CN107986294A - A kind of Titanium Sieve Molecular Sieve containing vanadium and its synthetic method and application - Google Patents
A kind of Titanium Sieve Molecular Sieve containing vanadium and its synthetic method and application Download PDFInfo
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- CN107986294A CN107986294A CN201610963960.7A CN201610963960A CN107986294A CN 107986294 A CN107986294 A CN 107986294A CN 201610963960 A CN201610963960 A CN 201610963960A CN 107986294 A CN107986294 A CN 107986294A
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- C01—INORGANIC CHEMISTRY
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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
- C01B39/08—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 the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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- B01J29/00—Catalysts comprising molecular sieves
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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
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- 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
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Abstract
The present invention relates to catalysis material field, and specifically providing a kind of Titanium Sieve Molecular Sieve containing vanadium and its synthetic method and application, this method includes：(1) by vanadium source, ammonia source, alternatively water is mixed to obtain the first mixture；(2) in the presence of template, by titanium source, organic silicon source, first mixture, alternatively water is mixed to get the second mixture；(3) second mixture is subjected to the first hydrothermal crystallizing, obtains the mixed slurry A that solid content is not higher than 20 weight %；(4) the mixed slurry A is concentrated to give to the mixed slurry B and liquid phase C of solid content increase at least 50%；(5) the mixed slurry B is subjected to the second hydrothermal crystallizing, recycling obtains Titanium Sieve Molecular Sieve containing vanadium.The Titanium Sieve Molecular Sieve containing vanadium of the present invention, high catalytic efficiency, application benefit are good.The method of the present invention is simple without particular/special requirement, preparation process to raw material.The method of the present invention improves solid content, which thereby enhances the production capacity of closed container.
Description
Technical field
The present invention relates to a kind of Titanium Sieve Molecular Sieve containing vanadium and its synthetic method and application.
Background technology
V-Si molecular sieve VS-1 with MFI crystal structures is to introduce transition metal vanadium with ZSM-5 structures
A kind of new V-Si molecular sieve with superior catalytic selective oxidation performance formed in framework of molecular sieve.VS-1 not only has
There are the catalysed oxidn of vanadium, but also the shape-selective effect with ZSM-5 molecular sieve and excellent stability.Due to VS-1 molecules
Sieve can use free of contamination low concentration hydrogen peroxide to avoid oxidizing process as oxidant in the oxidation reaction of organic matter
The problem of complex process and pollution environment, there is the unrivaled energy saving, economy of conventional oxidation system and advantages of environment protection,
And there is good reaction selectivity, therefore there is great prospects for commercial application.
The content of the invention
It is an object of the present invention to provide a kind of high Titanium Sieve Molecular Sieve containing vanadium of catalytic oxidation activity and its synthetic method and
Using.
To realize object defined above, according to the first aspect of the invention, the present invention provides a kind of Titanium Sieve Molecular Sieve containing vanadium
Synthetic method, this method include：(1) by vanadium source, ammonia source, alternatively water is mixed to obtain the first mixture；(2) in template
In the presence of, by titanium source, organic silicon source, first mixture, alternatively water is mixed to get the second mixture；(3) by described
Two mixtures carry out the first hydrothermal crystallizing, obtain the mixed slurry A that solid content is not higher than 20 weight %；(4) by the mixing slurry
Material A is concentrated to give the mixed slurry B and liquid phase C of solid content increase at least 50%；(5) the mixed slurry B is carried out
Second hydrothermal crystallizing, recycling obtain Titanium Sieve Molecular Sieve containing vanadium.
According to the second aspect of the invention, the present invention provides the silicon point of titanium containing vanadium that the method according to the invention synthesizes
Son sieve.
According to the third aspect of the invention we, the present invention provides Titanium Sieve Molecular Sieve containing vanadium of the present invention in oxidation reaction
In application.
The Titanium Sieve Molecular Sieve containing vanadium of the present invention, high catalytic efficiency, application benefit are good.
The method of the present invention is simple without particular/special requirement, preparation process to raw material.
The method of the present invention improves solid content, which thereby enhances the production capacity of closed container.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As it was previously stated, the present invention provides a kind of synthetic method of Titanium Sieve Molecular Sieve containing vanadium, this method includes：
(1) by vanadium source, ammonia source, alternatively water is mixed to obtain the first mixture；
(2) in the presence of template, by titanium source, organic silicon source, first mixture, alternatively water is mixed to get second
Mixture；
(3) second mixture is subjected to the first hydrothermal crystallizing, obtains the mixing slurry that solid content is not higher than 20 weight %
Expect A；
(4) the mixed slurry A is concentrated to give to the mixed slurry B and liquid phase C of solid content increase at least 50%；
(5) the mixed slurry B is subjected to the second hydrothermal crystallizing, recycling obtains Titanium Sieve Molecular Sieve containing vanadium.
, according to the invention it is preferred to non-water substance (solute) content is 0.01-50 weights in the first mixture in step (1)
% is measured, is preferably 0.02-25 weight %, more preferably 0.05-10 weight %, are most preferably 0.1-5 weight %.
According to the present invention, the condition being mixed in step (1) includes：Temperature is that room temperature to 80 DEG C and/or time are
0.1-24h, preferably room temperature are to 60 DEG C and/or time 0.5-12h.It is possible thereby to further improve the Titanium Sieve Molecular Sieve containing vanadium property
Energy.
In the present invention, the material that non-aqueous content of material (solutes content) refers to than water accounts for the weight hundred of total mixture
Divide ratio, i.e., non-water substance/(non-water substance+water) * 100 weight %.
With the method for the invention it is preferred to the solid content of mixed slurry A is 10-18 weight %.
With the method for the invention it is preferred to the solid content of mixed slurry B increases 50- relative to the solid content of mixed slurry A
500%.
The method according to the invention, the method for concentration is without particular/special requirement, the purpose is to remove solvent increase solid content, such as
Filtering, centrifugation etc..
, according to the invention it is preferred to ammonia source and the weight ratio in vanadium source are (5-50000)：100, be preferably (10-10000)：
100, more preferably (50-5000)：100, be most preferably (100-2000)：100.It is possible thereby to further improve titanium containing vanadium
The performance of si molecular sieves.
, according to the invention it is preferred to organic silicon source：Titanium source：Vanadium source：Template：Molar ratio=100 of water：(0.5-5)：
(0.5-5)：(5-50)：(200-5000)；Preferably 100：(1-4)：(1-4)：(6-15)：(300-800), wherein, organosilicon
Source is with SiO2Meter, titanium source are with TiO2Meter, vanadium source are in terms of v element, and template is with N or OH-Meter.
In accordance with the present invention it is preferred that this method further includes：The liquid phase C is mixed with obtained Titanium Sieve Molecular Sieve containing vanadium
The 3rd hydrothermal crystallizing is carried out afterwards.
, according to the invention it is preferred to the 3rd hydrothermal crystallizing carries out in confined conditions, undergo successively the stage (1), the stage (2) and
Stage (3), the stage (1) at 80-150 DEG C, preferably at 110-140 DEG C, more preferably at 120-140 DEG C, further preferably in 130-
140 DEG C processing 6-72 it is small when, when preferably 6-8 is small, the stage (2) be cooled to not higher than 70 DEG C and the residence time be at least 0.5 it is small when,
When preferably 1-5 is small, the stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C, reprocesses 6-96
Hour, when preferably 12-20 is small.
A preferred embodiment of the invention, preferably stage (1) and stage (3) meet one of the following conditions
Or both：
Condition 1：The temperature in stage (1) is less than the temperature in stage (3), it is preferable that the temperature in stage (1) is than the stage (3)
Temperature is 10-50 DEG C low, 20-40 DEG C preferably low；
Condition 2：The time in stage (1) is less than the time in stage (3), it is preferable that the time in stage (1) is than the stage (3)
When time short 5-24 is small, when preferably short 6-12 is small.
A preferred embodiment of the invention, stage (2) are cooled to not higher than 50 DEG C, are preferably 30-50 DEG C, and
Residence time be at least 1 it is small when, be preferably 1-5h.
The method according to the invention, temperature is adjusted can be according to tool to the heating rate of each phase temperature and rate of temperature fall
The type for the reactor that body uses makes choice, and is not particularly limited.In general, raise the temperature to stage (1) temperature
Heating rate can be 0.1-20 DEG C/min, be preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By stage (1) temperature
Rate of temperature fall to stage (2) temperature can be 1-50 DEG C/min, be preferably 2-20 DEG C/min, more preferably 5-10 DEG C/min.
It can be 1-50 DEG C/min by the heating rate of stage (2) temperature to stage (3) temperature, be preferably 2-40 DEG C/min, more preferably
For 5-20 DEG C/min.
The method according to the invention, optional wider range of condition of first hydrothermal crystallizing, as long as ensureing to be contained admittedly
Mixed slurry A of the amount not higher than 20 weight %, such as temperature can be 80-130 DEG C.
The method according to the invention, time optional wider range of first hydrothermal crystallizing, can carry out according to temperature
Appropriate adjustment, such as can be 12-96h.
The method according to the invention, optional wider range of condition of second hydrothermal crystallizing, as long as ensureing to obtain containing vanadium
Titanium Sieve Molecular Sieve, such as temperature can be 140-180 DEG C.
The method according to the invention, time optional wider range of second hydrothermal crystallizing, can carry out according to temperature
Appropriate adjustment, such as can be 6-24h.
, according to the invention it is preferred to the ammonia source is the one or more in the organic solution of ammonia, liquefied ammonia and ammonium hydroxide and ammonia；
One or more preferably in ammonia, liquefied ammonia and ammonium hydroxide, the organic solution of ammonia is, for example, the alcoholic solution of ammonia, further preferred ammonia
Water.
The method according to the invention, organic silicon source can form two to be various under the conditions of hydrolysis-condensation reaction
The silicon-containing compound of silica.Specifically, organic silicon source can be one kind in the silicon-containing compound shown in Formulas I or
It is a variety of,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as：R1、R2、R3And R4Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
Specifically, organic silicon source can be positive quanmethyl silicate, tetraethyl orthosilicate, four n-propyl of positive silicic acid and just
One or more in four N-butyl of silicic acid.Use in a specific embodiment of the present invention for ethyl orthosilicate or positive silicic acid first
Ester.
According to the present invention, optional wider range of the species of the template, specifically can be according to required titanium to be prepared
Si molecular sieves type is determined, and is, for example, in quaternary amine alkali cpd, aliphatic amine compound and aliphatic alcohol amine compounds
It is one or more.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be various NH3In
The compound that is formed after aliphatic alkyl (be preferably alkyl) substitution of at least one hydrogen, the aliphatic hydramine can be each
Kind NH3In the compound that is formed after aliphatic alkyl (the be preferably alkyl) substitution of hydroxyl of at least one hydrogen.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can be that formula III represents
Aliphatic amine, the aliphatic hydramine can be as formula IV represent aliphatic hydramine：
In Formula II, R5、R6、R7And R8Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as：R5、R6、R7And R8Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
R9(NH2)n(formula III)
In formula III, n is 1 or 2 integer.When n is 1, R9For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new penta
Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R9For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.It is more preferably fatty
Race's amine compounds are the one or more in ethamine, n-butylamine, butanediamine and hexamethylene diamine
(HOR10)mNH(3-m)(formula IV)
In formula IV, m R10It is identical or different, it is respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-C4
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is further preferred that the aliphatic alcohol
Amine compounds are the one or more in monoethanolamine, diethanol amine and triethanolamine.
The template used in a specific embodiment of the present invention is tetrapropylammonium hydroxide, hexamethylene diamine or n-butylamine.
In the present invention, the titanium source can be inorganic ti sources and/or organic titanium source.
A preferred embodiment of the invention, the titanium source are inorganic titanium salt and/or organic titanate.
In the present invention, the inorganic titanium salt is selected from various hydrolyzable titanium salts, such as can be selected from TiX4、TiOX2Or Ti
(SO4)2Containing titanium salt etc. various forms of, X is halogen in formula, is preferably chlorine, wherein, preferably described inorganic titanium salt is selected from TiCl4、
Ti(SO4)2And TiOCl2In one or more.
In the present invention, it is M that the organic titanate, which preferably has structural formula,4TiO4Organic titanate, wherein, M is preferred
For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, and 4 M can be identical or different, preferably
The one kind or more of the organic titanate in for isopropyl titanate, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate
Kind, what is used in a specific embodiment of the present invention is butyl titanate as example, but the model being not intended to limit the present invention
Enclose.
A preferred embodiment of the invention, preferably described vanadium source is the oxide of vanadium, the halide of vanadium, vanadic acid
(metavanadic acid (HVO3), positive vanadic acid (H3VO4), pyrovanadic acid (H4V2O7、H3V3O9)), vanadate (foregoing vanadic acid corresponding salt), vanadium
Carbonate, the nitrate of vanadium, the sulfate of vanadium and vanadium hydroxide in one or more.Including but not limited to sodium vanadate,
Ammonium metavanadate, vanadic anhydride, vanadium oxytrichloride, potassium metavanadate, vanadic sulfate, acetyl acetone vanadium etc..
With the method for the invention it is preferred to this method further includes：Obtained Titanium Sieve Molecular Sieve containing vanadium (including or is not included
The product of hydrothermal crystallizing processing is carried out after being mixed with liquid phase C) and the modification liquid containing nitric acid and at least one peroxide
Contact is modified processing.
With the method for the invention it is preferred to which this method further includes, the solid product after modification is dried.
Synthetic method according to the present invention, preferably in the modification, as raw material Titanium Sieve Molecular Sieve containing vanadium with
The molar ratio of the peroxide is 1：0.01-5, is preferably 1：0.05-3, more preferably 1：0.1-2, the peroxide with
The molar ratio of the nitric acid is 1：0.01-50, is preferably 1：0.1-20, more preferably 1：0.2-10, more preferably 1：
0.5-5, particularly preferably 1：0.6-3.5, the Titanium Sieve Molecular Sieve containing vanadium is in terms of silica.
With the method for the invention it is preferred in the modification liquid, the concentration of the peroxide and nitric acid is respectively 0.1-
50 weight %, are preferably 0.5-25 weight %, more preferably 5-15 weight %.
With the method for the invention it is preferred in the modification, as raw material Titanium Sieve Molecular Sieve containing vanadium with it is described
Modification liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, it is 60-200 DEG C further preferred at a temperature of connect
Touch, the contact carries out in the container that pressure is 0-5MPa, and the pressure is gauge pressure, and the duration of the contact is 1-10
Hour, when being preferably 3-5 small.
With the method for the invention it is preferred to the peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide, hydrogen peroxide
Isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
The method according to the invention, the process of the recovery product are well known to those skilled in the art, and are had no especially
Part, generally includes processes such as product filtering or natural subsidence, washing, drying, roastings.
The present invention provides the Titanium Sieve Molecular Sieve containing vanadium obtained according to the method described in the present invention.
The present invention provides the application of Titanium Sieve Molecular Sieve containing vanadium of the present invention in the oxidation reaction.
The Titanium Sieve Molecular Sieve containing vanadium of the present invention is suitable for the oxidation reactions of various molecules, for example, phenol, alkane, aldehyde, alcohol, ketone,
Alkene etc..The activity of titanium molecular sieve catalysis containing vanadium of the present invention is high.Illustrate in an embodiment of the present invention by taking oxidation of phenol as an example
The advantage of the present invention.
The present invention provides a kind of oxidation of phenol method, this method includes, and phenol, oxidant and catalyst is contacted, institute
State catalyst and contain Titanium Sieve Molecular Sieve containing vanadium of the present invention.
The method according to the invention, the condition of the contact can be the conventional selection of this area, for the present invention, preferably
The condition of contact includes：Temperature is 40-150 DEG C, is preferably 40-120 DEG C；Pressure is 0.1-3.0MPa, is preferably 0.1-
2.5MPa；Time is 0.1-24h, and the molar ratio of phenol and oxidant is 1：1-20, is preferably 1：2-15.
With the method for the invention it is preferred to the mass ratio of phenol and catalyst is 0.5-150：1.
With the method for the invention it is preferred to the contact carries out in the presence of solvent, wherein, preferred solvent and catalyst
Mass ratio is 1-200：1, it is preferably 2-150:1；More preferably described solvent is in water, alcohol, straight or branched ketone, acid and nitrile
One or more, preferably described solvent are water, the alcohol of C1-C5, the straight or branched ketone of C2-C6, the nitrile of C2-C8 and C2-C5
One or more in acid.
The method according to the invention, the solvent are preferably selected from water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, different
One or more in butanol, acetone, butanone, acetonitrile, propionitrile, benzene acetonitrile, acetic acid and propionic acid, more preferably described solvent are selected from second
One or more in nitrile, acetone, methanol, acetic acid and water.
The method according to the invention, charging order also require without special, can first add phenol, can also first add oxygen
Agent or solvent.
With the method for the invention it is preferred to the oxidant is hydrogen peroxide, tert-butyl hydroperoxide, peroxidating isopropyl
One or more in benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
The method according to the invention, after haptoreaction, the material after reaction can use the side of common distillation or rectifying
Method, after isolating target product, unreacted starting phenol etc. does not have to separating-purifying, directly backs within reaction unit relaying
Continuous reaction.
Following embodiment will be further described the present invention, but be not intended to limit the present invention.
Comparative example 1
(1) by vanadium source nitric acid vanadium, ammonium hydroxide (concentration is 20 weight %), butyl titanate, tetrapropylammonium hydroxide, positive silicic acid
Hydrothermal crystallizing is carried out after tetra-ethyl ester mixing；Silicon source：Titanium source：Vanadium source：Template：Water (mol)=100：2：1：15：1000；Vanadium source：
Ammonia source (weight ratio)=2:20；
Hydrothermal crystallizing：First stage 6h is undergone in 140 DEG C in reaction kettle is sealed, mixture is then cooled to 30 DEG C of warps
After going through second stage stop 2h, continue to undergo phase III 12h at a temperature of 170 DEG C in reaction kettle is sealed (wherein, by room
The heating rate that temperature is warming up to first stage temperature is 2 DEG C/min, the drop by first stage temperature to second stage treatment temperature
Warm speed is 5 DEG C/min, is 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature)；
(4) most afterwards through being cooled to room temperature and pressure release, by product in reaction kettle is filtered, washing, it is dry and 550 DEG C at roast
5 it is small when, obtain the sample of Titanium Sieve Molecular Sieve containing vanadium DB-1.
Comparative example 2
(1) vanadium source nitric acid vanadium and ammonium hydroxide (concentration is 20 weight %) are mixed to obtain mixture；Vanadium source：Ammonia source (weight
Measure ratio)=2:20, solutes content is 1 weight %, and the condition being mixed includes：30 DEG C, normal pressure, 4h；
(2) and then by mixture with butyl titanate, tetraethyl orthosilicate, tetrapropylammonium hydroxide mix；Mix laggard
Row hydrothermal crystallizing, temperature are 160 DEG C, time 120h；Silicon source：Titanium source：Vanadium source：Template：Water (mol)=100：2：1：15：
1000；By product in reaction kettle is filtered, washing, it is dry and 550 DEG C at roasting 5 it is small when, obtain the sample of Titanium Sieve Molecular Sieve containing vanadium
DB-2。
Embodiment 1
(1) vanadium source nitric acid vanadium and ammonium hydroxide are mixed to obtain mixture；Vanadium source：Ammonia source (weight ratio)=2:20, solute
Content is 1 weight %, and the condition being mixed includes：30 DEG C, normal pressure, 4h；
(2) and then by mixture with butyl titanate, tetraethyl orthosilicate, tetrapropylammonium hydroxide mix；Mix laggard
The first hydrothermal crystallizing of row, temperature are 120 DEG C, time 72h, obtain mixed serum A (solid content is 18 weight %)；Silicon source：Titanium
Source：Vanadium source：Template：Water (mol)=100：2：1：15：1000；
(3) mixed serum A is filtered, obtains mixed serum B (solid content is 40 weight %) and liquid phase C；
(4) mixed serum B being subjected to the second hydrothermal crystallizing, temperature is 170 DEG C, time 24h, filter, wash, is dry,
Roasting recycling obtains Titanium Sieve Molecular Sieve containing vanadium；
(5) the 3rd hydrothermal crystallizing is carried out after obtained Titanium Sieve Molecular Sieve containing vanadium is mixed with liquid phase C：
3rd hydrothermal crystallizing：First stage 6h is undergone in 140 DEG C in reaction kettle is sealed, mixture is then cooled to 30
After DEG C experience second stage stops 2h, continue in reaction kettle seal at a temperature of 170 DEG C experience phase III 12h (wherein,
It is 2 DEG C/min by the heating rate of room temperature to first stage temperature, by first stage temperature to second stage treatment temperature
Rate of temperature fall be 5 DEG C/min, be 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature)；
(6) most afterwards through being cooled to room temperature and pressure release, by product in reaction kettle is filtered, washing, it is dry and 550 DEG C at roast
5 it is small when, obtain the sample of Titanium Sieve Molecular Sieve containing vanadium A.
Through characterization：The crystal structure types of the Titanium Sieve Molecular Sieve containing vanadium of sample A are MFI.
Embodiment 2
(1) vanadium source vanadic sulfate and ammonium hydroxide are mixed to obtain mixture；Vanadium source：Ammonia source (weight ratio)=2:10, it is molten
Matter content is 2 weight %, and the condition being mixed includes：40 DEG C, normal pressure, 3h；
(2) and then by mixture with isopropyl titanate, positive quanmethyl silicate, n-butylamine mix, the first water is carried out after mixing
Thermal crystallisation, temperature are 100 DEG C, time 50h, obtain mixed serum A (solid content is 15 weight %)；Silicon source：Titanium source：Vanadium source：
Template：Water=100：3：2：35：3000；
(3) mixed serum A is filtered, obtains mixed serum B (solid content is 30 weight %) and liquid phase C；
(4) mixed serum B being subjected to the second hydrothermal crystallizing, temperature is 160 DEG C, time 30h, filter, wash, is dry,
Roasting recycling obtains Titanium Sieve Molecular Sieve containing vanadium；
(5) the 3rd hydrothermal crystallizing is carried out after obtained Titanium Sieve Molecular Sieve containing vanadium is mixed with liquid phase C：
3rd hydrothermal crystallizing：First stage 8h is undergone in 130 DEG C in reaction kettle is sealed, mixture is then cooled to 50
After DEG C experience second stage stops 5h, continue in reaction kettle seal at a temperature of 170 DEG C experience phase III 16h (wherein,
It is 1 DEG C/min by the heating rate of room temperature to first stage temperature, the drop by first stage temperature to second stage temperature
Warm speed is 10 DEG C/min, is 20 DEG C/min by the heating rate of second stage temperature to phase III temperature)；
(6) most afterwards through being cooled to room temperature and pressure release, by product in reaction kettle is filtered, washing, it is dry and 550 DEG C at roast
5 it is small when, obtain the sample of Titanium Sieve Molecular Sieve containing vanadium B.
Through characterization：The crystal structure types of the Titanium Sieve Molecular Sieve containing vanadium of sample B are MFI.
Embodiment 3
(1) vanadium source vanadium hydroxide and ammonium hydroxide are mixed to obtain mixture；Vanadium source：Ammonia source (weight ratio)=2:10, it is molten
Matter content is 5 weight %, and the condition being mixed includes：50 DEG C, normal pressure, 5h；
(2) and then by mixture with tetraethyl titanate, tetraethyl orthosilicate, hexamethylene diamine mix, the first water is carried out after mixing
Thermal crystallisation, temperature are 80 DEG C, time 96h, obtain mixed serum A (solid content is 10 weight %)；Silicon source：Titanium source：Vanadium source：Mould
Plate agent：Water (mol)=100：4：3：25：2000；
(3) mixed serum A is filtered, obtains mixed serum B (solid content is 50 weight %) and liquid phase C；
(4) mixed serum B being subjected to the second hydrothermal crystallizing, temperature is 150 DEG C, time 24h, filter, wash, is dry,
Roasting recycling obtains Titanium Sieve Molecular Sieve containing vanadium；
(5) the 3rd hydrothermal crystallizing is carried out after obtained Titanium Sieve Molecular Sieve containing vanadium is mixed with liquid phase C：
3rd hydrothermal crystallizing：First stage 6h is undergone in 140 DEG C in reaction kettle is sealed, mixture is then cooled to 40
After DEG C experience second stage stops 1h, continue in reaction kettle seal at a temperature of 160 DEG C experience phase III 12h (wherein,
It is 5 DEG C/min by the heating rate of room temperature to first stage temperature, the drop by first stage temperature to second stage temperature
Warm speed is 5 DEG C/min, is 5 DEG C/min by the heating rate of second stage temperature to phase III temperature)；
(6) most afterwards through being cooled to room temperature and pressure release, by product in reaction kettle is filtered, washing, it is dry and 550 DEG C at roast
5 it is small when, obtain the sample of Titanium Sieve Molecular Sieve containing vanadium C.
Through characterization：The crystal structure types of the Titanium Sieve Molecular Sieve containing vanadium of sample C are MFI.
Embodiment 4
The A of Titanium Sieve Molecular Sieve containing vanadium that embodiment 1 is obtained is with containing HNO3(HNO3Mass concentration 10%) and peroxidating for
The aqueous solution mixing of hydrogen (mass concentration of hydrogen peroxide is 7.5%), obtained mixture is stirred in closed container at 70 DEG C
Reaction 5h is mixed, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings
To constant weight, the D of Titanium Sieve Molecular Sieve containing vanadium of modification is obtained.Wherein, titanium-silicon molecular sieve TS-1 containing vanadium is with SiO2Meter, the silicon molecule of titanium containing vanadium
The molar ratio of sieve and hydrogen peroxide is 1：0.1.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.
Embodiment 5
The B of Titanium Sieve Molecular Sieve containing vanadium that embodiment 2 is obtained is with containing HNO3(HNO3Mass concentration 10%) and peroxidating for
The aqueous solution mixing of hydrogen (mass concentration of hydrogen peroxide is 5%), by obtained mixture in 120 DEG C of stirrings in closed container
4h is reacted, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings extremely
Constant weight, obtains the E of Titanium Sieve Molecular Sieve containing vanadium of modification.Wherein, titanium-silicon molecular sieve TS-1 containing vanadium is with SiO2Meter, Titanium Sieve Molecular Sieve containing vanadium
Molar ratio with hydrogen peroxide is 1：0.4.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 2 sample of embodiment through X-ray diffraction.
Embodiment 6
The C of Titanium Sieve Molecular Sieve containing vanadium that embodiment 3 is obtained is with containing HNO3(HNO3Mass concentration 15%) and peroxidating for
The aqueous solution mixing of hydrogen (mass concentration of hydrogen peroxide is 8%), by obtained mixture in 150 DEG C of stirrings in closed container
3h is reacted, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings extremely
Constant weight, obtains the F of Titanium Sieve Molecular Sieve containing vanadium of modification.Wherein, titanium-silicon molecular sieve TS-1 containing vanadium is with SiO2Meter, Titanium Sieve Molecular Sieve containing vanadium
Molar ratio with hydrogen peroxide is 1：2.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 3 sample of embodiment through X-ray diffraction.
Embodiment 7
Method according to embodiment 1 prepares molecular sieve, unlike, in the 3rd hydrothermal crystallization process, the crystalline substance of first stage
It is 110 DEG C to change temperature.Then it is consistent with comparative example 1 according to the method recovery product of embodiment 1, its XRD crystalline phases figure.
Embodiment 8
Method according to embodiment 1 prepares molecular sieve, unlike, in the 3rd hydrothermal crystallization process, the crystalline substance of first stage
The change time is 12h, and second stage is to be cooled to 70 DEG C of stop 2h.Then it is brilliant according to the method recovery product of embodiment 1, its XRD
Phasor is consistent with comparative example 1.
Embodiment 9
Method according to embodiment 1 prepares molecular sieve, unlike, the Titanium Sieve Molecular Sieve containing vanadium that step (4) obtains is direct
As product.
Test case 1
What the molecular sieve and the method for comparative example that this test case is obtained for explanation by method provided by the invention obtained
Molecular sieve is used for the reaction effect of phenol hydroxylation reaction.
By the sample prepared by above-described embodiment and comparative example according to sample：Phenol：Acetone=1：18：26 weight ratio exists
It is uniformly mixed in one three-necked flask with condenser pipe, 50 DEG C is warming up to, then according to phenol under stirring：Peroxidating
Hydrogen=3：1 molar ratio adds the hydrogen peroxide that concentration is 27.5 weight %, when reaction 2.5 is small at this temperature, products therefrom
Each product is measured using HP-5 capillary columns (30m × 0.25mm) to be distributed, the results are shown in Table 1 on Agilent6890N chromatographs.
Wherein：
Wherein, the benzenediol includes catechol, resorcinol and hydroquinone.
Table 1
| Sample source | Phenol conversion, % | Hydroquinone selectivity, % |
| Comparative example 1 | 16.6 | 47 |
| Comparative example 2 | 18.5 | 49 |
| Embodiment 1 | 22.8 | 61 |
| Embodiment 2 | 23.7 | 59 |
| Embodiment 3 | 24.4 | 62 |
| Embodiment 4 | 24.5 | 64 |
| Embodiment 5 | 25.3 | 65 |
| Embodiment 6 | 26.2 | 64 |
| Embodiment 7 | 20.8 | 58 |
| Embodiment 8 | 21.9 | 60 |
| Embodiment 9 | 21.3 | 59 |
From the results shown in Table 1, the catalysis for the Titanium Sieve Molecular Sieve containing vanadium that the method according to the invention is prepared is lived
Property it is high, reacted for phenol hydroxylation in when, the selectivity of phenol conversion and hydroquinone is obviously higher than by comparative example
Result obtained by sample prepared by method.
Test case 2
After drying being centrifuged after catalyst molecule sieve prepared by comparative example and embodiment is reacted according to test case 1
Continue to carry out oxidation of phenol reaction according to the reaction condition of testing example 1, reaction-separation-reaction cycle is repeated, circulates
2 are the results are shown in Table after 4 times.
Table 2
| Sample source | Phenol conversion, % | Hydroquinone selectivity, % |
| Comparative example 1 | 11.5 | 37 |
| Comparative example 2 | 13.5 | 40 |
| Embodiment 1 | 22.6 | 59 |
| Embodiment 2 | 23.4 | 58 |
| Embodiment 3 | 24.2 | 60 |
| Embodiment 4 | 24.4 | 61 |
| Embodiment 5 | 25.1 | 63 |
| Embodiment 6 | 26.1 | 62 |
| Embodiment 7 | 20.6 | 57 |
| Embodiment 8 | 21.6 | 59 |
| Embodiment 9 | 21.1 | 57 |
The catalyst stability of the present invention is high it can be seen from the data of table 2.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. the synthetic method of a kind of Titanium Sieve Molecular Sieve containing vanadium, it is characterised in that this method includes：
(1) by vanadium source, ammonia source, alternatively water is mixed to obtain the first mixture；
(2) in the presence of template, by titanium source, organic silicon source, first mixture, alternatively water is mixed to get the second mixing
Thing；
(3) second mixture is subjected to the first hydrothermal crystallizing, obtains the mixed slurry A that solid content is not higher than 20 weight %；
(4) the mixed slurry A is concentrated to give to the mixed slurry B and liquid phase C of solid content increase at least 50%；
(5) the mixed slurry B is subjected to the second hydrothermal crystallizing, recycling obtains Titanium Sieve Molecular Sieve containing vanadium.
2. synthetic method according to claim 1, wherein,
Non-aqueous content of material is 0.01-50 weight % in the first mixture in step (1), is preferably 0.02-25 weight %, into one
Step is preferably 0.05-10 weight %, is most preferably 0.1-5 weight %；And/or
The condition being mixed in step (1) includes：Temperature is room temperature to 80 DEG C, time 0.1-24h, preferably room temperature to 60
DEG C, time 0.5-12h.
3. synthetic method according to claim 1 or 2, wherein,
The solid content of mixed slurry A is 10-18 weight %；And/or
The solid content of mixed slurry B increases 50-500% relative to the solid content of mixed slurry A；And/or
Ammonia source and the weight ratio in vanadium source are (5-50000)：100, be preferably (10-10000)：100, more preferably (50-
5000)：100, be most preferably (100-2000)：100；And/or
Organic silicon source：Titanium source：Vanadium source：Template：Molar ratio=100 of water：(0.5-5)：(0.5-5)：(5-50)：(200-
5000) it is preferably, 100：(1-4)：(1-4)：(6-15)：(300-800)；Wherein, organic silicon source is with SiO2Meter, titanium source are with TiO2
Meter, vanadium source are in terms of v element, template is with N or OH-Meter.
4. synthetic method according to claim 1 or 2, wherein, this method further includes：The liquid phase C is contained with what is obtained
The 3rd hydrothermal crystallizing is carried out after the mixing of vanadium Titanium Sieve Molecular Sieve, the 3rd hydrothermal crystallizing carries out in confined conditions, undergoes the stage successively
(1), stage (2) and stage (3), the stage (1) at 80-150 DEG C, preferably at 110-140 DEG C, more preferably at 120-140 DEG C, into one
Step preferably 130-140 DEG C handle 6-72 it is small when, when preferably 6-8 is small, the stage (2) be cooled to not higher than 70 DEG C and the residence time extremely
When being 0.5 small less, when being preferably 1-5 small, the stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170
DEG C, when reprocessing 6-96 is small, when preferably 12-20 is small.
5. synthetic method according to claim 4, wherein, stage (1) and stage (3) meet one of the following conditions or
Both：
Condition 1：The temperature in stage (1) is less than the temperature in stage (3), it is preferable that temperature of the temperature in stage (1) than stage (3)
It is low 10-50 DEG C, 20-40 DEG C preferably low；
Condition 2：The time in stage (1) is less than the time in stage (3), it is preferable that time of the time in stage (1) than stage (3)
When short 5-24 is small, when preferably short 6-12 is small；
Stage (2) is cooled to not higher than 50 DEG C, and the residence time be at least 1 it is small when.
6. synthetic method according to claim 1 or 2, wherein,
The condition of first hydrothermal crystallizing includes：Temperature is 80-130 DEG C, time 12-96h；
The condition of second hydrothermal crystallizing includes：Temperature is 140-180 DEG C, time 6-24h.
7. synthetic method according to claim 1 or 2, wherein,
The ammonia source is the one or more in the organic solution of ammonia, liquefied ammonia, ammonium hydroxide and ammonia；Preferably ammonia, liquefied ammonia and ammonia
One or more in water, further preferred ammonium hydroxide；And/or
The template is the one or more in quaternary amine alkali cpd, aliphatic amine compound and aliphatic alcohol amine compounds；
And/or
Organic silicon source is the one or more in the silicon-containing compound shown in Formulas I,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl；And/or
The titanium source is inorganic titanium salt and/or organic titanate；And/or
The vanadium source is oxide, vanadic acid, vanadate, the halide of vanadium, the carbonate of vanadium, the nitrate of vanadium, the sulphur of vanadium of vanadium
One or more in the hydroxide of hydrochlorate and vanadium.
8. synthetic method according to claim 1 or 2, wherein, this method further includes：The Titanium Sieve Molecular Sieve containing vanadium that will be obtained
Contacted with the modification liquid containing nitric acid and at least one peroxide and be modified processing, in the modification, as original
The Titanium Sieve Molecular Sieve containing vanadium of material is 1 with the molar ratio of the peroxide：(0.01-5), is preferably 1：(0.05-3), more preferably
For 1：The molar ratio of (0.1-2), the peroxide and the nitric acid is 1：(0.01-50), is preferably 1：(0.1-20), it is more excellent
Elect 1 as：(0.2-10), more preferably 1：(0.5-5), particularly preferably 1：(0.6-3.5), the Titanium Sieve Molecular Sieve containing vanadium
In terms of silica.
9. synthetic method according to claim 8, wherein, in the modification liquid, the concentration of the peroxide and nitric acid
Respectively 0.1-50 weight %, is preferably 0.5-25 weight %, more preferably 5-15 weight %；Wherein, the peroxide choosing
From hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid
And Perpropionic Acid.
10. synthetic method according to claim 8, wherein, in the modification, the silicon point of titanium containing vanadium as raw material
Son sieve is with the modification liquid in 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, further preferred 60-200 DEG C of temperature
Contacted under degree, the contact carries out in the container that pressure is 0-5MPa, and the pressure is gauge pressure, and the contact continues
When time is 1-10 small, when being preferably 3-5 small.
11. the Titanium Sieve Molecular Sieve containing vanadium that the method in claim 1-10 described in any one obtains.
12. the application of Titanium Sieve Molecular Sieve containing vanadium in the oxidation reaction described in claim 11.
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