CN107986292A - A kind of Titanium Sieve Molecular Sieve and its synthetic method and application - Google Patents
A kind of Titanium Sieve Molecular Sieve and its synthetic method and application Download PDFInfo
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- CN107986292A CN107986292A CN201610953798.0A CN201610953798A CN107986292A CN 107986292 A CN107986292 A CN 107986292A CN 201610953798 A CN201610953798 A CN 201610953798A CN 107986292 A CN107986292 A CN 107986292A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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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- 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
- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
Abstract
The present invention relates to Titanium Sieve Molecular Sieve field, and specifically, the present invention provides a kind of Titanium Sieve Molecular Sieve and its synthetic method and application, this method includes：(1) the first silicon source, optional titanium source are mixed in the presence of aqueous solvent with alkaline template, and the mixture being mixed to get is carried out the first crystallization；(2) the second crystallization is carried out after mixing the first crystallization material, the second silicon source, titanium source, optional alkaline template, optional water.The method according to the invention synthesis of titanium silicon molecular sieve, can significantly improve catalytic activity, stability of Titanium Sieve Molecular Sieve etc..The method of the present invention is simple without particular/special requirement, preparation process to raw material.
Description
Technical field
The present invention relates to a kind of Titanium Sieve Molecular Sieve and its synthetic method and application.
Background technology
Titanium-silicon molecular sieve TS-1 is to introduce transition metal titanium formed in the framework of molecular sieve with ZSM-5 structures
A kind of novel titanosilicate with superior catalytic selective oxidation performance.TS-1 not only has the catalysed oxidn of titanium,
But also the shape-selective effect with ZSM-5 molecular sieve and excellent stability.Since TS-1 molecular sieves are anti-in the oxidation of organic matter
Ying Zhong, can use free of contamination low concentration hydrogen peroxide to avoid oxidizing process complex process and pollution environment as oxidant
The problem of, there is the unrivaled energy saving, economy of conventional oxidation system and advantages of environment protection, and select with good reaction
Selecting property, therefore there is great prospects for commercial application.
The synthetic method of TS-1 is first public by USP4410501 in 1981.This method is that first synthesis one kind contains silicon
Source, titanium source, the reaction mixture of organic base and/or basic anhydride, by this reaction mixture in 130-200 DEG C in autoclave
Hydrothermal crystallizing 6-30 days, then separates, washs, is dry, roasting and obtaining product.During plastic, the mixing of estersil and titanium esters
Solution hydrolysising condition is very harsh, because the hydrolysis rate of the two mismatches, the latter is higher than the former, adds the speed of organic base slightly
The polymer of irreversible titanium will be produced soon, the polymer of these titaniums is difficult to enter skeleton in crystallization process, and with non-bone
The form of frame titanium is entrained among molecular sieve, this partial-titanium may not only block duct, but also hydrogen peroxide can be catalytically decomposed, and is wasted former
Material.
Hereafter, researcher has carried out the synthetic method of Titanium Sieve Molecular Sieve many trials and has improved and optimizated, but existing production
Method is when still generally existing Titanium Sieve Molecular Sieve is applied in catalytic oxidation, the low problem of activity.
The content of the invention
It is an object of the present invention to for insufficient existing for existing process for preparing titanium-silicon molecular sieve, there is provided one kind can carry
The synthetic method of the Titanium Sieve Molecular Sieve of high titanium molecular sieve catalysis activity.
To realize object defined above, according to the first aspect of the invention, the present invention provides a kind of synthesis of Titanium Sieve Molecular Sieve
Method, this method include：
(1) the first silicon source, optional titanium source are mixed in the presence of aqueous solvent with alkaline template, and will be mixed to get
Mixture carry out the first crystallization；
(2) the first crystallization material, the second silicon source, titanium source, optional alkaline template, optional water are carried out the after mixing
Two crystallization.
According to the second aspect of the invention, the present invention provides the titanium silicon molecule that the method according to the invention synthesizes
Sieve.
According to the third aspect of the invention we, the present invention provides Titanium Sieve Molecular Sieve of the present invention in the oxidation reaction
Using.
The method according to the invention synthesis of titanium silicon molecular sieve, can significantly improve catalytic activity, the stabilization of Titanium Sieve Molecular Sieve
Property etc..
The method of the present invention is simple without particular/special requirement, preparation process to raw material.
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, this method includes：
(1) the first silicon source, optional titanium source are mixed in the presence of aqueous solvent with alkaline template, and will be mixed to get
Mixture carry out the first crystallization；
(2) the first crystallization material, the second silicon source, titanium source, optional alkaline template, optional water are carried out the after mixing
Two crystallization.
The method according to the invention, the catalytic activity of Titanium Sieve Molecular Sieve can be significantly improved according to preceding solution, right
For the condition of first crystallization and the second crystallization without particular/special requirement, conventional crystallization condition may be incorporated for the present invention, and described
The condition of one crystallization and the second crystallization can be identical or different.
For the present invention, the condition of preferably the first crystallization includes：Temperature is 80-220 DEG C, and/or the time is 12-96h.
For the present invention, the condition of preferably the second crystallization includes：Temperature is 140-180 DEG C, and/or the time is 6-24h.
A preferred embodiment of the invention, the first crystallization undergo stage (1), stage (2) and stage successively
(3), the stage (1) carries out crystallization at 80-120 DEG C, and the stage (2) is warming up to 180-220 DEG C of progress crystallization, and the stage (3) is cooled to
140-180 DEG C of progress crystallization；And/or
The condition of second crystallization includes：Temperature is 140-180 DEG C, and/or the time is 6-24h.
A preferred embodiment of the invention, stage (3) and the temperature difference in stage (2) are at least 20 DEG C, preferably
For 25-60 DEG C.
A preferred embodiment of the invention, the heating rate of room temperature to stage (1) is 0.1-20 DEG C/min, excellent
Elect 2-10 DEG C/min as；The heating rate that stage (1) is warming up to the stage (2) is 1-50 DEG C/min, is preferably 15-20 DEG C/min；
The rate of temperature fall that stage (2) cools to the stage (3) is 1-20 DEG C/min, is preferably 10-20 DEG C/min.
A preferred embodiment of the invention, is preferably 6-48h when the crystallization time in stage (1) is 2-72 small,
When preferably 20-30 is small；When the crystallization time in stage (2) is 0.1-12 small, when being preferably 0.5-8 small, when being preferably 4-6 small；
When the crystallization time in stage (3) is 6-96 small, when being preferably 12-48 small, when being preferably 30-48 small.
A preferred embodiment of the invention, in step (1) and step (2), silicon source：Titanium source：Alkaline template：
Total dosage molar ratio of water is 100：(0.5-5)：(10-50)：(500-5000), is preferably 100：(2-4)：(15-35)：
(1000-3000) wherein, silicon source is with SiO2Meter, titanium source are with TiO2Meter, alkaline template are with N or OH-Meter, silicon source include the first silicon
Source and the second silicon source.
With the method for the invention it is preferred in step (1), the molar ratio of the first silicon source, alkaline template and water is 50：
(10-50)：(500-5000).
With the method for the invention it is preferred in step (1), the first silicon source, titanium source, the molar ratio of alkaline template and water are
50：(0.25-1)：(10-50)：(500-5000).
The method according to the invention, the aqueous solvent contain water substantially, can also be according to addition cosolvent is needed, at this
In the embodiment of invention, aqueous solvent is water.
In the present invention, first silicon source and the second silicon source can be each inorganic silicon source and/or organic silicon source, Ke Yixiang
It is same or different.
Specifically, organic silicon source for example can be the one or more in the silicon-containing compound shown in Formulas I,
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 tetraethyl orthosilicate or positive silicic acid
Methyl esters is as example, but the scope being not intended to limit the present invention.
The method according to the invention, optional wider range of the species of the inorganic silicon source are preferably described for the present invention
Inorganic silicon source is the one or more in silicate, Ludox and silica gel, and heretofore described silica gel or Ludox can be each
The silica gel or Ludox that the kind various production methods of form obtain, silicate is, for example, sodium metasilicate.
In the present invention, the alkalescence template can be organic alkali source commonly used in the art and/or inorganic alkali source.
A preferred embodiment of the invention, the alkalescence template be organic base, the organic base be urea,
One or more in quaternary amine alkali cpd, aliphatic amine compound and aliphatic alcohol amine compounds.
A preferred embodiment of the invention, the organic base are urea, quaternary amine alkali cpd, aliphatic amination
One or more in compound and aliphatic alcohol amine compounds.
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-
C6Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new
Amyl group, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R9For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-
C6Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.More preferably fat
Fat race 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 alkaline template used in a specific embodiment of the present invention is tetrapropylammonium hydroxide, hexamethylene diamine or positive fourth
Amine.
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, step (1) and/or step (2) carry out in the presence of vfanadium compound,
It is preferred that the molar ratio of vfanadium compound and silicon source is (0.1-10)：100, more preferably step (1) carries out in the presence of vfanadium compound.
A preferred embodiment of the invention, preferably described vfanadium compound 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),
The carbonate of vanadium, the nitrate of vanadium, the sulfate of vanadium and vanadium hydroxide in one or more.Including but not limited to vanadic acid
Sodium, 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：By obtained Titanium Sieve Molecular Sieve and containing nitric acid and at least
A kind of modification liquid contact of peroxide 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 with it is described
The molar ratio of peroxide is 1：0.01-5, is preferably 1：0.05-3, more preferably 1：0.1-2, the peroxide with it is described
The molar ratio of 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 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, Titanium Sieve Molecular Sieve and the modification as raw material
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 contacted,
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 small for 1-10
When, 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 recycling solid product are well known to those skilled in the art, have no
Special feature, generally includes processes such as product filtering or natural subsidence, washing, drying, roastings.
The present invention provides the Titanium Sieve Molecular Sieve obtained according to the method described in the present invention.
The present invention provides the application of Titanium Sieve Molecular Sieve of the present invention in the oxidation reaction.
The Titanium Sieve Molecular Sieve of the present invention is suitable for the oxidation reaction of various molecules, such as phenol, alkane, aldehyde, alcohol, ketone, alkene
Deng.The titanium molecular sieve catalysis activity of the present invention is high.Illustrate the present invention's by taking oxidation of phenol as an example in an embodiment of the present invention
Advantage.
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 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.
The present invention is further illustrated for following embodiment, but the content being not intended to limit the present invention.Implement
All reagents used are commercially available chemically pure reagent in example and comparative example.
In embodiment and comparative example, using water as aqueous solvent, in mixed process, the contained water energy if other feed intake
Enough meet the requirement that feeds intake to water, then need not add water, if not satisfied, being then added as needed on water.
Comparative example 1
20 grams of silicon source tetraethyl orthosilicates are added in tetrapropylammonium hydroxide aqueous solution and are uniformly mixed, Ran Houjia
Enter butyl titanate and be mixed evenly, obtaining a mole composition is：Silicon source：Titanium source：Alkaline template：Water=100：2：15：1000
Mixture, gained mixture is stirred at 75 DEG C 3 it is small when, obtain clear colloid.It is anti-that this colloid is put into stainless steel
Kettle is answered, constant temperature is placed 3 days at a temperature of 170 DEG C, obtains the mixture of crystallization product；By the filtering of this mixture, it is washed with water
It is 6-8 to pH, and it is 60 minutes dry in 110 DEG C, obtain TS-1 original powders.This TS-1 original powder is small in 550 DEG C of roasting temperatures 3
When, obtain TS-1 molecular sieves DB-1.
Through characterization：The crystal structure types of sample DB-1 are MFI.
Embodiment 1
(1) 20 gram of first silicon source tetraethyl orthosilicate is added in tetrapropylammonium hydroxide aqueous solution and be stirred
It is even, mixture is placed in stainless steel sealing reaction kettle and carries out the first crystallization, is put forward kettle temperature with 2 DEG C/min heating rates by room temperature
Be raised to 100 DEG C and when hydro-thermal process 24 is small at this temperature, then with 15 DEG C/min heating rates by kettle temperature lifted to 190 DEG C and
When hydro-thermal process 6 is small at a temperature of this；Then kettle temperature is reduced to by 170 DEG C and at this temperature hydro-thermal with 10 DEG C/min rate of temperature fall
Handle 48 it is small when obtain the first crystallization material, the molar ratio of the first silicon source, alkaline template and water is 50：15：1000；
(2) crystallization is carried out after being mixed evenly the first crystallization material, the second silicon source tetraethyl orthosilicate, butyl titanate
(temperature is 140 DEG C, 24h)；
Wherein, silicon source (first the+the second silicon source of silicon source)：Titanium source：Alkaline template：Dosage molar ratio=100 of water：2：
15：1000, 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 roasting 5 it is small
When, Titanium Sieve Molecular Sieve sample A is obtained, the crystal structure types of the Titanium Sieve Molecular Sieve of sample A are MFI.
Embodiment 2
(1) positive four n-propyl of silicic acid of 20 gram of first silicon source is added in alkaline template n-butylamine aqueous solution and be stirred
Uniformly, mixture is placed in stainless steel sealing reaction kettle, is lifted kettle temperature to 80 DEG C with 10 DEG C/min heating rates by room temperature
And when hydro-thermal process 30 is small at this temperature, then with 20 DEG C/min heating rates lifted kettle temperature to 180 DEG C and at this temperature
When hydro-thermal process 4 is small；Then kettle temperature is reduced to 140 DEG C with 10 DEG C/min rate of temperature fall and hydro-thermal process 30 is small at this temperature
When obtain the first crystallization material, the molar ratio of the first silicon source, alkaline template and water is 40：35：3000；
(2) crystallization is carried out after being mixed evenly the first crystallization material, the second silicon source tetraethyl orthosilicate, isopropyl titanate
(160 DEG C, 18h)；
Wherein, silicon source (first the+the second silicon source of silicon source)：Titanium source：Alkaline template：Dosage molar ratio=100 of water：3：
35：3000, 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 roasting 5 it is small
When, obtain Titanium Sieve Molecular Sieve sample B.
Through characterization：The crystal structure types of the Titanium Sieve Molecular Sieve of sample B are MFI.
Embodiment 3
(1) 20 gram of first positive quanmethyl silicate of silicon source is added in alkaline template hexamethylene diamine aqueous solution and be stirred
It is even, mixture is placed in stainless steel sealing reaction kettle, is lifted kettle temperature to 120 DEG C simultaneously with 5 DEG C/min heating rates by room temperature
When hydro-thermal process 20 is small at this temperature, then kettle temperature lifted by 200 DEG C and at this temperature water with 15 DEG C/min heating rates
Be heat-treated 4 it is small when；Then kettle temperature is reduced to 160 DEG C with 20 DEG C/min rate of temperature fall and when hydro-thermal process 40 is small at this temperature
The first crystallization material is obtained, the molar ratio of the first silicon source, alkaline template and water is 80：25：2000；
(2) crystallization is carried out after being mixed evenly the first crystallization material, the positive quanmethyl silicate of the second silicon source, tetraethyl titanate
(180 DEG C, 10h)；
Silicon source (first the+the second silicon source of silicon source)：Titanium source：Alkaline template：Dosage molar ratio=100 of water：4：25：
2000, 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 roasting 5 it is small when,
Obtain Titanium Sieve Molecular Sieve sample C.
Through characterization：The crystal structure types of the Titanium Sieve Molecular Sieve of sample C are MFI.
Embodiment 4
By Titanium Sieve Molecular Sieve A that embodiment 1 obtains and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide for
The aqueous solution mixing of (mass concentration of hydrogen peroxide is 7.5%), by obtained mixture in 70 DEG C of stirrings in closed container
5h 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 modified Titanium Sieve Molecular Sieve D.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide
Molar ratio is 1：0.1.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.
Embodiment 5
By Titanium Sieve Molecular Sieve B that embodiment 2 obtains and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide for
The aqueous solution mixing of (mass concentration of hydrogen peroxide is 5%), obtained mixture is anti-in 120 DEG C of stirrings in closed container
4h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C
Weight, obtains modified Titanium Sieve Molecular Sieve E.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub
You are than being 1：0.4.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 2 sample of embodiment through X-ray diffraction.
Embodiment 6
By Titanium Sieve Molecular Sieve C that embodiment 3 obtains and contain HNO3(HNO3Mass concentration 15%) and hydrogen peroxide for
The aqueous solution mixing of (mass concentration of hydrogen peroxide is 8%), obtained mixture is anti-in 150 DEG C of stirrings in closed container
3h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C
Weight, obtains modified Titanium Sieve Molecular Sieve F.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub
You are than being 1：2.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 3 sample of embodiment through X-ray diffraction.
Embodiment 7
Carried out according to the method for embodiment 1, unlike, in step (1), vfanadium compound is introduced, it is specific as follows；
20 gram of first silicon source tetraethyl orthosilicate, ammonium metavanadate are added to stir in tetrapropylammonium hydroxide aqueous solution and mixed
Close uniform, mixture is placed in stainless steel sealing reaction kettle and carries out the first crystallization, by room temperature with 2 DEG C/min heating rates by kettle
Temperature lifting to 100 DEG C and when hydro-thermal process 24 is small at this temperature, then with 15 DEG C/min heating rates by kettle temperature lifting to 190 DEG C
And when hydro-thermal process 6 is small at this temperature；Then kettle temperature is reduced to 170 DEG C and at this temperature with 10 DEG C/min rate of temperature fall
Hydro-thermal process 48 obtains the first crystallization material when small, the first silicon source, vfanadium compound, the molar ratio of alkaline template and water are 50：
2：15：1000；
Remaining step and condition are same as Example 1.
Embodiment 8
Carried out according to the method for embodiment 1, unlike, the condition of hydrothermal crystallizing is as follows in step (1), by room temperature with 2
DEG C/min heating rates lift kettle temperature to 100 DEG C and when hydro-thermal process 24 is small at this temperature, then it is fast with 15 DEG C/min heatings
When rate lifts kettle temperature to 180 DEG C and hydro-thermal process 6 is small at this temperature；Then kettle temperature is reduced with 10 DEG C/min rate of temperature fall
When to 170 DEG C and hydro-thermal process 48 is small at this temperature.I.e. stage (2) and stage (3) temperature difference are 10 DEG C.
Embodiment 9
Carried out according to the method for embodiment 4, unlike, the condition of hydrothermal crystallizing is as follows, is heated up by room temperature with 2 DEG C/min
When speed lifts kettle temperature to 100 DEG C and hydro-thermal process 24 is small at this temperature, then kettle temperature is carried with 15 DEG C/min heating rates
It is raised to 180 DEG C and when hydro-thermal process 6 is small at this temperature；Then kettle temperature is reduced to 170 DEG C simultaneously with 10 DEG C/min rate of temperature fall
When hydro-thermal process 48 is small at this temperature.I.e. stage (2) and stage (3) temperature difference are 10 DEG C.
Embodiment 10
Carried out according to the method for embodiment 7, unlike, the condition of hydrothermal crystallizing is as follows, is heated up by room temperature with 2 DEG C/min
When speed lifts kettle temperature to 100 DEG C and hydro-thermal process 24 is small at this temperature, then kettle temperature is carried with 15 DEG C/min heating rates
It is raised to 190 DEG C and when hydro-thermal process 6 is small at this temperature；Then kettle temperature is reduced to 150 DEG C simultaneously with 10 DEG C/min rate of temperature fall
When hydro-thermal process 24 is small at this temperature.I.e. stage (2) and stage (3) temperature difference are 40 DEG C.
Embodiment 11
According to the method for embodiment 1, the difference is that, in step (1), the first titanium source is introduced, it is specific as follows：
(1) by 20 gram of first silicon source tetraethyl orthosilicate, the first titanium source butyl titanate, be added to tetrapropylammonium hydroxide
Be uniformly mixed in aqueous solution, by mixture be placed in stainless steel sealing reaction kettle in carry out the first crystallization, by room temperature with 2 DEG C/
When min heating rates lift kettle temperature to 100 DEG C and hydro-thermal process 24 is small at this temperature, then will with 15 DEG C/min heating rates
When kettle temperature is lifted to 190 DEG C and hydro-thermal process 6 is small at this temperature；Then kettle temperature is reduced to 10 DEG C/min rate of temperature fall
170 DEG C and when hydro-thermal process 48 is small at this temperature, obtain the first crystallization material, the first silicon source, the first titanium source, alkaline template
Molar ratio with water is 50：1：15：1000；
(2) the first crystallization material, the second silicon source tetraethyl orthosilicate, the second titanium source butyl titanate are mixed evenly laggard
Row crystallization (temperature is 140 DEG C, 24h), wherein, silicon source (first the+the second silicon source of silicon source)：Titanium source (first the+the second titanium source of titanium source)：
Alkaline template：Dosage molar ratio=100 of water：2：15：1000, it will most be produced afterwards through being cooled to room temperature and pressure release in reaction kettle
Thing is filtered, washing, it is dry and 550 DEG C at roasting 5 it is small when.
Embodiment 12
Carried out according to the method for embodiment 1, unlike, the condition of the first crystallization includes：Temperature is 220 DEG C, and the time is
96h。
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=1：18：29 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 2.8 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
From the results shown in Table 1, the catalytic activity for the Titanium Sieve Molecular Sieve that the method according to the invention is prepared is high,
When in being reacted for phenol hydroxylation, the selectivity of phenol conversion and hydroquinone is obviously higher than the method system by comparative example
Result obtained by standby sample.
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 | 10.6 | 40 |
| Embodiment 1 | 21.9 | 53 |
| Embodiment 2 | 21.4 | 51 |
| Embodiment 3 | 18.9 | 47 |
| Embodiment 4 | 24.7 | 63 |
| Embodiment 5 | 24.9 | 58 |
| Embodiment 6 | 24.8 | 57 |
| Embodiment 7 | 24.8 | 57 |
| Embodiment 8 | 20.7 | 52 |
| Embodiment 9 | 23.8 | 58 |
| Embodiment 10 | 25.2 | 62 |
| Embodiment 11 | 23.9 | 60 |
| Embodiment 12 | 18.9 | 46 |
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 (13)
1. a kind of synthetic method of Titanium Sieve Molecular Sieve, it is characterised in that this method includes：
(1) the first silicon source, optional titanium source are mixed with alkaline template in the presence of aqueous solvent, and it is mixed by what is be mixed to get
Compound carries out the first crystallization；
(2) it is brilliant to carry out second after mixing the first crystallization material, the second silicon source, titanium source, optional alkaline template, optional water
Change, then recycle solid product.
2. synthetic method according to claim 1, wherein,
The condition of first crystallization includes：Temperature is 80-220 DEG C, and/or the time is 12-96h；And/or
The condition of second crystallization includes：Temperature is 140-180 DEG C, and/or the time is 6-24h.
3. synthetic method according to claim 1 or 2, wherein,
First crystallization undergoes stage (1), stage (2) and stage (3) successively, and the stage (1) carries out crystallization, stage at 80-120 DEG C
(2) 180-220 DEG C of progress crystallization is warming up to, the stage (3) is cooled to 140-180 DEG C of progress crystallization；And/or
The condition of second crystallization includes：Temperature is 140-180 DEG C, and/or the time is 6-24h.
4. synthetic method according to claim 3, wherein, stage (3) and the temperature difference in stage (2) they are at least 20 DEG C, excellent
Elect 25-60 DEG C as；The heating rate in room temperature to stage (1) is 0.1-20 DEG C/min, and the stage (1) is warming up to the heating of stage (2)
Speed is 1-50 DEG C/min, and the rate of temperature fall that the stage (2) cools to the stage (3) is 1-20 DEG C/min.
5. synthetic method according to claim 3, wherein, it is preferably 6-48 when the crystallization time in stage (1) is 2-72 small
Hour；When the crystallization time in stage (2) is 0.1-12 small, when being preferably 0.5-8 small；The crystallization time in stage (3) is small for 6-96
When, when being preferably 12-48 small.
6. synthetic method according to claim 1 or 2, wherein, in step (1) and step (2), silicon source：Titanium source：Alkaline mould
Plate agent：Total dosage molar ratio of water is 100：(0.5-5)：(10-50)：(500-5000), wherein, silicon source is with SiO2Meter, titanium source
With TiO2Meter, alkaline template are with N or OH-Meter, silicon source include the first silicon source and the second silicon source；
In step (1), the molar ratio of the first silicon source, alkaline template and water is 50：(10-50)：(500-5000)；It is preferred that
In step (1), the first silicon source, titanium source, the molar ratio of alkaline template and water are 50：(0.25-1)：(10-50)：(500-
5000)。
7. synthetic method according to claim 1 or 2, wherein,
The alkalescence template is one in urea, quaternary amine alkali cpd, aliphatic amine compound and aliphatic alcohol amine compounds
Kind is a variety of；
First silicon source and the second silicon source are respectively inorganic silicon source and/or organic silicon source；
The titanium source is inorganic titanium salt and/or organic titanate.
8. synthetic method according to claim 1 or 2, wherein, step (1) and/or step (2) are in the presence of vfanadium compound
Carry out, the molar ratio of vfanadium compound and silicon source is (0.1-10)：100, preferred steps (1) carry out in the presence of vfanadium compound；
It is preferred that the vfanadium compound is oxide, vanadic acid, vanadate, the halide of vanadium, the carbonate of vanadium, the nitric acid of vanadium of vanadium
One or more in the hydroxide of salt, the sulfate of vanadium and vanadium.
9. synthetic method according to claim 1 or 2, wherein, this method further includes：By obtained Titanium Sieve Molecular Sieve with containing
There is the contact of the modification liquid of nitric acid and at least one peroxide to be modified processing, in the modification, as raw material
Titanium Sieve Molecular Sieve and the molar ratio of the peroxide are 1：(0.01-5), is preferably 1：(0.05-3), more preferably 1：(0.1-
2), the molar ratio of the peroxide and 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 is with silica
Meter.
10. synthetic method according to claim 9, 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.
11. synthetic method according to claim 9, wherein, in the modification, the Titanium Sieve Molecular Sieve as raw material
With the 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
Contacted, the contact carries out in the container that pressure is 0-5MPa, and the pressure is gauge pressure, the duration of the contact
For 1-10 it is small when, be preferably 3-5 it is small when.
12. the Titanium Sieve Molecular Sieve that the method in claim 1-11 described in any one obtains.
13. the application of Titanium Sieve Molecular Sieve in the oxidation reaction described in claim 12.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294030A (en) * | 1999-10-27 | 2001-05-09 | 中国石油化工集团公司 | Process for preparing Fe-Si Molecular sieve |
| EP0958861B1 (en) * | 1998-05-19 | 2002-06-05 | Polimeri Europa S.r.l. | Activation method of titanium silicalite and its use in oxidation processes with hydrogen peroxide |
| US20050171364A1 (en) * | 2004-01-30 | 2005-08-04 | Onimus Wilson H. | Catalyst preparation |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
| CN103818924A (en) * | 2014-03-07 | 2014-05-28 | 中国天辰工程有限公司 | Preparation method of titanium-silicon molecular sieve and application |
| CN105271294A (en) * | 2014-06-24 | 2016-01-27 | 中国石油化工股份有限公司 | Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method |
-
2016
- 2016-10-27 CN CN201610953798.0A patent/CN107986292B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0958861B1 (en) * | 1998-05-19 | 2002-06-05 | Polimeri Europa S.r.l. | Activation method of titanium silicalite and its use in oxidation processes with hydrogen peroxide |
| CN1294030A (en) * | 1999-10-27 | 2001-05-09 | 中国石油化工集团公司 | Process for preparing Fe-Si Molecular sieve |
| US20050171364A1 (en) * | 2004-01-30 | 2005-08-04 | Onimus Wilson H. | Catalyst preparation |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
| CN103818924A (en) * | 2014-03-07 | 2014-05-28 | 中国天辰工程有限公司 | Preparation method of titanium-silicon molecular sieve and application |
| CN105271294A (en) * | 2014-06-24 | 2016-01-27 | 中国石油化工股份有限公司 | Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method |
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