CN108706607A - A kind of zeolite molecular sieve, preparation method and applications - Google Patents

A kind of zeolite molecular sieve, preparation method and applications Download PDF

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CN108706607A
CN108706607A CN201810711970.0A CN201810711970A CN108706607A CN 108706607 A CN108706607 A CN 108706607A CN 201810711970 A CN201810711970 A CN 201810711970A CN 108706607 A CN108706607 A CN 108706607A
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vanadium
zeolite molecular
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zeolite
molecular sieve
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CN108706607B (en
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王军
周瑜
唐俊杰
马志盼
刘佩雯
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Nanjing Tech University
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention discloses a kind of zeolite molecular sieve and preparation method thereof and applications, belong to technical field of chemistry.The present invention synthesizes the V-Si-ZSM-22 zeolite molecular sieves of different content of vanadium (0-25%) using ionic liquid dry gum method, and wherein vanadium species are mainly with the poly- VO of chain type3 ‑Form, which exists, to be simultaneously connected by vanadium oxygen key with zeolitic frameworks, applied to the quick hydroxylating of aromatic hydrocarbons, substrate and hydrogen peroxide equimolar than ideal conditions under, high phenolic product yield is obtained in the 30s reaction time.Catalyst preparation used in the present invention is simple；Reaction time is extremely short, energy-efficient；Phenolic product high income, lower by-product generate；Using hydrogen peroxide as oxidant, economy and Environmental costs are low；Product and catalyst are easily separated, and post-processing is simple；Catalyst is easy to reuse, environmentally protective, has highly important application prospect.

Description

A kind of zeolite molecular sieve, preparation method and applications
Technical field
The present invention relates to technical field of chemistry, and in particular to be a kind of zeolite catalyst, preparation method and applications.
Background technology
On phenyl ring the aromatic compound (such as phenol and cresols etc.) with hydroxyl group be it is a kind of it is important it is organic in Mesosome, they are widely used as dyestuff, polymer, plastics, the presoma of the chemicals such as drug and pesticide.But for phenols The preparation of compound has energy consumption big during industrial production, and the defect of environmental pollution and peroxidating generates, and anti- The phenolic product yield that should be generated is very low.The direct hydroxylating of phenyl ring of hydrogen peroxide oxidation always is coke of people's attention Point is mainly faced with following challenge however, to design effective catalyst system and catalyzing in such reaction：(1) for benzene On ring (especially for benzene) inertia sp2The activation of c h bond is very difficult；(2) excessive oxidation of part phenolic product makes yield With selective decline；(3) in the oxidation reaction of aromatic compound, the sp on side chain3C h bond is than the sp on aromatic ring2C h bond more holds It is easily aoxidized, because the former bond dissociation energy is more much lower than the latter, is easier to be aoxidized, so that reaction is difficult to give birth to At phenolic product.
When hydrogen peroxide and aromatic compound substrate molar ratio are 1, it is low that there are yields, and selectivity, reaction generally requires ten The reaction time of a few houres completes the reaction.
Invention content
The invention discloses a kind of vanadium base zeolite molecular sieve and its synthetic methods, and by the vanadium base zeolite molecular sieve application In the hydroxylating of aromatic hydrocarbons, aromatic hydrocarbons quickly (30s) hydroxylating can be realized.
The present invention relates to the application of a kind of catalyst, method for preparing catalyst and catalyst, relate generally to pass through ion Liquid dry gum method synthesizes the vanadium base zeolite catalyst of content of vanadium (0-25%), and vanadium species are mainly with the poly- VO of chain type in zeolite3 -Shape Formula, which exists, to be simultaneously connected by vanadium oxygen key with zeolitic frameworks, and in vanadium base zeolite, acetonitrile, and realization is fragrant under the catalystic converter system of sulfuric acid Quickly (30s) hydroxylating, the present invention have probed into the influence and microscopic appearance that different Si/V rate of charges synthesize zeolite to hydrocarbon Influence.The catalytic performance for improving vanadium base zeolite catalyst is will focus on, and there is high selectivity, stability is high, durability is good Feature.
A kind of zeolite molecular sieve, vanadium species are with the poly- VO of chain type in the zeolite molecules sieve structure3 -Form exist and lead to Vanadium oxygen key is crossed with zeolitic frameworks to be connected.
The zeolite molecules sieve structure is V-Si-ZSM-22.
The zeolite molecules sieve structure is 0.05V-Si-ZSM-22, and n represents the molar ratio of V/Si.
By silicon source and vanadium ion complete hydrolysis under acidic aqueous solution, contracting is completed in the environment of template and lye It closes, preparing dry glue, crystallization synthesizes target material in an oven, and the silicon source is positive quanmethyl silicate, tetraethyl orthosilicate, just Tetrabutyl silicate, tetramethoxy-silicane, silicic acid, Ludox or silica, the vanadium ion be ammonium metavanadate, sodium metavanadate, Vanadic sulfate or vanadium acetylacetonate, the acidic aqueous solution are sulfuric acid, nitric acid, hydrochloric acid or perchloric acid, and the template is 1- butyl -3- methylimidazole bromides, 1- butyl -3- methylimidazole villaumites, 1- butyl -3- methylimidazoles salt compounded of iodine or 1- butyl -3- Methyl imidazolium tetrafluoroborate.
Hydrolytic process is happened at acidic aqueous solution and is mixed with tetraethyl orthosilicate and ammonium metavanadate, wherein V/Si's Molar ratio is 0-0.25.In actual mechanical process, calculated with the molar ratio of tetraethyl orthosilicate and ammonium metavanadate.
The step of condensation course is the addition template 1- butyl -3- methylimidazole bromides into mixed solution, is stirred evenly After its dissolving, it is 11 that NaOH solution to pH of latex gel, which is added, this gel is placed in and is stirred at room temperature, dry, is removed in gel Water prepares dry glue.
Crystallization process is dry glue to be put on polytetrafluoroethylene (PTFE) holder, then the holder is put into the polytetrafluoroethylene (PTFE) containing water In the reaction kettle of lining, after which is placed in baking oven crystallization for a period of time, solid product is taken out, washing is filtered, dried Final catalyst nV-Si-ZSM-22 zeolite molecular sieves are obtained after dry, roasting, wherein n represents the molar ratio of V/Si, finally obtains The V-Si-ZSM-22 zeolite molecular sieves of different content of vanadium are expressed as nV-Si-ZSM-22.
The Zeolite molecular sieve catalysis arene hydroxylation reaction.
For vanadium base zeolite molecular sieve as catalyst, acetonitrile is solvent, and sulfuric acid is additive, and hydrogen peroxide is the catalysis of oxidant Arene hydroxylation reaction is carried out under reaction system.
Aromatic hydrocarbons in the arene hydroxylation reaction has benzene, toluene, ethylbenzene, isopropylbenzene, trimethylbenzene, durene, tertiary fourth Base benzene, ortho-xylene, paraxylene, meta-xylene, chlorobenzene, bromobenzene, iodobenzene, benzaldehyde, naphthalene.
ZSM is a kind of molecular sieve, and TON types topological structure, the positive orthorhombic forms in center, port size 4.5 are multiplied by 5.5 angstroms.Nothing Intersect one-dimensional 10 membered ring channel, adjustable acid and duct shape selectivity.
Advantageous effect：
Vanadium species are introduced into zeolite molecular sieve by the present invention by ionic liquid dry gum method, vanadium species in the target material Mainly with the poly- VO of chain type3 -Form exist and be connected with zeolitic frameworks by vanadium oxygen key, in the catalystic converter system, sulfuric acid second Vanadium species are reduced into 4 valence states by nitrile solution, and 4 valence vanadium species are to complete the catalysis to react main activated centre.
Traditional dipping vanadium species there are vanadium state be difficult to control, vanadium species stablize difference the problems such as, and the present invention use from Sub- liquid dry gum method synthesis vanadium base zeolite molecular sieve (V-Si-ZSM-22), with good stability and durability.Through excessively high The valence state of 5 valences is presented in vanadium in the V-Si-ZSM-22 of temperature roasting, and it is activated centre to be different from 5 traditional valence vanadium species, using sulfuric acid Acetonitrile solution restores vanadium species, and 4 valence vanadium species embody fabulous catalytic effect in the quick hydroxylating of aromatic hydrocarbons.
The yield of arene hydroxylation product phenolic compound is 20%~31%, and selectivity is 90%~100%, and conversion is frequently Rate superelevation, vanadium species are with the poly- VO of chain type in zeolite3 -Form exist, under the catalystic converter system of vanadium base zeolite-acetonitrile-sulfuric acid Realize aromatic hydrocarbons quickly (30s) hydroxylating.
After reaction, it is washed with acetonitrile, recycles catalyst, keep good stability and durability.
Catalyst preparation used in the present invention is simple；Reaction time is extremely short, energy-efficient；Phenolic product high income, it is relatively low By-product generate；Using hydrogen peroxide as oxidant, economy and Environmental costs are low；Product and catalyst are easily separated, post-processing letter It is single；Catalyst is easy to reuse, environmentally protective, has highly important application prospect.
Description of the drawings
Fig. 1 is the XRD diagram of nV-Si-ZSM-22.N=0,0.01,0.03,0.05,0.1,0.15,0.2,0.25 is respectively a、b、c、d、e、f、g、h
Fig. 2 is the TEM figures that the SEM (b-d) that (a) is 0.05V-Si-ZSM-22 is 0.05V-Si-ZSM-2
The EXAFS of Fig. 3 (a) (b) (c) 5%V-Si-ZSM-22 schemes.
Fig. 4 is vanadium species structural schematic diagram in zeolite.
Fig. 5 is the schematic diagram that 5%V-Si-ZSM-22 is catalyzed different aromatic hydrocarbons substrates.
Fig. 6 is that 5%V-Si-ZSM-22 is catalyzed reaction stability and durability figure.
Specific implementation mode
Embodiment 1
The dilute acid soln (pH value is about 1~2) that the 4g concentrated sulfuric acids are configured to 1L is weighed first, this for then weighing 25.2g is dilute The TEOS of acid solution and 7.39g and respectively with 0,0.04g, 0.124g, 0.207g, 0.414g, 0.621g, 0.828g, Ammonium metavanadate (the NH of 1.035g4VO3) mixed, magnetic agitation 24 hours at 25 DEG C are placed in, to promote TEOS and metavanadic acid Ammonium (NH4VO3) complete cohydrolysis.After hydrolysis, 2.72g&#91 is added into the mixed solution;Bmim]Br is stirred evenly and is waited for that its is molten 1.7gNaOH solution (12.5mol/L) is added dropwise in Xie Hou.The proportioning for being respectively synthesized gel is 1SiO2∶n NH4VO3∶0.35[Bmim] Br∶0.2Na2O∶40H2O (n=0,0.01,0.03,0.05,0.1,0.15,0.2,0.25) is old under 25 DEG C of water-baths by this gel Change 24 hours, then the gel after aging is placed in 100 DEG C of baking ovens dry 4-5 hours, dry glue is made.
It weighs 0.5g dry glues to be put on polytetrafluoroethylene (PTFE) holder, then the holder is put into the polytetrafluoroethylene (PTFE) containing 0.5g water In the reaction kettle of lining.After the reaction kettle is placed in 170 DEG C of baking ovens crystallization for a period of time, solid product is taken out, by ethyl alcohol And after deionized water washing filters, the molecular screen primary powder not roasted can be obtained within dry 12 hours in 100 DEG C of baking ovens.By the sample Product remove template, the V-Si-ZSM-22 zeolite molecular sieves after being roasted in 5 hours in 550 DEG C of Muffle kiln roastings.(wherein n Represent the molar ratio b, n 0,0.01 of V/Si, 0.03,0.05,0.1,0.15,0.2,0.25, finally obtain different content of vanadium V-Si-ZSM-22 zeolite molecular sieves are expressed as nV-Si-ZSM-22.) such as Fig. 1, shown in 2,3,4.From the EXAFS collection of illustrative plates of Fig. 3 It sees, the state of vanadium species is similar with ammonium metavanadate in 0.05V-Si-ZSM-22, is in the poly- VO of chain type3 -Structure.
Embodiment 2
In order to detect V-Si-ZSM-22 of the present invention, to aromatic hydrocarbons, quickly hydroxylated ability, the present invention answer V-Si-ZSM-22 In being reacted for benzene-series arene hydroxylation, arene compounds quick high-selectivity is quickly produced into phenolic product in 30s. To the yield chromatographic of product phenolic compound, such as Fig. 5, shown in 6 in embodiment.
The hydroxylating of benzene-series aromatic compound carries out in the quartz glass pipe reactor of 25mL, and is having magnetic Heating stirring in the water-bath of power agitating device.
The hydroxylated reaction condition of toluene, chlorobenzene is：By 5mmol toluene, chlorobenzene, 0.1g catalyst (5%V-Si-ZSM- 22), 12mL acetonitriles are added sequentially in reaction tube, and the concentrated sulfuric acid of 0.15g is then added dropwise again.Then in 80 DEG C of heating conditions Under pre- thermal agitation 5mmol hydrogen peroxide is added dropwise afterwards for a period of time, after being added dropwise react 30s after stop reaction.
The hydroxylated reaction condition of benzene, ethylbenzene, tert-butyl benzene, ortho-xylene, meta-xylene is：By 5mmol benzene, ethylbenzene, Tert-butyl benzene, ortho-xylene, meta-xylene, 0.1g catalyst (5%V-Si-ZSM-22), 14mL acetonitriles are added sequentially to react The concentrated sulfuric acid of 0.15g is then added dropwise in Guan Zhong again.Then add dropwise after pre- thermal agitation for a period of time under 80 DEG C of heating conditions Enter 5mmol hydrogen peroxide, stops reaction after 30s is reacted after being added dropwise.
The hydroxylated reaction condition of bromobenzene, iodobenzene, paraxylene is：By 5mmol bromobenzenes, iodobenzene, paraxylene, 0.1g is urged Agent (5%V-Si-ZSM-22), 14mL acetonitriles are added sequentially in reaction tube, and the concentrated sulfuric acid of 0.15g is then added dropwise again. Then 5mmol hydrogen peroxide is added dropwise in pre- thermal agitation afterwards for a period of time under 82 DEG C of heating conditions, after reacting 30s after being added dropwise Stop reaction.
The hydroxylated reaction condition of isopropylbenzene, trimethylbenzene, durene is：By 5mmol isopropylbenzenes, trimethylbenzene, durene, 0.1g catalyst (5%V-Si-ZSM-22), 16mL acetonitriles are added sequentially in reaction tube, and the dense of 0.15g is then added dropwise again Sulfuric acid.Then 5mmol hydrogen peroxide is added dropwise in pre- thermal agitation afterwards for a period of time under 82 DEG C of heating conditions, is reacted after being added dropwise Stop reaction after 30s.
The hydroxylated reaction condition of naphthalene, methyl phenyl ethers anisole is：By 5mmol naphthalenes, methyl phenyl ethers anisole, 0.1g catalyst (5%V-Si-ZSM- 22), 12mL acetonitriles are added sequentially in reaction tube, and the concentrated sulfuric acid of 0.15g is then added dropwise again.Then in 80 DEG C of heating conditions Under pre- thermal agitation 2.5mmol hydrogen peroxide is added dropwise afterwards for a period of time, after being added dropwise react 30s after stop reaction.
It waits for after reaction, Isosorbide-5-Nitrae-dioxane of 30mg is added into reaction solution as internal standard, after 10min is mixed It centrifuges, is 26.2% with the yield of gas chromatographic analysis cresols, selectivity is 91.8%.
In case study on implementation, by taking toluene as an example, selection acetonitrile, water, methanol, ethyl alcohol, dimethylformamide, benzonitrile, acetone, Dimethyl sulfoxide (DMSO) is listed in as solvent, influence of the solvent to toluene hydroxylating in following table 1.
Influence of the different solvent of table 1 to toluene hydroxylating.
The result shows that only acetonitrile as solvent when detect phenolic product, and yield, selectivity and TOF values are all very It is high.The yield of cresols is 26.2% under this condition, and it is 1969h that selectivity, which is 91.8%, TOF values,-1。
In catalysis is reacted, sour introducing can change catalystic converter system to a certain extent, while influence vanadium in catalyst Valence state, by taking toluene hydroxylating as an example, we have chosen different types of influence of the acid to arene compounds hydroxylating. In case study on implementation, sulfuric acid is selected, ascorbic acid, acetic acid, perchloric acid, hydrochloric acid, trifluoromethanesulfonic acid is as acid assistant, and acid assistant is to first The influence of benzene hydroxylation reaction is listed in following table 2.
Influence of the different acid assistant of table 2 to toluene hydroxylating.
The result shows that only under the system that sulfuric acid is added, the yield of phenolic product, selectivity and TOF values reach most Height, this is because under system of the sulfuric acid as auxiliary agent, 5 valence vanadium species are reduced into 4 valences, and 4 valence vanadium species are that may be present Activated centre.
The content of active specy vanadium can also influence aromatic hydrocarbons quickly hydroxylated reaction effect, by taking toluene hydroxylating as an example, I Have chosen the catalyst (0-25%) of different content of vanadium, influence of the different content of vanadium catalyst to toluene hydroxylating is listed in In following table 3.
Influence of the different content of vanadium catalyst of table 3 to toluene hydroxylating.
The result shows that under the system originally the yield of hydroxylating and selectivity increase with the increase of V content, connect It and drastically declines with continuing growing for V content, generate such result, it may be possible to as V content increases to certain journey When spending, the specific surface of catalyst drastically declines to hinder the acquisition of amount of activated position.
Include no acid assistant in addition, we also design influence of several groups of comparative catalysts to toluene hydroxylating, five V 2 O, ammonium metavanadate, V-A1Si-ZSM-22, V2O5@Si-ZSM-22, shadow of the comparative catalyst to toluene hydroxylating Sound is listed in following table 4.
Influence of 4 comparative catalyst of table to toluene hydroxylating.
The result shows that by comparative sample catalyst carry out parallel laboratory test, obtained yield within the scope of 8.3-11.9%, and And its selectivity is relatively low (70.8-83.9%).

Claims (10)

1. a kind of zeolite molecular sieve, it is characterised in that：Vanadium species are with the poly- VO of chain type in the zeolite molecules sieve structure3 -Form It is connected with zeolitic frameworks in the presence of and by vanadium oxygen key.
2. zeolite molecular sieve according to claim 1, it is characterised in that：The zeolite molecules sieve structure is nV-Si- ZSM-22, n represent the molar ratio of V/Si, n 0-0.25.
3. zeolite molecular sieve according to claim 1, it is characterised in that：The zeolite molecules sieve structure is 0.05V- Si-ZSM-22。
4. a kind of preparation method of zeolite molecular sieve, which is characterized in that under acidic aqueous solution that silicon source and vanadium ion is complete Condensation is completed in hydrolysis in the environment of template and lye, and preparing dry glue, crystallization synthesizes target material, the silicon in an oven Source be positive quanmethyl silicate, tetraethyl orthosilicate, positive tetrabutyl silicate, tetramethoxy-silicane, silicic acid, Ludox or silica, The vanadium ion be ammonium metavanadate, sodium metavanadate, vanadic sulfate or vanadium acetylacetonate, the acidic aqueous solution be sulfuric acid, Nitric acid, hydrochloric acid or perchloric acid, the template be 1- butyl -3- methylimidazole bromides, 1- butyl -3- methylimidazole villaumites, 1- butyl -3- methylimidazoles salt compounded of iodine or 1- butyl -3- methyl imidazolium tetrafluoroborates.
5. preparation method according to claim 4, it is characterised in that：Hydrolytic process is happened in acidic aqueous solution medium, It is mixed with tetraethyl orthosilicate and ammonium metavanadate, wherein the molar ratio of V/Si is 0-0.25.
6. preparation method according to claim 4, it is characterised in that：The step of condensation course, is added into mixed solution Template 1- butyl -3- methylimidazole bromides stir evenly after its dissolving, and it is 11 that NaOH solution to pH of latex gel, which is added, by this Gel is placed in be stirred at room temperature, dry, and the water removed in gel prepares dry glue.
7. preparation method according to claim 3, it is characterised in that：Crystallization process is that dry glue is put in polytetrafluoroethylene (PTFE) branch On frame, then the holder is put into the reaction kettle of the teflon lined containing water, which is placed in crystallization in baking oven Afterwards, solid product is taken out, washing is filtered, is dried, obtaining final catalyst nV-Si-ZSM-22 zeolite molecular sieves after roasting, Middle n represents the molar ratio of V/Si, and the V-Si-ZSM-22 zeolite molecular sieves for finally obtaining different content of vanadium are expressed as nV-Si-ZSM- 22。
8. a kind of application of zeolite molecular sieve as described in claim 1-7 any one, it is characterised in that：The zeolite point Son sieve catalyzing aromatic hydrocarbon hydroxylating.
9. application according to claim 8, it is characterised in that：For vanadium base zeolite molecular sieve as catalyst, acetonitrile is solvent, Sulfuric acid is additive, and hydrogen peroxide is progress arene hydroxylation reaction under the catalystic converter system of oxidant.
10. application according to claim 8, it is characterised in that：Aromatic hydrocarbons in the arene hydroxylation reaction has benzene, first Benzene, ethylbenzene, isopropylbenzene, trimethylbenzene, durene, tert-butyl benzene, ortho-xylene, paraxylene, meta-xylene, chlorobenzene, bromobenzene, iodine Benzene, benzaldehyde, naphthalene.
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