CN106904632A - 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
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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Abstract
The present invention relates to molecular sieve art, a kind of HTS and its synthetic method and application are specifically provided, the method includes：(1) organic silicon source, titanium source, noble metal source are hydrolyzed with alkaline template and obtain mixture A, the mixture A is carried out into the first crystallization；(2) material after the first crystallization and HTS original powder are mixed to get mixture B, the mixture B is carried out into the second crystallization, the consumption of HTS original powder causes that the solid content of mixture B is 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 surface silicon titanium is more more uniform than high, particle size, and height is measured on Ti, and pore volume and external surface area are big.
Description
Technical field
A kind of synthetic method the present invention relates to HTS and the synthetic method by HTS are closed
Into the HTS for obtaining, and HTS of the invention application in the oxidation reaction and one kind
Method for hydroxylation of phenol.
Background technology
Titanium-silicon molecular sieve TS-1 is that transition metal titanium is introduced into the molecule sieve skeleton with ZSM-5 structures
A kind of novel titanosilicate with superior catalytic selective oxidation performance formed in frame.TS-1 is not only
Catalysed oxidn with titanium, but also the shape-selective effect with ZSM-5 molecular sieve and excellent steady
It is qualitative.Because TS-1 molecular sieves are in the oxidation reaction of organic matter, free of contamination low concentration mistake can be used
Hydrogen oxide is used as oxidant, it is to avoid the problem of oxidizing process complex process and pollution environment, with tradition
The unrivaled energy-conservation of oxidation system, economy and advantages of environment protection, and with good selecting response
Property, therefore with great prospects for commercial application.
The synthetic method of TS-1 is in 1981 by first public (USP4410501).The method is first to close
It is into a kind of reactant mixture containing silicon source, titanium source, organic base and/or basic anhydride, this reaction is mixed
Compound, in 130-200 DEG C of hydrothermal crystallizing 6-30 days, is then peeled off, washs, dries, roasts in autoclave
Burn and obtain product.During plastic, the mixed solution hydrolysising condition control of estersil and titanium esters is very harsh,
Because the hydrolysis rate of the two is mismatched, the latter is higher than the former, adds the speed of organic base and will slightly produce soon
The polymer of the irreversible titanium of life, the polymer of these titaniums is difficult to enter skeleton in crystallization process, and many
It is entrained in the middle of molecular sieve in the form of extra-framework titanium, this partial-titanium may both 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 has that solid content is low, the production cycle is long, titanium skewness, prepare poor repeatability
The problems such as；Particularly HTS is applied when in catalytic oxidation, generally existing HTS
The big activity of crystal grain is low, and crystal grain is small the problems such as be separated by filtration difficulty.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of new HTS, and by the method
The HTS that synthesis is obtained.
The present inventor has been surprisingly found that in research process, in the preparation process of HTS,
First organic silicon source, titanium source, noble metal source and alkaline template are hydrolyzed, and obtain mixed will be hydrolyzed
Compound carries out Crystallizing treatment, and HTS original powder to solid content is then added in the material after crystallization
30-80 weight %, then carry out Crystallizing treatment again by mixture, so obtained HTS
Relative crystallinity and the parameter such as particle diameter distribution and hole and specific surface area further improve.Based on this discovery,
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 point
The synthetic method of son sieve, the method includes：
(1) organic silicon source, titanium source, noble metal source are hydrolyzed with alkaline template and obtain mixture
A, the first crystallization is carried out by the mixture A；
(2) material after the first crystallization and HTS original powder are mixed to get mixture B, by institute
Stating mixture B carries out the second crystallization, wherein, the consumption of HTS original powder causes mixture B's
Solid content is 30-80 weight %.
According to the second aspect of the invention, the invention provides synthesizing the titanium silicon molecule that obtains by preceding method
Sieve.
According to the third aspect of the invention we, the invention provides synthesizing the titanium silicon that obtains by the method for 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, the catalyst
Contain HTS of the present invention.
The relative crystallinity of the HTS prepared according to the method for the present invention is higher, particle size
It is more uniform.And it was unexpected that molecular screen primary powder method phase is not added with conventional using the method for the present invention
Than, to measure bigger on Ti, surface silicon titanium is than high, and pore volume and external surface area are bigger.
The synthetic method that the present invention is provided, can suppress the decomposition of organic base template, organic base therein
Template can be recycled (such as embodiment 5), reduces cost, mitigate environmental pollution.
When the molecular sieve prepared using the method for the present invention is used for during phenol hydroxylation reacts, phenol conversion
The result obtained by sample prepared obviously higher than the method as comparative example with the selectivity of hydroquinones.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As it was previously stated, the invention provides a kind of synthetic method of HTS, the method includes：
(1) organic silicon source, titanium source, noble metal source are hydrolyzed with alkaline template and obtain mixture
A, the first crystallization is carried out by the mixture A；
(2) material after the first crystallization and HTS original powder are mixed to get mixture B, by institute
Stating mixture B carries out the second crystallization, wherein, the consumption of HTS original powder causes mixture B's
Solid content is 30-80 weight %.
Synthetic method of the invention, solid content principle refers to that the quality of solid matter in reactor accounts for reaction
The percentage composition of material gross mass in kettle, general is in reactor using by the total material metage in reactor
The gross weight of material, is then taken the solid matters such as the molecular sieve in reactor by steps such as filterings
Weighed after going out to 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.Specific real
During applying, it is not necessary to directly specifically go to determine solid content, and can be first solid after laboratory is according to centrifugation
Body and the volume ratio of liquid, provide respective volume than the working curve with solid content, and then the song that whereby works
Line can intuitively provide the solid content of material in implementation method each time.It is preferred that the use of HTS original powder
Amount causes that the solid content of mixture B is 50-60 weight %.Thus the HTS Ti for preparing
Be more evenly distributed, relative crystallinity is higher, particle size also evenly, and for oxidation reaction such as benzene
Phenol conversion is higher and selectivity of hydroquinones is higher in phenolic hydroxyl groupization reaction.
Synthetic method of the invention, the preferably temperature of the second crystallization are higher than the temperature of the first crystallization
It is 20-100 DEG C, more preferably high 50-70 DEG C.Thus the HTS Ti for preparing is more evenly distributed,
Surface silicon titanium is than higher, and relative crystallinity is higher, particle size also evenly, and for oxidation reaction example
As phenol conversion in phenol hydroxylation reaction is higher and selectivity of hydroquinones is higher.
The method according to the invention, the hydrolysis is carried out in the presence of aqueous solvent, the aqueous solvent
Species 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 in aqueous solvent can meet the bar that organic silicon source generates HTS in crystallization process
Part.The solvent is preferably water, also can be according to needing to add other cosolvents, 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, for example, can be directed to the solvent portion of the alkaline 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 is required, then without adding aqueous solvent again, if it is not satisfied, then needing additionally to add aqueous solvent.
Synthetic method of the invention, is to be capable of achieving the purpose of the present invention, pin according to preceding solution
To the present invention, the condition of preferably the first crystallization includes：Crystallization is carried out in confined conditions, and temperature is 70-130
DEG C, preferably 80-120 DEG C.
Synthetic method of the invention, the time of the first crystallization can enter according to specific crystallization temperature etc.
Row adjustment, 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 at autogenous pressures carried out.
Synthetic method of the invention, is to be capable of achieving the purpose of the present invention, pin according to preceding solution
To the present invention, the condition of preferably the second crystallization includes：Crystallization is carried out in confined conditions, and temperature is
140-180 DEG C, preferably 150-170 DEG C.
Synthetic method of the invention, the time of the second crystallization can enter according to specific crystallization temperature etc.
Row adjustment, 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 at autogenous pressures carried out.
Synthetic method of the invention, preferably the method also include：The titanium silicon that will be obtained after second crystallization
Molecular sieve is contacted with the modification liquid containing nitric acid and at least one peroxide and is modified treatment.
With the method for the invention it is preferred to, the method also includes, the solid product after modification is entered
Row drying.
Synthetic method of the invention, preferably in the modification, as the titanium silicon molecule of raw material
It is 1 to sieve with the mol ratio of the peroxide：0.01-5, preferably 1：0.05-3, more preferably 1：
0.1-2, the peroxide is 1 with the mol ratio of the nitric acid：0.01-50, preferably 1：0.1-20,
More preferably 1：0.2-10, more preferably 1：0.5-5, particularly preferably 1：0.6-3.5, it is described
HTS is in terms of silica.
Synthetic method of the invention, in preferably described modification liquid, the peroxide and nitric acid it is dense
Degree is respectively 0.1-50 weight %, more preferably preferably 0.5-25 weight %, 5-15 weight %.
Synthetic method of the invention, preferably in the modification, as the titanium silicon molecule of raw material
Sieve with the modification liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, further preferably
Contacted at a temperature of 60-200 DEG C, the contact is carried out in the container that pressure is 0-5MPa, institute
Pressure is stated for gauge pressure, the duration of the contact is 1-10 hours, preferably 3-5 hours.
Synthetic method of the invention, preferably described peroxide is selected from hydrogen peroxide, t-butyl peroxy
Change hydrogen, cumyl hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and peroxide
Propionic acid.
Synthetic method of the invention, preferably in the modification, as the titanium silicon molecule of raw material
Sieve caused with the exposure level of the modification liquid, as the HTS of raw material on the basis of, ultraviolet
In-visible spectrum, the peak area reduction of the absworption peak of modified HTS between 230-310nm
More than 2%, 2-30% is preferably reduced, 2.5-15% is more preferably reduced, 3-10% is further preferably reduced,
Still more preferably reduce 3-6%；The pore volume of modified HTS reduces more than 1%, preferably reduces
1-20%, more preferably reduces 1.5-10%, further preferably reduces 2-5%, and the pore volume uses static nitrogen
Determination of adsorption method.
Synthetic method of the invention, the condition of preferably the first crystallization includes：Carry out in confined conditions
Crystallization, temperature is 70-130 DEG C, and the time is 12-96h；
Second crystallization experiences stage (1), stage (2) and stage (3), rank successively in confined conditions
Section (1) 80-150 DEG C, preferably 110-140 DEG C, more preferably 120-140 DEG C, further preferably
130-140 DEG C crystallization 6-72 hours, preferably 6-8 hours, the stage (2) was cooled to not higher than 70 DEG C
And the residence time is at least 0.5 hour, preferably 1-5 hours, the stage (3) be warming up to 120-200 DEG C,
It is preferred that 140-180 DEG C, more preferably 160-170 DEG C, then crystallization 6-96 hours, preferably 12-20 hours.
Synthetic method of the invention, preferably stage (1) and stage (3) are met in following condition
One or both：
Condition 1：Crystallization temperature of the crystallization temperature in stage (1) less than the stage (3), it is preferable that rank
The crystallization temperature of section (1) is lower 10-50 DEG C than the crystallization temperature in stage (3), preferably low 20-40 DEG C；
Condition 2：Crystallization time of the crystallization time in stage (1) less than the stage (3), it is preferable that rank
The crystallization time of section (1) is shorter 5-24 hours than the crystallization time in stage (3), preferably short 6-12 hours.
A preferred embodiment of the invention, the stage (2) is cooled to not higher than 50 DEG C, preferably
It is 30-50 DEG C, and the residence time is at least 1 hour, preferably 1-5h.
The method according to the invention, the heating rate and rate of temperature fall that temperature is adjusted to each phase temperature can
Selected with according to the type of the specific crystallization device for using, be not particularly limited.In general,
Can be 0.1-20 DEG C/min by the heating rate that temperature is increased to stage (1) crystallization temperature, preferably
0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By the drop of stage (1) temperature to stage (2) temperature
Warm speed can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-10 DEG C/min.By rank
The heating rate of section (2) temperature to stage (3) crystallization temperature can be 1-50 DEG C/min, preferably
2-40 DEG C/min, more preferably 5-20 DEG C/min.
Synthetic method of the invention, the percent hydrolysis of organic silicon source is 10-100% in preferred mixture A,
More preferably 50-90%, more preferably 60-80%.Thus the HTS Ti for preparing
Be more evenly distributed, relative crystallinity is higher, particle size also evenly, and for oxidation reaction such as benzene
Phenol conversion is higher and selectivity of hydroquinones is higher in phenolic hydroxyl groupization reaction.
Synthetic method of the invention, in preferred steps (1), with SiO2Meter organic silicon source, with
TiO2The titanium source of meter, noble metal source, with NH3The alkaline template of meter is 100 with the consumption mol ratio of water：
(0.005-10)：(0.1-10)：(0.005-40)：(200-10000), preferably 100：(0.05-5)：
(0.5-2.0)：(0.05-20)：(500-5000).
The method according to the invention, organic silicon source can be the various energy under the conditions of hydrolysis-condensation reaction
Enough form the silicon-containing compound of silica.Specifically, organic silicon source can be selected from shown in Formulas I
Silicon-containing compound in one or more,
In Formulas I, R1、R2、R3And R4Respectively C1~C4Alkyl, including C1~C4Straight chain alkane
Base and C3~C4Branched alkyl, for example：R1、R2、R3And R4Each can for methyl, ethyl,
N-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
Specifically, organic silicon source can be positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four
One or more in n-propyl and the N-butyl of positive silicic acid four.Use in a particular embodiment of the present invention
It is tetraethyl orthosilicate.
The method according to the invention, the titanium source can be the conventional selection of this area, for the present invention,
It is preferred that the 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, for example, can be selected from TiX4、
TiOX2Or Ti (SO4)2Etc. various forms of containing titanium salt, X is halogen in formula, preferably chlorine, wherein,
It is preferred that the inorganic titanium salt is selected from TiCl4、Ti(SO4)2And TiOCl2In one or more.
In the present invention, it is M that the organic titanate is preferably with structural formula4TiO4Organic titanate,
Wherein, M is preferably with the 1-4 alkyl of carbon atom, and 4 M can be excellent with identical or different
The 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, what is used in a particular embodiment of the present invention is butyl titanate as reality
Example, but and it is not so limited the scope of the present invention.
With the method for the invention it is preferred to oxide, the halogen of noble metal of the noble metal source for noble metal
Compound, the carbonate of noble metal, the nitrate of noble metal, the ammonium salt of noble metal, the chlorine of noble metal
Change one or more in ammonia salt, the hydroxide of noble metal and the complex compound of noble metal, the noble metal
One or more in for Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au；It is preferred that described expensive
Metal is Pd, Ag, Au and/or Pt, and by taking palladium as an example, the noble metal source is selected from palladium oxide, carbonic acid
Palladium, palladium bichloride, palladium nitrate, ammonium nitrate palladium, sal-ammoniac palladium, acid chloride, palladium dydroxide, the complexing of palladium
One or more in thing, palladium and palladium acetylacetonate.
The method according to the invention, optional wider range of the species of the alkaline template, it can be
One or more in aliphatic amine compound, aliphatic alcohol amines and quaternary ammonium alkali cpd.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be
Various NH3At least one of hydrogen by aliphatic alkyl (preferably alkyl) replace after formed compound,
The aliphatic hydramine can be various NH3At least one of hydrogen it is (excellent by the aliphatic alkyl of hydroxyl
Elect alkyl as) substitution after formed compound.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can be
The aliphatic amine that formula III is represented, the aliphatic hydramine can be the aliphatic hydramine represented such as formula IV：
In Formula II, R5、R6、R7And R8Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl
And C3-C4Branched alkyl, for example：R5、R6、R7And R8It can 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 1 or 2 integer.When n is 1, R9It is C1~C6Alkyl, including C1~
C6Straight chained alkyl and C3-C6Branched alkyl, such as methyl, ethyl, n-propyl, 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, R9It is C1-C6Alkylidene, including C1~C6Straight-chain alkyl-sub and C3~C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or Asia
N-hexyl.More preferably aliphatic amine compound is the one kind in ethamine, n-butylamine, butanediamine and hexamethylene diamine
Or it is various
(HOR10)mNH(3-m)(formula IV)
In formula IV, m R10It is identical or different, respectively C1-C4Alkylidene, including C1-C4's
Straight-chain alkyl-sub and C3-C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- positive fourth
Base；M is 1,2 or 3.It is further preferred that the aliphatic alcohol amines is MEA, diethanol amine
With one or more in triethanolamine.
It should be noted that when using the organic base such as quaternary ammonium base of strong basicity as alkaline template, by
It is stronger in its alkalescence, the requirement to mixture alkalescence in HTS building-up process can be met, therefore,
Quaternary ammonium base is in HTS building-up process not only as template but also as alkali source.
When using other alkaline templates, the alkalescence of the mixture obtained after mixing can not meet titanium silicon
When in sieve synthesis procedure to the alkaline requirement of mixture, those skilled in the art can lead to as needed
The mode of addition alkali source is crossed to adjust the alkalescence of mixture.Optional wider range of the species of the alkali source,
Preferably inorganic alkali source.Wherein, inorganic alkali source can be alkali metal or alkaline earth gold for ammoniacal liquor or cation
The alkaline matter of category, such as can be NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate and potassium carbonate
In one or more.
In the present invention, exemplary use TPAOH illustrates of the invention excellent as template
Gesture.
With the method for the invention it is preferred to step (2) is by the material and HTS after the first crystallization
When former powder mixes, the material after first crystallization cooled after referring to the first crystallization (without particular/special requirement,
Being down to room temperature can open crystallizing kettle) after without other materials obtained from any treatment.
With the method for the invention it is preferred to the method also includes：By the filtering of the second crystallization products therefrom, wash
Wash and obtain solid, by gained solid dry or it is moist after be calcined.
In the present invention, optional wider range of the dry condition is specifically referred to prior art and enters
OK.For the present invention, preferably described dry condition includes：Temperature be room temperature to 200 DEG C, more preferably
It is 80-120 DEG C；Time is 1-24h, preferably 2-10h.
In the present invention, optional wider range of the condition of the roasting, for the preferably roasting of the 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 more preferably described roasting includes：First at 350-600 DEG C in nitrogen
0.5-6h is calcined in atmosphere, 0.5-12h is then calcined in air atmosphere at 350-600 DEG C.
The method according to the invention, the species of HTS original powder without particular/special requirement, can be containing
The HTS original powder for having template can also be the HTS original powder without template, for example may be used
Think by Template removal step or the HTS without Template removal step after synthesizing, for this
Invention, the content of template is less than 0.1 weight % in preferably described HTS original powder, i.e., by de-
The HTS original powder of template.
The synthetic method that the present invention is provided, tool has the advantage that：
1st, high solids content synthesis, improves production efficiency；
2nd, the HTS relative crystallinity that obtains of synthesis is improved, and surface silicon titanium is than high, and Ti contents are high,
Pore volume and external surface area increase；
3rd, particle diameter distribution of HTS crystal grain that synthesis is obtained etc. is also improved, and particle diameter is general
Integrated distribution is in 150nm-350nm, it can be seen that, nucleation and life of the method for the present invention to poromerics
Growth process is optimized and adjusts so that crystal grain is more homogeneous；
4th, the synthetic method that the present invention is provided, can suppress the decomposition of organic base template, therein to have
Machine alkali template can be recycled, reduces cost, mitigate environmental pollution；
5th, when the molecular sieve prepared using the method for the present invention is used for during phenol hydroxylation reacts, phenol turns
The knot obtained by sample that the selectivity of rate and hydroquinones is prepared obviously higher than the method as comparative example
Really.
The invention provides a kind of HTS obtained according to synthetic method of the invention synthesis.
HTS of the invention, the surface silicon titanium ratio of the HTS is not less than body phase silicon
Titanium ratio, the silicon titanium than refer to silica and titanium oxide mol ratio, the surface silicon titanium ratio penetrated using X
Photoelectron Spectroscopy is determined, and the body phase silicon titanium ratio uses x-ray fluorescence spectrometry；Preferably,
The surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2；It is highly preferred that the surface
Silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；It is further preferred that the surface silicon titanium ratio
With the body phase silicon titanium than ratio be 1.5-4.5.
HTS of the invention has catalysis activity higher.Specifically, by side of the invention
HTS prepared by method shows catalysis higher in the catalyst reacted as phenol hydroxylation
Activity and hydroquinones selectivity.In a particular embodiment of the present invention using phenol hydroxylation reaction as in fact
Example illustrates advantage of the invention, but HTS of the invention is not limited only to be reacted for phenol hydroxylation
With advantage, equally there is good effect for other oxidation reactions.
The invention provides HTS of the invention application in the oxidation reaction.
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, the catalyst contains titanium silicon of the present invention point
Son sieve.
The method according to the invention, it is excellent as long as the catalyst contains HTS of the invention
The content of HTS in the catalyst is selected for more than 50 weight %, more preferably content is 60-100
Weight %.The content for being HTS for using 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 is referred to without carrier
When catalyst composition.
When the catalyst is formed body, the catalyst also includes carrier, wherein, carrier can be
Al2O3、ZnO、MgO、SiO2, CaO and TiO2, rare earth oxide RE2O3(RE be La, Ce,
Y or Nd etc.).
In the present invention, in the catalyst, in addition to including HTS, can also there are other to commonly use
The catalyst for phenol hydroxylation.
Preferred embodiment, preferably described catalyst is HTS, institute to one kind of the invention
Stating phenol hydroxylation condition includes：Temperature be 30-120 DEG C, preferably 50-90 DEG C, in implementation of the 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, preferably (0.01-0.08)：1,
More preferably (0.04-0.06)：1.In this way, more preferable phenol conversion and hydroquinones selection can be obtained
Property.
Special instruction is needed exist for, to those skilled in the art, is converted in close phenol high
Under rate, merely by the change of method for preparing catalyst, hydroquinones selectivity is improved more difficult (particularly
Improve more than 5 percentage points).And the present inventor is found surprisingly that, using of the present invention
HTS be catalyst, relative to conventional titanium-silicon molecular sieve catalyst, can effectively improve to benzene
Diphenol selectivity (improves more than 5 percentage points).
The present invention is further illustrated for following embodiment, but and is not so limited in of the invention
Hold.All reagents used are commercially available chemically pure reagent in embodiment and comparative example.
In embodiment and comparative example, using water as aqueous solvent, in mixed process, if other feed intake
Contained water disclosure satisfy that the requirement that feeds intake to water, then need not add water, if it is not satisfied, then adding as needed
Add water.
The measure of X-ray diffraction (XRD) crystalline phase figure of embodiment and comparative example is in Siemens
Carried out on D5005 type x-ray diffractometers, wherein, with sample and authentic specimen in 2 θ as 22.5 ° -25.0 °
Between the ratio of diffracted intensity (peak height) sum at the five fingers diffractive features peak represent sample relative to base
The crystallinity of quasi- sample, wherein, the sample on the basis of the sample of comparative example 1, its crystallinity is calculated as 100%；
Relative crystallinity data and grain size distribution data of each sample etc. are shown in Table 1.Wherein, 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 (using PHILIPS companies of Holland XL 30ESEM type SEM SEM, observes sample
Product granular size simultaneously carries out grain size distribution statistics, and wherein accelerating potential is 20kV).Each sample it is red
Outer spectrogram is obtained by the type Fourier infrared spectrographs of Nicolet 8210.
In the present invention, external surface area, pore volume are measured using BET method.
The surface Si/Ti (mol ratio) of embodiment and comparative example is than passing through x-ray photoelectron power spectrum
Analysis (XPS) measurement and calculating are obtained.Body phase Si/Ti (mol ratio) is than by XRF point
Analysis (XRF) measurement and calculating are obtained.Surface silicon titanium ratio/body phase silicon titanium 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, are 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, is used
Used as carrier gas, the flow velocity of carrier gas is 25mL/min to nitrogen.Specific method is：Take a certain amount of mixture
From gas chromatograph injection port sample introduction, detected using TCD and by external standard method after flowing through chromatographic column
Quantified.Organic silicon source percent hydrolysis is calculated using below equation：
XOrganic silicon source[(m ° of %=Organic silicon source-mOrganic silicon source)/m°Organic silicon source] × 100%
In formula, XOrganic silicon sourceRepresent the percent hydrolysis of organic silicon source；m°Organic silicon sourceRepresent the matter of the organic silicon source for adding
Amount；mOrganic silicon sourceRepresent 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)
TS-1 molecular sieves are prepared, 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 are mixed with 7.0 grams of TPAOHs
Close, and add 59.8 grams of distilled water, stirring mixing is obtained after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C
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 constituted, gained mixture is stirred 3 hours at 75 DEG C, is obtained
Clear colloid.This colloid is put into stainless steel sealed reactor, constant temperature is put at a temperature of 170 DEG C
Put 3 days, obtain the mixture of crystallization product；By the filtering of this mixture, wash with water, and in 110 DEG C
Dry 60 minutes, obtain TS-1 original powder.This TS-1 original powder is roasted in 550 DEG C of temperature in air atmosphere
Burn 3 hours, obtain TS-1 molecular sieves B1.
After testing, between being 22.5 ° -25.0 ° in 2 θ there is MFI in the XRD crystalline phases of gained molecular sieve B1
The five fingers diffractive features peak specific to structure, shows that molecular sieve B1 has the MFI structure of similar TS-1.
In 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
Method according to comparative example 1 prepares HTS, the difference is that after crystallization condition difference and crystallization
Add HTS.Detailed process is as follows：
At room temperature (20 DEG C), by 22.5 grams of tetraethyl orthosilicates and 7.0 grams of TPAOHs and
0.2 gram of palladium bichloride mixing, and 59.8 grams of distilled water are added, stirring mixing is after hydrolysis at normal pressure and 60 DEG C
1.0 hours, the hydrating solution of tetraethyl orthosilicate is obtained, be slowly added into vigorous stirring by 1.1
The solution that gram butyl titanate and 5.0 grams of anhydrous isopropyl alcohols are constituted, gained mixture is stirred at 75 DEG C
Mix 3 hours, obtain clear colloid (percent hydrolysis of organic silicon source is 100%).This colloid is put into
Stainless steel sealed reactor, constant temperature is placed 3 days at a temperature of 110 DEG C, obtains the mixing of crystallization product
Thing, adds HTS original powder (B1) to the weight % of solid content 50 after release, then slurry exists
In processing 24h under 160 DEG C and self-generated pressure in closed reactor；By the filtering of this mixture, wash with water,
And in 110 DEG C of dryings 60 minutes, be calcined in air atmosphere 3 hours in 550 DEG C of temperature, obtain TS-1
Molecular sieve-4 A 1.
After testing, between being 22.5 ° -25.0 ° in 2 θ there is MFI in the XRD crystalline phases of gained molecular sieve-4 A 1
The five fingers diffractive features peak specific to structure, shows that molecular sieve-4 A 1 has the MFI structure of similar TS-1.
In 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 the TPAOH aqueous solution and metatitanic acid that concentration is 10 weight %
Four butyl esters mix, and are subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2Meter is just
Tetraethyl orthosilicate, with TiO2The butyl titanate of meter, 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 stainless steel sealed reactor, constant temperature places 3 at a temperature of 120 DEG C
My god, the mixture of crystallization product is obtained, by the filtering of gained crystallization product, wash with water, and in 110 DEG C
Drying 120 minutes, is then calcined 3 hours in 550 DEG C of temperature in air atmosphere, obtains molecular sieve B2.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve B2 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 2
At a temperature of 20 DEG C, first by the TPAOH aqueous solution and metatitanic acid that concentration is 10 weight %
Four butyl esters mix, and are subsequently added into tetraethyl orthosilicate and palladium bichloride, form mixture.In mixture with
SiO2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium bichloride, with NH3The four of meter
The mol ratio of propyl group ammonium hydroxide and water is 100：5：2：10：800.By gained mixture at 75 DEG C
Lower stirring 3 hours, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).By this colloid
Stainless steel sealed reactor is put into, constant temperature is placed 3 days at a temperature of 120 DEG C, obtains crystallization product
Mixture, adds HTS original powder (B1) to the weight % of solid content 60 after release, then will slurry
Material, in crystallization 12 hours at 170 DEG C of temperature and self-generated pressure, gained crystallization is produced in closed reactor
Thing is filtered, washed with water, and is dried 120 minutes in 110 DEG C, then in 550 DEG C of temperature in air gas
It is calcined 3 hours in atmosphere, obtains molecular sieve-4 A 2.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 2 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 3
At a temperature of 20 DEG C, first by the TPAOH aqueous solution and metatitanic acid that concentration is 25 weight %
Four butyl esters mix, and are subsequently added into tetraethyl orthosilicate and palladium bichloride, form mixture.In mixture with
SiO2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium bichloride, with NH3The four of meter
The mol ratio of propyl group ammonium hydroxide and water is 100：2：1：15：1500.By gained mixture at 75 DEG C
Lower stirring 3 hours, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).By this colloid
Stainless steel sealed reactor is put into, constant temperature is placed 3 days at a temperature of 100 DEG C, obtains crystallization product
Mixture, adds HTS original powder (B1) to the weight % of solid content 30 after release, then will slurry
Material, in crystallization 6 hours at 170 DEG C of temperature and self-generated pressure, gained crystallization is produced in closed reactor
Thing is filtered, washed with water, and is dried 120 minutes in 110 DEG C, then in 550 DEG C of temperature in air gas
It is calcined 3 hours in atmosphere, obtains molecular sieve-4 A 3.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 3 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 4
Using the method synthesis of molecular sieve of embodiment 1, unlike, add HTS former after release
Powder (B1) obtains molecular sieve-4 A 4 to the weight % of solid content 70.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 4 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 5
Using the method synthesis of molecular sieve of embodiment 1, unlike, TPAOH used is
Embodiment 1 reclaims what is obtained, obtains molecular sieve-4 A 5.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 5 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 6
Using the method synthesis of molecular sieve of embodiment 3, unlike, add HTS former after release
Powder (B1) obtains molecular sieve-4 A 6 to the weight % of solid content 55.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 6 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 7
Using the method synthesis of molecular sieve of embodiment 3, unlike, the temperature of the second crystallization is 190 DEG C,
Obtain molecular sieve-4 A 7.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 7 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 8
Using the method synthesis of molecular sieve of embodiment 3, unlike, adjust hydrolysising condition so that hydrolysis
The percent hydrolysis of organic silicon source is 60% in the colloid for obtaining, and obtains molecular sieve-4 A 8.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 8 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 9
Using the method synthesis of molecular sieve of embodiment 3, unlike, adjust hydrolysising condition so that hydrolysis
The percent hydrolysis of organic silicon source is 80% in the colloid for obtaining, and obtains molecular sieve-4 A 9.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 9 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 10
Using the method synthesis of molecular sieve of embodiment 3, unlike, adjust hydrolysising condition so that hydrolysis
The percent hydrolysis of organic silicon source is 40% in the colloid for obtaining, and obtains molecular sieve-4 A 10.
The X-ray diffraction and Fourier infrared spectrum of gained molecular sieve-4 A 10 are characterized and the sample of embodiment 1
The SPECTROSCOPIC CHARACTERIZATION of A1 is basically identical.
Embodiment 11
The TS-1 molecular sieve-4 As 1 that embodiment 1 is obtained with contain HNO3(HNO3Mass concentration be
10%) with the aqueous solution mixing of hydrogen peroxide (mass concentration of hydrogen peroxide is 7.5%), by what is obtained
In 70 DEG C of stirring reaction 5h in closed container, the temperature of the reactant mixture for obtaining is down to room to mixture
Filtered after temperature, the solid matter that will be obtained obtains modified titanium silicon point in 120 DEG C of dryings to constant weight
Son sieve A11.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS rubs with hydrogen peroxide
You are than being 1：0.1.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 1 through X-ray diffraction.With
HTS A1 is compared, in the UV-Vis spectrum of the modified HTS A11 for obtaining
The peak area of the absworption peak between 230-310nm reduces 3.4%, is subtracted by the pore volume of static determination of nitrogen adsorption
Few 2.7%.
Embodiment 12
The TS-1 molecular sieve-4 As 2 that embodiment 2 is obtained with contain HNO3(HNO3Mass concentration be
10%) with the aqueous solution mixing of hydrogen peroxide (mass concentration of hydrogen peroxide is 5%), by what is obtained
In 120 DEG C of stirring reaction 4h in closed container, the temperature of the reactant mixture for obtaining is down to room to mixture
Filtered after temperature, the solid matter that will be obtained obtains modified titanium silicon point in 120 DEG C of dryings to constant weight
Son sieve A12.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS rubs with hydrogen peroxide
You are than being 1：0.4.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 1 through X-ray diffraction.With
Raw material HTS A2 is compared, in the UV-Vis spectrum of the modified HTS A12 for obtaining
The peak area of the absworption peak between 230-310nm reduces 4.1%, by the hole of static determination of nitrogen adsorption
Hold and reduce 3.3%.
Embodiment 13
The TS-1 molecular sieve-4 As 3 that embodiment 3 is obtained with contain HNO3(HNO3Mass concentration be
15%) with the aqueous solution mixing of hydrogen peroxide (mass concentration of hydrogen peroxide is 8%), by what is obtained
In 150 DEG C of stirring reaction 3h in closed container, the temperature of the reactant mixture for obtaining is down to room to mixture
Filtered after temperature, the solid matter that will be obtained obtains modified titanium silicon point in 120 DEG C of dryings to constant weight
Son sieve A13.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS rubs with hydrogen peroxide
You are than being 1：2.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 1 through X-ray diffraction.With original
Material HTS A3 compare, in the UV-Vis spectrum of the modified HTS A13 for obtaining
The peak area of the absworption peak between 230-310nm reduces 4.5%, is subtracted by the pore volume of static determination of nitrogen adsorption
Few 4.4%.
Embodiment 14
It is prepared by the method according to embodiment 1, unlike, specifically carry out as follows：
At room temperature (20 DEG C), by 22.5 grams of tetraethyl orthosilicates and 7.0 grams of TPAOHs and
0.2 gram of palladium bichloride mixing, and 59.8 grams of distilled water are added, stirring mixing is after hydrolysis at normal pressure and 60 DEG C
1.0 hours, the hydrating solution of tetraethyl orthosilicate is obtained, be slowly added into vigorous stirring by 1.1
The solution that gram butyl titanate and 5.0 grams of anhydrous isopropyl alcohols are constituted, gained mixture is stirred at 75 DEG C
Mix 3 hours, obtain clear colloid (percent hydrolysis of organic silicon source is 100%).This colloid is put into
Stainless steel sealed reactor, constant temperature is placed 3 days at a temperature of 110 DEG C, obtains the mixing of crystallization product
Thing, adds HTS original powder (B1) to the weight % of solid content 50 after release, then slurry exists
First stage crystallization 6h is experienced at 140 DEG C in closed reactor, mixture is then cooled to 30 DEG C of experience
After second stage stops 2h, continue to experience phase III crystalline substance at a temperature of 170 DEG C in sealed reactor
Change 12h (it is wherein, 2 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by
The rate of temperature fall of first stage crystallization temperature to second stage treatment temperature is 5 DEG C/min, by second stage
Treatment temperature to phase III crystallization temperature heating rate be 10 DEG C/min)；Crystallization product is filtered,
Wash with water, and in 110 DEG C of dryings 60 minutes, be calcined in air atmosphere 3 hours in 550 DEG C of temperature,
Obtain TS-1 molecular sieve-4 As 14.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 1 through X-ray diffraction.
Embodiment 15
It is prepared by the method according to embodiment 2, unlike, specifically carry out as follows：
At a temperature of 20 DEG C, first by the TPAOH aqueous solution and metatitanic acid that concentration is 10 weight %
Four butyl esters mix, and are subsequently added into tetraethyl orthosilicate and palladium bichloride, form mixture.In mixture with
SiO2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium bichloride, with NH3The four of meter
The mol ratio of propyl group ammonium hydroxide and water is 100：5：2：10：800.By gained mixture at 75 DEG C
Lower stirring 3 hours, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).By this colloid
Stainless steel sealed reactor is put into, constant temperature is placed 3 days at a temperature of 120 DEG C, obtains crystallization product
Mixture, adds HTS original powder (B1) to the weight % of solid content 60 after release, then will slurry
Material experiences first stage crystallization 8h in closed reactor at 130 DEG C, and mixture then is cooled into 50
DEG C experience second stage stop 5h after, continue in sealed reactor at a temperature of 170 DEG C experience the 3rd
Stage crystallization 16h (it is wherein, 1 DEG C/min by the heating rate of room temperature to first stage crystallization temperature,
It is 10 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by second-order
Section treatment temperature to phase III crystallization temperature heating rate be 20 DEG C/min), by gained crystallization product
Filter, wash with water, and dried 120 minutes in 110 DEG C, then in 550 DEG C of temperature in air atmosphere
Middle roasting 3 hours, obtains molecular sieve-4 A 15.The sample is through X-ray diffraction and the spectrum of the sample of embodiment 1
Feature is learned to be similar to.
Embodiment 16
It is prepared by the method according to embodiment 3, unlike, specifically carry out as follows：
At a temperature of 20 DEG C, first by the TPAOH aqueous solution and metatitanic acid that concentration is 25 weight %
Four butyl esters mix, and are subsequently added into tetraethyl orthosilicate and palladium bichloride, form mixture.In mixture with
SiO2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium bichloride, with NH3The four of meter
The mol ratio of propyl group ammonium hydroxide and water is 100：2：1：15：1500.By gained mixture at 75 DEG C
Lower stirring 3 hours, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).By this colloid
Stainless steel sealed reactor is put into, constant temperature is placed 3 days at a temperature of 100 DEG C, obtains crystallization product
Mixture, adds HTS original powder (B1) to the weight % of solid content 30 after release, then will slurry
Material experiences first stage crystallization 6h in closed reactor at 140 DEG C, and mixture then is cooled into 40
DEG C experience second stage stop 1h after, continue in sealed reactor at a temperature of 160 DEG C experience the 3rd
Stage crystallization 12h (it is wherein, 5 DEG C/min by the heating rate of room temperature to first stage crystallization temperature,
It is 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by second-order
Section treatment temperature to phase III crystallization temperature heating rate be 5 DEG C/min), by gained crystallization product mistake
Filter, wash with water, and dried 120 minutes in 110 DEG C, then in 550 DEG C of temperature in air atmosphere
Roasting 3 hours, obtains molecular sieve-4 A 16.The sample is through X-ray diffraction and the spectroscopy of the sample of embodiment 1
Feature is similar to.
Embodiment 17
Method according to embodiment 14 prepares HTS A17, unlike, the crystalline substance of phase III
It is also 140 DEG C to change temperature.
Embodiment 18
Method according to embodiment 14 prepares HTS A18, unlike, the crystalline substance of first stage
It is 110 DEG C to change temperature.
Embodiment 19
Method according to embodiment 14 prepares HTS A19, unlike, the crystalline substance of first stage
The change time is 12h, and second stage is to be cooled to 70 DEG C of stop 2h.
Embodiment 20
The HTS A14 that embodiment 14 is obtained with contain HNO3(HNO3Mass concentration be
10%) with the aqueous solution mixing of hydrogen peroxide (mass concentration of hydrogen peroxide is 7.5%), by what is obtained
In 70 DEG C of stirring reaction 5h in closed container, the temperature of the reactant mixture for obtaining is down to room to mixture
Filtered after temperature, the solid matter that will be obtained obtains modified titanium silicon point in 120 DEG C of dryings to constant weight
Son sieve A20.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS rubs with hydrogen peroxide
You are than being 1：0.1.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 1 through X-ray diffraction.With
HTS A14 is compared, in the UV-Vis spectrum of the modified HTS A20 for obtaining
The peak area of the absworption peak between 230-310nm reduces 5.8%, is subtracted by the pore volume of static determination of nitrogen adsorption
Few 4.3%.
Test case
This test case is used to illustrate the side of the molecular sieve and comparative example obtained by the method for present invention offer
The molecular sieve that method is obtained is used for the reaction effect of phenol hydroxylation reaction.
By the sample prepared by above-described embodiment 1-20 and comparative example 1-2 according to sample：Phenol：Acetone=1：
20：16 weight is warming up to 80 DEG C than being well mixed in a there-necked flask with condenser pipe,
Then according to phenol under stirring：Hydrogen peroxide=3：It is 27.5 weight that 1 mol ratio adds concentration
The hydrogen peroxide of %, reacts 3 hours at this temperature, and products therefrom is on Agilent6890N chromatographs
Each product slates are determined using HP-5 capillary columns (30m × 0.25mm), 1 is the results are shown in Table.
Wherein：
Wherein, the molal quantity of phenol of reaction is participated in the total of the molal quantity of the molal quantity of benzenediol and benzoquinones
Molal quantity meter, the benzenediol includes catechol, resorcinol and hydroquinones.
Table 1
From the results shown in Table 1, the phase of the HTS for being prepared according to the method for the present invention
It is higher to crystallinity, and particle size is more uniform, surface silicon titanium than high, pore volume and external surface area compared with
Greatly.In addition, when being used for during phenol hydroxylation reacts using molecular sieve prepared by the method for the present invention, phenol
Obtained by the sample that the selectivity of conversion ratio and hydroquinones is prepared obviously higher than the method as comparative example
As a result.In addition, in the synthetic method that the present invention is provided, organic base template is recycled, and still may be used
To obtain relative crystallinity higher and more uniform particle size and higher phenol conversion and right
The selectivity of benzenediol, so while combined coefficient is improved, also significantly reduces consumption of raw materials, subtracts
Light environmental pollution.
From the result of embodiments of the invention 11-20, it is modified using the method for the present invention and brilliant
Change, the HTS physico-chemical property and catalysis activity for enabling to are greatly improved.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
Claims (20)
1. a kind of synthetic method of HTS, it is characterised in that the method includes：
(1) organic silicon source, titanium source, noble metal source are hydrolyzed with alkaline template and obtain mixture
A, the first crystallization is carried out by the mixture A；
(2) material after the first crystallization and HTS original powder are mixed to get mixture B, by institute
Stating mixture B carries out the second crystallization, wherein, the consumption of HTS original powder causes mixture B's
Solid content is 30-80 weight %.
2. synthetic method according to claim 1, wherein, the consumption of HTS original powder makes
The solid content for obtaining mixture B is 50-60 weight %.
3. synthetic method according to claim 1, wherein, the temperature of the second crystallization is more brilliant than first
The temperature of change is high 20-100 DEG C, preferably high 50-70 DEG C.
4. the synthetic method according to any one in claim 1-3, wherein,
The condition of the first crystallization includes：Crystallization is carried out in confined conditions, and temperature is 70-130 DEG C, time
It is 12-96h；
The condition of the second crystallization includes：Crystallization is carried out in confined conditions, and temperature is 140-180 DEG C, when
Between be 6-24h.
5. synthetic method according to claim 1, wherein, the method also includes：It is brilliant by second
The HTS obtained after change is contacted with the modification liquid containing nitric acid and at least one peroxide and carried out
Modification.
6. synthetic method according to claim 5, wherein, in the modification, as
The HTS of raw material is 1 with the mol ratio of the peroxide：0.01-5, preferably 1：0.05-3,
More preferably 1：0.1-2, the peroxide is 1 with the mol ratio of the nitric acid：0.01-50, preferably
It is 1：0.1-20, more preferably 1：0.2-10, more preferably 1：0.5-5, particularly preferably 1：
0.6-3.5, the HTS is in terms of silica.
7. synthetic method according to claim 5, wherein, in the modification liquid, the peroxide
The concentration of compound and nitric acid is respectively 0.1-50 weight %, preferably 0.5-25 weight %, more preferably 5-15
Weight %.
8. synthetic method according to claim 5, wherein, in the modification, as
The HTS of raw material is with the modification liquid at 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250
DEG C, contacted at a temperature of further preferred 60-200 DEG C, the contact is 0-5MPa's in pressure
Carried out in container, the pressure is gauge pressure, and the duration of the contact is 1-10 hours, preferably
3-5 hours.
9. synthetic method according to claim 5, wherein, the peroxide is selected from peroxidating
Hydrogen, TBHP, cumyl hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide,
Peracetic acid and Perpropionic Acid.
10. the synthetic method according to any one in claim 5-9, wherein, described modified
In treatment, caused as the HTS and the exposure level of the modification liquid of raw material, as raw material
HTS on the basis of, in ultraviolet-visible spectrum, modified HTS is in 230-310nm
Between absworption peak peak area reduction by more than 2%, preferably reduce 2-30%, more preferably reduce 2.5-15%,
3-10% is further preferably reduced, 3-6% is still more preferably reduced；The hole of modified HTS
Hold and reduce more than 1%, preferably reduce 1-20%, more preferably reduce 1.5-10%, further preferably reduce
2-5%, the pore volume is using static determination of nitrogen adsorption.
11. synthetic method according to any one in claim 1-3, wherein,
The condition of the first crystallization includes：Crystallization is carried out in confined conditions, and temperature is 70-130 DEG C, time
It is 12-96h；
Second crystallization experiences stage (1), stage (2) and stage (3), rank successively in confined conditions
Section (1) 80-150 DEG C, preferably 110-140 DEG C, more preferably 120-140 DEG C, further preferably
130-140 DEG C crystallization 6-72 hours, preferably 6-8 hours, the stage (2) was cooled to not higher than 70 DEG C
And the residence time is at least 0.5 hour, preferably 1-5 hours, the stage (3) be warming up to 120-200 DEG C,
It is preferred that 140-180 DEG C, more preferably 160-170 DEG C, then crystallization 6-96 hours, preferably 12-20 hours.
12. synthetic methods according to claim 11, wherein, stage (1) and stage (3)
Meet one of following condition or both：
Condition 1：Crystallization temperature of the crystallization temperature in stage (1) less than the stage (3), it is preferable that rank
The crystallization temperature of section (1) is lower 10-50 DEG C than the crystallization temperature in stage (3), preferably low 20-40 DEG C；
Condition 2：Crystallization time of the crystallization time in stage (1) less than the stage (3), it is preferable that rank
The crystallization time of section (1) is shorter 5-24 hours than the crystallization time in stage (3), preferably short 6-12 hours；
Stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
13. synthetic method according to any one in claim 1-3, wherein, in mixture A
The percent hydrolysis of organic silicon source is 10-100%, more preferably preferably 50-90%, 60-80%.
14. synthetic method according to any one in claim 1-3, wherein, step (1)
In, with SiO2Meter organic silicon source, with TiO2The titanium source of meter, noble metal source, with NH3The alkalescence of meter
Template is 100 with the consumption mol ratio of water：(0.005-10)：(0.1-10)：(0.005-40)：
(200-10000)。
15. synthetic method according to any one in claim 1-3, wherein, step (1)
In, organic silicon source is selected from one or more in the silicon-containing compound shown in Formulas I, the titanium source
Selected from inorganic titanium salt and/or organic titanate, the alkaline template is selected from quaternary ammonium base, aliphatic amine and fat
One or more in fat race hydramine；
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl；
The noble metal source is the oxide of noble metal, the halide of noble metal, the carbonate of noble metal,
The nitrate of noble metal, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide of noble metal
One or more in the complex compound of thing and noble metal, the noble metal be Ru, Rh, Pd, Re, Os,
One or more in Ir, Pt, Ag and Au.
The HTS that synthetic method synthesis in 16. claim 1-15 described in any one is obtained.
17. HTSs according to claim 16, wherein, the table of the HTS
Face silicon titanium ratio is not less than body phase silicon titanium ratio, the silicon titanium than refer to silica and titanium oxide mol ratio, institute
State surface silicon titanium ratio to be determined using X-ray photoelectron spectroscopy, the body phase silicon titanium ratio uses X-ray
Fluorescence spectrum method for measuring；Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2
More than；It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；Enter one
Step preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5.
The application in the oxidation reaction of HTS described in 18. claims 16 or 17.
A kind of 19. method for hydroxylation of phenol, the method includes：Under the conditions of phenol hydroxylation, by benzene
Phenol, hydrogen peroxide are contacted with catalyst, it is characterised in that the catalyst contain claim 16 or
HTS described in 17.
20. methods according to claim 19, wherein, the catalyst is described titanium silicon point
Son sieve, the 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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