CN107840346A - A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst - Google Patents
A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst Download PDFInfo
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- CN107840346A CN107840346A CN201610838978.4A CN201610838978A CN107840346A CN 107840346 A CN107840346 A CN 107840346A CN 201610838978 A CN201610838978 A CN 201610838978A CN 107840346 A CN107840346 A CN 107840346A
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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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
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- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The present invention relates to catalysis material to synthesize field, discloses the application of a kind of preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst, this method includes：(1) template, tetraalkoxysilane and water are mixed, gained mixture is hydrolyzed and removes alcohol；(2) step (1) products therefrom is mixed with the compound of structure shown in formula (I), gained mixture is subjected to crystallization；Wherein, i be 1 10 in any integer, R1、R2、R3It is each independently methyl, ethyl, propyl group or butyl；R4、R5It is independently of one another the organic group being made up of 1 20 carbon atoms, 05 nitrogen-atoms, 03 oxygen atoms and hydrogen, or R4With R5It is connected, forms 5 yuan 10 yuan of azacyclo- or nitrogen oxa- ring.The micro- mesoporous molecular sieve composite material of total silicon provided by the invention has higher specific surface area and mesopore volume, improves diffusion of the macromolecule substrate inside its duct, the catalytic activity of molecular sieve significantly improves.
Description
Technical field
The present invention relates to a kind of preparation method of silica zeolite, processing method and silica zeolite, catalyst and urge
The application of agent, more particularly to a kind of micro- mesoporous silica zeolite and preparation method thereof, processing method and contain the total silicon point
The application of the catalyst and catalyst of son sieve.
Background technology
The aperture of porous material is generally divided into three-level：Hole of the aperture less than 2nm is referred to as micropore；Aperture is between 2-50nm
Hole is referred to as mesopore (also known as mesoporous material)；Aperture is referred to as macropore for the hole more than 50nm to 1000nm.Micro porous molecular sieve has height
Specific surface area, flourishing microcellular structure, stronger acid and high hydrothermal stability, but there is the less deficiency in aperture in it, limit
Its application in bulky molecular catalysis reaction is made.Although mesoporous molecular sieve aperture is bigger, stability and acidity are weaker.This
Wish to prepare the molecular sieve with multi-stage artery structure, the advantages of making it have micropore and mesoporous molecular sieve concurrently in field.
Silicalite-1 molecular sieves are a kind of silica zeolites with MFI topologies, are UCC companies
What E.M.Flanigen et al. was synthesized first in 1977.As a member important in Pentasil families,
Silicalite-1 molecular sieves have the crystal structure of type ZSM 5 molecular sieve, possess abundant microcellular structure and regular uniform
3 D pore canal, there is higher specific surface area and the preferably property such as absorption and desorption ability.Due to Silicalite-1 molecules
Sieve be free of aluminium atom, the generation for phenomena such as not having dealuminzation under the high temperature conditions, compared with ZSM-5, shows preferably resistance to height
Warm nature energy；As well as not having tradable cation on skeleton, the adsorption capacity of hydrone is far below to organic matter
Adsorption capacity, there is higher hydrophobicity, thus separation membrane and catalysis material can be used as, be also used as preparing other urge
Change the fertile material of material.
Solid can be selected in the method that US4061724 reports direct hydrothermal synthesis all-silica MFI structure molecular screen earliest, silicon source
Silica, Ludox, organosilicon etc., organic formwork agent Q=R4X+, R is the alkyl of 2-6 carbon atom, and X is P or N.From the patent
Since announcement, the application field of Silicalite-1 molecular sieves is constantly expanded, and its synthetic method also gradually tends to be ripe, and is
Industrial applications are realized in the important chemical reaction such as cyclohexanone oxime Beckmann rearrangement.However, because Silicalite-1 belongs to
A member in MFI topological structure molecular sieves, its less pore passage structure ([100]：0.51×0.55nm；[010]：0.53
× 0.56nm) diffusions of bigger molecule size reactants is limited, constrain it and further apply.
1992, Mobil companies were found that M41S series mesoporous materials.Compared with micropore, aperture larger M41S overcomes
The deficiencies of poromerics aperture is small, and macromolecule reactant is difficult to enter inside duct, reduces expansion of the reactant to outside duct
Limitation is dissipated, reaction is carried out to greatest extent in duct.M41S discovery has been broken micro porous molecular sieve and divided in residual oil cracking, greatly
The limitation for the field applications such as muonic catalysis converts and macromolecular Subjective and Objective separates.However, because mesoporous material is amorphous hole wall,
The shortcomings of hydrothermal stability is poor in actual applications, and mechanical strength is relatively low is gradually exposed, and which prevent mesoporous material to walk
To commercial Application.
In addition, although researcher has been attempted to introduce additional duct into molecular sieve crystal to reach improvement molecule
The purpose of diffusion is sieved, while develops the beta-molecular sieve containing twelve-ring three-dimensional open-framework, containing twelve-ring supercage
The molecular sieve of structure and MWW, SBA-15, HMS etc. have the total silicon material in larger duct, but these catalysis materials are big at some
The expection of people is still not up in the catalyzing and synthesizing of molecular chemistry product.
The content of the invention
It is an object of the invention to provide a kind of preparation method containing silica zeolite more mesoporous and with crystalline structure,
Processing method, and the application of silica zeolite, the catalyst containing the silica zeolite and catalyst.
To achieve these goals, according to an aspect of the present invention, the present invention provides a kind of preparation of silica zeolite
Method, wherein, this method includes：
(1) template, tetraalkoxysilane and water are mixed, gained mixture is hydrolyzed and removes alcohol；
(2) step (1) products therefrom is mixed with the compound of structure shown in formula (I), gained mixture is subjected to crystallization；
Wherein, i be 1-10 in any integer, R1、R2、R3It is each independently methyl, ethyl, propyl group or butyl；R4、R5
It is independently of one another the organic group being made up of 1-20 carbon atom, 0-5 nitrogen-atoms, 0-3 oxygen atom and hydrogen, or R4With
R5It is connected, forms 5 yuan -10 yuan of azacyclo- or nitrogen oxa- ring.
According to the second aspect of the invention, the invention provides a kind of processing method of silica zeolite, wherein, will be complete
Si molecular sieves mix with quaternary ammonium salt and/or quaternary ammonium base and water, and by gained mixture in room temperature to 200 DEG C, preferably 50-
Crystallization -10 days 1 hour at 200 DEG C, preferably -10 days 12 hours, the silica zeolite are by method system of the present invention
.
According to the third aspect of the present invention, the invention provides a kind of silica zeolite, wherein, have MFI structure and
Mesopore volume is not less than 0.16cm3/ g, micro pore volume are not less than 0.1cm3/g。
According to the fourth aspect of the present invention, the invention provides a kind of catalyst, wherein, the catalyst contains the present invention
Described silica zeolite.
According to the fifth aspect of the present invention, present invention also offers a kind of cyclohexanone oxime Beckmann rearrangement to produce oneself
The method of lactams, wherein, use catalyst of the present invention.
The micro- mesoporous molecular sieve composite material of total silicon provided by the invention, mesopore volume are not less than 0.16cm3/ g, micro pore volume
Not less than 0.1cm3/ g, it is not less than 450m than surface2/ g, deposited between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature
In hysteresis loop, crystal grain is single crystal grain or the aggregation crystal grain being gathered into by multiple crystal grain.
The micro- mesoporous molecular sieve composite material of total silicon provided by the invention has higher specific surface area and mesopore volume, improves
Diffusion of the macromolecule substrate inside its duct, the catalytic activity of molecular sieve significantly improve.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
The TEM figures that Fig. 1 a are the zeolite product DB-1 that comparative example 1 obtains；Fig. 1 b are the molecular sieve production that comparative example 2 obtains
Product DB-2 TEM figures；The TEM figures that Fig. 1 c are the zeolite product MS-1 that the embodiment of the present invention 1 obtains；Fig. 1 d are implemented for the present invention
The zeolite product HMS-1 TEM figures after processing that example 1 obtains；
Fig. 2 is the graph of pore diameter distribution for the zeolite product that comparative example 2 obtains；
Fig. 3 is the graph of pore diameter distribution of zeolite product after processing that the embodiment of the present invention 1 obtains.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
Alkyl in the present invention, such as do not point out specific structure, then represent alkyl, for example, propyl group represent n-propyl,
Butoxy represents n-butoxy.
In the present invention, the implication of " optional " is " being with or without ".
According to the present invention, the preparation method of the silica zeolite includes：
(1) template, tetraalkoxysilane and water are mixed, gained mixture is hydrolyzed and removes alcohol；
(2) step (1) products therefrom is mixed with the compound of structure shown in formula (I), gained mixture is subjected to crystallization；
Wherein, i be 1-10 in any integer, R1、R2、R3It is each independently methyl, ethyl, propyl group or butyl；R4、R5
It is independently of one another the organic group being made up of 1-20 carbon atom, 0-5 nitrogen-atoms, 0-3 oxygen atom and hydrogen, or R4With
R5It is connected, forms 5 yuan -10 yuan of azacyclo- or nitrogen oxa- ring.
Under preferable case, in the compound of structure shown in formula (I), described R1、R2、R3It is identical, be methyl, ethyl,
Propyl group or butyl.
Under preferable case, in the compound of structure shown in formula (I), described i is any integer in 2-5.
Under preferable case, in the compound of structure shown in formula (I), R4、R5Independently of one another be by 2-10 carbon atom,
The organic group of 0-5 nitrogen-atoms, 0-3 oxygen atom and hydrogen composition；Or R4With R5Be connected, formed 5 yuan -8 yuan azacyclo- or
Nitrogen oxa- ring.It is highly preferred that in the compound of structure shown in formula (I), described R4、R5Be each independently C2-C8 alkyl,
C6-C8 aryl, C2-C8 acyl group, carbamoyl or by the alkyl-substituted carbamoyls of C1-C6；Or R4With R5Phase
Even, 5 yuan -7 yuan of azacyclo- or nitrogen oxa- ring is formed.It is further preferred that in the compound of structure shown in formula (I), it is described
R4、R5It is each independently C2-C4 alkyl, C2-C4 acyl group, carbamoyl or by the alkyl-substituted carbamyls of C1-C2
Base, such as R4、R5It can be ethyl；Or R4With R5It is connected, forms 5 yuan -6 yuan of azacyclo- or nitrogen oxa- ring, such as formed
Quinoline ring.
According to the present invention, the selectable range of the template is wider, for example, can be quaternary ammonium salt and/or quaternary ammonium base.
Under preferable case, the template is the quaternary ammonium salt or quaternary ammonium base shown in formula (II).
Wherein, R6-R9It is each independently selected from C1-C20 alkyl, M OH-、F-、Cl-、Br-Or I-.Described C1-C20
Alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group, amyl group, hexyl, 2- ethylhexyls, heptyl,
Octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecane
Base, octadecyl, nonadecyl or eicosyl.
Specifically, the template can be TMAH, tetraethyl ammonium hydroxide, TPAOH,
TBAH, trimethyl ammonium hydroxide, trimethyl heptyl ammonium hydroxide, trimethyldecylammonium ammonium hydroxide, front three
Base dodecyl ammonium hydroxide, trimethyl tetradecyl base ammonium hydroxide, trimethyl palmityl ammonium hydroxide, trimethyloctadecyl
Ammonium hydroxide, triethyl group hexyl ammonium hydroxide, triethyl group heptyl ammonium hydroxide, triethyl group decyl ammonium hydroxide, triethyl group 12
Alkyl ammonium hydroxide, triethyl group myristyl ammonium hydroxide, triethyl group palmityl ammonium hydroxide, triethyl group octadecyl hydroxide
Ammonium, tripropyl hexyl ammonium hydroxide, tripropyl heptyl ammonium hydroxide, tripropyl decyl ammonium hydroxide, tripropyl dodecyl hydrogen
Amine-oxides, tripropyl myristyl ammonium hydroxide, tripropyl palmityl ammonium hydroxide, tripropyl octadecyl ammonium hydroxide, three fourths
Base hexyl ammonium hydroxide, tributyl heptyl ammonium hydroxide, tributyl decyl ammonium hydroxide, tributyl dodecyl ammonium hydroxide,
Tributyl myristyl ammonium hydroxide, tributyl palmityl ammonium hydroxide, tributyl octadecyl ammonium hydroxide, tetramethyl bromination
Ammonium, tetraethylammonium bromide, 4-propyl bromide, TBAB, tetramethyl ammonium chloride, etamon chloride, tetrapropyl chlorine
Change ammonium, tetrabutylammonium chloride, trimethyl hexyl ammonium bromide, trimethyl heptyl ammonium bromide, trimethyl dcyl ammonium chloride, trimethyl ten
Dialkylammonium bromide, trimethyl tetradecyl base ammonium bromide, trimethyl palmityl ammonium bromide, trimethyl octadecyl ammonium bromide, three second
Base hexyl ammonium bromide, triethyl group heptyl ammonium bromide, triethyl group decyl ammonium bromide, triethyl group dodecyl bromination ammonium, triethyl group ten
Tetraalkyl ammonium bromide, triethyl group palmityl ammonium bromide, triethyl group octadecyl ammonium bromide, tripropyl hexyl ammonium bromide, tripropyl heptan
Base ammonium bromide, tripropyl decyl ammonium bromide, tripropyl dodecyl bromination ammonium, tripropyl Tetra-n-decylammonium bromide, tripropyl ten
Six base ammonium bromides, tripropyl octadecyl ammonium bromide, tributyl hexyl ammonium bromide, tributyl heptyl ammonium bromide, tributyl decyl bromide
Change ammonium, tributyl dodecyl bromination ammonium, tributyl Tetra-n-decylammonium bromide, tributyl palmityl ammonium bromide, tributyl 18
Base ammonium bromide, trimethyl chlorination ammonium, trimethyl heptyl ammonium chloride, trimethyldecyl ammonium chloride, trimethyldodecane base chlorine
Change ammonium, trimethyl tetradecyl ammonium chloride, trimethyl palmityl ammonium chloride, trimethyl octadecyl ammonium chloride, triethyl group hexyl chloride
Change ammonium, triethyl group heptyl ammonium chloride, triethyl group decyl ammonium chloride, triethyl group lauryl ammonium chloride, triethyl group myristyl chlorine
Change ammonium, triethyl group palmityl ammonium chloride, triethyl group octadecyl ammonium chloride, tripropyl hexyl ammonium chloride, tripropyl heptyl ammonium chloride,
Tripropyl decyl ammonium chloride, tripropyl lauryl ammonium chloride, tripropyl tetradecyl ammonium chloride, tripropyl palmityl chlorination
Ammonium, tripropyl octadecyl ammonium chloride, tributyl hexyl ammonium chloride, tributyl heptyl ammonium chloride, tributyl decyl ammonium chloride, three fourths
Base lauryl ammonium chloride, tributyl tetradecyl ammonium chloride, tributyl palmityl ammonium chloride and tributyl octadecyl ammonium chloride
In one or more.
According to the present invention, in the tetraalkoxysilane (tetraalkyl orthosilicate), four alkoxies can be independently of one another
For C1-C6 alkoxy；It is preferred that four alkoxies are identical, for example, being methoxyl group, ethyoxyl, propoxyl group, butoxy, penta oxygen
Base or hexyloxy.
Specifically, described tetraalkoxysilane can be selected from tetramethoxy-silicane (methyl silicate), tetraethoxy-silicane
Alkane (tetraethyl orthosilicate), tetrapropoxysilane (positive silicic acid propyl ester), four butoxy silanes (butyl silicate) and dimethoxy two
One or more in Ethoxysilane.
According to the present invention, in step (1), as long as the dosage of template, tetraalkoxysilane and water can ensure that this is made
The described silica zeolite of invention.
Under preferable case, counted using the mole of tetraalkoxysilane as 1, the mole of template is 0.04-0.6, preferably
For 0.05-0.45, more preferably 0.08-0.3, more preferably 0.1-0.2.
Under preferable case, in step (1), counted using the mole of tetraalkoxysilane as 1, the mole of water is 5-100, excellent
Elect 10-60 as.
In step (1), described hydrolysis is to instigate tetraalkoxysilane to hydrolyze.The present invention is not special to the condition of hydrolysis
Limitation, any known suitable condition can use, for example, the temperature of hydrolysis can be 0 DEG C -150 DEG C, hydrolysis time can
To be -3000 minutes 10 minutes.Preferably, in step (1), described being hydrolyzed to " at least carries out 10 points at 50 DEG C -95 DEG C
Clock ".It is highly preferred that in step (1), described is hydrolyzed to " being carried out -30 hours 2 hours at 50 DEG C -95 DEG C ".
In step (1), described " removing alcohol " refers to remove tetraalkoxysilane hydrolysis from the reaction system of step (1)
The alcohol of generation.The present invention has no particular limits to the mode and condition that remove alcohol, and any known suitable mode and condition are equal
It can use, it is for instance possible to use the mode of azeotropic distillation removes alcohol from reaction system, and supplement what is lost during azeotropic distillation
Water.
In step (1), after hydrolyzing and removing alcohol, the hydrolyzate of the tetraalkoxysilane of clear is obtained.The hydrolysis
In liquid, alcohol content in mass is generally not more than 10ppm.
In step (2), although as long as step (1) products therefrom is mixed with the compound of structure shown in formula (I), and carry out
The purpose of the present invention can be achieved in crystallization, it is preferred that in the case of, using the mole of tetraalkoxysilane in step (1) as 1 meter,
The mole of the compound of structure shown in formula (I) is 0.005-0.5, preferably 0.01-0.4, more preferably 0.05-0.3.
In step (2), when step (1) products therefrom is mixed with the compound of structure shown in formula (I), the temperature of reaction system
Degree can be room temperature to 110 DEG C, be preferably room temperature to 90 DEG C, more preferably 50 DEG C -90 DEG C.Wherein, by step (1) products therefrom with
The method of the compound mixing of structure shown in formula (I) is not particularly limited, for example, can be by the chemical combination of structure shown in formula (I)
Thing is added in step (1) products therefrom.
In step (2), crystallization temperature can be 90 DEG C -200 DEG C, preferably 110 DEG C -180 DEG C, more preferably 130 DEG C -
180℃；Crystallization time is -20 days 1 hour, and preferably -6 days 4 hours, more preferably -6 days 6 hours, more preferably 8 is small
When -3 days.
Under preferable case, this method is additionally included in before carrying out step (2), by the reaction system after progress step (1)
0.5-60 hours are stood at 50 DEG C -110 DEG C.
According to the present invention, reaction product obtained by step (2) is passed through into separation of solid and liquid, obtains molecular screen primary powder.
According to the present invention, the molecular screen primary powder is calcined between 300 DEG C -650 DEG C, the molecular sieve after being calcined.
In the present invention, described silica zeolite, both including unfired molecular screen primary powder, also including after fired
Molecular sieve.
Present invention also offers a kind of processing method of silica zeolite, by silica zeolite and quaternary ammonium salt and/or quaternary ammonium
Alkali and water mixing, and by gained mixture in room temperature to crystallization at 200 DEG C, preferably 50-200 DEG C -10 days 1 hour, preferably
For -8 days 12 hours, the silica zeolite was that method of the present invention is made.Wherein, by silica zeolite and quaternary ammonium salt
And/or quaternary ammonium base and water mixing method be not particularly limited, preferably can be by silica zeolite be added to quaternary ammonium salt and/
Or in the aqueous solution of quaternary ammonium base.
Treatment in accordance with the present invention method, counted using the mole of silicon in the silica zeolite as 1, the quaternary ammonium salt and season
The mole of ammonium alkali is 0.02-0.5.
Treatment in accordance with the present invention method, by the molecular sieve after foregoing molecular screen primary powder and/or roasting and quaternary ammonium salt and/
Or quaternary ammonium base and aqueous mixtures (preferably, by the molecular sieve after foregoing molecular screen primary powder and/or roasting, be added to quaternary ammonium salt and/
Or in the aqueous solution of quaternary ammonium base), and in room temperature to crystallization at 200 DEG C 1 hour to 10 days.In the processing method, crystallization temperature is excellent
Elect 30 DEG C -200 DEG C, more preferably 50 DEG C -200 DEG C as；Crystallization time is preferably -8 days 12 hours, more preferably -6 days 1 day.Should
In processing method, counted using the mole of silicon in the silica zeolite as 1, the integral molar quantity of the quaternary ammonium salt and quaternary ammonium base is
(if comprising only quaternary ammonium salt or quaternary ammonium base, integral molar quantity refers to mole of quaternary ammonium salt or quaternary ammonium base by 0.02-0.5, preferably 0.02-0.2
Amount).In the processing method, counted using the mole of silicon in the silica zeolite as 1, the mole of water is 2-50, preferably 2-
30.In the processing method, described quaternary ammonium salt, quaternary ammonium base are identical with the quaternary ammonium salt in foregoing template part, quaternary ammonium base, herein
Repeat no more.
According to the present invention, the heating mode of either step in molecular sieve preparation method and processing method is limited without special
System, can be by the way of temperature programming, such as 0.5 DEG C -1 DEG C/min.
According to the present invention, the crystallization pressure of either step in molecular sieve preparation method and processing method is not limited particularly
System, can be the self-generated pressure of crystallization system.
According to the present invention, to the equal nothing of post-processing approach of any product of gained in molecular sieve preparation method and processing method
Special limitation, can use existing suitable method, such as crystallization product is filtered, (optional) is washed and dries, can score
Son sieves former powder；Crystallization product is filtered, wash (optional), dries (optional) and is calcined, the molecular sieve after must being calcined.Washing one
As in room temperature to being mixed or being eluted with water at 50 DEG C, water is generally 1-20 times of crystallization product quality.Drying temperature one
As be 100 DEG C -200 DEG C.Sintering temperature is generally 350 DEG C -650 DEG C.
To the subsequent treatment process of molecular sieve, i.e. molecular sieve rearrangement step, this process can be carried out once, can also be repeated
It is one or many, the repetition, it will reset and handle the obtained micro- mesoporous molecular sieve composite material of total silicon according still further to rearrangement step
Method handled.Handled by rearrangement, the micro- mesoporous molecular sieve composite material of total silicon with secondary pore structure can be obtained,
The crystal grain of the micro- mesoporous molecular sieve composite material of gained total silicon has bigger pore volume and specific surface area, the cryogenic nitrogen of the molecular sieve
Hysteresis loop be present between the adsorption isotherm and desorption isotherm of absorption.
Present invention also offers a kind of silica zeolite, and the molecular sieve has MFI structure and mesopore volume is not less than
0.16cm3/ g, micro pore volume are not less than 0.1cm3/g。
According to the present invention, in the silica zeolite, mesopore volume is preferably not less than 0.18cm3/ g, more desirably not less than
0.36cm3/g.In the silica zeolite, mesopore volume is generally 0.16cm3/g-0.5cm3/g。
According to the present invention, in the silica zeolite, micro pore volume is generally 0.1cm3/g-0.3cm3/ g, it is preferably
0.1cm3/g-0.2cm3/ g, more preferably 0.1cm3/g-0.15cm3/g。
According to the present invention, described silica zeolite can contain or not contain Si-C keys.
Present invention also offers a kind of catalyst, the catalyst contains the foregoing silica zeolite of the present invention.
Present invention also offers a kind of method of cyclohexanone oxime Beckmann rearrangement production caprolactam, wherein, use
Catalyst of the present invention.
Template in the present invention, in the art also referred to as structure directing agent or organic directing agent.
All features disclosed in this invention can in any combination, and these combinations should be understood presently disclosed or note
The content of load, unless those skilled in the art think that the combination is substantially unreasonable.Numerical point disclosed in this specification, is not only wrapped
Include specifically disclosed numerical point in embodiment, in addition in specification each number range end points, any group of these numerical points institute
The scope of conjunction is regarded as the scope that the present invention is disclosed or records.
The present invention will be described in detail by way of examples below.
In embodiment and comparative example, the X-ray diffraction of sample is carried out on Siemens D5005 type x-ray diffractometers
(XRD) crystalline phase figure determines, and radiographic source is CuK alphatrons voltage 40kV, tube current 40mA, 0.5 °/min of sweep speed, the θ of scanning range 2
=4 ° -40 °.
In embodiment and comparative example, the method for testing of specific surface area and pore volume uses N2 adsorption volumetric method, according to BET,
T-plot and BJH computational methods.(referring to Petrochemical Engineering Analysis method (RIPP test methods), RIPP151-90, scientific publication
Society, nineteen ninety publish).
In embodiment and comparative example, TPAOH is technical grade, purchased from Guangdong great You chemical plant, silicic acid tetrem
Ester, analysis is pure, and purchased from Chemical Reagent Co., Ltd., Sinopharm Group, remaining medicament is that analysis is pure, and all medicaments are commercially available obtain
.
In embodiment and comparative example, compound (CAS shown in formula (III):41051-80-3) it is purchased from Tokyo chemical conversion industry
Co., Ltd. (TCI)；Compound (CAS shown in formula (IV):31024-54-1) it is purchased from Noah's ark chemical material Co., Ltd (Ark)；
Compound (CAS shown in formula (V)：71408-48-5) purchased from Toronto research chemical company (TRC).
Comparative example 1
23.1g tetraethyl orthosilicates are mixed with the 22.1g TPAOHs aqueous solution (the weight % of concentration 24.4), added
7.2g deionized waters uniformly mix；Then in the presence of being stirred vigorously, the mixture is stirred at 75 DEG C and catches up with alcohol 6 hours,
Obtain the colloid of clear.The colloid is moved into stainless steel closed reactor again, thermostatic crystallization 3 days at 170 DEG C；Will
The sample that arrives is filtered, washing, and 110 DEG C of drying and 550 DEG C are calcined, you can are obtained conventional Silicalite-1 molecular sieves, be denoted as
DB-1。
Nitrogen adsorption desorption result shows that its specific surface area is 422m2/ g, micro pore volume 0.172ml/g, mesopore volume are
0.098ml/g, transmission electron microscope photo is as shown in Figure 1a.
Comparative example 2
This comparative example illustrates that post processing molecular sieve used is prepared according to method disclosed in patent CN1338427A.
22.5g tetraethyl orthosilicates are mixed with the 21g TPAOHs aqueous solution (the weight % of concentration 24.4), added
7.0g deionized waters uniformly mix；Then alcohol 7h is caught up with the mixture is stirred at 75 DEG C, obtain the colloid of clear.Again
The colloid is moved into stainless steel closed reactor, thermostatic crystallization 3 days at 170 DEG C, you can obtain conventional Silicalite-1
Molecular sieve.
The Silicalite-1 molecular sieves of above-mentioned preparation are taken, with TPAOH and deionized water according to 1:3:50
Molar ratio is mixed, and scattered suspension is put into stainless steel cauldron, placed 3 days at 165 DEG C, you can described in obtaining
Silicalite-1 molecular sieves are post-processed, are denoted as DB-2.
Nitrogen adsorption desorption result shows that its specific surface area is 431m2/ g, micro pore volume 0.173ml/g, mesopore volume are
0.126ml/g, as shown in Figure 1 b, pore-size distribution is as shown in Figure 2 for transmission electron microscope photo.
Embodiment 1
The present embodiment is used for the preparation for illustrating silica zeolite provided by the invention.
(1) 30.0g tetraethyl orthosilicates are mixed with 19.2g TPAOHs solution (mass concentration 24.4%), it is acute
25g deionized waters are added under strong stirring, and hydrolysis catches up with alcohol 4 hours at a temperature of 80 DEG C, supplements the moisture content of evaporation at any time, obtains nothing
Color transparent aqueous solution；
(2) step (1) products therefrom is fitted into stainless steel closed reactor, in 80 DEG C of pre- crystallization 24 hours, obtained pre-
Crystallization product；
(3) compound shown in 1.7g formulas (III) is added into above-mentioned pre- crystallization product, it is small to be stirred vigorously 2 in room temperature
When, transparent viscous liquid is formed, aforesaid liquid is transferred in stainless steel closed reactor, the thermostatic crystallization 12 under the conditions of 90 DEG C
Hour, 165 DEG C then are to slowly warm up to 1 DEG C/min speed, thermostatic crystallization 2 days, that is, the micro- mesopore molecular sieve of total silicon is obtained and answers
Condensation material, obtained material is filtered, washing, 120 DEG C of drying 12 hours, 550 DEG C of roastings 6 hours, you can obtain the present invention
The micro- mesoporous molecular sieve composite material of total silicon, is denoted as MS-1.Nitrogen adsorption desorption result shows that its specific surface area is 622m2/ g,
Micro pore volume is 0.275ml/g, and mesopore volume 0.201ml/g, transmission electron microscope photo is as illustrated in figure 1 c.
(4) cetyltrimethylammonium hydroxide by the MS-1 samples prepared by 6.0g with concentration for 10 weight %
(CTAOH) aqueous solution uniformly mixes, and adds to stainless steel closed reactor, wherein the MS-1 and the weight of the CTAOH aqueous solution
Than for 1:3, handle 3 days, filtered, washing, dried at 120 DEG C 12 hours, 550 DEG C are calcined 3h, i.e., under the conditions of temperature 50 C
The micro- mesoporous molecular sieve composite material of total silicon that can be reset, is denoted as HMS-1.Nitrogen adsorption desorption result shows that its specific surface area is
646m2/ g, micro pore volume 0.143ml/g, mesopore volume 0.462ml/g, transmission electron microscope photo as shown in Figure 1 d,
Pore-size distribution is as shown in Figure 3.
Comparative example 3
Method according to embodiment 1 prepares silica zeolite, unlike, it is added without compound shown in formula (III), gained
Molecular sieve is denoted as DB-3.Nitrogen adsorption desorption result shows that its specific surface area is 438m2/ g, micro pore volume 0.239ml/g, it is mesoporous
Volume is 0.125ml/g.After step (4) processing, products obtained therefrom is denoted as DB-3H, specific surface area 425m2/ g, micro pore volume
For 0.221ml/g, mesopore volume 0.136ml/g.
Embodiment 2
The present embodiment is used for the preparation for illustrating silica zeolite provided by the invention.
(1) by 31.0g tetraethoxysilanes (tetraethyl orthosilicate) and 15g TPAOH solution (mass concentrations
24.4%) mix, stir lower addition 25g deionized waters, and hydrolyzed at a temperature of 80 DEG C and remove alcohol 4 hours, while supplement steaming
The moisture of hair, obtain slightly yellow transparent aqueous solution；
(2) step (1) products therefrom is fitted into stainless steel closed reactor, stands 6 hours at 100 DEG C, obtain pre- crystalline substance
Change product；
(3) compound shown in 0.8g formulas (IV) is added into above-mentioned pre- crystallization product, be stirred at room temperature 2 hours, formed
Transparent viscous liquid, aforesaid liquid is transferred in stainless steel closed reactor, constant temperature 48 hours under the conditions of 90 DEG C, then with
1 DEG C/min speed is to slowly warm up to 165 DEG C, and constant temperature 0.5 day is then filtered, washing, 120 DEG C of dryings 12 hours, 550 DEG C
Roasting 6 hours, produces product, is denoted as MS-2.Its nitrogen adsorption desorption result shows that its specific surface area is 601m2/ g, micro pore volume
For 0.243ml/g, mesopore volume 0.208ml/g；
(4) by TPAOH (TPAOH) water that the MS-2 samples prepared by 6.0g and mass concentration are 24.4%
Solution uniformly mixes, and adds to stainless steel closed reactor, wherein, the mass ratio of the MTS-2 and the TPAOH aqueous solution is 1:5,
Handled 1 day under the conditions of 110 DEG C of temperature, filtered, washing, dried at 120 DEG C 12 hours, 550 DEG C of roasting 3h, produce product,
It is denoted as HMS-2.Nitrogen adsorption desorption result shows that its specific surface area is 591m2/ g, micro pore volume 0.247ml/g, mesopore volume
For 0.224ml/g.
Comparative example 4
Silica zeolite is prepared according to method same as Example 2, unlike, it is added without chemical combination shown in formula (IV)
Thing, gained molecular sieve are denoted as DB-4.Nitrogen adsorption desorption result shows that its specific surface area is 428m2/ g, micro pore volume are
0.201ml/g, mesopore volume 0.126ml/g.After step (4) processing, products obtained therefrom is denoted as DB-4H, nitrogen adsorption desorption knot
Fruit shows that its specific surface area is 417m2/ g, micro pore volume 0.221ml/g, mesopore volume 0.124ml/g.
Embodiment 3
The present embodiment is used for the preparation for illustrating silica zeolite provided by the invention.
(1) 30.0g tetraethyl orthosilicates are mixed with 20.4g TPAOHs solution (mass concentration 24.4%), it is acute
15g deionized waters are added under strong stirring, and hydrolysis catches up with alcohol 7 hours at a temperature of 60 DEG C, supplements the moisture of evaporation at any time, obtains nothing
Color transparent aqueous solution；
(2) step (1) products therefrom is fitted into stainless steel closed reactor, in 80 DEG C of pre- crystallization 1 hour, obtains pre- crystalline substance
Change product；
(3) compound shown in 0.5g formulas (III) is added into above-mentioned pre- crystallization product, it is small to be stirred vigorously 2 in room temperature
When, transparent viscous liquid is formed, aforesaid liquid is transferred in stainless steel closed reactor, constant temperature 24 is small under the conditions of 80 DEG C
When, 155 DEG C then are to slowly warm up to 1 DEG C/min speed, constant temperature 3 days, that is, obtains the micro- mesoporous molecular sieve composite material of total silicon,
Obtained material is filtered, washing, 120 DEG C of drying 12 hours, 550 DEG C of roastings 6 hours, you can obtain total silicon of the present invention
Micro- mesoporous molecular sieve composite material, is denoted as MS-3.Nitrogen adsorption desorption result shows that its specific surface area is 522m2/ g, micro pore volume
For 0.231ml/g, mesopore volume 0.193ml/g.
(4) the dodecyl tripropyl ammonium hydroxide by the MS-3 samples prepared by 6.0g with concentration for 12.0 weight %
(DDTPAOH) aqueous solution uniformly mixes, and adds to stainless steel closed reactor, wherein the MS-3 and the DDTPAOH aqueous solution
Weight ratio is 1:3, handle 1 day, filtered, washing, dried at 120 DEG C 12 hours, 550 DEG C of roastings under the conditions of 100 DEG C of temperature
3h, you can the micro- mesoporous molecular sieve composite material of total silicon reset, be denoted as HMS-3.Nitrogen adsorption desorption result shows that it compares table
Area is 604m2/ g, micro pore volume 0.129ml/g, mesopore volume 0.346ml/g.
Embodiment 4
The present embodiment is used for the preparation for illustrating silica zeolite provided by the invention.
The micro- mesoporous molecular sieve composite material of total silicon is prepared according to the method in embodiment 3, difference is, omits step
(2) and (4), gained molecular sieve are denoted as MS-4, and nitrogen adsorption desorption result shows that its specific surface area is 516m2/ g, micro pore volume are
0.214ml/g, mesopore volume 0.199ml/g.
Embodiment 5
The present embodiment is used for the preparation for illustrating silica zeolite provided by the invention.
(1) 25.0g tetraethyl orthosilicates are mixed with 4.0g 4-propyl ammonium chlorides, the ammonia spirit that 3.0g concentration is 20%,
Lower addition 16g deionized waters are stirred vigorously, and hydrolysis catches up with alcohol 4 hours at a temperature of 80 DEG C, supplements the moisture of evaporation at any time, obtains
Slightly yellow transparent aqueous solution；
(2) step (1) products therefrom is fitted into stainless steel closed reactor, in 90 DEG C of pre- crystallization 2 hours, obtains pre- crystalline substance
Change product；
(3) compound shown in 0.40g formulas (IV) is added into above-mentioned pre- crystallization product, it is small to be stirred vigorously 2 in room temperature
When, transparent viscous liquid is formed, aforesaid liquid is transferred in stainless steel closed reactor, constant temperature 0.5 is small under the conditions of 90 DEG C
When, 165 DEG C then are to slowly warm up to 1 DEG C/min speed, constant temperature 24 hours, that is, obtains the micro- mesopore molecular sieve composite wood of total silicon
Material, obtained material is filtered, washing, 120 DEG C of drying 12 hours, 550 DEG C of roastings 6 hours, you can obtain of the present invention
The micro- mesoporous molecular sieve composite material of total silicon, is denoted as MS-5.Nitrogen adsorption desorption result shows that its specific surface area is 502m2/ g, micropore
Volume is 0.327ml/g, mesopore volume 0.195ml/g.
(4) the hexyl tripropyl ammonium hydroxide (HTPAOH) by the MS-5 samples prepared by 6.0g with concentration for 15 weight %
The aqueous solution uniformly mixes, and adds to stainless steel closed reactor, wherein the MS-5 and the weight ratio of the HTPAOH aqueous solution are 1:
3, handle 2 days, filtered, washing, dried at 120 DEG C 12 hours, 550 DEG C of roasting 3h, you can obtain under the conditions of 150 DEG C of temperature
The micro- mesoporous molecular sieve composite material of total silicon of rearrangement, is denoted as HMS-5.Nitrogen adsorption desorption result shows that its specific surface area is 571m2/
G, micro pore volume 0.211ml/g, mesopore volume 0.372ml/g.
Comparative example 5
The micro- mesoporous molecular sieve composite material of total silicon is prepared according to method same as Example 3, difference is, by formula
(IV) compound shown in is changed to the compound shown in formula (V), the micro- mesopore molecular sieve composite wood of the total silicon that can be reset
Material, is denoted as DB-5H.Nitrogen adsorption desorption result shows that its specific surface area is 453m2/ g, micro pore volume 0.182ml/g, mesoporous body
Product is 0.121ml/g.
Thus illustrate when the structure that the structure non-invention of organo-silicon compound is limited, resulting silica zeolite
Without more mesoporous.
Embodiment 6
The present embodiment is used for the preparation for illustrating silica zeolite provided by the invention.
(1) 26.0g tetraethyl orthosilicates are mixed with 15.5g tetraethyl ammonium hydroxides solution (mass concentration 18.2%), it is acute
12g deionized waters are added under strong stirring, and hydrolysis catches up with alcohol 4 hours at a temperature of 80 DEG C, supplements the moisture of evaporation at any time, obtains micro-
The yellow transparent aqueous solution；
(2) step (1) products therefrom is fitted into stainless steel closed reactor, in 90 DEG C of pre- crystallization 18 hours, obtained pre-
Crystallization product；
(3) compound shown in 3.0g formulas (IV) is added into above-mentioned pre- crystallization product, it is small to be stirred vigorously 2 in room temperature
When, transparent viscous liquid is formed, aforesaid liquid is transferred in stainless steel closed reactor, in 155 DEG C of thermostatic crystallizations 3 days, i.e.,
The micro- mesoporous molecular sieve composite material of total silicon is obtained, obtained material is filtered, washing, 120 DEG C of drying 12 hours, 550 DEG C roast
Burn 6 hours, you can obtain the micro- mesoporous molecular sieve composite material of total silicon of the present invention, be denoted as MS-6.Nitrogen adsorption desorption result shows
It is 642m to show its specific surface area2/ g, micro pore volume 0.197ml/g, mesopore volume 0.184ml/g.
(4) the myristyl triethylammonium hydroxide by the MS-6 samples prepared by 16.0g with concentration for 10 weight %
(TDTPAOH) aqueous solution uniformly mixes, and adds to stainless steel closed reactor, wherein the MS-6 and the weight of the HTPAOH aqueous solution
Amount is than being 1:5, reset processing 1 day under the conditions of 130 DEG C of temperature, filtered, washing, dry 12 hours at 120 DEG C, 550 DEG C of roastings
Burn 3h, you can the micro- mesoporous molecular sieve composite material of total silicon reset, be denoted as HMS-6.Nitrogen adsorption desorption result shows its ratio
Surface area is 711m2/ g, micro pore volume 0.125ml/g, mesopore volume 0.495ml/g.
Embodiment 7
Molecular sieve after the silica zeolite do not reset provided above-described embodiment and comparative example and rearrangement is evaluated.
The catalytic performance of gained silica zeolite is evaluated using cyclohexanone oxime Beckmann rearrangement.Silica zeolite pressure
Piece, then crush, take the particle of 20-60 mesh as catalyst.Evaluation result is shown in Table 1.Appreciation condition is as follows：
Reaction unit is that normal pressure continuously flows fixed bed, and reactor inside diameter is 5 millimeters, catalyst (silica zeolite) filling
Measure as 0.5g, the grain graininess of catalyst is 20-60 mesh.
After catalyst loads reaction tube, pre-processed 2 hours in normal pressure, 350 DEG C of nitrogen atmosphere.
The concentration of cyclohexanone oxime is 35.7 weight %, and weight space velocity (WHSV) is 7.5h-1, solvent is methanol, reaction temperature
For 350 DEG C, the flow velocity of nitrogen is 1.8 ls/h, the sampling of 3 hours reaction time.
Reaction product is collected after being condensed by water circulation, hydrogen flame detector, and gas chromatography measures its composition, as a result sees
Table 1.Gas-chromatography used is 7890 type gas chromatographs of Agilent companies production；Analysis chromatographic column used is that HP-5 is non-
Polar column.
Table 1 gives the total silicon material structure synthesized under different condition and catalysis of pimelinketone oxime Beckmann rearrangement knot
Fruit.
Table 1
From the result of table 1, the silica zeolite synthesized by method of the invention has higher mesopore volume, this point
Son sieve has higher catalytic activity in cyclohexanone oxime Beckmann rearrangement, and the selectivity of caprolactam is obviously improved；
And the mesopore volume for the silica zeolite that the method for using comparative example to provide synthesizes is relatively low and anti-in cyclohexanone oxime Beckmann rearrangement
Catalytic activity is not high in answering.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (16)
1. a kind of preparation method of silica zeolite, it is characterised in that this method includes：
(1) template, tetraalkoxysilane and water are mixed, gained mixture is hydrolyzed and removes alcohol；
(2) step (1) products therefrom is mixed with the compound of structure shown in formula (I), gained mixture is subjected to crystallization；
Wherein, i be 1-10 in any integer, R1、R2、R3It is each independently methyl, ethyl, propyl group or butyl；R4、R5Each
It independently is the organic group being made up of 1-20 carbon atom, 0-5 nitrogen-atoms, 0-3 oxygen atom and hydrogen, or R4With R5Phase
Even, 5 yuan -10 yuan of azacyclo- or nitrogen oxa- ring is formed.
2. according to the method for claim 1, wherein, i is any integer in 2-5.
3. the method according to claim 11, wherein, in the compound of structure shown in formula (I), R4、R5Serve as reasons independently of one another
The organic group that 2-10 carbon atom, 0-5 nitrogen-atoms, 0-3 oxygen atom and hydrogen form；Or R4With R5It is connected, 5 yuan of formation-
8 yuan of azacyclo- or nitrogen oxa- ring, it is preferable that R4、R5It is ethyl, or R4With R5It is connected, forms morpholine ring.
4. according to the method for claim 1, wherein, described template is quaternary ammonium salt and/or quaternary ammonium base.
5. according to the method for claim 1, wherein, described tetraalkoxysilane is selected from tetramethoxy-silicane, four ethoxies
One or more in base silane, tetrapropoxysilane, four butoxy silanes and dimethoxy diethoxy silane.
6. according to the method for claim 1, wherein, in step (1), counted using the mole of tetraalkoxysilane as 1, template
The mole of agent is 0.04-0.6, and the mole of water is 5-100.
7. according to the method for claim 1, wherein, in step (1), gained mixture is hydrolyzed and removes the process of alcohol,
Carried out at 50 DEG C -95 DEG C at least 10 minutes.
8. according to the method for claim 1, wherein, this method is additionally included in before carrying out step (2), will carry out step
(1) reaction system after stands 0.5-60 hours at 50 DEG C -110 DEG C.
9. according to the method for claim 1, wherein, counted using the mole of tetraalkoxysilane in step (1) as 1, in step
Suddenly in (2), the mole of the compound of structure shown in formula (I) is 0.005-0.5.
10. according to the method for claim 1, wherein, in step (2), crystallization temperature is 90 DEG C -200 DEG C, crystallization time
For -20 days 1 hour.
A kind of 11. processing method of silica zeolite, it is characterised in that by silica zeolite and quaternary ammonium salt and/or quaternary ammonium base with
And water mixing, and by gained mixture in room temperature to crystallization at 200 DEG C, preferably 50-200 DEG C -10 days 1 hour, preferably 12
- 8 days hours, the silica zeolite are to be made as the method described in any one in claim 1-10.
12. according to the method for claim 11, wherein, counted using the mole of silicon in the silica zeolite as 1, quaternary ammonium salt
Integral molar quantity with quaternary ammonium base is 0.02-0.5.
13. a kind of silica zeolite, it is characterised in that there is MFI structure and mesopore volume is not less than 0.16cm3/ g, micro pore volume
Not less than 0.1cm3/g。
14. silica zeolite according to claim 13, wherein, the silica zeolite contains Si-C keys.
15. a kind of catalyst, it is characterised in that the catalyst contains the silica zeolite described in claim 13 or 14.
A kind of 16. method of cyclohexanone oxime Beckmann rearrangement production caprolactam, it is characterised in that usage right requirement 15
Described catalyst.
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