CN106276944B - A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol - Google Patents
A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol Download PDFInfo
- Publication number
- CN106276944B CN106276944B CN201510289657.9A CN201510289657A CN106276944B CN 106276944 B CN106276944 B CN 106276944B CN 201510289657 A CN201510289657 A CN 201510289657A CN 106276944 B CN106276944 B CN 106276944B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- titanium
- crystallization
- mixture
- sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to molecular sieve arts, specifically provide a kind of HTS and its synthetic method and application, this method comprises: (1) is hydrolyzed organic silicon source, titanium source and alkaline template to obtain mixture A, the mixture A is subjected to the first crystallization；(2) material after the first crystallization is mixed to get mixture B with Titanium Sieve Molecular Sieve original powder, is 30-80 weight % by the solid content that the mixture B dosage for carrying out the second crystallization Titanium Sieve Molecular Sieve original powder makes mixture B.The present invention also provides a kind of method for hydroxylation of phenol.The relative crystallinity for the Titanium Sieve Molecular Sieve that the method according to the invention is prepared is higher, and particle size is more uniform, and height is measured on Ti, and Kong Rong and external surface area are big.
Description
Technical field
It is synthesized the present invention relates to a kind of synthetic method of Titanium Sieve Molecular Sieve and by the synthetic method of Titanium Sieve Molecular Sieve
The application and a kind of method for hydroxylation of phenol of Titanium Sieve Molecular Sieve and Titanium Sieve Molecular Sieve of the invention in phenol hydroxylation.
Background technique
Titanium-silicon molecular sieve TS-1 is introduced transition metal element titanium formed in the framework of molecular sieve with ZSM-5 structure
A kind of novel titanosilicate with superior catalytic selective oxidation performance.TS-1 not only has the catalysed oxidn of titanium,
But also shape-selective effect and excellent stability with ZSM-5 molecular sieve.Since TS-1 molecular sieve is anti-in the oxidation of organic matter
Ying Zhong can be used free of contamination low concentration hydrogen peroxide as oxidant, avoid oxidation process complex process and pollution environment
The problem of, there is the unrivaled energy conservation of conventional oxidation system, economy and advantages of environment protection, and there is good reaction choosing
Selecting property, therefore there is great prospects for commercial application.
The synthetic method of TS-1 is in 1981 by first public (USP4410501).This method is first to synthesize one kind to contain silicon
Source, titanium source, organic base and/or basic anhydride reaction mixture, by this reaction mixture in 130-200 DEG C in autoclave
It hydrothermal crystallizing 6-30 days, then separates, washes, dries, roast and obtains product.During plastic, the mixing of estersil and titanium esters
The control of solution hydrolysising condition is very harsh, because the hydrolysis rate of the two mismatches, the latter is higher than the former, and the speed of organic base is added
Degree will slightly generate the polymer of irreversible titanium fastly, and the polymer of these titaniums is difficult to enter skeleton in crystallization process, and more
It being entrained in molecular sieve in the form of extra-framework titanium, this partial-titanium may not only block duct, but also hydrogen peroxide can be catalytically decomposed,
Waste raw material.
Hereafter, researcher has carried out many trials to the synthetic method of Titanium Sieve Molecular Sieve and has improved and optimizated, but existing production
Method still has that solid content is low, the production cycle is long, titanium is unevenly distributed, prepares the problems such as poor repeatability more；Especially titanium silicon molecule
For sieve when applying in catalytic oxidation, the generally existing big activity of Titanium Sieve Molecular Sieve crystal grain is low, and crystal grain is small is separated by filtration difficulty
The problems such as.
Summary of the invention
The purpose of the present invention is to provide a kind of synthetic methods of new Titanium Sieve Molecular Sieve, and synthesize to obtain by this method
Titanium Sieve Molecular Sieve.
The present inventor has been surprisingly found that in the course of the research, first will be organic in the preparation process of Titanium Sieve Molecular Sieve
The mixture that silicon source, titanium source are hydrolyzed with alkaline template, and hydrolysis obtained carries out Crystallizing treatment, then after crystallization
Titanium Sieve Molecular Sieve original powder is added in material to solid content 30-80 weight %, mixture is then subjected to Crystallizing treatment again, so
The parameters such as the relative crystallinity and particle diameter distribution of Titanium Sieve Molecular Sieve obtained and hole and specific surface area further improve.Based on this
It was found that completing the present invention.
In order to realize foregoing purpose, according to the first aspect of the invention, the present invention provides a kind of conjunctions of Titanium Sieve Molecular Sieve
At method, this method comprises:
(1) it is hydrolyzed organic silicon source, titanium source and alkaline template to obtain mixture A, the mixture A is carried out the
One crystallization；
(2) by after the first crystallization material and Titanium Sieve Molecular Sieve original powder be mixed to get mixture B, by the mixture B into
The second crystallization of row, wherein the dosage of Titanium Sieve Molecular Sieve original powder makes the solid content of mixture B be 30-80 weight %.
According to the second aspect of the invention, the present invention provides the Titanium Sieve Molecular Sieve synthesized by preceding method.
According to the third aspect of the invention we, the present invention provides the Titanium Sieve Molecular Sieve synthesized by method of the invention to exist
Application in oxidation reaction.
According to the fourth aspect of the invention, the present invention provides a kind of method for hydroxylation of phenol, this method comprises: in benzene
Under the conditions of phenolic hydroxyl group, phenol, hydrogen peroxide are contacted with catalyst, the catalyst contains titanium silicon molecule of the present invention
Sieve.
The relative crystallinity for the Titanium Sieve Molecular Sieve that the method according to the invention is prepared is higher, and particle size is more uniform.
And it was unexpected that using method of the invention compared with routinely molecular screen primary powder method not being added, measured on Ti it is bigger, Kong Rong and
External surface area is bigger.
Synthetic method provided by the invention is able to suppress the decomposition of organic base template, and organic base template therein can
With recycling (such as embodiment 5), cost is reduced, mitigates environmental pollution.
When the molecular sieve prepared using method of the invention is in phenol hydroxylation reaction, phenol conversion and to benzene two
Sample resulting result of the selectivity of phenol obviously higher than the method preparation by comparative example.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
As previously mentioned, the present invention provides a kind of synthetic methods of Titanium Sieve Molecular Sieve, this method comprises:
(1) it is hydrolyzed organic silicon source, titanium source and alkaline template to obtain mixture A, the mixture A is carried out the
One crystallization；
(2) by after the first crystallization material and Titanium Sieve Molecular Sieve original powder be mixed to get mixture B, by the mixture B into
The second crystallization of row, wherein the dosage of Titanium Sieve Molecular Sieve original powder makes the solid content of mixture B be 30-80 weight %.
Synthetic method according to the present invention, solid content principle refer to that the quality of solid matter in reaction kettle accounts for material in reactor
The percentage composition of gross mass, it is general using by the total weight of total material metage, that is, material in reactor in reaction kettle, then will
The solid matters such as the molecular sieve in reaction kettle are weighed after filtering is drawn off dry (temperature is less than 200 DEG C), are counted
The percent data for the total weight that the solid matters weight such as the molecular sieve after calculating drying account for material in reactor is denoted as in reaction kettle
The solid content of material.In the specific implementation process, it is not necessary to directly specifically go measurement solid content, but can first laboratory according to
The volume ratio of solid and liquid after centrifugation, providing respective volume, working curve can than the working curve with solid content, and then whereby
Intuitively provide the solid content of material in embodiment each time.It is preferred that the dosage of Titanium Sieve Molecular Sieve original powder makes mixture B's
Solid content is 50-60 weight %.Thus the Titanium Sieve Molecular Sieve Ti being prepared is more evenly distributed, and relative crystallinity is higher, particle
Size also more evenly, and higher for phenol conversion in oxidation reaction such as phenol hydroxylation reaction and hydroquinone choosing
Selecting property is higher.
Synthetic method according to the present invention, the preferably temperature of the second crystallization are 20-100 DEG C higher than the temperature of the first crystallization, more
It is preferred that 50-70 DEG C high.Thus the Titanium Sieve Molecular Sieve Ti being prepared is more evenly distributed, and relative crystallinity is higher, particle size
More evenly, and for phenol conversion is higher in oxidation reaction such as phenol hydroxylation reaction and the selectivity of hydroquinone more
It is high.
According to the method for the present invention, the hydrolysis carries out in the presence of aqueous solvent, and the type of the aqueous solvent can be with
For the conventional selection of this field, various aqueous solvents may be incorporated for realizing the present invention, as long as the wherein water in aqueous solvent
It is able to satisfy the condition that organic silicon source generates Titanium Sieve Molecular Sieve in crystallization process.The solvent is preferably water, can also foundation
Need to be added other cosolvents, to this present invention without specific requirement, this is not described in detail here.It should be noted that containing water-soluble
Agent can arise directly from the solvent portion of other material solutions, such as can be directed to the molten of alkaline template aqueous solution
Agent part；It can also directly add, if the solvent portion of other aqueous solution of raw material can satisfy the requirement that feeds intake of aqueous solvent,
Addition aqueous solvent is no longer needed to, if not satisfied, then needing that aqueous solvent additionally is added.
The purpose of the present invention can be realized according to preceding solution in synthetic method according to the present invention, for the present invention,
It is preferred that the condition of the first crystallization includes: to carry out crystallization in confined conditions, temperature is 70-130 DEG C, preferably 80-120 DEG C.
The time of synthetic method according to the present invention, the first crystallization can be adjusted according to specific crystallization temperature etc.,
For the present invention, the preferably time of the 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.
The purpose of the present invention can be realized according to preceding solution in synthetic method according to the present invention, for the present invention,
It is preferred that the condition of the second crystallization includes: to carry out crystallization in confined conditions, temperature is 140-180 DEG C, preferably 150-170 DEG C.
The time of synthetic method according to the present invention, the second crystallization can be adjusted according to specific crystallization temperature etc.,
For the present invention, the preferably time of the 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.
Synthetic method according to the present invention, the percent hydrolysis of organic silicon source is 10-100% in preferred mixture A, further excellent
It is selected as 50-90%, more preferably 60-80%.Thus the Titanium Sieve Molecular Sieve Ti being prepared is more evenly distributed, and relative crystallinity is more
Height, particle size are also more evenly, and higher for phenol conversion in oxidation reaction such as phenol hydroxylation reaction and to benzene two
The selectivity of phenol is higher.
Synthetic method according to the present invention, in preferred steps (1), with SiO2The organic silicon source of meter, with TiO2The titanium source of meter,
With NH3The alkaline template of meter and the dosage molar ratio of water are 100:(0.005-10): (0.005-40): (200-10000), it is excellent
It is selected as 100:(0.05-5): (0.05-20): (500-5000).
According to the method for the present invention, the organic silicon source can be capable of forming two under the conditions of hydrolysis-condensation reaction to be various
The silicon-containing compound of silica.Specifically, the organic silicon source can for one of silicon-containing compound shown in the Formulas I or
It is a variety of,
In Formulas I, R1、R2、R3And R4Respectively C1~C4Alkyl, including C1~C4Straight chained alkyl and C3~C4Branch
Alkyl, such as: R1、R2、R3And R4Respectively can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or
Tert-butyl.
Specifically, the organic silicon source can be positive quanmethyl silicate, tetraethyl orthosilicate, four n-propyl of positive silicic acid and just
One of four N-butyl of silicic acid is a variety of.Use in a specific embodiment of the present invention is tetraethyl orthosilicate.
According to the method for the present invention, the titanium source can be the conventional selection of this field, for the present invention, the preferably described titanium
Source is selected from inorganic titanium salt and/or organic titanate, preferably 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)2Contain titanium salt etc. various forms of, X is halogen in formula, preferably chlorine, wherein the preferred inorganic titanium salt is selected from TiCl4、
Ti(SO4)2And TiOCl2One of or it is a variety of.
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 1-4 carbon atom, and 4 M can be identical or different, and it is metatitanic acid isopropyl that the preferably described organic titanate, which is selected from,
One of ester, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate are a variety of, use in a specific embodiment of the present invention
It is butyl titanate as example, but the range being not intended to limit the present invention.
According to the method for the present invention, optional wider range of the type of the alkaline template, can be aliphatic amine
One of compound, aliphatic alcohol amine compounds and quaternary ammonium alkali cpd are a variety of.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be various NH3In
At least one hydrogen replaced by aliphatic alkyl (preferably alkyl) after the compound that is formed, the aliphatic hydramine can be each
Kind NH3In at least one hydrogen replaced by the aliphatic alkyl (preferably alkyl) of hydroxyl after the compound that is formed.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can indicate for formula III
Aliphatic amine, the aliphatic hydramine can for as formula IV indicate 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 R8It respectively can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
R9(NH2)n(formula III)
In formula III, n is an 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-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, new
Amyl, 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
Aliphatic amine compound is one of ethamine, n-butylamine, butanediamine and hexamethylene diamine or a variety of
(HOR10)mNH(3-m)(formula IV)
In formula IV, m R10It is identical or different, 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 one of monoethanolamine, diethanol amine and triethanolamine or a variety of.
It should be noted that when such as quaternary ammonium base of the organic base using strong basicity is as alkaline template, due to its alkalinity
It is relatively strong, it can satisfy the requirement in Titanium Sieve Molecular Sieve synthesis process to mixture alkalinity, therefore, quaternary ammonium base is closed in Titanium Sieve Molecular Sieve
Alkali source is used as at template is not only used as in the process.
When using other alkaline templates, the alkalinity of the mixture obtained after mixing is not able to satisfy Titanium Sieve Molecular Sieve conjunction
When at requirement to mixture alkalinity in the process, those skilled in the art can according to need by way of adding alkali source and adjust
The alkalinity of whole mixture.Optional wider range of the type of the alkali source, preferably inorganic alkali source.Wherein, inorganic alkali source can be with
It is the alkaline matter of alkali or alkaline earth metal for ammonium hydroxide or cation, such as can is sodium hydroxide, potassium hydroxide, hydroxide
One of calcium, sodium carbonate and potassium carbonate are a variety of.
In the present invention, advantage of the invention is illustratively illustrated as template using tetrapropylammonium hydroxide.
With the method for the invention it is preferred to when step (2) mixes the material after the first crystallization with Titanium Sieve Molecular Sieve original powder,
Material after first crystallization cools (no particular/special requirement, crystallizing kettle can be opened by being down to room temperature) after referring to the first crystallization
Afterwards without material obtained from other any processing.
With the method for the invention it is preferred to this method further include: be filtered, washed the second crystallization products therefrom and consolidated
Body, by obtained solid it is dry or not dry after roast.
In the present invention, optional wider range of the condition of the drying is specifically referred to prior art progress.For this
Invention, the condition of the preferably described drying include: that temperature is room temperature to 200 DEG C, more preferably 80-120 DEG C；Time is 1-24h, excellent
It is selected as 2-10h.
In the present invention, optional wider range of the condition of the roasting, for the condition packet of the preferably roasting of the invention
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；More preferably
The condition of the roasting includes: to roast 0.5-6h in nitrogen atmosphere at 350-600 DEG C first, then at 350-600 DEG C in sky
0.5-12h is roasted in gas atmosphere.
According to the method for the present invention, the type of the Titanium Sieve Molecular Sieve original powder can be containing template without particular/special requirement
Titanium Sieve Molecular Sieve original powder may be the Titanium Sieve Molecular Sieve original powder without template, such as can for synthesis after by stripper plate
Agent step or Titanium Sieve Molecular Sieve without Template removal step, for the present invention, mould in the preferably described Titanium Sieve Molecular Sieve original powder
The content of plate agent is lower than 0.1 weight %, that is, passes through the Titanium Sieve Molecular Sieve original powder of Template removal.
Synthetic method provided by the invention, has an advantage that
1, high solids content synthesizes, and improves production efficiency；
2, the Titanium Sieve Molecular Sieve relative crystallinity that synthesis obtains improves, and Ti content is high, and Kong Rong and external surface area increase；
3, the particle diameter distribution etc. for the Titanium Sieve Molecular Sieve crystal grain that synthesis obtains also is improved, and the general integrated distribution of partial size exists
150nm-350nm, it can be seen that, method of the invention is optimized and adjusts to the nucleation and growth course of poromerics,
So that crystal grain is more uniform；
4, synthetic method provided by the invention is able to suppress the decomposition of organic base template, organic base template therein
It can be recycled, reduce cost, mitigate environmental pollution；
5, when the molecular sieve prepared using method of the invention is in phenol hydroxylation reaction, phenol conversion and to benzene
Sample resulting result of the selectivity of diphenol obviously higher than the method preparation by comparative example.
The present invention provides a kind of Titanium Sieve Molecular Sieve that synthetic method according to the invention synthesizes.
Titanium Sieve Molecular Sieve according to the present invention has higher catalytic activity.Specifically, it is prepared by method of the invention
Titanium Sieve Molecular Sieve shows higher catalytic activity and hydroquinone selection when being used as the catalyst of phenol hydroxylation reaction
Property.Advantage of the invention is illustrated as example using phenol hydroxylation reaction in a specific embodiment of the present invention, but of the invention
Titanium Sieve Molecular Sieve is not limited only to have advantage for phenol hydroxylation reaction, equally has good effect for other oxidation reactions
Fruit.
The present invention provides the application of Titanium Sieve Molecular Sieve of the invention in the oxidation reaction.
The present invention provides a kind of method for hydroxylation of phenol, this method comprises: under the conditions of phenol hydroxylation, by benzene
Phenol, hydrogen peroxide are contacted with catalyst, and the catalyst contains Titanium Sieve Molecular Sieve of the present invention.
According to the method for the present invention, preferably described to urge as long as the catalyst contains Titanium Sieve Molecular Sieve of the invention
The content of Titanium Sieve Molecular Sieve is 50 weight % or more in agent, and more preferable content is 60-100 weight %.Of the invention specific
The content for used in embodiment being Titanium Sieve Molecular Sieve is the catalyst of 100 weight %, but this is not intended to limit the present invention
Range.Catalyst composition when content herein is referred to without carrier.
When the catalyst is formed body, the catalyst further includes carrier, wherein carrier can be Al2O3、ZnO、
MgO、SiO2, CaO and TiO2, rare earth oxide RE2O3(RE La, Ce, Y or Nd etc.).
In the present invention, in the catalyst, in addition to including Titanium Sieve Molecular Sieve, also other it commonly can also to be used for phenol
Hydroxylated catalyst.
According to a preferred embodiment of the present invention, the preferably described catalyst is Titanium Sieve Molecular Sieve, the phenol hydroxyl
Base condition includes: that temperature is 30-120 DEG C, and preferably 50-90 DEG C, the temperature used in an embodiment of the present invention is 80 DEG C, benzene
The molar ratio of phenol and hydrogen peroxide is (1-10): 1, more preferable (2-5): 1, the weight ratio of Titanium Sieve Molecular Sieve and phenol is
(0.001-0.5): 1, preferably (0.01-0.08): 1, more preferably (0.04-0.06): 1.In this way, can get better phenol
Conversion ratio and hydroquinone selectivity.
It is necessary to be noted that those skilled in the art, under close high phenol conversion, merely
By the change of method for preparing catalyst, it is more difficult (especially improving 5 percentage points or more) to improve hydroquinone selectivity.And this
The inventor of invention is but found surprisingly that, uses Titanium Sieve Molecular Sieve of the present invention for catalyst, relative to conventional titanium silicon point
Sub- sieve catalyst can effectively improve hydroquinone selectivity (improving 5 percentage points or more).
The present invention is further illustrated for embodiment below, 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 requirements that feeds intake met to water, then without adding water, if not satisfied, water is then added as needed.
The measurement of X-ray diffraction (XRD) crystalline phase figure of embodiment and comparative example sample is penetrated in Siemens D5005 type X-
It is carried out on line diffractometer, wherein with sample and authentic specimen in 2 θ be spreading out for the five fingers diffractive features peak between 22.5 ° -25.0 °
The crystallinity for penetrating the ratio of the sum of intensity (peak height) to indicate sample relative to authentic specimen, wherein the sample with comparative example 1 is
Authentic specimen, crystallinity are calculated as 100%；Relative crystallinity data and grain size distribution data of each sample etc. are shown in Table 1.Its
In, crystal grain (particle) size distribution data is the percentage that crystal grain quantity of the sample between 150nm-350nm accounts for total crystal grain quantity
Number (uses PHILIPS company, Holland XL 30ESEM type scanning electron microscope SEM, observes sample particle size and carry out crystal grain
Size distribution statistics, wherein acceleration voltage is 20kV).The infrared spectrum of each sample passes through 8210 type fourier infrared of Nicolet
Spectrometer obtains.
In the present invention, external surface area, Kong Rong are measured using BET method.
The Si/Ti (molar ratio) of embodiment and comparative example sample by x-ray fluorescence analysis (XRF) than being measured and being calculated
It obtains.Wherein, Si/Ti illustrates that the Ti content in molecular sieve is higher than smaller.The Si/Ti of each sample is shown in Table 1 than data.
In the present invention, organic silicon source amount of hydrolysis is measured by gas chromatography.Gas-chromatography used is Agilent
6890N is equipped with the capillary column (30m*320 μm * 25 μm) of thermal conductivity detector (TCD) TCD and HP-5.Wherein, injector temperature 180
DEG C, column temperature is 150 DEG C, uses nitrogen as carrier gas, and the flow velocity of carrier gas is 25mL/min.Method particularly includes: it takes a certain amount of mixed
Object is closed from gas chromatograph injection port sample introduction, detect and quantified by external standard method using TCD after flowing through chromatographic column.It adopts
Organic silicon source percent hydrolysis is calculated with following formula:
XOrganic silicon source%=[(mo Organic silicon source-mOrganic silicon source)/mo Organic silicon source] × 100%
In formula, XOrganic silicon sourceIndicate the percent hydrolysis of organic silicon source；mo Organic silicon sourceIndicate the quality for the organic silicon source being added；mOrganic silicon sourceTable
Show the quality of unhydrolysed organic silicon source.
Comparative example 1
Method described in this comparative example reference literature (Zeolites, volume 1992,12,943-950 pages) prepares TS-1 points
Son sieve, for illustrating the process according to conventional hydrothermal crystallization method synthesis of titanium silicon molecular sieve.
22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of tetrapropylammonium hydroxide, and are added by (20 DEG C) at room temperature
59.8 grams of distilled water hydrolyze 1.0 hours at normal pressure and 60 DEG C after being stirred, obtain the hydrating solution of tetraethyl orthosilicate,
It is slowly added into the solution as composed by 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring, gained is mixed
It closes object to stir 3 hours at 75 DEG C, obtains clear colloid.This colloid is put into stainless steel sealing reaction kettle, at 170 DEG C
At a temperature of constant temperature place 3 days, obtain the mixture of crystallization product；It by the filtering of this mixture, is washed with water, and in 110 DEG C of dryings
60 minutes, obtain TS-1 original powder.This TS-1 original powder is roasted 3 hours in 550 DEG C of temperature in air atmosphere, obtains TS-1 molecular sieve
B1。
Through detecting, the XRD crystal phase of gained molecular sieve B1 is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ
The five fingers diffractive features peak shows that molecular sieve B1 has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Near
There is the unexistent characteristic absorption peak of silica zeolite in place, shows that titanium has entered sample skeleton.
Embodiment 1
Titanium Sieve Molecular Sieve is prepared according to the method for comparative example 1, the difference is that titanium silicon is added after crystallization condition difference and crystallization
Molecular sieve.Detailed process is as follows:
22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of tetrapropylammonium hydroxide, and are added by (20 DEG C) at room temperature
59.8 grams of distilled water hydrolyze 1.0 hours at normal pressure and 60 DEG C after being stirred, obtain the hydrating solution of tetraethyl orthosilicate,
It is slowly added into the solution as composed by 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring, gained is mixed
It closes object to stir 3 hours at 75 DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).This colloid is put into
Stainless steel seals reaction kettle, places 3 days in 110 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, titanium is added after release
Si molecular sieves original powder (B1) to 50 weight % of solid content, then by slurry in closed reactor under 160 DEG C and self-generated pressure
Processing is for 24 hours；It by the filtering of this mixture, is washed with water, and 60 minutes dry in 110 DEG C, is roasted in air atmosphere in 550 DEG C of temperature
It burns 3 hours, obtains TS-1 molecular sieve-4 A 1.
Through detecting, the XRD crystal phase of gained molecular sieve-4 A 1 is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ
The five fingers diffractive features peak shows that molecular sieve-4 A 1 has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Near
There is the unexistent characteristic absorption peak of silica zeolite in place, shows that titanium has entered sample skeleton.
Comparative example 2
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 10 weight % is mixed with butyl titanate
It closes, is subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The titanium of meter
Sour four butyl esters, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:5:10:800.By gained mixture at 75 DEG C
Lower stirring 3 hours, obtains clear colloid.This colloid is put into stainless steel sealing reaction kettle, in 120 DEG C of at a temperature of constant temperature
It places 3 days, obtains the mixture of crystallization product, by the filtering of gained crystallization product, be washed with water, and dry 120 points in 110 DEG C
Then clock roasts 3 hours in 550 DEG C of temperature in air atmosphere, obtain molecular sieve B2.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve B2
It is almost the same.
Embodiment 2
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 10 weight % is mixed with butyl titanate
It closes, is subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The titanium of meter
Sour four butyl esters, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:5:10:800.By gained mixture at 75 DEG C
Lower stirring 3 hours obtains clear colloid (percent hydrolysis of organic silicon source is 100%).This colloid is put into stainless steel sealing
Reaction kettle is placed 3 days in 120 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, it is former that Titanium Sieve Molecular Sieve is added after release
Powder (B1) to 60 weight % of solid content, then by slurry in closed reactor at 170 DEG C of temperature and self-generated pressure crystallization
It 12 hours, by the filtering of gained crystallization product, is washed with water, and dried 120 minutes in 110 DEG C, then in 550 DEG C of temperature in air
It is roasted 3 hours in atmosphere, obtains molecular sieve-4 A 2.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 2
It is almost the same.
Embodiment 3
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 25 weight % is mixed with butyl titanate
It closes, is subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The titanium of meter
Sour four butyl esters, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:2:15:1500.By gained mixture 75
It is stirred 3 hours at DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).It is close that this colloid is put into stainless steel
Reaction kettle is sealed, is placed 3 days in 100 DEG C of at a temperature of constant temperature, is obtained the mixture of crystallization product, Titanium Sieve Molecular Sieve is added after release
Original powder (B1) is then brilliant at 170 DEG C of temperature and self-generated pressure in closed reactor by slurry to 30 weight % of solid content
Change 6 hours, by the filtering of gained crystallization product, is washed with water, and dried 120 minutes in 110 DEG C, then in 550 DEG C of temperature in sky
It is roasted 3 hours in gas atmosphere, obtains molecular sieve-4 A 3.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 3
It is almost the same.
Embodiment 4
Using the method synthesis of molecular sieve of embodiment 1, the difference is that, Titanium Sieve Molecular Sieve original powder (B1) is added after release to admittedly
70 weight % of content obtains molecular sieve-4 A 4.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 4
It is almost the same.
Embodiment 5
Using the method synthesis of molecular sieve of embodiment 1, the difference is that, tetrapropylammonium hydroxide used is that embodiment 1 is returned
What receipts obtained, obtain molecular sieve-4 A 5.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 5
It is almost the same.
Embodiment 6
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, Titanium Sieve Molecular Sieve original powder (B1) is added after release to admittedly
55 weight % of content obtains molecular sieve-4 A 6.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 6
It is almost the same.
Embodiment 7
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, the temperature of the second crystallization is 190 DEG C, obtains molecular sieve
A7。
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 7
It is almost the same.
Embodiment 8
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, hydrolysising condition is adjusted, so that the colloid that hydrolysis obtains
The percent hydrolysis of middle organic silicon source is 60%, obtains molecular sieve-4 A 8.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 8
It is almost the same.
Embodiment 9
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, hydrolysising condition is adjusted, so that the colloid that hydrolysis obtains
The percent hydrolysis of middle organic silicon source is 80%, obtains molecular sieve-4 A 9.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 9
It is almost the same.
Embodiment 10
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, hydrolysising condition is adjusted, so that the colloid that hydrolysis obtains
The percent hydrolysis of middle organic silicon source is 40%, obtains molecular sieve-4 A 10.
X-ray diffraction and the Fourier infrared spectrum characterization of gained molecular sieve-4 A 10 and the spectroscopy of 1 sample A1 of embodiment are special
It levies almost the same.
Test case
This test case is for illustrating what the method for the molecular sieve that the method provided through the invention obtains and comparative example obtained
Molecular sieve is used for the reaction effect of phenol hydroxylation reaction.
By sample prepared by above-described embodiment 1-10 and comparative example 1-2 according to sample: phenol: acetone=1:20:16
Weight ratio is uniformly mixed in a three-necked flask with condenser pipe, 80 DEG C is warming up to, then according to benzene under stirring
Phenol: the hydrogen peroxide that concentration is 27.5 weight % is added in hydrogen peroxide=3:1 molar ratio, reacts 3 hours at this temperature, institute
It obtains product and measures each product distribution using HP-5 capillary column (30m × 0.25mm) on Agilent6890N chromatograph, as a result
It is shown in Table 1.
Wherein:
Wherein, the molal quantity of the phenol of reaction is participated in the total mole number of the molal quantity of benzenediol and the molal quantity of benzoquinones
Meter, the benzenediol includes catechol, resorcinol and hydroquinone.
Table 1
From the results shown in Table 1, the relative crystallinity for the Titanium Sieve Molecular Sieve that the method according to the invention is prepared
It is higher, and particle size is more uniform, and Kong Rong and external surface area are larger.In addition, the molecule prepared using method of the invention
When sieve is in phenol hydroxylation reaction, the selectivity of phenol conversion and hydroquinone is obviously higher than the method by comparative example
The resulting result of the sample of preparation.In addition, organic base template is recycled, still in synthetic method provided by the invention
The choosing of higher relative crystallinity and more uniform particle size and higher phenol conversion and hydroquinone can be obtained
Selecting property also significantly reduces consumption of raw materials in this way while improving combined coefficient, mitigates environmental pollution.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
Claims (11)
1. a kind of synthetic method of Titanium Sieve Molecular Sieve, which is characterized in that this method comprises:
(1) it is hydrolyzed organic silicon source, titanium source and alkaline template to obtain mixture A, it is brilliant that the mixture A is carried out first
Change, the percent hydrolysis of organic silicon source is 60-80% in mixture A；
(2) by after the first crystallization material and Titanium Sieve Molecular Sieve original powder be mixed to get mixture B, the mixture B is carried out the
Two crystallization, wherein the dosage of Titanium Sieve Molecular Sieve original powder makes the solid content of mixture B be 50-60 weight %；
Wherein, the temperature of the second crystallization is 20-100 DEG C higher than the temperature of the first crystallization.
2. synthetic method according to claim 1, wherein the temperature of the second crystallization is 50-70 higher than the temperature of the first crystallization
℃。
3. synthetic method according to claim 1 or 2, wherein
The condition of first crystallization includes: to carry out crystallization in confined conditions, and temperature is 70-130 DEG C, time 12-96h；
The condition of second crystallization includes: to carry out crystallization in confined conditions, and temperature is 140-180 DEG C, time 6-24h.
4. synthetic method according to claim 1 or 2, wherein in step (1), with SiO2The organic silicon source of meter, with TiO2
The titanium source of meter, with NH3The alkaline template of meter and the dosage molar ratio of water are 100:(0.005-10): (0.005-40): (200-
10000)。
5. synthetic method according to claim 1 or 2, wherein in step (1), the organic silicon source is selected from shown in Formulas I
One of silicon-containing compound or a variety of, the titanium source is selected from inorganic titanium salt and/or organic titanate, the alkalinity template
Selected from one of quaternary ammonium base, aliphatic amine and aliphatic hydramine or a variety of；
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl.
6. synthetic method according to claim 1 or 2, wherein this method further include: by the second crystallization products therefrom mistake
Filter, washing obtain solid, by obtained solid it is dry or not dry after roast.
7. synthetic method according to claim 1 or 2, wherein the content of template is low in the Titanium Sieve Molecular Sieve original powder
In 0.1 weight %.
8. the Titanium Sieve Molecular Sieve that synthetic method described in any one of claim 1-7 synthesizes.
9. the application of Titanium Sieve Molecular Sieve according to any one of claims 8 in the oxidation reaction.
10. a kind of method for hydroxylation of phenol, this method comprises: by phenol, hydrogen peroxide and being urged under the conditions of phenol hydroxylation
Agent contact, which is characterized in that the catalyst contains Titanium Sieve Molecular Sieve according to any one of claims 8.
11. according to the method described in claim 10, wherein, the catalyst is the Titanium Sieve Molecular Sieve, the phenol hydroxyl
Base condition includes: that temperature is 30-120 DEG C, and the molar ratio of phenol and hydrogen peroxide is (1-10): 1, Titanium Sieve Molecular Sieve and phenol
Weight ratio be (0.001-0.5): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510289657.9A CN106276944B (en) | 2015-05-29 | 2015-05-29 | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510289657.9A CN106276944B (en) | 2015-05-29 | 2015-05-29 | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106276944A CN106276944A (en) | 2017-01-04 |
| CN106276944B true CN106276944B (en) | 2019-03-22 |
Family
ID=57655978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510289657.9A Active CN106276944B (en) | 2015-05-29 | 2015-05-29 | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106276944B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721064B (en) * | 2017-10-31 | 2020-10-27 | 中国石油化工股份有限公司 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
| CN109721071B (en) * | 2017-10-31 | 2020-10-27 | 中国石油化工股份有限公司 | Method for producing titanium-silicon molecular sieve, titanium-silicon molecular sieve produced by method and hydroxylation reaction method |
| CN109721066B (en) * | 2017-10-31 | 2021-02-09 | 中国石油化工股份有限公司 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
| CN110961141B (en) * | 2018-09-30 | 2022-10-21 | 中国石油化工股份有限公司 | Vanadium-silicon molecular sieve, synthesis method and application thereof, and phenol oxidation method |
| CN111072528B (en) * | 2018-10-18 | 2022-05-17 | 中国石油化工股份有限公司 | Method for preparing sulfoxide |
| CN112279262A (en) * | 2020-11-16 | 2021-01-29 | 四川奥力奋催化材料有限公司 | Silicoaluminophosphate molecular sieve, catalyst for preparing olefin from methanol, preparation method and application thereof |
Citations (3)
| 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 |
| CN102502686A (en) * | 2011-10-06 | 2012-06-20 | 大连理工大学 | Method for synthesizing titanium silicon molecular sieve |
| CN104418354A (en) * | 2013-09-09 | 2015-03-18 | 中国石油化工股份有限公司 | Titanium-silicon microporous material and synthetic method thereof |
-
2015
- 2015-05-29 CN CN201510289657.9A patent/CN106276944B/en active Active
Patent Citations (3)
| 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 |
| CN102502686A (en) * | 2011-10-06 | 2012-06-20 | 大连理工大学 | Method for synthesizing titanium silicon molecular sieve |
| CN104418354A (en) * | 2013-09-09 | 2015-03-18 | 中国石油化工股份有限公司 | Titanium-silicon microporous material and synthetic method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106276944A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106276944B (en) | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol | |
| CN105728019B (en) | A kind of preparation method and application of the ZSM-5 molecular sieve with Jie's micropore | |
| CN104556111B (en) | A kind of Titanium Sieve Molecular Sieve and its synthetic method | |
| CN106904632B (en) | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol | |
| CN105271294B (en) | Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method | |
| CN101190793B (en) | Method for synthesizing TS-1 molecular screen | |
| CN101190792A (en) | Method for synthesizing titanium-silicon molecular screen | |
| TW201632463A (en) | A method for the synthesis of a type of FER/MOR composite molecular sieve | |
| CN104556115A (en) | Titanium silicalite molecular sieve synthesizing method | |
| CN104556104A (en) | Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent | |
| CN1102442C (en) | Preparation method for Ti-Si molecular sieve | |
| CN103058222B (en) | Method for synthesizing ZSM-35 molecular sieve | |
| CN105217650B (en) | Mesoporous titanium silicate molecular sieve, synthetic method therefor and application thereof as well as method for oxidizing 2,6-di-tert-butylphenol | |
| CN104556103B (en) | A kind of method that utilization quaternary ammonium salt. template agent synthesizes silica zeolite | |
| CN104418344B (en) | A kind of synthetic method of total silicon mesoporous material | |
| CN104944440B (en) | A kind of HTS poromerics and its synthetic method | |
| CN104418354B (en) | A kind of titanium silicon poromerics and synthetic method thereof | |
| CN109721071B (en) | Method for producing titanium-silicon molecular sieve, titanium-silicon molecular sieve produced by method and hydroxylation reaction method | |
| CN104556110B (en) | Tin-silicon molecular sieve as well as synthesis method and application thereof | |
| CN101434399B (en) | Method for synthesizing TS-1 molecular sieve | |
| CN105084382B (en) | A kind of mesoporous titanium-silicon material and its synthetic method | |
| CN108002404B (en) | One kind Titanium Sieve Molecular Sieve containing noble metal and its synthetic method and application | |
| CN103058211B (en) | Method for synthesizing BETA molecular sieve | |
| CN109019627B (en) | Titanium-silicon molecular sieve, preparation method thereof and preparation method of propylene glycol ether | |
| CN101434400B (en) | Method for synthesizing TS-1 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |