CN108017488A - The method of alcohol and/or ether catalytic material conversion for preparing arene - Google Patents
The method of alcohol and/or ether catalytic material conversion for preparing arene Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/80—Mixtures of different zeolites
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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
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- 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
Abstract
The present invention relates to a kind of method of alcohol and/or ether catalytic material conversion for preparing arene, mainly solves the problems, such as that aromatics yield is low in the prior art.The present invention obtains reaction product I by alcohol and/or ether raw material into fluidized-bed reactor I, the reaction product I obtains gas-phase product into separative element I, water-phase product and aromatic product I, described gas-phase product at least a portion enters the reaction of fluidized-bed reactor II and obtains reaction product II, the reaction product II obtains lighter hydrocarbons product into separative element II, heavy products and aromatic product II, described heavy products at least a portion obtains reaction product III into aromatization reactor, the reaction product III enters separative element I, the technical solution of II common regenerator of fluidized-bed reactor I and fluidized-bed reactor, preferably solves the problems, such as this, available in arene industrial production.
Description
Technical field
The present invention relates to a kind of method of alcohol and/or ether catalytic material conversion for preparing arene.
Background technology
Aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) is important basic
Organic synthesis raw material.Driven by downstream derivative thing demand, the market demand sustainable growth of aromatic hydrocarbons.
It is the main life of aromatic hydrocarbons with the steam cracking process of liquid hydrocarbon (such as naphtha, diesel oil, secondary operation oil) for raw material
Production. art.The technique belongs to petroleum path production technology, in recent years, due to the limited supply of petroleum resources and higher valency
Lattice, cost of material are continuously increased.By factor, alternative materials prepare aromatic hydrocarbons technology and cause to be paid close attention to more and more widely.China's coal
Charcoal resource relative abundance.With in recent years efficiently, long period catalyst for methanol and methanol device maximize the succeeding in developing of technology, coal
The production cost of base methanol and/or dimethyl ether is greatly lowered, this is methanol and/or dimethyl ether downstream product (alkene, aromatic hydrocarbons
Deng) production provide cheap raw material sources.Accordingly, it is considered to aromatic hydrocarbons is prepared as raw material using methanol and/or dimethyl ether.
The technology initially see Chang of Mobil companies in 1977 et al. (Journal of Catalysis, 1977,
47,249) methanol and its oxygenate conversion on ZSM-5 molecular sieve catalyst are reported and prepares the hydrocarbons such as aromatic hydrocarbons
Method.1985, Mobil companies disclosed methanol, dimethyl ether turns first in its United States Patent (USP) applied US1590321
Change the result of study of aromatic hydrocarbons processed, it is catalyst which, which uses the phosphorous ZSM-5 molecular sieve for 2.7 weight %, and reaction temperature is
400~450 DEG C, methanol, dimethyl ether air speed 1.3h-1。
Chinese patent 201010111821.4,200910090002.3,200810102684.0,200910135643.6,
200910089699.2 use a reactor, and reactor only has a reaction zone, using single reaction temperature.Chinese patent
Liquefied gas and ethene in 201410447321.6 systems proposed in the lighter hydrocarbons of aromatization of methanol reaction generation return to methanol virtue
Structure reactor further converts.Alcohol/ether aromatization device in the system that Chinese patent 201410106062.0 proposes
Below the C7 oil phases hydro carbons that product is isolated to further is reacted into alcohol/ether aromatization device.Oxygenatedchemicals exists
At a temperature of higher than 500 DEG C, heat scission reaction easily occurs and generates low value-added methane, carbon monoxide, while increases coke
Content.To reduce this partial reaction, reaction temperature is generally below 500 DEG C, and aromatization of low carbon hydrocarbon reacts suitable reaction temperature
Higher than 500 DEG C, therefore the problem of cause such prior art arenes selectivity relatively low.
The method that Chinese patent 200610012703.1 is introduced, methanol react obtained gas phase lower carbon number hydrocarbons at one section and enter two
Section reactor, the reaction was continued at a temperature of 250~500 DEG C, and two-stage catalytic agent is different.Chinese patent 200910089698.8 is situated between
The method to continue, methanol or/and dimethyl ether isolate propylene in the product of fixed bed reactors reaction generation, into the second fixed bed
Reactor, reacts under conditions of 250~350 DEG C.The reaction temperature of two sections of the above method or second reactor is relatively low, aromatic hydrocarbons choosing
Selecting property is not high.
Alkylation reaction first occurs for the method that Chinese patent 20100108008.1 is introduced, methanol, and reaction product fully enters virtue
Structure reactor, finally obtains ethene, propylene, butylene and benzene,toluene,xylene.This method is since there are low in final product
Carbon olefin, arenes selectivity are relatively low.
The not outer row's C 2 hydrocarbon of the method piece-rate system that Chinese patent 201010146915.5 is introduced, and changed using Zn, Mo
ZSM-5, ZSM-35 catalyst of property, do not introduce the arenes selectivity of light-hydrocarbon aromatized process.
In above-mentioned patented technology all there are arenes selectivity it is low the problem of.The present invention pointedly proposes technical solution,
Solves the above problem.
The content of the invention
The technical problems to be solved by the invention are the non-aromatics productions that alcohol and/or ether raw material aromatisation obtain in the prior art
Thing continues arenes selectivity low technical problem during aromatisation, there is provided a kind of side of alcohol and/or ether catalytic material conversion for preparing arene
Method, this method have the advantages that non-aromatic hydrocarbon products aromatization process arenes selectivity is high.
To solve the above problems, the technical solution adopted by the present invention is as follows：Alcohol and/or ether raw material (7) are anti-into fluidized bed
Device I (1) is answered to obtain reaction product I (8), the reaction product I (8) obtains gas-phase product (11), water into separative element I (5)
Phase product (12) and aromatic product I (13), the gas-phase product (11) enter fluidized-bed reactor II (3) and react at least partially
Reaction product II (14) is obtained, the reaction product II (14) obtains lighter hydrocarbons product (15), heavy hydrocarbon production into separative element II (6)
Thing (16) and aromatic product II (18), the heavy products (16) are reacted into aromatization reactor (4) at least partially
Product III (17), the reaction product III (17) enter separative element I (5)；Lighter hydrocarbons product (15) includes at least part C2 alkane.
In above-mentioned technical proposal, it is preferable that lighter hydrocarbons product (15) includes whole C2 alkane in reaction product II (14).
In above-mentioned technical proposal, it is preferable that heavy products (16) do not include C2 alkene.
In above-mentioned technical proposal, it is preferable that fluidized-bed reactor I (1) and fluidized-bed reactor II (3) common regenerator
(2)。
In above-mentioned technical proposal, it is preferable that fluidized-bed reactor I (1) and fluidized-bed reactor II (3) use same catalysis
Agent, catalyst are ZSM-5 molecular sieve catalyst.
In above-mentioned technical proposal, it is preferable that the reaction bed temperature of fluidized-bed reactor I (1) is 420~550 DEG C, weight
Amount air speed is 0.2~6h-1, reaction pressure is 0~0.5 megapascal in terms of gauge pressure.
In above-mentioned technical proposal, it is preferable that the reaction bed temperature of fluidized-bed reactor II (3) is 480~600 DEG C,
Weight space velocity is 0.2~5h-1, reaction pressure is 0~0.5 megapascal in terms of gauge pressure.
In above-mentioned technical proposal, it is preferable that the active component for the catalyst II that aromatization reactor (4) uses is including extremely
Few a kind of selection ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, MCM-22 molecular sieves or the composite molecular screen formed each other；Urge
Agent load includes element at least one selection Zn, P, Ga, La, Ag, Cu, Mn, Mg；The each element that catalyst is loaded is to urge
The mass percent meter of agent, content are 0.01~15%.
In above-mentioned technical proposal, it is preferable that reaction bed temperature is 500~600 DEG C in aromatization reactor (4), weight
Amount air speed is 0.3~5h-1, reaction pressure is 0~0.5 megapascal in terms of gauge pressure.
In above-mentioned technical proposal, it is preferable that lighter hydrocarbons product (15) includes hydrogen, methane and C 2 hydrocarbon, heavy products (16)
Including more than three non-aromatics of carbon.
In above-mentioned technical proposal, it is preferable that aromatization reactor (4) is fixed for heat-insulating fixed bed reactors or shell and tube
Bed reactor or isotherm formula fixed bed reactors.
In above-mentioned technical proposal, it is preferable that aromatization reactor (4) sets at least two, at least one open it is one standby, reaction and
Regeneration switching, when the regeneration period is 10~720 small.
In above-mentioned technical proposal, it is preferable that regeneration condition is：Regeneration temperature is 450~650 DEG C, and regenerating medium is oxygen-containing
Gas, oxygen volume content are 0.1~21%.
In above-mentioned technical proposal, it is preferable that by weight, the 10~100% of gas-phase product (11) enters fluidized-bed reaction
Device II (3)；By weight, the 10~100% of heavy products (16) enter aromatization reactor (4).
In above-mentioned technical proposal, it is preferable that the reaction bed temperature of aromatisation fluidized-bed reactor I (1) for 470~
530℃。
In above-mentioned technical proposal, it is preferable that catalyst I is modified ZSM-5 catalyst；Modifying element include Zn, P, Ga,
At least one of La, Ag element；For modifying element in terms of the mass percent of catalyst, total content is 0.01~10%.
In above-mentioned technical proposal, it is preferable that catalyst II is loads the ZSM-5 molecular sieve catalyst of Zn, Ga, La, to urge
The mass percent meter of agent, carried metal total content are 0.1~10%.
In above-mentioned technical proposal, it is preferable that alcohol and/or ether raw material (7) include methanol, ethanol, normal propyl alcohol, isopropanol, C4
~C20At least one of alcohol, ethyl methyl ether, dimethyl ether, diethyl ether, Di Iso Propyl Ether；The mass percentage of oxygenatedchemicals is
At least 10%.
Research shows there is the low-carbon of 35~45% carbon-based C1~C6 in the product of alcohol and/or ether raw material aromatization process
Hydrocarbon, if aromatization further occurs for this part lower carbon number hydrocarbons, can effectively improve the virtue of alcohol and/or ether raw material aromatization process
Hydrocarbon-selective.Since alcohol and/or ether raw material aromatization process are there are substantial amounts of dehydrogenation, hydrogen transfer reaction, the alkane in lower carbon number hydrocarbons,
Especially propane, content is higher, and propane content can reach more than 30%.Lower carbon number hydrocarbons obtained by alcohol and/or ether raw material aromatization process
Mixture is the mixture of C1~C6 alkene and alkane.The hydrocarbon and high stability of carbon-carbon bond, aromatization in low-carbon alkanes
Middle to need first dehydrogenation activation generation low-carbon alkene, so being compared with low-carbon alkene aromatisation, difficulty is larger.In addition, C1~C6
Lower carbon number hydrocarbons, carbon number is smaller, and activation difficulty is bigger, is more not susceptible to aromatization.As it can be seen that alcohol and/or ether raw material aromatisation mistake
The Aromatization Activity of all kinds of lower carbon number hydrocarbons differs greatly in low-carbon hydrocarbon mixture obtained by journey.If only with a kind of catalyst and reaction
Condition, otherwise the arenes selectivity that will certainly cause that the lower carbon number hydrocarbons of aromatization easily occurs declines, otherwise difficult occur aromatisation
The lower carbon number hydrocarbons of reaction is largely enriched with because aromatisation conversion ratio is low in reactor, reduces economy.To avoid the phenomenon from occurring,
The arenes selectivity of aromatization of low carbon hydrocarbon obtained by alcohol and/or ether raw material aromatization process is improved, technical scheme is to alcohol
And/or ether raw material enters fluidized-bed reactor I and reacts methane, the C 2 hydrocarbon discharge that aromatisation difficulty is larger in obtained lower carbon number hydrocarbons
System, more than three non-aromatics of carbon enter fluidized-bed reactor II and use relatively mild reaction condition, wherein being easier to that aromatisation occurs
The hydrocarbon of reaction completes the conversion to aromatic hydrocarbons, and the remaining more difficult hydrocarbon that aromatization occurs goes successively to aromatization reactor, uses
Relatively harsh reaction condition.Technical solution using the present invention, aromatic hydrocarbons carbon base absorption rate reach the 78.2 carbon-based receipts of weight %, BTX
Rate reaches 62.6 weight %, achieves preferable technique effect.
Brief description of the drawings
Fig. 1 is the flow diagram of the present invention.
In Fig. 1,1 is fluidized-bed reactor I；2 be regenerator；3 be fluidized-bed reactor II；4 be aromatization reactor；5
For separative element I；6 be separative element II；7 be alcohol and/or ether raw material；8 be reaction product I；9 be main wind；10 be flue gas；11 are
Gas-phase product；12 be water-phase product；13 be aromatic product I；14 be reaction product II；15 be lighter hydrocarbons product；16 be heavy products；
17 be reaction product III；18 be aromatic product II.
Alcohol and/or ether raw material 7 obtain reaction product I 8 into fluidized-bed reactor I 1, and the reaction product I 8 enters separation
Unit I 5 obtains gas-phase product 11, water-phase product 12 and aromatic product I 13, and the gas-phase product 11 fully enters fluidized-bed reaction
The reaction of device II 3 obtains reaction product II 14, and the reaction product II 14 obtains lighter hydrocarbons product 15, heavy hydrocarbon into separative element II 6
Product 16 and aromatic product II 18, the heavy products 16 fully enter aromatization reactor 4 and obtain reaction product III 17, described
Reaction product III 17 enters separative element I 5.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
The raw material that methanol weight percentage composition is 95% obtains reaction product I (8) into fluidized-bed reactor I (1), described
Reaction product I (8) obtains gas-phase product (11), water-phase product (12) and aromatic product I (13) into separative element I (5), described
Gas-phase product (11) fully enters fluidized-bed reactor II (3) reaction and obtains reaction product II (14), the reaction product II
(14) lighter hydrocarbons product (15), heavy products (16) and aromatic product II (18), the heavy hydrocarbon production are obtained into separative element II (6)
Thing (16) fully enters aromatization reactor (4) and obtains reaction product III (17), and it is single that the reaction product III (17) enters separation
First I (5).Lighter hydrocarbons product (15) includes whole C2 alkane in reaction product II (14).Heavy products (16) do not include C2 alkene.
Fluidized-bed reactor I (1) and fluidized-bed reactor II (3) use the Zn-ZSM-5 molecular sieve catalysts that P is modified, Zn
Load quality percentage composition is 0.1%.The reaction bed temperature of fluidized-bed reactor I (1) is 420 DEG C, and weight space velocity is
0.2h-1, reaction pressure is normal pressure.The reaction bed temperature of fluidized-bed reactor II (3) is 480 DEG C, weight space velocity 0.2h-1, reaction pressure is normal pressure.
Aromatization reactor (4) is using the ZSM-5 molecular sieve catalyst for loading Zn, Ga, La, with the quality percentage of catalyst
Than meter, carried metal total content is 0.01%；Reaction bed temperature is 500 DEG C, weight space velocity 0.3h-1, reaction pressure is
Normal pressure.Aromatization reactor (4) is heat-insulating fixed bed reactors, sets two, and one opens standby, reaction and a regeneration switching, then
When the raw cycle is 10 small；Regeneration condition is：Regeneration temperature is 450 DEG C, and regenerating medium is oxygen-containing gas, and oxygen volume content is
0.1%.
Lighter hydrocarbons product (15) is hydrogen, methane and C 2 hydrocarbon, and heavy products (16) are more than three non-aromatics of carbon.
The result shows that it is 52.4 weight % that aromatic hydrocarbons carbon base absorption rate, which is 65.5 weight %, BTX carbon base absorption rates,.
【Embodiment 2】
According to the condition and step described in embodiment 1, the raw material that methanol weight percentage composition is 10% is anti-into fluidized bed
Device I (1) is answered to obtain reaction product I (8)；By weight, the 10% of the gas-phase product (11) enters fluidized-bed reactor II
(3)；By weight, the 10% of the heavy products (16) enters aromatization reactor (4).Lighter hydrocarbons product (15) includes reaction and produces
Whole C2 alkane in thing II (14).Heavy products (16) do not include C2 alkene.
Fluidized-bed reactor I (1) and fluidized-bed reactor II (3) use the Zn-ZSM-5 molecular sieve catalysts that P is modified, Zn
Load quality percentage composition is 10%.The reaction bed temperature of fluidized-bed reactor I (1) is 550 DEG C, weight space velocity 6h-1,
Reaction pressure is 0.5 megapascal in terms of gauge pressure.The reaction bed temperature of fluidized-bed reactor II (3) is 600 DEG C, weight space velocity
For 5h-1, reaction pressure is 0.5 megapascal in terms of gauge pressure.
Aromatization reactor (4) is using the ZSM-5 molecular sieve catalyst for loading Zn, Ga, La, with the quality percentage of catalyst
Than meter, carried metal total content is 15%；Reaction bed temperature is 600 DEG C, weight space velocity 5h-1, reaction pressure is with gauge pressure
Meter, is 0.5 megapascal.Aromatization reactor (4) is calandria type fixed bed reactor, sets two, and one opens standby, reaction and a regeneration
Switching, when the regeneration period is 720 small；Regeneration condition is：Regeneration temperature is 650 DEG C, and regenerating medium is oxygen-containing gas, oxygen volume
Content is 21%.
The result shows that it is 56.8 weight % that aromatic hydrocarbons carbon base absorption rate, which is 72.8 weight %, BTX carbon base absorption rates,.
【Embodiment 3】
According to the condition and step described in embodiment 1, the raw material that methanol weight percentage composition is 10% is anti-into fluidized bed
Device I (1) is answered to obtain reaction product I (8)；By weight, the 100% of the gas-phase product (11) enters fluidized-bed reactor II
(3)；By weight, the 100% of the heavy products (16) enters aromatization reactor (4).Lighter hydrocarbons product (15) includes reaction
Whole C2 alkane in product II (14).Heavy products (16) do not include C2 alkene.
Fluidized-bed reactor I (1) and fluidized-bed reactor II (3) use the Zn-ZSM-5 molecular sieve catalysts that P is modified, Zn
Load quality percentage composition is 5%.The reaction bed temperature of fluidized-bed reactor I (1) is 500 DEG C, weight space velocity 2h-1,
Reaction pressure is 0.2 megapascal in terms of gauge pressure.The reaction bed temperature of fluidized-bed reactor II (3) is 550 DEG C, weight space velocity
For 2h-1, reaction pressure is 0.2 megapascal in terms of gauge pressure.
Aromatization reactor (4) is using the ZSM-5 molecular sieve catalyst for loading Zn, Ga, La, with the quality percentage of catalyst
Than meter, carried metal total content is 5%；Reaction bed temperature is 550 DEG C, weight space velocity 1.5h-1, reaction pressure is with gauge pressure
Meter, is 0.2 megapascal.Aromatization reactor (4) is heat-insulating fixed bed reactors, sets two, and one opens standby, reaction and a regeneration
Switching, when the regeneration period is 200 small；Regeneration condition is：Regeneration temperature is 560 DEG C, and regenerating medium is oxygen-containing gas, oxygen volume
Content is 10%.
The result shows that it is 62.6 weight % that aromatic hydrocarbons carbon base absorption rate, which is 78.2 weight %, BTX carbon base absorption rates,.
【Embodiment 4】
According to the raw material described in embodiment 3, condition and step.
Fluidized-bed reactor I (1) and fluidized-bed reactor II (3) use the Zn-ZSM-5 molecular sieve catalysts that P is modified, Zn
Load quality percentage composition is 3%.
Aromatization reactor (4) is using the ZSM-5 molecular sieve catalyst for loading Zn, Ga, La, with the quality percentage of catalyst
Than meter, carried metal total content is 10%.
The result shows that it is 58.7 weight % that aromatic hydrocarbons carbon base absorption rate, which is 73.4 weight %, BTX carbon base absorption rates,.
【Embodiment 5】
According to the raw material described in embodiment 3, catalyst and step.By weight, the 80% of the gas-phase product (11) into
Fluidized bed reactor II (3)；By weight, the 80% of the heavy products (16) enters aromatization reactor (4).
The result shows that it is 61.4 weight % that aromatic hydrocarbons carbon base absorption rate, which is 76.8 weight %, BTX carbon base absorption rates,.
【Embodiment 6】
According to the catalyst described in embodiment 3, condition and step.Methanol and the original that ethanol gross weight percentage composition is 70%
(weight ratio of methanol and ethanol is 1 to material:1) reaction product I (8) is obtained into fluidized-bed reactor I (1).
The result shows that it is 56.7 weight % that aromatic hydrocarbons carbon base absorption rate, which is 71.8 weight %, BTX carbon base absorption rates,.
【Embodiment 7】
According to the catalyst described in embodiment 3, reaction condition and step.Lighter hydrocarbons product (15) includes reaction product II (14)
In 70% C2 alkane, residue C2 alkane enters heavy products (16) in reaction product II (14).
The result shows that it is 59.5 weight % that aromatic hydrocarbons carbon base absorption rate, which is 75.3 weight %, BTX carbon base absorption rates,.
【Comparative example 1】
According to the catalyst described in embodiment 3, reaction condition and step, lighter hydrocarbons product (15) does not include C2 alkane, reaction
C2 alkane enters heavy products (16) in product II (14).The result shows that aromatic hydrocarbons carbon base absorption rate is carbon-based for 60.2 weight %, BTX
Yield is 48.9 weight %.
【Comparative example 2】
According to the catalyst described in embodiment 3, reaction condition and step, heavy products (16) include C2 alkene.As a result table
Bright, aromatic hydrocarbons carbon base absorption rate is that 69.2 weight %, BTX carbon base absorption rates are 55.4 weight %.
Claims (18)
1. a kind of method of alcohol and/or ether catalytic material conversion for preparing arene, alcohol and/or ether raw material (7) enter fluidized-bed reactor I
(1) reaction product I (8) is obtained, the reaction product I (8) obtains gas-phase product (11), water-phase product into separative element I (5)
(12) enter fluidized-bed reactor II (3) reaction at least partially with aromatic product I (13), the gas-phase product (11) and obtain instead
Product II (14) is answered, the reaction product II (14) obtains lighter hydrocarbons product (15), heavy products (16) into separative element II (6)
With aromatic product II (18), the heavy products (16) obtain reaction product III into aromatization reactor (4) at least partially
(17), the reaction product III (17) enters separative element I (5)；Lighter hydrocarbons product (15) includes at least part C2 alkane.
2. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that lighter hydrocarbons product
(15) whole C2 alkane in reaction product II (14) is included.
3. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that heavy products
(16) C2 alkene is not included.
4. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that fluid bed is anti-
Answer device I (1) and fluidized-bed reactor II (3) common regenerator (2).
5. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that fluid bed is anti-
Device I (1) and fluidized-bed reactor II (3) is answered to use same catalyst, catalyst is ZSM-5 molecular sieve catalyst.
6. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that fluid bed is anti-
The reaction bed temperature for answering device I (1) is 420~550 DEG C, and weight space velocity is 0.2~6h-1, reaction pressure is 0 in terms of gauge pressure
~0.5 megapascal.
7. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that fluid bed is anti-
The reaction bed temperature for answering device II (3) is 480~600 DEG C, and weight space velocity is 0.2~5h-1, reaction pressure is 0 in terms of gauge pressure
~0.5 megapascal.
8. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that aromatisation is anti-
Answer the active component of the catalyst II that device (4) uses for including at least one selection ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve,
MCM-22 molecular sieves or the composite molecular screen formed each other；Catalyst load include it is at least one select Zn, P, Ga, La, Ag,
Element in Cu, Mn, Mg；For each element that catalyst is loaded in terms of the mass percent of catalyst, content is 0.01~15%.
9. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that aromatisation is anti-
It is 500~600 DEG C to answer reaction bed temperature in device (4), and weight space velocity is 0.3~5h-1, reaction pressure in terms of gauge pressure, be 0~
0.5 megapascal.
10. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that lighter hydrocarbons produce
Thing (15) includes hydrogen, methane and C 2 hydrocarbon, and heavy products (16) include more than three non-aromatics of carbon.
11. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that aromatisation
Reactor (4) is heat-insulating fixed bed reactors or calandria type fixed bed reactor or isotherm formula fixed bed reactors.
12. the method for alcohol according to claim 12 and/or ether catalytic material conversion for preparing arene, it is characterised in that aromatisation
Reactor (4) sets at least two, and at least one opens standby, reaction and a regeneration switching, when the regeneration period is 10~720 small.
13. the method for alcohol according to claim 4 and/or ether catalytic material conversion for preparing arene, it is characterised in that the carded sliver again
Part is：Regeneration temperature is 450~650 DEG C, and regenerating medium is oxygen-containing gas, and oxygen volume content is 0.1~21%.
14. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that with weight
Meter, the 10~100% of gas-phase product (11) enters fluidized-bed reactor II (3)；By weight, the 10 of heavy products (16)~
100% enters aromatization reactor (4).
15. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that aromatisation
The reaction bed temperature of fluidized-bed reactor I (1) is 470~530 DEG C.
16. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that catalyst I
For modified ZSM-5 catalyst；Modifying element includes at least one of Zn, P, Ga, La, Ag element；Modifying element is with catalyst
Mass percent meter, total content be 0.01~10%.
17. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that catalyst
II is loads the ZSM-5 molecular sieve catalyst of Zn, Ga, La, and in terms of the mass percent of catalyst, carried metal total content is
0.1~10%.
18. the method for alcohol according to claim 1 and/or ether catalytic material conversion for preparing arene, it is characterised in that alcohol and/or
Ether raw material (7) includes methanol, ethanol, normal propyl alcohol, isopropanol, C4~C20Alcohol, ethyl methyl ether, dimethyl ether, diethyl ether, Di Iso Propyl Ether
At least one of；The mass percentage of oxygenatedchemicals is at least 10%.
Priority Applications (1)
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| CN111116283A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon by using methanol and fusel oil as raw materials |
| CN113121296A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Method for producing light aromatic hydrocarbon |
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| US4590321A (en) * | 1985-06-12 | 1986-05-20 | Mobil Oil Corporation | Aromatization reactions with zeolites containing phosphorus oxide |
| CN101671226A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Process for preparing dimethylbenzene by aromatization of methanol |
| CN101823929A (en) * | 2010-04-14 | 2010-09-08 | 清华大学 | System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether |
| CN103936541A (en) * | 2014-02-24 | 2014-07-23 | 中国海洋石油总公司 | Integrated system and method used for preparing aromatic hydrocarbons from methyl alcohol |
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| US4590321A (en) * | 1985-06-12 | 1986-05-20 | Mobil Oil Corporation | Aromatization reactions with zeolites containing phosphorus oxide |
| CN101671226A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Process for preparing dimethylbenzene by aromatization of methanol |
| CN101823929A (en) * | 2010-04-14 | 2010-09-08 | 清华大学 | System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether |
| CN103936541A (en) * | 2014-02-24 | 2014-07-23 | 中国海洋石油总公司 | Integrated system and method used for preparing aromatic hydrocarbons from methyl alcohol |
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| CN111116283A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon by using methanol and fusel oil as raw materials |
| CN113121296A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Method for producing light aromatic hydrocarbon |
| CN113121296B (en) * | 2020-01-15 | 2022-12-02 | 中国石油天然气股份有限公司 | Method for producing light aromatic hydrocarbon |
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