimethyl ether production aromatic hydrocarbons and propylene simultaneously |
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| CN101177374A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Method for producing propylene by carbinol or dimethyl ether |
| CN101602643A (en) * | 2009-07-24 | 2009-12-16 | 中国海洋石油总公司 | A kind of methyl alcohol/dimethyl ether conversion is produced the method for ethylene and propylene and co-producing p-Xylol |
| CN101607858A (en) * | 2009-07-24 | 2009-12-23 | 中国海洋石油总公司 | The method of a kind of methyl alcohol/dimethyl ether production aromatic hydrocarbons and propylene simultaneously |
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