CN106866328A - A kind of method of methyl alcohol high selectivity aromatic hydrocarbons - Google Patents
A kind of method of methyl alcohol high selectivity aromatic hydrocarbons Download PDFInfo
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- CN106866328A CN106866328A CN201710029643.2A CN201710029643A CN106866328A CN 106866328 A CN106866328 A CN 106866328A CN 201710029643 A CN201710029643 A CN 201710029643A CN 106866328 A CN106866328 A CN 106866328A
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- 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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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/76—Iron group metals or copper
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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Abstract
A kind of method of methyl alcohol high selectivity aromatic hydrocarbons, is related to aromatic hydrocarbons.Catalyst is pre-processed；Catalytic reaction：Catalyst after pretreatment, is passed through reaction raw materials, and it is that methyl alcohol and hydrogen capture remove agent to constitute, and is 500~10000h in air speed‑1Under conditions of react to obtain product aromatics by solid catalyst bed.Ultrasonic disperse is carried out during the salt compounds of metallic element are added into solvent, modified acidic zeolite is added, continues ultrasonic disperse, obtain mixture；After by mixture suction filtration, washing, by gained filtration cakes torrefaction；By the roasting of dried sample, after reduction, catalyst is obtained final product.Implementing the reaction of methyl alcohol aromatic hydrocarbons using the method has excellent arenes selectivity, low methane and C5+The characteristics of hydrocarbon-selective, high catalyst stability, wherein arenes selectivity, methane selectively was less than 2% up to more than 85%.
Description
Technical field
The present invention relates to aromatic hydrocarbons, more particularly, to a kind of method of methyl alcohol high selectivity aromatic hydrocarbons.
Background technology
Aromatic hydrocarbons is important Elementary Chemical Industry raw material, and the benzene, toluene and dimethylbenzene (i.e. BTX) in light aromatics are petrochemical industries
The most important basic chemical of product.The production of current aromatic hydrocarbons is mainly derived from petroleum path, including catalytic reforming, naphtha add
Hydrogen, pyrolysis gasoline hydrogenation and aromatic hydrocarbons conversion etc..A large amount of by oil use brought resource exhaustion and environmental pollution etc. to ask
Topic is increasingly serious, therefore the method for exploitation Non oil-based route production aromatic hydrocarbons is particularly urgent.On the other hand, from coal methyl alcohol skill
Art is quite ripe, and methyl alcohol can be obtained including the important industrial chemicals including alkene, aromatic hydrocarbons through acid catalyzed conversion.Therefore, open
Hair methyl alcohol aromatic hydrocarbons technology can provide a kind of good approach for high-efficiency cleaning using coal resources, and can substitute or partly replace
It is a kind of strategy of sustainable development for tallying with the national condition for petroleum resources route.
The Research Challenges of the direct aromatic hydrocarbons processed of methyl alcohol essentially consist in high selectivity, the development of high stability catalyst.Wei Fei etc.
It was found that the selectivity of aromatic hydrocarbons is 55% on the H-ZSM-5 catalyst of Ag loads, and based on dimethylbenzene, modified with Zn and P
Aromatics yield improves to 75% (Acta Phys.-Chim.Sin., 2013,29,1281) on H-ZSM-5 catalyst.Freeman
Etc. the methyl alcohol aromatic hydrocarbons performance for having investigated 13 groups of oxides and H-ZSM-5 molecular sieve physical mixeds, the addition energy of gallium oxide is issued
Significantly improve C8And C9The yield (Catal.Lett., 2002,82,217) of aromatic hydrocarbons.Ono etc. is it has also been found that Ga/H-ZSM-5 and Zn/H-
ZSM-5 is preferable aromatization of methanol catalyst, yield be respectively 48% and 67% (Faraday Transactions, 1988,
84,1091).Barthos etc. has investigated metal carbides Mo2The MTA reactions of the H-ZSM-5 catalyst of C loads, as a result show carbon
Changing molybdenum equally can well improve the yield of aromatic hydrocarbons, and aromatics yield can reach 63% when the load capacity of molybdenum carbide is 5%, than nothing
The yield of load improves twice (J.Catal., 2007,247,368).Additionally, La helping as Zn/H-ZSM-5 catalyst
Agent, it is also possible to improve the yield of aromatic hydrocarbons, aromatics yield is 64% (J.Chem.Eng., 2011,19,439).Chinese patent
CN200610012703.1 reports the process that methyl alcohol is converted into aromatic hydrocarbons, with modified zsm-5 zeolite as catalyst, such as Ga and La
Modified arenes selectivity is 70%~75%.Chinese patent CN 201010261730.9 reports Zn and Ni or P and H-ZSM-
5 mixture is catalyst, and arenes selectivity is about 70%.
Although result above can obtain of a relatively high arenes selectivity, C in partial catalyst9+Arene content compared with
Greatly, and light aromatics BTX selectivity it is then not high, and the studies above major part be all within the shorter reaction time (typically it is small
In 10h) obtain experimental data.In majority reaction, with the carrying out of reaction, there is carbon distribution on catalyst, cover catalysis
Acid activity center in agent, causes catalyst activity to reduce, or even catalyst promoter metal sintering phenomenon, catalyst stabilization occurs
Poor, the lifetime of property.Therefore it is this that exploitation has aromatics yield high, the method for the methyl alcohol aromatic hydrocarbons of high stability and catalyst
Can reaction industrialized key.
The content of the invention
The present invention is intended to provide a kind of method of methyl alcohol high selectivity aromatic hydrocarbons.
The method of the methyl alcohol high selectivity aromatic hydrocarbons is comprised the following steps：
1) catalyst pretreatment, the catalyst is metal oxide/acidic zeolite compound；
In step 1) in, the preparation method of the metal oxide/acidic zeolite compound can be：
(1) ultrasonic disperse is carried out in the salt compounds of metallic element being added into solvent, modified acid zeolite point is added
Son sieve, continues ultrasonic disperse, obtains mixture；
In step (1), the salt compounds of the metallic element and the mass ratio of solvent can be 1 ︰ (0-100)；It is described
Salt compounds may be selected from least one in nitrate, hydrochloride, acetylacetonate, acetate, bromide etc.；The ultrasound
The scattered time can be 0.5~10h；The time for continuing ultrasonic disperse can be 0.5~10h.
(2) after the mixture suction filtration, the washing that obtain step (1), by gained filtration cakes torrefaction；
In step (2), the drying can be using vacuum drying, and dry temperature can be 40~100 DEG C, dry time
Can be 1~48h.
(3) by the dried sample roasting of step (2), after reduction, catalyst is obtained final product.
In step (3), the method for the roasting can be：Dried sample is moved in tube furnace and is used containing NO
NO/Ar mixed gas are calcined, heating rate be 0.5~2 DEG C/min, temperature be 300~650 DEG C, roasting time be 1~
24h；The percent by volume of NO can be 5%~20% in the NO/Ar mixed gas；The reduction can be using containing H2Atmosphere enter
Row reduction, H2Percent by volume can be 5%~50%, heating rate be 0.5~5 DEG C/min, temperature be 250~500 DEG C, also
The former time is 0.5~10h.
The specific method of catalyst pretreatment can be：By catalyst in the inert gas of nitrogen, argon gas or helium
300~650 DEG C are heated to from room temperature to be not higher than the heating rate of 20 DEG C/min, and keep 10~300min.
2) catalytic reaction：Catalyst after pretreatment, is passed through reaction raw materials, constitute capture for methyl alcohol and hydrogen-remove agent,
Air speed is 500~10000h-1Under conditions of react to obtain product aromatics by solid catalyst bed.
In step 2) in, the methyl alcohol and hydrogen capture-remove the mol ratio that methyl alcohol in agent captured-removed agent with hydrogen can be
(0.05~100) ︰ 1；The hydrogen captures-removes agent and may be selected from carbon monoxide, carbon dioxide, sulfur dioxide, unsaturated olefin, no
At least one in saturation alkynes, nitrogen oxides, aldehyde compound, ketone compounds etc.；The unsaturated olefin may be selected from second
At least one in alkene, propylene, butylene, amylene, hexene etc.；The unsaturated alkyne is acetylene, propine, one kind of butine or many
Kind, the nitrogen oxides is at least one in nitric oxide, nitrogen dioxide, nitrous oxide etc., and the aldehyde compound is
At least one in acetaldehyde, propionic aldehyde, butyraldehyde, valeral, benzaldehyde etc., the ketone compounds may be selected from acetone, butanone, pentanone,
At least one in cyclohexanone etc.；The unsaturated olefin may be selected from least in ethene, propylene, butylene, amylene, hexene etc.
Kind；The unsaturated alkyne may be selected from least one in acetylene, propine, butine etc., and the nitrogen oxides may be selected from an oxidation
At least one in nitrogen, nitrogen dioxide, nitrous oxide etc., the aldehyde compound may be selected from acetaldehyde, propionic aldehyde, butyraldehyde, valeral,
At least one in benzaldehyde etc., the ketone compounds may be selected from least one in acetone, butanone, pentanone, cyclohexanone etc..
The composition of the solid catalyst is metal and the mixture of modified acidic zeolite, or metal oxide and modified acidity
The mass percent of the mixture of zeolite molecular sieve, wherein metal or metal oxide can be 0.5%~40%, and remaining is modified
Acidic zeolite；The metal may be selected from Cu, Fe, Ni, Co, Ru, Au, Pt, Pd, Ir, Zn, Zr, Ga, Cr, M, Ti, W etc.
In at least one, the metal oxide may be selected from Cu, Fe, Ni, Co, Ru, Au, Pt, Pd, Ir, Zn, Zr, Ga, Cr, M, Ti,
At least one in oxide of the metals such as W etc.；The optional Zn that hangs oneself of modified acidic zeolite, Zr, Mn, Mo, Cu,
At least one element in Cr, Ga etc. carries out the modified zeolite molecular sieve of the method such as including ion exchange, wherein modifying element
Weight/mass percentage composition can be 0.1%~10.0%, and remaining is acidic zeolite；The acidic zeolite may be selected from H-
At least one in MCM-22, H-Beta, H-Y, H-X, H-ZSM-5, H-MOR, H-SSZ-13 etc.；The temperature of the reaction can be
300~600 DEG C, the pressure of reaction can be 0.1~5.0MPa.
Compared with prior art, technique effect of the invention is as follows：
(1) present invention shows that excellent methyl alcohol arenes catalytic performance, i.e. hydrogen capture-remove the addition of agent and remarkably promotes
The selectivity of aromatic hydrocarbons, product is distributed the characteristics of being in low methane, low heavy paraffin hydrocarbon, arenes selectivity high, and arenes selectivity is reachable
More than 90%.
(2) reaction raw materials hydrogen capture-remove agent can under catalyst action with aromatization of methanol remove hydrogen enter
One step hydrogenation reaction, so as to suppress hydrogen transfer reaction, improves arenes selectivity.
(3) catalyst for being used is the new catalyst of multi-functional collaboration coupling, and modified zeolite molecular sieve is responsible for methyl alcohol
The dehydrogenation reaction of aromatisation aromatic hydrocarbons, metal or metal oxide promoted aromatization process, further improves arenes selectivity.
(4) because course of reaction has a large amount of hydrogen elimination reactions, hydrogen can at reaction conditions eliminate the product on catalyst
Carbon, therefore improve the reaction life-span.
(5) catalyst preparation process for being used is simple and controllable, and easily prepared by being amplified.
To sum up, aromatic product selectivity high can be obtained using the present invention, and is had good stability, should with preferable industry
Use prospect.
Specific embodiment
The method for illustrating methyl alcohol high selectivity aromatic hydrocarbons provided by the present invention in detail further below, but the present invention is not
Therefore it is any way limited.
Embodiment 1
Weigh 2.0g Cu (NO3)2·3H2O, being added in 30g absolute ethyl alcohols carries out ultrasonic disperse, and the time is 4h；Weigh
The Zn ion modification H-beta zeolite molecular sieves (Zn contents are 0.5wt%) of 3.0g, are added in above-mentioned solution, continue ultrasound
5h；By the mixture suction filtration after ultrasonic disperse, washing, gained filter cake is moved in vacuum drying chamber in drying 24h at 80 DEG C；By institute
Obtain sample to move in tube furnace, be passed through the NO/Ar mixed gas containing volume fraction 10%NO, be warming up to the speed of 2 DEG C/min
6h is calcined at 550 DEG C；By the sample after calcining using containing 10%H2The atmosphere of/Ar is under 400 DEG C (heating rate is 1 DEG C/min)
Reduction 4h, gained sample is catalyst.
Catalytic reaction is carried out in fixed-bed micro-reactor.1.0g catalyst is taken, from room temperature with 5 in nitrogen atmosphere
DEG C/heating rate of min is heated to 550 DEG C, and keeps 60min.Be passed through afterwards methyl alcohol and carbon monoxide (methyl alcohol and carbon monoxide
Mol ratio is 10:1), reaction pressure be 0.5MPa, air speed be 4000h-1, reaction temperature be 500 DEG C under conditions of by catalysis
Agent bed reacts, and the time is 50h.The gas-chromatography on-line analysis of product and unstripped gas.Specific reactivity worth result is listed in
In table 1.
Table 1
Note：C2-4It is C2-C4Hydrocarbon, Aromatics is aromatic hydrocarbons (benzene and many methyl substituted benzenes), Other C5+It is carbon number >=5
Alkane and alkene.
Embodiment 2
Weigh 3.5g Fe (NO3)3·9H2O, being added in 50g water carries out ultrasonic disperse, and the time is 4h；Weigh 3.0g's
Zr ion modification H-MOR zeolite molecular sieves (Zr contents are 0.5wt%), are added in above-mentioned solution, continue ultrasound 5h；By ultrasound
Mixture suction filtration after dispersion, washing, gained filter cake are moved in vacuum drying chamber in drying 24h at 80 DEG C；Gained sample is moved
To tube furnace, the NO/Ar mixed gas containing volume fraction 10%NO are passed through, are warming up at 550 DEG C with the speed of 2 DEG C/min and forged
Burn 6h；By the sample after calcining using containing 10%H2The atmosphere of/Ar in reducing 4h under 400 DEG C (heating rates be 1 DEG C/min), institute
Obtain sample and be catalyst.
Catalytic reaction is carried out in fixed bed high pressure microreactor, is methyl alcohol and ethene (charging mole except raw material is added
Than being 10:1) outward, with embodiment 1, reactivity worth is shown in Table 1 for reaction condition and product analysis.
Embodiment 3
Weigh 3.0g Co (NO3)2·6H2O, (water and ethanol mass ratio are 1 in being added to 45g water and alcohol mixed solution:
1) ultrasonic disperse is carried out, the time is 4h；(Cu contents are to weigh the Cu ion modification H-MCM-22 zeolite molecular sieves of 3.0g
0.5wt%), it is added in above-mentioned solution, continues ultrasound 5h；Mixture suction filtration after ultrasonic disperse, washing, gained filter cake are moved
In drying 24h at 80 DEG C in vacuum drying chamber；Gained sample is moved in tube furnace, is passed through containing volume fraction 10%NO's
NO/Ar mixed gas, are warming up at 550 DEG C with the speed of 2 DEG C/min and calcine 6h；By the sample after calcining using containing 10%H2/
In 4h is reduced under 400 DEG C (heating rate is 1 DEG C/min), gained sample is catalyst to the atmosphere of Ar.
Catalytic reaction is carried out in fixed bed high pressure microreactor, is methyl alcohol and acetaldehyde (charging mole except raw material is added
Than being 15:1) outward, with embodiment 1, reactivity worth is shown in Table 1 for reaction condition and product analysis.
Embodiment 4
Weigh 5.2g Zn (NO3)2·6H2O, being added in 50g absolute ethyl alcohols carries out ultrasonic disperse, and the time is 4h；Weigh
The Mo ion modification H-ZSM-5 zeolite molecular sieves (Mo contents are 0.5wt%) of 3.0g, are added in above-mentioned solution, continue ultrasound
5h；By the mixture suction filtration after ultrasonic disperse, washing, gained filter cake is moved in vacuum drying chamber in drying 24h at 80 DEG C；By institute
Obtain sample to move in tube furnace, be passed through the NO/Ar mixed gas containing volume fraction 10%NO, be warming up to the speed of 2 DEG C/min
6h is calcined at 550 DEG C；By the sample after calcining using containing 10%H2The atmosphere of/Ar is under 400 DEG C (heating rate is 1 DEG C/min)
Reduction 4h, gained sample is catalyst.
Catalytic reaction is carried out in fixed bed high pressure microreactor, is methyl alcohol and carbon dioxide (charging except raw material is added
Mol ratio is 8:1) outward, with embodiment 1, reactivity worth is shown in Table 1 for reaction condition and product analysis.
Embodiment 5
Weigh 1.2g PdCl2, being added in 50g water carries out ultrasonic disperse, and the time is 4h；The Zr ions for weighing 3.0g change
Property H-Y zeolite molecular sieves (Zr contents are 0.5wt%), be added in above-mentioned solution, continue ultrasound 5h；It is mixed after by ultrasonic disperse
Compound suction filtration, washing, gained filter cake are moved in vacuum drying chamber in drying 24h at 80 DEG C；Gained sample is moved in tube furnace,
The NO/Ar mixed gas containing volume fraction 10%NO are passed through, are warming up at 550 DEG C with the speed of 2 DEG C/min and are calcined 6h；Will calcining
Sample afterwards is using containing 10%H2In 4h is reduced under 400 DEG C (heating rate is 1 DEG C/min), gained sample is the atmosphere of/Ar
Catalyst.
Catalytic reaction is carried out in fixed bed high pressure microreactor, is methyl alcohol and acetylene (charging mole except raw material is added
Than being 15:1) outward, with embodiment 1, reactivity worth is shown in Table 1 for reaction condition and product analysis.
Embodiment 6
Weigh 5.2g NiCl2·6H2O, being added in 50g absolute ethyl alcohols carries out ultrasonic disperse, and the time is 4h；Weigh 3.0g
Ga ion modification H-SSZ-13 zeolite molecular sieves (Ga contents be 0.5wt%), be added in above-mentioned solution, continue ultrasound 5h；
By the mixture suction filtration after ultrasonic disperse, washing, gained filter cake is moved in vacuum drying chamber in drying 24h at 80 DEG C；By gained
Sample is moved in tube furnace, is passed through the NO/Ar mixed gas containing volume fraction 10%NO, and 550 are warming up to the speed of 2 DEG C/min
6h is calcined at DEG C；By the sample after calcining using containing 10%H2The atmosphere of/Ar is gone back under 400 DEG C (heating rate is 1 DEG C/min)
Former 4h, gained sample is catalyst.
Catalytic reaction is carried out in fixed bed high pressure microreactor, is methyl alcohol and butanone (charging mole except raw material is added
Than being 10:1) outward, with embodiment 1, reactivity worth is shown in Table 1 for reaction condition and product analysis.
Embodiment 7
Weigh 1.8g RuCl3, being added in 30g water carries out ultrasonic disperse, and the time is 4h；The Cr ions for weighing 3.0g change
Property H-X zeolite molecular sieves (Cr contents are 0.5wt%), be added in above-mentioned solution, continue ultrasound 5h；It is mixed after by ultrasonic disperse
Compound suction filtration, washing, gained filter cake are moved in vacuum drying chamber in drying 24h at 80 DEG C；Gained sample is moved in tube furnace,
The NO/Ar mixed gas containing volume fraction 10%NO are passed through, are warming up at 550 DEG C with the speed of 2 DEG C/min and are calcined 6h；Will calcining
Sample afterwards is using containing 10%H2In 4h is reduced under 400 DEG C (heating rate is 1 DEG C/min), gained sample is the atmosphere of/Ar
Catalyst.
Catalytic reaction is carried out in fixed bed high pressure microreactor, and reaction condition and product analysis are with embodiment 1, reaction
Performance is shown in Table 1.
Embodiment 8
Weigh 1.5g IrCl3, being added in 30g absolute ethyl alcohols carries out ultrasonic disperse, and the time is 4h；Weigh the Mn of 3.0g
Ion modification H-ZSM-5 zeolite molecular sieves (Mn contents are 0.5wt%), are added in above-mentioned solution, continue ultrasound 5h；By ultrasound
Mixture suction filtration after dispersion, washing, gained filter cake are moved in vacuum drying chamber in drying 24h at 80 DEG C；Gained sample is moved
To tube furnace, the NO/Ar mixed gas containing volume fraction 10%NO are passed through, are warming up at 550 DEG C with the speed of 2 DEG C/min and forged
Burn 6h；By the sample after calcining using containing 10%H2The atmosphere of/Ar in reducing 4h under 400 DEG C (heating rates be 1 DEG C/min), institute
Obtain sample and be catalyst.
Catalytic reaction is carried out in fixed bed high pressure microreactor, and reaction condition and product analysis are with embodiment 2, reaction
Performance is shown in Table 1.
Comparative example 1
Catalyst preparation is with embodiment 4.
Catalytic reaction is carried out in fixed bed high pressure microreactor, in addition to only methyl alcohol is added in reaction raw materials, reacts bar
, with embodiment 4, reactivity worth is shown in Table 1 for part and product analysis.
Comparative example 2
1.0gH-ZSM-5 molecular sieves are weighed, through compression molding as catalyst.
Catalytic reaction is carried out in fixed bed high pressure microreactor, and reaction condition and product analysis are with embodiment 4, reaction
Performance is shown in Table 1.
Claims (10)
1. a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that it is comprised the following steps：
1) catalyst pretreatment, the catalyst is metal oxide/acidic zeolite compound；
2) catalytic reaction：Catalyst after pretreatment, is passed through reaction raw materials, constitute capture for methyl alcohol and hydrogen-agent is removed, in air speed
It is 500~10000h-1Under conditions of react to obtain product aromatics by solid catalyst bed.
2. as claimed in claim 1 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that in step 1) in, the gold
Belong to oxide/acidic zeolite compound preparation method be：
(1) ultrasonic disperse is carried out in the salt compounds of metallic element being added into solvent, modified acidic zeolite is added,
Continue ultrasonic disperse, obtain mixture；
(2) after the mixture suction filtration, the washing that obtain step (1), by gained filtration cakes torrefaction；
(3) by the dried sample roasting of step (2), after reduction, catalyst metal oxide/acidic zeolite is obtained final product multiple
Compound.
3. as claimed in claim 2 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that in step 1) (1st) part
In, the salt compounds of the metallic element are 1 ︰ (0~100) with the mass ratio of solvent；The salt compounds are selected from nitric acid
At least one in salt, hydrochloride, acetylacetonate, acetate, bromide；The time of the ultrasonic disperse is 0.5~10h；
The time for continuing ultrasonic disperse is 0.5~10h.
4. as claimed in claim 2 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that in step 1) (2nd) part
In, described dry using vacuum drying, dry temperature is 40~100 DEG C, and the dry time is 1~48h.
5. as claimed in claim 2 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that in step 1) (3rd) part
In, the method for the roasting is：Dried sample is moved in tube furnace and is roasted using the NO/Ar mixed gas containing NO
Burn, heating rate is 0.5~2 DEG C/min, temperature is 300~650 DEG C, and roasting time is 1~24h；The NO/Ar mixed gas
The percent by volume of middle NO is 5%~20%；The reduction can be using containing H2Atmosphere reduced, H2Percent by volume can
It is 5%~50%, heating rate is 0.5~5 DEG C/min, temperature is 250~500 DEG C, and the recovery time is 0.5~10h.
6. as claimed in claim 1 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that in step 1) in, it is described to urge
Agent pretreatment specific method be：By catalyst in the inert gas of nitrogen, argon gas or helium from room temperature being not higher than 20
DEG C/heating rate of min is heated to 300~650 DEG C, and keeps 10~300min.
7. as claimed in claim 1 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that in step 2) in, the first
It is (0.05~100) ︰ 1 that alcohol and hydrogen capture-remove the mol ratio that methyl alcohol captured-removed agent with hydrogen in agent；The hydrogen capture-remove
Agent is selected from carbon monoxide, carbon dioxide, sulfur dioxide, unsaturated olefin, unsaturated alkyne, nitrogen oxides, aldehyde compound, ketone
At least one in class compound；The unsaturated olefin is selected from least one in ethene, propylene, butylene, amylene, hexene；
The unsaturated alkyne is selected from least one in acetylene, propine, butine, and the nitrogen oxides is selected from nitric oxide, titanium dioxide
At least one in nitrogen, nitrous oxide, the aldehyde compound be selected from acetaldehyde, propionic aldehyde, butyraldehyde, valeral, benzaldehyde in extremely
Few one kind, the ketone compounds are selected from least one in acetone, butanone, pentanone, cyclohexanone；The unsaturated olefin is selected from
At least one in ethene, propylene, butylene, amylene, hexene；The unsaturated alkyne be selected from acetylene, propine, butine at least
One kind, the nitrogen oxides is selected from least one in nitric oxide, nitrogen dioxide, nitrous oxide, the aldehyde compound
Selected from least one in acetaldehyde, propionic aldehyde, butyraldehyde, valeral, benzaldehyde, the ketone compounds be selected from acetone, butanone, pentanone,
At least one in cyclohexanone.
8. as claimed in claim 1 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that in step 2) in, it is described solid
The mixture constituted as metal and modified acidic zeolite of body catalyst, or metal oxide and modified acid zeolite point
The mixture of son sieve, the wherein mass percent of metal or metal oxide are 0.5%~40%, and remaining is modified acid zeolite
Molecular sieve；The metal is selected from least one in Cu, Fe, Ni, Co, Ru, Au, Pt, Pd, Ir, Zn, Zr, Ga, Cr, M, Ti, W,
The metal oxide be selected from Cu, Fe, Ni, Co, Ru, Au, Pt, Pd, Ir, Zn, Zr, Ga, Cr, M, Ti, W oxide in extremely
Few one kind.
9. as claimed in claim 8 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that the modified acid zeolite
Molecular sieve is selected from the zeolite molecular sieve being modified through at least one element in Zn, Zr, Mn, Mo, Cu, Cr, Ga, wherein modified
The weight/mass percentage composition of element is 0.1%~10.0%, and remaining is acidic zeolite；The temperature of the reaction be 300~
600 DEG C, the pressure of reaction is 0.1~5.0MPa.
10. as claimed in claim 9 a kind of method of methyl alcohol high selectivity aromatic hydrocarbons, it is characterised in that the side being modified
Method uses ion-exchange process.
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