CN106276944A - A kind of HTS and synthetic method thereof and application and a kind of method for hydroxylation of phenol - Google Patents
A kind of HTS and synthetic method thereof and application and a kind of method for hydroxylation of phenol Download PDFInfo
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Abstract
The present invention relates to molecular sieve art, specifically provide a kind of HTS and synthetic method thereof and application, the method includes: organosilicon source, titanium source are hydrolyzed with alkalescence template and obtain mixture A by (1), and described mixture A is carried out the first crystallization；(2) material after the first crystallization and the former powder of HTS are mixed to get mixture B, described mixture B are carried out the consumption of the second former powder of crystallization HTS and makes the solid content of mixture B be 30-80 weight %.Present invention also offers a kind of method for hydroxylation of phenol.The relative crystallinity of the HTS prepared according to the method for the present invention is higher, and particle size is more uniform, and it is big to measure height, pore volume and external surface area on Ti.
Description
Technical field
The present invention relates to the synthetic method of a kind of HTS and closed by the synthetic method of HTS
Become the HTS obtained, and the application and that the HTS of the present invention is in phenol hydroxylation
Plant method for hydroxylation of phenol.
Background technology
Titanium-silicon molecular sieve TS-1 is the molecule sieve skeleton being introduced by transition metal titanium and having ZSM-5 structure
A kind of novel titanosilicate with superior catalytic selective oxidation performance formed in frame.TS-1 is not only
There is the catalysed oxidn of titanium, but also there is the shape-selective effect of ZSM-5 molecular sieve and excellent steady
Qualitative.Owing to TS-1 molecular sieve is in organic oxidation reaction, free of contamination low concentration mistake can be used
Hydrogen oxide is as oxidant, it is to avoid oxidizing process complex process and pollute the problem of environment, has tradition
Unrivaled energy-conservation, the economy of oxidation system and advantages of environment protection, and there is good selecting response
Property, therefore there is great prospects for commercial application.
The synthetic method of TS-1 in 1981 by first public (USP4410501).The method is first to close
Become a kind of containing silicon source, titanium source, organic base and/or the reactant mixture of basic anhydride, by mixed for this reaction
Compound in 130-200 DEG C of hydrothermal crystallizing 6-30 days, is then peeled off, washs, is dried, roasts in autoclave
Burn and obtain product.During plastic, the mixed solution hydrolysising condition of estersil and titanium esters controls the harshest,
Because the hydrolysis rate of the two does not mates, the latter is higher than the former, and the speed adding organic base will be produced the soonest
The polymer of raw irreversible titanium, the polymer of these titaniums is difficult to enter skeleton in crystallization process, and many
Being entrained in the middle of molecular sieve with the form of extra-framework titanium, this partial-titanium both may block duct, can be catalyzed again
Decomposition of hydrogen peroxide, wastes raw material.
Hereafter, researcher has carried out many trials to the synthetic method of HTS and has improved and optimizated, but
Existing production method is still more exists that solid content is low, production cycle length, titanium skewness, preparation poor repeatability
Etc. problem；When particularly HTS is applied in catalytic oxidation, generally there is HTS
The big activity of crystal grain is low, and the little problems such as separating difficulty that filters of crystal grain.
Summary of the invention
It is an object of the invention to provide the synthetic method of a kind of new HTS, and by the method
The HTS that synthesis obtains.
The present inventor has been surprisingly found that in research process, in the preparation process of HTS,
First organosilicon source, titanium source are hydrolyzed with alkalescence template, and mixture hydrolysis obtained carries out crystalline substance
Change process, then in the material after crystallization add the former powder of HTS to solid content 30-80 weight %,
Then mixture is carried out again Crystallizing treatment, the relative crystallinity of the HTS so prepared and grain
Footpath distribution and the parameter such as hole and specific surface area are improved further.Find based on this, complete the present invention.
In order to realize object defined above, according to the first aspect of the invention, the invention provides a kind of titanium silicon to divide
The synthetic method of son sieve, the method includes:
(1) organosilicon source, titanium source and alkalescence template are hydrolyzed and obtain mixture A, by described
Mixture A carries out the first crystallization；
(2) material after the first crystallization and the former powder of HTS are mixed to get mixture B, by institute
Stating mixture B and carry out the second crystallization, wherein, the consumption of the former powder of HTS makes mixture B's
Solid content is 30-80 weight %.
According to the second aspect of the invention, the invention provides the titanium silicon molecule obtained by preceding method synthesis
Sieve.
According to the third aspect of the invention we, the invention provides the titanium silicon obtained by the method synthesis of the present invention
Molecular sieve application in the oxidation reaction.
According to the fourth aspect of the invention, the invention provides a kind of method for hydroxylation of phenol, the method
Including: under the conditions of phenol hydroxylation, phenol, hydrogen peroxide are contacted with catalyst, described catalyst
Containing HTS of the present invention.
The relative crystallinity of the HTS prepared according to the method for the present invention is higher, particle size
More uniform.And it was unexpected that use the method for the present invention not add molecular screen primary powder method phase with routine
Ratio, the upper amount of Ti is bigger, and pore volume and external surface area are bigger.
The synthetic method that the present invention provides, it is possible to the decomposition of suppression organic base template, organic base therein
Template can recycle (such as embodiment 5), reduces cost, alleviates environmental pollution.
When molecular sieve prepared by the method for the employing present invention is in phenol hydroxylation reacts, phenol conversion
With the selectivity of hydroquinone obviously higher than the result of the sample gained prepared by the method for comparative example.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
As it was previously stated, the invention provides the synthetic method of a kind of HTS, the method includes:
(1) organosilicon source, titanium source and alkalescence template are hydrolyzed and obtain mixture A, by described
Mixture A carries out the first crystallization；
(2) material after the first crystallization and the former powder of HTS are mixed to get mixture B, by institute
Stating mixture B and carry out the second crystallization, wherein, the consumption of the former powder of HTS makes mixture B's
Solid content is 30-80 weight %.
According to the synthetic method of the present invention, solid content principle refers to that the quality of solid matter accounts for reaction in reactor
The percentage composition of material gross mass in still, typically uses in the total material metage i.e. reactor in reactor
The gross weight of material, is then taken solid matters such as the molecular sieves in reactor through steps such as filtrations
Weigh after going out dry (temperature is less than 200 DEG C), calculate the solid matter weight such as dried molecular sieve and account for
The percent data of the gross weight of material in reactor is designated as the solid content of material in reactor.Concrete real
During executing, it is not necessary to the most specifically remove to measure solid content, but can first consolidate after centrifugal at laboratory
Body and the volume ratio of liquid, provide respective volume ratio and the working curve of solid content, and then the song that works whereby
Line can provide the solid content of material in embodiment each time intuitively.The preferably use of the former powder of HTS
Amount makes the solid content of mixture B be 50-60 weight %.The HTS Ti thus prepared
Being more evenly distributed, relative crystallinity is higher, and particle size the most evenly, and is used for oxidation reaction such as benzene
In phenolic hydroxyl groupization reaction, higher and hydroquinone the selectivity of phenol conversion is higher.
According to the synthetic method of the present invention, the temperature of the preferably second crystallization is higher than the temperature of the first crystallization
20-100 DEG C, the highest 50-70 DEG C.The HTS Ti thus prepared is more evenly distributed,
Relative crystallinity is higher, and particle size the most evenly, and is reacted for oxidation reaction such as phenol hydroxylation
Higher and hydroquinone the selectivity of middle phenol conversion is higher.
The method according to the invention, described hydrolysis is carried out in the presence of aqueous solvent, described aqueous solvent
Kind can be the conventional selection of this area, and various aqueous solvents may be incorporated for realizing the present invention, wherein
As long as the water yield in aqueous solvent can meet organosilicon source generates the bar of HTS in crystallization process
Part.Described solvent is preferably water, it is possible to according to needing to add other cosolvent, to this present invention
Without specific requirement, it is not described here in detail.It should be noted that aqueous solvent can arise directly from it
The solvent content of his material solution, such as, can be directed to the solvent portion of alkalescence template aqueous solution
Point；Can also directly add, if the solvent content of other aqueous solution of raw material disclosure satisfy that the throwing of aqueous solvent
Material requirement, then without adding aqueous solvent again, if being unsatisfactory for, then need additionally to add aqueous solvent.
According to the synthetic method of the present invention, the purpose of the present invention, pin can be realized according to preceding solution
To the present invention, the condition of the preferably first crystallization includes: carry out crystallization in confined conditions, and temperature is 70-130
DEG C, preferably 80-120 DEG C.
According to the synthetic method of the present invention, the time of the first crystallization can enter according to concrete crystallization temperature etc.
Row sum-equal matrix, for the present invention, the time of the preferably first crystallization is 12-96h, more preferably 60-80h.
In the present invention, to the pressure of the first crystallization without particular/special requirement, crystallization can be carried out at autogenous pressures.
According to the synthetic method of the present invention, the purpose of the present invention, pin can be realized according to preceding solution
To the present invention, the condition of the preferably second crystallization includes: carry out crystallization in confined conditions, and temperature is
140-180 DEG C, preferably 150-170 DEG C.
According to the synthetic method of the present invention, the time of the second crystallization can enter according to concrete crystallization temperature etc.
Row sum-equal matrix, for the present invention, the time of the preferably second crystallization is 6-24h.
In the present invention, to the pressure of the second crystallization without particular/special requirement, crystallization can be carried out at autogenous pressures.
According to the synthetic method of the present invention, in preferred mixture A, the percent hydrolysis in organosilicon source is 10-100%,
More preferably 50-90%, more preferably 60-80%.The HTS Ti thus prepared
Being more evenly distributed, relative crystallinity is higher, and particle size the most evenly, and is used for oxidation reaction such as benzene
In phenolic hydroxyl groupization reaction, higher and hydroquinone the selectivity of phenol conversion is higher.
According to the synthetic method of the present invention, in preferred steps (1), with SiO2Meter organosilicon source, with
TiO2Meter titanium source, with NH3The alkaline template of meter is 100:(0.005-10 with the consumption mol ratio of water):
(0.005-40): (200-10000), preferably 100:(0.05-5): (0.05-20): (500-5000).
The method according to the invention, described organosilicon source can be various energy under the conditions of hydrolysis-condensation reaction
Enough form the silicon-containing compound of silicon dioxide.Specifically, described organosilicon source can be for selected from shown in Formulas I
Silicon-containing compound in one or more,
In Formulas I, R1、R2、R3And R4It is respectively C1～C4Alkyl, including C1～C4Straight chain alkane
Base and C3～C4Branched alkyl, such as: R1、R2、R3And R4Can be each methyl, ethyl,
N-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
Specifically, described organosilicon source can be positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four
One or more in n-propyl and positive silicic acid four N-butyl.Use in a particular embodiment of the present invention
For tetraethyl orthosilicate.
The method according to the invention, described titanium source can be the conventional selection of this area, for the present invention,
The most described titanium source is selected from inorganic titanium salt and/or organic titanate, preferably organic titanate.
In the present invention, described inorganic titanium salt is selected from various hydrolyzable titanium salts, such as, can be selected from TiX4、
TiOX2Or Ti (SO4)2Etc. various forms of containing titanium salt, in formula, X is halogen, preferably chlorine, wherein,
The most described inorganic titanium salt is selected from TiCl4、Ti(SO4)2And TiOCl2In one or more.
In the present invention, it is M that described organic titanate preferably has structural formula4TiO4Organic titanate,
Wherein, M preferably has the alkyl of 1-4 carbon atom, and 4 M can be identical or different, excellent
Described organic titanate is selected to be selected from as isopropyl titanate, metatitanic acid n-propyl, butyl titanate and metatitanic acid tetrem
One or more in ester, use in a particular embodiment of the present invention for butyl titanate as reality
Example, but and it is not so limited the scope of the present invention.
The method according to the invention, optional wider range of the kind of described alkalescence template, it can be
One or more in aliphatic amine compound, aliphatic alcohol amines and quaternary ammonium base compound.
In the present invention, described quaternary ammonium base can be various organic level Four ammonium alkali, and described aliphatic amine can be
Various NH3In at least one hydrogen by aliphatic alkyl (preferably alkyl) replace after formed compound,
Described aliphatic hydramine can be various NH3In at least one hydrogen (excellent by the aliphatic alkyl of hydroxyl
Elect alkyl as) replace after formed compound.
Specifically, described quaternary ammonium base can be for the quaternary ammonium base as shown in Formula II, and described aliphatic amine can be
The aliphatic amine that formula III represents, described aliphatic hydramine can be the aliphatic hydramine represented such as formula IV:
In Formula II, R5、R6、R7And R8It is respectively C1-C4Alkyl, including C1-C4Straight chained alkyl
And C3-C4Branched alkyl, such as: R5、R6、R7And R8Can be each methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
R9(NH2)n(formula III)
In formula III, n is the integer of 1 or 2.When n is 1, R9For C1～C6Alkyl, including C1~
C6Straight chained alkyl and C3-C6Branched alkyl, such as methyl, ethyl, n-pro-pyl, isopropyl, positive fourth
Base, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl and just oneself
Base.When n is 2, R9For C1-C6Alkylidene, including C1～C6Straight-chain alkyl-sub-and C3～C6
Branched alkylidene, such as methylene, ethylidene, sub-n-pro-pyl, sub-normal-butyl, sub-n-pentyl or Asia
N-hexyl.One during more preferably aliphatic amine compound is ethamine, n-butylamine, butanediamine and hexamethylene diamine
Or it is multiple
(HOR10)mNH(3-m)(formula IV)
In formula IV, m R10Identical or different, respectively C1-C4Alkylidene, including C1-C4's
Straight-chain alkyl-sub-and C3-C4Branched alkylidene, such as methylene, ethylidene, sub-n-pro-pyl and the positive fourth in Asia
Base；M is 1,2 or 3.It is further preferred that described aliphatic alcohol amines is monoethanolamine, diethanolamine
With one or more in triethanolamine.
It should be noted that when using alkaline organic base such as quaternary ammonium base as alkalescence template, by
Relatively strong in its alkalescence, can meet the requirement to mixture alkalescence in HTS building-up process, therefore,
Quaternary ammonium base in HTS building-up process not only as template but also as alkali source.
When using other alkalescence template, when the alkalescence of the mixture obtained after mixing can not meet titanium silicon
Time in sieve synthesis procedure to the requirement that mixture is alkaline, those skilled in the art can be led to as required
Cross and add the mode of alkali source to adjust the alkalescence of mixture.Optional wider range of the kind of described alkali source,
It is preferably inorganic alkali source.Wherein, inorganic alkali source can be ammonia or cation is alkali metal or alkaline earth gold
The alkaline matter belonged to, as being sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and potassium carbonate
In one or more.
In the present invention, as template, the exemplary TPAOH that uses illustrates that the present invention's is excellent
Gesture.
With the method for the invention it is preferred to step (2) is by the material after the first crystallization and HTS
Former powder mixing time, the material after described first crystallization cool after referring to the first crystallization (without particular/special requirement,
Be down to room temperature and can open crystallizing kettle) after the material that obtains without other any process.
With the method for the invention it is preferred to the method also includes: the second crystallization products therefrom is filtered, washes
Wash and obtain solid, after being dried or be moist by gained solid, carry out roasting.
In the present invention, optional wider range of described dry condition, specifically it is referred to prior art and enters
OK.For the present invention, the most described dry condition includes: temperature be room temperature to 200 DEG C, more preferably
For 80-120 DEG C；Time is 1-24h, preferably 2-10h.
In the present invention, optional wider range of the condition of described roasting, for the preferred described roasting of the present invention
Condition include: the temperature of roasting is 300-800 DEG C, preferably 450-550 DEG C；The time of roasting is
2-12h, preferably 2-4h；The condition of the most described roasting includes: first at 350-600 DEG C in nitrogen
Roasting 0.5-6h in atmosphere, then at 350-600 DEG C of roasting 0.5-12h in air atmosphere.
The method according to the invention, the kind of the former powder of described HTS, without particular/special requirement, can be to contain
The former powder of HTS having template can also such as may be used for the former powder of HTS without template
Think through Template removal step or without the HTS of Template removal step after synthesis, for this
Invention, in the former powder of the most described HTS, the content of template is less than 0.1 weight %, i.e. through de-
The former powder of HTS of template.
The synthetic method that the present invention provides, has an advantage that
1, high solids content synthesis, improves production efficiency；
2, the HTS relative crystallinity that obtains of synthesis improves, and Ti content is high, pore volume and outer compare table
Area increases；
3, the particle diameter distribution etc. of the HTS crystal grain that synthesis obtains have also been obtained improvement, and particle diameter is general
Integrated distribution is at 150nm-350nm, it can be seen that, the method for the present invention is to the nucleation of poromerics and life
Growth process is optimized and adjusts so that crystal grain is more homogeneous；
4, the synthetic method that the present invention provides, it is possible to the decomposition of suppression organic base template, therein have
Machine alkali template can recycle, and reduces cost, alleviates environmental pollution；
5, when molecular sieve prepared by the method for the employing present invention is in phenol hydroxylation reacts, phenol turns
The selectivity of rate and hydroquinone is obviously higher than the knot of the sample gained prepared by the method for comparative example
Really.
The invention provides a kind of synthetic method according to the present invention and synthesize the HTS obtained.
HTS according to the present invention has higher catalysis activity.Specifically, by the side of the present invention
HTS prepared by method, when the catalyst reacted as phenol hydroxylation, demonstrates higher catalysis
Activity and hydroquinone selectivity.In a particular embodiment of the present invention using phenol hydroxylation reaction as real
The advantage of the example explanation present invention, but the HTS of the present invention is not limited only to react for phenol hydroxylation
There is advantage, for other oxidation reactions, there is good effect equally.
The invention provides the application in the oxidation reaction of the HTS of the present invention.
The invention provides a kind of method for hydroxylation of phenol, the method includes: in phenol hydroxylation condition
Under, phenol, hydrogen peroxide are contacted with catalyst, described catalyst contains titanium silicon of the present invention and divides
Son sieve.
The method according to the invention, as long as the HTS that described catalyst is containing the present invention, excellent
Select the content of HTS in described catalyst be more than 50 weight %, more preferably content be 60-100
Weight %.The content being HTS used in a particular embodiment of the present invention is 100 weight
The catalyst of %, but this and be not so limited the scope of the present invention.Content herein refers to without carrier
Time catalyst composition.
When described catalyst is molded body, described catalyst also includes carrier, and wherein, carrier can be
Al2O3、ZnO、MgO、SiO2, CaO and TiO2, rare earth oxide RE2O3(RE is La, Ce,
Y or Nd etc.).
In the present invention, in described catalyst, in addition to including HTS, it is also possible to also have other to commonly use
The catalyst for phenol hydroxylation.
Preferred embodiment, the most described catalyst is HTS to one according to the present invention, institute
State phenol hydroxylation condition to include: temperature is 30-120 DEG C, preferably 50-90 DEG C, in the enforcement of the present invention
The temperature used in example is 80 DEG C, and phenol is (1-10) with the mol ratio of hydrogen peroxide: 1, more preferably (2-5):
1, HTS is (0.001-0.5) with the weight ratio of phenol: 1, is preferably (0.01-0.08): 1,
More preferably (0.04-0.06): 1.So, more preferable phenol conversion can be obtained and hydroquinone selects
Property.
Need exist for special instruction, to those skilled in the art, convert at close high phenol
Under rate, merely by the change of method for preparing catalyst, improve hydroquinone selectivity more difficult (particularly
Improve more than 5 percentage points).And the present inventor is found surprisingly that, use of the present invention
HTS be catalyst, relative to conventional titanium-silicon molecular sieve catalyst, can be effectively improved benzene
Diphenol selectivity (improves more than 5 percentage points).
The present invention is further illustrated for below example, but and is not so limited the interior of the present invention
Hold.In embodiment and comparative example, all reagent used are commercially available chemically pure reagent.
In embodiment and comparative example, adopt and use water as aqueous solvent, in mixed process, if other feed intake
Contained water disclosure satisfy that the requirement that feeds intake water, then without adding water, if being unsatisfactory for, add the most as required
Add water.
The mensuration of X-ray diffraction (XRD) the crystalline phase figure of embodiment and comparative example is at Siemens
Carry out on D5005 type x-ray diffractometer, wherein, be 22.5 °-25.0 ° with sample and authentic specimen at 2 θ
Between the ratio of diffracted intensity (peak height) sum at the five fingers diffractive features peak represent that sample is relative to base
The degree of crystallinity of quasi-sample, wherein, sample on the basis of the sample of comparative example 1, its degree of crystallinity is calculated as 100%；
The relative crystallinity data of each sample and grain size distribution data etc. are shown in Table 1.Wherein, crystal grain (granule)
Size distribution data is the percentage that sample crystal grain quantity between 150nm-350nm accounts for total crystal grain quantity
Number (uses PHILIPS company of Holland XL 30ESEM type scanning electron microscope SEM, observes sample
Product granular size also carries out grain size distribution statistics, and wherein accelerating potential is 20kV).Each sample red
Outer spectrogram is obtained by Nicolet 8210 type Fourier infrared spectrograph.
In the present invention, external surface area, pore volume use BET method to record.
Si/Ti (mol ratio) ratio of embodiment and comparative example is by x-ray fluorescence analysis (XRF)
Measure and calculate and obtain.Wherein, Si/Ti ratio is the least, illustrates that the Ti content in molecular sieve is the highest.Various kinds
The Si/Ti of product is shown in Table 1 than data.
In the present invention, organosilicon source amount of hydrolysis is recorded by gas chromatography.Gas chromatogram used is
Agilent 6890N, is equipped with the capillary column of thermal conductivity detector (TCD) TCD and HP-5
(30m*320μm*25μm).Wherein, injector temperature is 180 DEG C, and column temperature is 150 DEG C, uses
Nitrogen is as carrier gas, and the flow velocity of carrier gas is 25mL/min.Method particularly includes: take a certain amount of mixture
From gas chromatograph injection port sample introduction, TCD after flowing through chromatographic column, is utilized to carry out detecting and passing through external standard method
Carry out quantitatively.Employing below equation calculating organosilicon source percent hydrolysis:
XOrganosilicon source%=[(mo Organosilicon source-mOrganosilicon source)/mo Organosilicon source] × 100%
In formula, XOrganosilicon sourceRepresent the percent hydrolysis in organosilicon source；mo Organosilicon sourceRepresent the matter in the organosilicon source added
Amount；mOrganosilicon sourceRepresent the quality in unhydrolysed organosilicon source.
Comparative example 1
Method described in this comparative example reference literature (Zeolites, volume 1992,12,943-950 page)
Preparation TS-1 molecular sieve, for illustrating the process according to conventional hydrothermal crystallization method synthesis of titanium silicon molecular sieve.
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates and 7.0 grams of TPAOHs are mixed
Close, and add 59.8 grams of distilled water, hydrolyze 1.0 hours at normal pressure and 60 DEG C after stirring mixing, obtain
The hydrating solution of tetraethyl orthosilicate, be slowly added into vigorous stirring by 1.1 grams of butyl titanates with
The solution that 5.0 grams of anhydrous isopropyl alcohols are formed, stirs gained mixture 3 hours at 75 DEG C, obtains
Clear colloid.This colloid is put into rustless steel sealed reactor, and at a temperature of 170 DEG C, constant temperature is put
Put 3 days, obtain the mixture of crystallization product；This mixture is filtered, washes with water, and in 110 DEG C
It is dried 60 minutes, obtains the former powder of TS-1.Former for this TS-1 powder is roasted in air atmosphere in 550 DEG C of temperature
Burn 3 hours, obtain TS-1 molecular sieve B1.
After testing, the XRD crystalline phase of gained molecular sieve B1 is to there is MFI between 22.5 °-25.0 ° at 2 θ
The five fingers diffractive features peak specific to structure, shows that molecular sieve B1 has the MFI structure of similar TS-1.
At 960cm in fourier infrared spectrogram-1There is the unexistent characteristic absorption peak of silica zeolite in vicinity,
Show that titanium has been enter into sample skeleton.
Embodiment 1
Preparing HTS according to the method for comparative example 1, except for the difference that crystallization condition is different and after crystallization
Add HTS.Detailed process is as follows:
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates and 7.0 grams of TPAOHs are mixed
Close, and add 59.8 grams of distilled water, hydrolyze 1.0 hours at normal pressure and 60 DEG C after stirring mixing, obtain
The hydrating solution of tetraethyl orthosilicate, be slowly added into vigorous stirring by 1.1 grams of butyl titanates with
The solution that 5.0 grams of anhydrous isopropyl alcohols are formed, stirs gained mixture 3 hours at 75 DEG C, obtains
Clear colloid (percent hydrolysis in organosilicon source is 100%).This colloid is put into rustless steel and seals reaction
Still, at a temperature of 110 DEG C, constant temperature is placed 3 days, obtains the mixture of crystallization product, adds after release
The former powder of HTS (B1) to solid content 50 weight %, then by slurry in closed reactor in
24h is processed under 160 DEG C and self-generated pressure；This mixture is filtered, washes with water, and is dried in 110 DEG C
60 minutes, in 550 DEG C of temperature roasting 3 hours in air atmosphere, obtain TS-1 molecular sieve-4 A 1.
After testing, the XRD crystalline phase of gained molecular sieve-4 A 1 is to there is MFI between 22.5 °-25.0 ° at 2 θ
The five fingers diffractive features peak specific to structure, shows that molecular sieve-4 A 1 has the MFI structure of similar TS-1.
At 960cm in fourier infrared spectrogram-1There is the unexistent characteristic absorption peak of silica zeolite in vicinity,
Show that titanium has been enter into sample skeleton.
Comparative example 2
At a temperature of 20 DEG C, first by TPAOH aqueous solution that concentration is 10 weight % and metatitanic acid
Four butyl ester mixing, are subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2Meter is just
Tetraethyl orthosilicate, with TiO2Meter butyl titanate, with NH3The TPAOH of meter and water
Mol ratio is 100:5:10:800.Gained mixture is stirred 3 hours at 75 DEG C, is clarified
Transparent colloid.This colloid is put into rustless steel sealed reactor, and at a temperature of 120 DEG C, constant temperature places 3
My god, obtain the mixture of crystallization product, gained crystallization product is filtered, washes with water, and in 110 DEG C
Dry 120 minutes, then in 550 DEG C of temperature roasting 3 hours in air atmosphere, it is thus achieved that molecular sieve B2.
The X-ray diffraction of gained molecular sieve B2 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 2
At a temperature of 20 DEG C, first by TPAOH aqueous solution that concentration is 10 weight % and metatitanic acid
Four butyl ester mixing, are subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2Meter is just
Tetraethyl orthosilicate, with TiO2Meter butyl titanate, with NH3The TPAOH of meter and water
Mol ratio is 100:5:10:800.Gained mixture is stirred 3 hours at 75 DEG C, is clarified
Transparent colloid (percent hydrolysis in organosilicon source is 100%).This colloid is put into rustless steel sealed reactor,
At a temperature of 120 DEG C, constant temperature is placed 3 days, obtains the mixture of crystallization product, adds titanium silicon after release
Molecular screen primary powder (B1) to solid content 60 weight %, then by slurry in closed reactor in 170
DEG C temperature and self-generated pressure under crystallization 12 hours, gained crystallization product is filtered, washes with water, and
Dry 120 minutes in 110 DEG C, then in 550 DEG C of temperature roasting 3 hours in air atmosphere, it is thus achieved that
Molecular sieve-4 A 2.
The X-ray diffraction of gained molecular sieve-4 A 2 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 3
At a temperature of 20 DEG C, first by TPAOH aqueous solution that concentration is 25 weight % and metatitanic acid
Four butyl ester mixing, are subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2Meter is just
Tetraethyl orthosilicate, with TiO2Meter butyl titanate, with NH3The TPAOH of meter and water
Mol ratio is 100:2:15:1500.Gained mixture is stirred 3 hours at 75 DEG C, obtains clear
Clear transparent colloid (percent hydrolysis in organosilicon source is 100%).This colloid is put into rustless steel sealed reactor,
At a temperature of 100 DEG C, constant temperature is placed 3 days, obtains the mixture of crystallization product, adds titanium silicon after release
Molecular screen primary powder (B1) to solid content 30 weight %, then by slurry in closed reactor in 170
DEG C temperature and self-generated pressure under crystallization 6 hours, gained crystallization product is filtered, washes with water, and in
Dry 120 minutes, then in 550 DEG C of temperature roasting 3 hours in air atmosphere, it is thus achieved that molecule for 110 DEG C
Sieve A3.
The X-ray diffraction of gained molecular sieve-4 A 3 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 4
Use the method synthesis of molecular sieve of embodiment 1, except for the difference that, add HTS after release former
Powder (B1) is to solid content 70 weight %, it is thus achieved that molecular sieve-4 A 4.
The X-ray diffraction of gained molecular sieve-4 A 4 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 5
Using the method synthesis of molecular sieve of embodiment 1, except for the difference that, TPAOH used is
Embodiment 1 recovery obtains, it is thus achieved that molecular sieve-4 A 5.
The X-ray diffraction of gained molecular sieve-4 A 5 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 6
Use the method synthesis of molecular sieve of embodiment 3, except for the difference that, add HTS after release former
Powder (B1) is to solid content 55 weight %, it is thus achieved that molecular sieve-4 A 6.
The X-ray diffraction of gained molecular sieve-4 A 6 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 7
Using the method synthesis of molecular sieve of embodiment 3, except for the difference that, the temperature of the second crystallization is 190 DEG C,
Obtain molecular sieve-4 A 7.
The X-ray diffraction of gained molecular sieve-4 A 7 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 8
Use the method synthesis of molecular sieve of embodiment 3, except for the difference that, regulate hydrolysising condition so that hydrolysis
In the colloid obtained, the percent hydrolysis in organosilicon source is 60%, it is thus achieved that molecular sieve-4 A 8.
The X-ray diffraction of gained molecular sieve-4 A 8 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 9
Use the method synthesis of molecular sieve of embodiment 3, except for the difference that, regulate hydrolysising condition so that hydrolysis
In the colloid obtained, the percent hydrolysis in organosilicon source is 80%, it is thus achieved that molecular sieve-4 A 9.
The X-ray diffraction of gained molecular sieve-4 A 9 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 10
Use the method synthesis of molecular sieve of embodiment 3, except for the difference that, regulate hydrolysising condition so that hydrolysis
In the colloid obtained, the percent hydrolysis in organosilicon source is 40%, it is thus achieved that molecular sieve-4 A 10.
The X-ray diffraction of gained molecular sieve-4 A 10 and Fourier infrared spectrum characterize and embodiment 1 sample
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Test case
This test case is used for molecular sieve and the side of comparative example that explanation is obtained by the method that the present invention provides
The reaction effect that the molecular sieve that method obtains reacts for phenol hydroxylation.
By the sample prepared by above-described embodiment 1-10 and comparative example 1-2 according to sample: phenol: acetone=1:
The weight ratio of 20:16 is mix homogeneously in a there-necked flask with condensing tube, is warming up to 80 DEG C,
Then according to phenol under stirring: it is 27.5 weight that the mol ratio of hydrogen peroxide=3:1 adds concentration
The hydrogen peroxide of %, at this temperature reaction 3 hours, products therefrom is on Agilent6890N chromatograph
Use HP-5 capillary column (30m × 0.25mm) to measure each product slates, the results are shown in Table 1.
Wherein:
Wherein, total with the molal quantity of the molal quantity of Benzodiazepines and benzoquinone of the molal quantity of phenol of reaction is participated in
Molal quantity meter, described Benzodiazepines includes catechol, resorcinol and hydroquinone.
Table 1
From the results shown in Table 1, the phase of the HTS prepared according to the method for the present invention
Higher to degree of crystallinity, and particle size is more uniform, and pore volume and external surface area are bigger.It addition, use
When molecular sieve prepared by the method for the present invention is in phenol hydroxylation reacts, phenol conversion and to benzene two
The selectivity of phenol is obviously higher than the result of the sample gained prepared by the method for comparative example.It addition, at this
In the synthetic method that invention provides, organic base template recycles, and still can obtain higher relative
Degree of crystallinity and more uniform particle size, and higher phenol conversion and the selectivity of hydroquinone,
So while improving combined coefficient, also significantly reduce consumption of raw materials, alleviate environmental pollution.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
Claims (14)
1. the synthetic method of a HTS, it is characterised in that the method includes:
(1) organosilicon source, titanium source and alkalescence template are hydrolyzed and obtain mixture A, by described
Mixture A carries out the first crystallization；
(2) material after the first crystallization and the former powder of HTS are mixed to get mixture B, by institute
Stating mixture B and carry out the second crystallization, wherein, the consumption of the former powder of HTS makes mixture B's
Solid content is 30-80 weight %.
Synthetic method the most according to claim 1, wherein, the consumption of the former powder of HTS makes
The solid content obtaining mixture B is 50-60 weight %.
Synthetic method the most according to claim 1, wherein, the temperature of the second crystallization is more brilliant than first
Temperature height 20-100 DEG C changed.
Synthetic method the most according to claim 3, wherein, the temperature of the second crystallization is more brilliant than first
Temperature height 50-70 DEG C changed.
5. according to the synthetic method described in any one in claim 1-4, wherein,
The condition of the first crystallization includes: carry out crystallization in confined conditions, and temperature is 70-130 DEG C, the time
For 12-96h；
The condition of the second crystallization includes: carry out crystallization in confined conditions, and temperature is 140-180 DEG C, time
Between be 6-24h.
6. according to the synthetic method described in any one in claim 1-4, wherein, in mixture A
The percent hydrolysis in organosilicon source is 10-100%, preferably 50-90%, more preferably 60-80%.
7. according to the synthetic method described in any one in claim 1-4, wherein, in step (1),
With SiO2Meter organosilicon source, with TiO2Meter titanium source, with NH3The alkaline template of meter and the use of water
Amount mol ratio is 100:(0.005-10): (0.005-40): (200-10000).
8. according to the synthetic method described in any one in claim 1-4, wherein, in step (1),
Described organosilicon source is one or more in the silicon-containing compound shown in Formulas I, and described titanium source is selected from
Inorganic titanium salt and/or organic titanate, described alkalescence template is selected from quaternary ammonium base, aliphatic amine and aliphatic
One or more in hydramine；
In Formulas I, R1、R2、R3And R4It is respectively C1-C4Alkyl.
9. according to the synthetic method described in any one in claim 1-4, wherein, the method is also wrapped
Include: filtered by the second crystallization products therefrom, washing obtains solid, after being dried or be moist by gained solid
Carry out roasting.
10. according to the synthetic method described in any one in claim 1-4, wherein, described titanium silicon divides
Son sieves the content of template in former powder and is less than 0.1 weight %.
In 11. claim 1-10, the synthetic method described in any one synthesizes the HTS obtained.
The application in the oxidation reaction of HTS described in 12. claim 11.
13. 1 kinds of method for hydroxylation of phenol, the method includes: under the conditions of phenol hydroxylation, by benzene
Phenol, hydrogen peroxide contact with catalyst, it is characterised in that described catalyst contains claim 11 institute
The HTS stated.
14. methods according to claim 13, wherein, the titanium silicon that described catalyst is described divides
Son sieve, described phenol hydroxylation condition includes: temperature is 30-120 DEG C, phenol and hydrogen peroxide mole
Than being (1-10): 1, HTS is (0.001-0.5) with the weight ratio of phenol: 1.
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