CN108439425A - A kind of ETL types molecular sieve and its manufacturing method - Google Patents
A kind of ETL types molecular sieve and its manufacturing method Download PDFInfo
- Publication number
- CN108439425A CN108439425A CN201810396244.4A CN201810396244A CN108439425A CN 108439425 A CN108439425 A CN 108439425A CN 201810396244 A CN201810396244 A CN 201810396244A CN 108439425 A CN108439425 A CN 108439425A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- etl
- molecular sieves
- type molecular
- manufacture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The present invention provides a kind of new method of manufacture ETL type molecular sieves, this method is used carries out hydrothermal synthesis by aqueous gel, the raw material of quadrivalent element Y atomic raw materials and triad X atoms is included at least in the aqueous gel, and cesium ion and quaternary ammonium salt are selected as template to prepare ETL type molecular sieves, the limitation of ETL type molecular sieve methods can only be synthesized using rubidium ion and organic matter as template in the past by having broken, micropore specific area higher, the more preferable ETL type molecular sieves with more patterns of crystallinity are synthesized.
Description
Technical field
The present invention relates to a kind of molecular sieve and its manufacturing methods.
Background technology
Molecular sieve is with a wide range of applications in the characteristics such as catalysis, ion exchange, gas absorption and separation, Ke Yiyong
Make industrial catalyst, ion-exchanger, sorbing material etc..The basic unit of molecular sieve is SiO4Or AlO4Tetrahedral structure.
ETL type molecular sieves have two-dimensional octatomic ring channel system, for aluminosilicate molecular sieves, from its stabilization in practical applications
Property, catalytic performance etc. considers, it is desirable that there is high SiO2/Al2O3Molar ratio (hereinafter referred to as " SAR ").Although in alkaline condition
Silicon in lower removing framework of molecular sieve, or remove in acid condition at the aluminium and high-temperature vapor in framework of molecular sieve
The post-processing means such as reason can also be used to the SAR ratios for adjusting molecular sieve, but these post-processings not only increase manufacturing cost, past
Toward many defective bits are formed in the skeleton of molecular sieve, the ion exchange of molecular sieve, absorption and separating property are affected.At present
Usually all it is that template is used as using rubidium ion and tetramethylammonium hydroxide (TMAOH) in some synthesis ETL type molecular sieve methods
(non-patent literature 1) is synthesized, also has (non-patent literature 2) is synthesized as template using rubidium ion and choline, these sides
The ETL type molecular sieves that method is synthesized, micropore specific area is relatively low, and highest only has 210m2/g.For molecular sieve,
Micropore specific area is the major criterion for weighing a crystallization of molecular sieves, and the better molecular sieve of crystallinity is handed in catalysis, ion
It changes, all show better advantage in the characteristics such as gas absorption and separation.
Existing technical literature
Patent document
Patent document 1：U.S. Patent No. 4581211
Non-patent literature
Non-patent literature 1：Zeolites, 1992,12,24-31.
Non-patent literature 2：Angew.Chem.Int.Ed.2016,55,7369-7373.
Invention content
Problems to be solved by the invention
Problem of the present invention is that provide using except rubidium ion alkali metal ion and quaternary ammonium salt as template synthesize
The new method of ETL type molecular sieves, synthetic microporous specific surface area higher, crystallinity is more preferable and the more ETL types molecular sieves of pattern.
The solution to the problem
The inventors of the present invention further investigate, as a result, it has been found that, it can be synthetic microporous as template using cesium ion and quaternary ammonium salt
Specific surface area higher, crystallinity is more preferable and the more ETL types molecular sieves of pattern, preferred high silicon dioxide molecular sieve, to solve
The above problem.
The present invention is completed based on such opinion, and objective is as described below.
1. a kind of ETL types molecular sieve uses29When Si solid state nmrs measure, between -122~-107ppm the intensity at peak with -
The intensity ratio at peak is 1.33 or more between 107~-100ppm.
2. the ETL type molecular sieves according to 1, micropore specific area 220m2/ g or more.
3. a kind of method of manufacture ETL type molecular sieves, which is characterized in that aqueous gel is carried out hydrothermal synthesis, this is aqueous
Gel includes at least the raw material and cesium ion and quaternary ammonium salt of the raw material and triad X atoms of quadrivalent element Y atoms.
4. the method for the manufacture ETL type molecular sieves according to 3, wherein X includes at least aluminium.
5. the method for the manufacture ETL type molecular sieves according to any one of 3~4, wherein Y includes at least silicon.
6. the method for the manufacture ETL type molecular sieves according to any one of 3~5, wherein contain crown ether in aqueous gel
Class compound.
7. the method for the manufacture ETL type molecular sieves according to 6, wherein crown ether compound is 12-crown-4 ether, 15-
One in crown- 5- ethers, 18- crown- 6- ethers, 24- crown- 8- ethers, dibenzo-18 crown-6-ether, cave ether [2.2] or cave ether [2.2.2]
Kind is several.
8. the method for the manufacture ETL type molecular sieves according to any one of 3~7, wherein quaternary ammonium salt is tetramethyl hydrogen-oxygen
Change one in ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dimethyl diethyl ammonium hydroxide
Kind is several.
9. according to any one of 3~8 manufacture ETL type molecular sieves method, wherein in aqueous gel containing fluorine from
Son.
The effect of invention
According to the present invention, ETL type molecular sieves are synthesized as the new method of template using cesium ion and quaternary ammonium salt, are broken
The limitation of ETL type molecular sieve methods was synthesized as template only with rubidium ion and organic matter, and can manufacture in the past
Go out micropore specific area higher, crystallinity is more preferable and the more ETL types molecular sieves of pattern, preferred high silicon dioxide molecular sieve.
Description of the drawings
Fig. 1 is the figure for the XRD spectrum for indicating molecular sieve 1.
Fig. 2 is the figure for the XRD spectrum for indicating molecular sieve 2.
Fig. 3 is the solid state nmr for indicating molecular sieve 229The figure of Si spectrums.
Fig. 4 is the SEM figures for indicating molecular sieve 2.
Fig. 5 is the solid state nmr for indicating molecular sieve 429The figure of Si spectrums.
Fig. 6 is the solid state nmr for indicating molecular sieve 629The figure of Si spectrums.
Fig. 7 is the solid state nmr for indicating molecular sieve 829The figure of Si spectrums.
Fig. 8 is the SEM figures for indicating molecular sieve 8.
Fig. 9 is the solid state nmr for indicating molecular sieve 1029The figure of Si spectrums.
Figure 10 is the SEM figures for indicating molecular sieve 10.
Figure 11 is the solid state nmr for indicating molecular sieve 1229The figure of Si spectrums.
Figure 12 is the SEM figures for indicating molecular sieve 12.
Specific implementation mode
Hereinafter, detailed description of embodiments of the present invention, explanation is the representative of embodiments of the present invention below
Example, the present invention is not by any restriction of these contents.
The molecular sieve of the present invention refers to International Molecular sieve association (International Zeolite Association)
Molecular sieve as defined in (hereinafter referred to as IZA).Molecular sieve is usually by skeletal atom tetrahedron (such as SiO4Tetrahedron, AlO4Tetrahedron
Or PO4Tetrahedron, and the Elements Atom except oxygen element is usually referred to as non-oxygen atom or T atom) each vertex
Oxygen atom pass through share be coupled made of regular mesh-like structure.One of the basic unit of mesh structure is N number of TO4Tetrahedron
The ring-type being formed by connecting.In embodiments of the present invention, the molecular sieve is ETL types.Quadrivalent element Y atoms and triad
X atoms are the skeletal atom of molecular sieve.
Whether it is molecular sieve of the invention as got off can for example judge.
First, XRD determining is carried out to sample, at least detected following<Table 1>Shown in interplanar distance。
<Table 1>
Confirm that its result has<Table 1>Interplanar distance, as ETL types molecular sieve.
Later, by icp analysis, the type and amount of the element of anion are measured.Except measured triad and tetravalence
The element for detecting the peak of the compound of the metallic element or the metallic element in element by XRD determining, if it is three
Valence element is then used as Y2O3, if it is quadrivalent element, it is used as XO2, confirm its molar ratio n=YO2/X2O3。
Later, the measurement of BET and solid state nmr are carried out to sample.If the result that BET and solid state nmr measure meets this
The regulation of invention can then be judged as the molecular sieve of the present invention.
[manufacturing method of ETL type molecular sieves of the invention]
In the present invention, first, the raw material containing X atoms is added in the solution of the atomic raw material containing Y, is then sequentially added
Including the raw material of cesium ion, aqueous solution and quaternary ammonium salt aqueous solution containing basic ion, after evenly mixing, by the aqueous solidifying of preparation
Glue carries out hydrothermal synthesis, and to obtain micropore specific area higher, crystallinity is more preferable and the more ETL types molecular sieves of pattern.
<Molecular sieve raw material>
The raw material used in the ETL type molecular sieves manufacture of the present invention basically comprises the raw material of quadrivalent element Y, includes trivalent
The raw material of element X is constituted as components such as the raw material comprising cesium ion, quaternary ammonium salt, alkali and the water of template.Make hereinafter, illustrating
The case where typically used as silicon for quadrivalent element Y, typically used as aluminium as triad X, that is, use silicon atom raw material conduct
Including the raw material of quadrivalent element Y, illustrating using aluminium atom raw material as comprising the case where triad X raw materials.In addition, this
In invention, can also add crystal seed etc. has the ingredient of crystallization facilitation.
As silicon atom raw material, colloidal silicon dioxide, amorphous silica, aerosil, silicic acid can be used
It is one kind or two or more in sodium, trimethylethoxysilane, tetraethyl orthosilicate, aluminium silicate salt gel etc..As aluminium atom original
Material can use aluminum sulfate, aluminum nitrate, sodium aluminate, aluminium oxide, aluminium hydroxide, boehmite, aluminium chloride, aluminium silicate salt gel, gold
Belong to one kind or two or more in aluminium etc..Wherein it is desirable to can be with the raw material of the full and uniform form mixed of other ingredients.
Include the raw material of cesium ion, cesium hydroxide, cesium fluoride, cesium sulfate, cesium chloride, cesium silicate, cesium nitrate can be used
It is one kind or two or more in.
Quaternary ammonium salt is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,
One or more of dimethyl diethyl ammonium hydroxide.
As alkali, the aluminium of sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, above-mentioned aluminium atom raw material can be used
Hydrochlorate, silicon atom raw material silicate in alkali composition, alkali composition in silicate gel etc. in it is one kind or two or more.This hair
In bright molecular sieve manufacture, as alkali metal ion or alkaline-earth metal ions, it is preferable to use free lithium, sodium, potassium, rubidium, caesium, calcium,
At least one of the group of magnesium, strontium and barium composition alkali metal ion exists and is crystallized.By including these alkali metal
Ion is easy to be crystallized and is not easy to generate by-product (impurity crystal).
It should be noted that in aqueous gel add organic matter come when synthesizing ETL type molecular sieves, it is preferable to use with crown ether
For the Macrocyclic compound of representative, Macrocyclic compound is not particularly limited, particularly preferred 12-crown-4 ether, 15- crown- 5- ethers,
18- crown- 6- ethers, 24- crown- 8- ethers, dibenzo-18 crown-6-ether, cave ether [2.2] or cave ether [2.2.2].
In addition to this, fluoride is added in aqueous gel come when synthesizing ETL type molecular sieves, it is not special as fluoride
It limits, preferably the kinds such as hydrofluoric acid, sodium fluoride, cesium fluoride is one kind or two or more.
<The preparation of aluminium atom material solution>
Aluminium atom material solution makes aforementioned aluminium atom dissolution of raw material in water to prepare.The aluminium of aluminium atom material solution is former
Sub- material concentration prepares easy degree from gel, from the aspect of production efficiency, preferably 5~50 weight %, particularly preferably 10~
40 weight %.
It should be noted that the aluminium atom material solution contains substantially no silicon atom raw material.Here, it " is substantially free of
Have " refer to content in aluminium atom material solution it is 1 weight % hereinafter, preferably finger has been entirely free of.
<The preparation of aqueous gel>
In aluminium atom material solution when raw material of the addition containing silicon atom, there is no limit according to using item for adding speed
Part suitably selects.The mixed solution of the raw material comprising cesium ion and quaternary ammonium salt and alkali and water, adding speed are added dropwise again
Also there is no limit suitably select according to use condition.
It should be noted that the raw material containing silicon atom is if it is liquid, as long as silicon atom raw material is molten as silica
Glue has formed the liquid of the aqueous dispersions of the silica of 5~60 weight % or so like that, so that it may to use the liquid.It prepares
When other liquid containing silicon atom raw material, it is preferably prepared to be denoted as 5 weight % or more, particularly 10 with silicon atom material concentration
The aqueous solution or aqueous dispersions of weight % or more and the left and right 60 weight % or less, particularly 50 weight % or less.
It is same as aluminium atom material solution, it is somebody's turn to do the liquid containing silicon atom raw material and contains substantially no aluminium atom raw material.This
In, it is 1 weight % hereinafter, preferably finger has been entirely free of that " containing substantially no ", which refers to content in silicon atom material solution,.
Water content for the aqueous gel for being supplied to hydrothermal synthesis, the easy degree generated from molecular sieve crystal, manufacture
From the aspect of cost, it is preferred that be 20 weight % or more, especially 30 weight % or more and be 80 weight % or less, special
It is 70 weight % or less.
As above operation aqueous gel obtained can carry out hydrothermal synthesis immediately after preparation, but have high knot in order to obtain
The molecular sieve of crystalline substance preferably cures specific time under the conditions of set point of temperature.Curing temperature is usually 100 DEG C or less, is preferably
80 DEG C or less, it is more optimized be 60 DEG C hereinafter, its lower limit is not particularly limited, usually 0 DEG C or more, preferably 10 DEG C or more.It is ripe
Changing temperature can be constant in curing, can also gradual or consecutive variations.Curing time is not particularly limited, usually 2 hours
Above, be preferably 3 hours or more, more preferably 5 hours or more, usually 30 days or less, preferably 10 days or less, be more preferably 4
It is following.
<Hydrothermal synthesis>
Hydrothermal synthesis such as gets off progress：Operation as above aqueous gel obtained is put into pressure vessel, at autogenous pressures,
Or do not hinder under the gas pressurized of degree of crystallization, under stiring or container is made to rotate or wave, or under static condition
Temperature is kept, is thus carried out.
Reaction temperature when hydrothermal synthesis is usually 90 DEG C or more, preferably 120 DEG C or more, more preferably 150 DEG C or more, is led to
Normal 300 DEG C or less, preferably 250 DEG C or less, further preferably 220 DEG C or less.Reaction time is not particularly limited, usually
2 hours or more, preferably 3 hours or more, more preferable 5 hours or more, usually 30 days or less, preferably 10 days or less, further
Preferably 7 days or less.Reaction temperature in the reaction can be constant, can also gradual or consecutive variations.
After above-mentioned hydrothermal synthesis, it will be detached from hydrothermal synthesis reaction liquid as the ETL types molecular sieve of product.It obtains
ETL types molecular sieve (hereinafter referred to as " the ETL types molecular sieve containing template etc. ".) quaternary ammonium salt and caesium containing template in pore
Ion and otheralkali metal three or any one.The method for detaching the molecular sieve containing template etc. from hydrothermal synthesis reaction liquid does not have
It is particularly limited to, can usually enumerate and utilize the methods of filtering, decantation or convection drying.
For removals such as the quaternary ammonium salt of template used when will manufacture and cesium ions, separated and recovered from hydrothermal synthesis reaction liquid
The ETL types molecular sieve containing template etc. can as needed washing, it is dry after calcine etc..
It is excellent when by the ETL type molecular sieves of the present invention for purposes such as catalyst (also including catalyst carrier), sorbing materials
It is selected in after removing them and reuses.
The chemistry that the removal processing of template and/or alkali metal may be used using acid solution, include template decomposition ingredient
The liquid phase processing of solution, the ion-exchange treatment using resin etc., thermal decomposition process, can also be applied in combination these processing.It is logical
Often, it is forged with 300 DEG C~1000 DEG C of temperature using under air or containing aerobic nonactive or non-active gas atmosphere
Burn or the methods of extracted using organic solvents such as ethanol waters, can by containing organic matter (template etc.) remove.From
From the aspect of manufacturing, preferably by calcining removals such as templates.At this moment, calcination temperature is preferably 400 DEG C or more, is more preferably
450 DEG C or more, further preferably 500 DEG C or more, preferably 900 DEG C or less, more preferably 850 DEG C or less, further preferred
It is 800 DEG C or less.As non-active gas, nitrogen etc. can be used.
In turn, it can also utilize the ion-exchange capacity of zeolite that alkali metal moieties are transformed into H-type, NH4Type and use,
Well known technology may be used in method.It can be by using NH4NO3、NH4The ammonium salts such as Cl or hydrochloric acid etc. acid usual room temperature~
Method washed after being handled at 100 DEG C etc. carries out.
<Embodiment>
Hereinafter, the present invention is specifically described using embodiment, the present invention is as long as being no more than its purport not by following
Embodiment any restriction.
[measurement of powder X-ray RD]
The x-ray powder diffraction instrument measurement device (Ulitma IV) manufactured using Rigaku is measured.
[measurement of elemental constituent]
Using the silent winged generation of match, your ICP of scientific and technological (China) Co., Ltd manufacture composes direct emission spectrometer measurement device entirely
(IRIS Advantage) is measured.
[measurement of BET specific surface area]
Use the high-performance specific surface and micropore diameter analyzer (3H- of scientific and technological (Beijing) Co., Ltd manufacture of Bei Shide instruments
2000) it is measured.
[measurement of solid state nmr]
Using the wide chamber solid spectrometer of varian 400,29Si mas rotating speeds 8000/ second, relaxation delay 4 seconds, each sample
Sampling number is not fixed,29The resonant frequency 79MHz of Si, using pi/2 excitation pulse.27Al mas rotating speeds 8000/ second, relaxation is prolonged
Slow 1 second, the sampling number of each sample was not fixed,27The resonant frequency 104MHz of Al, using the excitation pulses of π/12.
[measurement of surface topography]
It is observed using the scanning electron microscope (MERLIN Compact) manufactured by ZEISS.
<Embodiment 1>
1.42gCsOH solution (CsOH concentration is added in 2.05g water：50 weight %, Aldrich system) and
0.27gNaOH (Tianjin chemical reagent supply and marketing corporation) is made into mixed solution.
By the NaAlO of 0.42g2(purity：Al2O345 weight % of ＞ ＞, Tianjin recovery fine chemistry industry research are made) dissolving
After in 2.8g water, 3.38g aerosils (Shanghai simon Chemical Co., Ltd.) are added in the solution, are then dripped successively
In addition stating prepared mixed solution and 1.75gTMAOH (TMAOH concentration：25 weight %, SACHEM Wuxi Co, Ltd.
System) and 13.69g water, obtain aqueous gel after stirring evenly.
By the aqueous gel after room temperature curing 24 hours, it is put into pressure vessel, while being warming up to 160 DEG C in 8 hours
It is rotated in baking oven, side carries out 6 days hydrothermal synthesis.After the hydrothermal synthesis reaction, cooling reaction solution, the crystalline substance that recycling filtering generates
Body.The crystal of recycling is 12 hours dry at 100 DEG C, then, the XRD of obtained molecular sieve powder is measured, as a result can
Enough synthesis are represented to be indicated such as with interplanar distance<Table 2>Shown in position have peak and relative intensity XRD spectrum ETL
Type molecular sieve 1.The XRD spectrum of the molecular sieve 1 is shown in Fig. 1.
<Table 2>
In turn, molecular sieve 1 is calcined 6 hours under 600 DEG C of air draught, by organic matter removal, obtains molecular sieve 2.
The XRD of thus obtained molecular sieve 2 is measured, as a result, represent and indicated such as with interplanar distance<Table 3>Shown in position
The ETL types molecular sieve 2 of XRD spectrum with peak and relative intensity.The XRD spectrum of the molecular sieve 2 is shown in Fig. 2.
<Table 3>
The result SAR ratios that the elemental constituent of molecular sieve 2 measures are 18.7.
The solid state nmr 29Si spectrums that molecular sieve 2 measures are shown in Fig. 3, wherein29Si composes the intensity at peak between -122~-107ppm
The intensity ratio at peak is 1.44 between -107~-100ppm.
BET measurement results are：Total specific surface area 331m2/ g, micropore specific area 255m2/ g, external surface area 76m2/
g。
The SEM of molecular sieve 2 is illustrated in Fig. 4.
The ETL type molecular sieves that this method is synthesized, micropore specific area higher, compared in the past using rubidium ion with
The ETL type molecular sieves that organic matter is synthesized as template, crystallinity are more preferable.
<Embodiment 2>
42.4g18- crown- 6- ethers (SIGMA-ALDRICH corporations) are dissolved in 28g water, are added in obtained solution
Add 5.8gNaOH (Tianjin chemical reagent supply and marketing corporation) and 16gCsOH solution (CsOH concentration：50 weight %, Aldrich
Corporation), it is stirred 3 hours at 80 DEG C, takes upper solution, obtain the mixed solution of crown ether-buck as a result,.
By the NaAlO of 0.42g2(purity：Al2O345 weight % of ＞ ＞, Tianjin recovery fine chemistry industry research are made) dissolving
After in 2.8g water, 3.38g aerosils (Shanghai simon Chemical Co., Ltd.) are added in the solution, are then dripped successively
Add above-mentioned the prepared mixed solutions of 9g and 1.75gTMAOH (TMAOH concentration：25 weight %, SACHEM Wuxi Co, Ltd.
System) and 13.69g water, obtain aqueous gel after stirring evenly.
By the aqueous gel after room temperature curing 24 hours, it is put into pressure vessel, while being warming up to 160 DEG C in 8 hours
It is rotated in baking oven, side carries out 6 days hydrothermal synthesis.After the hydrothermal synthesis reaction, cooling reaction solution, the crystalline substance that recycling filtering generates
Body.The crystal of recycling is 12 hours dry at 100 DEG C, then, the XRD of obtained molecular sieve powder is measured, as a result can
Enough synthesis are represented to be indicated such as with interplanar distance<Table 2>Shown in position have peak and relative intensity XRD spectrum ETL
Type molecular sieve 3.The XRD spectrum of the molecular sieve 3 is consistent with the XRD spectrum of molecular sieve 1.
In turn, molecular sieve 3 is calcined 6 hours under 600 DEG C of air draught, by organic matter removal, obtains molecular sieve 4.
The XRD of thus obtained molecular sieve 4 is measured, as a result, represent and indicated such as with interplanar distance<Table 3>Shown in position
The ETL types molecular sieve 4 of XRD spectrum with peak and relative intensity.The XRD diagram of the XRD spectrum and molecular sieve 2 of the molecular sieve 4
Spectrum is consistent.
The result SAR ratios that the elemental constituent of molecular sieve 4 measures are 19.9.
The solid state nmr that molecular sieve 4 measures29Si spectrums are shown in Fig. 5, wherein29Si composes the intensity at peak between -122~-107ppm
The intensity ratio at peak is 1.39 between -107~-100ppm.
BET measurement results are：Total specific surface area 378m2/ g, micropore specific area 273m2/ g, external surface area 105m2/
g。
The consistent appearance that the SEM figures of molecular sieve 4 and the SEM figures of molecular sieve 2 are shown.
The molecular sieve is equally compared to the previous ETL type molecules being synthesized as template with organic matter using rubidium ion
Micropore specific area higher is sieved, and ETL type molecular sieves are synthesized using the complex compound of crown ether and cesium ion and TMAOH jointly,
The crystallinity of molecular sieve is improved to a certain extent.
<Embodiment 3>
1.42gCsOH solution (CsOH concentration is added in 2.05g water：50 weight %, Aldrich system) and
0.27gNaOH (Tianjin chemical reagent supply and marketing corporation) is made into mixed solution.
By the NaAlO of 0.42g2(purity：Al2O345 weight % of ＞ ＞, Tianjin recovery fine chemistry industry research are made) and
After 0.2gNaF (Tianjin chemical reagent supply and marketing corporation) is dissolved in 2.8g water, 3.38g gas phase dioxies are added in the solution
SiClx (Shanghai simon Chemical Co., Ltd.), is then added dropwise above-mentioned prepared mixed solution and 1.75gTMAOH successively
(TMAOH concentration：25 weight %, SACHEM Wuxi Co, Ltd. systems) and 13.69g water, obtain aqueous gel after stirring evenly.
By the aqueous gel after room temperature curing 24 hours, it is put into pressure vessel, while being warming up to 160 DEG C in 8 hours
It is rotated in baking oven, side carries out 6 days hydrothermal synthesis.After the hydrothermal synthesis reaction, cooling reaction solution, the crystalline substance that recycling filtering generates
Body.The crystal of recycling is 12 hours dry at 100 DEG C, and then, the XRD of the molecular sieve powder to obtaining is measured, as a result
It can synthesize to represent and be indicated such as with interplanar distance<Table 2>Shown in position there is the XRD spectrum of peak and relative intensity
ETL types molecular sieve 5.The XRD spectrum of the molecular sieve 5 is consistent with the XRD spectrum of molecular sieve 1.
In turn, molecular sieve 5 is calcined 6 hours under 600 DEG C of air draught, by organic matter removal, obtains molecular sieve 6.
The XRD of thus obtained molecular sieve 6 is measured, as a result, represent and indicated such as with interplanar distance<Table 3>Shown in position
The ETL types molecular sieve 6 of XRD spectrum with peak and relative intensity.The XRD diagram of the XRD spectrum and molecular sieve 2 of the molecular sieve 6
Spectrum is consistent.
The result SAR ratios that the elemental constituent of molecular sieve 6 measures are 19.4.
The solid state nmr that molecular sieve 6 measures29Si spectrums are shown in Fig. 6, wherein29Si composes the intensity at peak between -122~-107ppm
The intensity ratio at peak is 1.33 between -107~-100ppm.
BET measurement results are：Total specific surface area 322m2/ g, micropore specific area 260m2/ g, external surface area 62m2/
g。
The consistent appearance that the SEM figures of molecular sieve 6 and the SEM figures of molecular sieve 2 are shown.
<Embodiment 4>
42.4g18- crown- 6- ethers (SIGMA-ALDRICH corporations) are dissolved in 28g water, are added in obtained solution
Add 5.8gNaOH (Tianjin chemical reagent supply and marketing corporation) and 16gCsOH solution (CsOH concentration：50 weight %, Aldrich
Corporation), it is stirred 3 hours at 70 DEG C, takes upper solution, obtain the mixed solution of crown ether-buck as a result,.
By the NaAlO2 (purity of 0.42g：Al2O345 weight % of ＞ ＞, Tianjin recovery fine chemistry industry research are made) dissolving
After in 2.8g water, 3.38g aerosils (Shanghai simon Chemical Co., Ltd.) are added in the solution, are then dripped successively
Add above-mentioned the prepared mixed solutions of 9g and 1.75gTMAOH (TMAOH concentration：25 weight %, SACHEM Wuxi Co, Ltd.
System) and 13.69g water, 0.24gHF (HF concentration is finally added dropwise：40 weight %, Tianjin Fu Yu Fine Chemical Co., Ltd system),
Aqueous gel is obtained after stirring evenly.
The aqueous gel is directly placed into pressure vessel, is rotated while being warming up in 160 DEG C of baking oven in 8 hours, Bian Jin
6 days hydrothermal synthesis of row.After the hydrothermal synthesis reaction, cooling reaction solution, the crystal that recycling filtering generates.By the crystal of recycling
Dry 12 hours at 100 DEG C, then, the XRD of obtained molecular sieve powder is measured, as a result can synthesize represent with
Interplanar distance indicates such as<Table 2>Shown in position have peak and relative intensity XRD spectrum ETL types molecular sieve 7.The molecule
The XRD spectrum of sieve 7 is consistent with the XRD spectrum of molecular sieve 1.
In turn, molecular sieve 7 is calcined 6 hours under 600 DEG C of air draught, by organic matter removal, obtains molecular sieve 8.
The XRD of thus obtained molecular sieve 8 is measured, as a result, represent and indicated such as with interplanar distance<Table 3>Shown in position
The ETL types molecular sieve 8 of XRD spectrum with peak and relative intensity.The XRD diagram of the XRD spectrum and molecular sieve 2 of the molecular sieve 8
Spectrum is consistent.
The result SAR ratios that the elemental constituent of molecular sieve 8 measures are 21.
The solid state nmr that molecular sieve 8 measures29Si spectrums are shown in Fig. 7, wherein29Si composes the intensity at peak between -122~-107ppm
The intensity ratio at peak is 1.8 between -107~-100ppm.
BET measurement results are：Total specific surface area 347m2/ g, micropore specific area 266m2/ g, external surface area 81m2/
g。
The SEM of molecular sieve 8 is illustrated in Fig. 8.
The molecular sieve is equally compared to the previous ETL type molecules being synthesized as template with organic matter using rubidium ion
Sifter device has micropore specific area higher, the more preferable feature of crystallinity.The molecular sieve both topographically has larger change simultaneously, by
The pattern of tip-like becomes in order to spherical, this is the pattern that FER type molecular sieves synthesized in document did not occur, this makes this
Molecular sieve has more purposes and characteristic.
<Embodiment 5>
42.4g18- crown- 6- ethers (SIGMA-ALDRICH corporations) are dissolved in 28g water, are added in obtained solution
Add 5.8gNaOH (Tianjin chemical reagent supply and marketing corporation) and 16gCsOH solution (CsOH concentration：50 weight %, Aldrich
Corporation), it is stirred 3 hours at 80 DEG C, takes upper solution, obtain the mixed solution of crown ether-buck as a result,.
By the NaAlO of 0.32g2(purity：Al2O345 weight % of ＞ ＞, Tianjin recovery fine chemistry industry research are made) and
After 0.8gNaF (Tianjin chemical reagent supply and marketing corporation) is dissolved in 2.8g water, 3.38g gas phase dioxies are added in the solution
9g above-mentioned prepared mixed solution and 1.75gTMAOH is then added dropwise in SiClx (Shanghai simon Chemical Co., Ltd.) successively
(TMAOH concentration：25 weight %, SACHEM Wuxi Co, Ltd. systems) and 13.69g water, it finally adds and is obtained in 0.17g embodiments 4
The molecular sieve 10 obtained does crystal seed, and aqueous gel is obtained after stirring evenly.
By the aqueous gel after room temperature curing 24 hours, it is put into pressure vessel, while being warming up to 160 DEG C in 8 hours
It is rotated in baking oven, side carries out 6 days hydrothermal synthesis.After the hydrothermal synthesis reaction, cooling reaction solution, the crystalline substance that recycling filtering generates
Body.The crystal of recycling is 12 hours dry at 100 DEG C, then, the XRD of obtained molecular sieve powder is measured, as a result can
Enough synthesis are represented to be indicated such as with interplanar distance<Table 2>Shown in position have peak and relative intensity XRD spectrum ETL
Type molecular sieve 9.The XRD spectrum of the XRD spectrum molecular sieve 1 of the molecular sieve 9 is consistent.
In turn, molecular sieve 9 is calcined 6 hours under 600 DEG C of air draught, by organic matter removal, obtains molecular sieve 10.
The XRD of thus obtained molecular sieve 10 is measured, as a result, represent and indicated such as with interplanar distance<Table 3>Shown in position
Set the ETL types molecular sieve 10 of the XRD spectrum with peak and relative intensity.The XRD of the XRD spectrum molecular sieve 2 of the molecular sieve 10
Collection of illustrative plates is consistent.
The result SAR ratios that the elemental constituent of molecular sieve 10 measures are 25.
The solid state nmr that molecular sieve 10 measures29Si spectrums are shown in Fig. 9, wherein29Peak is strong between -122~-107ppm of Si spectrums
The intensity ratio at peak is 2.1 between degree and -107~-100ppm.
BET measurement results are：Total specific surface area 351m2/ g, micropore specific area 263m2/ g, external surface area 88m2/
g。
The SEM of molecular sieve 10 is illustrated in Figure 10.
The molecular sieve is equally compared to the previous ETL type molecules being synthesized as template with organic matter using rubidium ion
Sifter device has micropore specific area higher, the more preferable feature of crystallinity.The molecular sieve has the pattern of block simultaneously.This pattern is same
Sample is unexistent pattern in document.
<Embodiment 6>
NaAlO will be added2Quality be changed to 0.255g, can synthesize higher sial with method same as Example 5
The molecular sieve 11 of ratio.With 5 identical method organics removal of embodiment, molecular sieve 12 is obtained.
The result SAR ratios that the elemental constituent of molecular sieve 12 measures are 31.
The solid state nmr that molecular sieve 12 measures29Si spectrums are shown in Figure 11, wherein29Peak is strong between -122~-107ppm of Si spectrums
The intensity ratio at peak is 2.3 between degree and -107~-100ppm.
BET measurement results are：Total specific surface area 340m2/ g, micropore specific area 288m2/ g, external surface area 52m2/
g。
The SEM of molecular sieve 12 is illustrated in Figure 12.
<Comparative example 1>
In aqueous gel, TMAOH is not added, remaining fails to synthesize ETL type molecules according to 1 same method of embodiment
Sieve.
<Comparative example 2>
In aqueous gel, TMAOH is not added, remaining fails to synthesize ETL type molecules according to 2 same method of embodiment
Sieve.
<Comparative example 3>
In aqueous gel, cesium ion is not added, remaining fails to synthesize ETL types point according to 2 same method of embodiment
Son sieve.
Claims (9)
1. a kind of ETL types molecular sieve uses29When Si solid state nmrs measure, the intensity and -107 at peak between -122~-107ppm
The intensity ratio at peak is 1.33 or more between~-100ppm.
2. ETL types molecular sieve according to claim 1, micropore specific area 220m2/ g or more.
3. a kind of method of manufacture ETL type molecular sieves, which is characterized in that aqueous gel is carried out hydrothermal synthesis, the aqueous gel
The raw material and cesium ion and quaternary ammonium salt of raw material and triad X atoms including at least quadrivalent element Y atoms.
4. the method for manufacture ETL type molecular sieves according to claim 3, wherein X includes at least aluminium.
5. according to the method for the manufacture ETL type molecular sieves described in claim 3~4, wherein Y includes at least silicon.
6. according to the method for the manufacture ETL type molecular sieves described in claim 3~5, wherein contain crown ether-like in aqueous gel
Close object.
7. it is according to claim 6 manufacture ETL type molecular sieves method, wherein crown ether compound be 12- be preced with 4 ethers,
In 15- crown- 5- ethers, 18- crown- 6- ethers, 24- crown- 8- ethers, dibenzo-18 crown-6-ether, cave ether [2.2] or cave ether [2.2.2]
It is one or more of.
8. according to the method for the manufacture ETL type molecular sieves described in claim 3~7, wherein quaternary ammonium salt is tetramethyl hydroxide
One kind in ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dimethyl diethyl ammonium hydroxide
Or it is several.
9. according to the method for the manufacture ETL type molecular sieves described in claim 3~8, wherein contain fluorine ion in aqueous gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810396244.4A CN108439425A (en) | 2018-04-27 | 2018-04-27 | A kind of ETL types molecular sieve and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810396244.4A CN108439425A (en) | 2018-04-27 | 2018-04-27 | A kind of ETL types molecular sieve and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108439425A true CN108439425A (en) | 2018-08-24 |
Family
ID=63201914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810396244.4A Pending CN108439425A (en) | 2018-04-27 | 2018-04-27 | A kind of ETL types molecular sieve and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108439425A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348661A (en) * | 2018-12-21 | 2020-06-30 | 株式会社模范 | ETL molecular sieve, metal modified ETL molecular sieve and application thereof in carbonylation reaction |
| CN112892242A (en) * | 2021-01-29 | 2021-06-04 | 江西师范大学 | High-flux mordenite molecular sieve membrane and preparation method and application thereof |
| WO2022190793A1 (en) * | 2021-03-10 | 2022-09-15 | 日本碍子株式会社 | Zeolite membrane complex, separation device, membrane reaction device, and method for manufacturing zeolite membrane complex |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4581211A (en) * | 1982-10-04 | 1986-04-08 | Imperial Chemical Industries Plc | Zeolite EU-12 |
| CN101024499A (en) * | 2007-02-02 | 2007-08-29 | 华东理工大学 | Method for synthesizing MWW mole cular sieve |
| US20120095276A1 (en) * | 2010-10-13 | 2012-04-19 | Zhang Zhizhi | Nu-85 molecular sieve having a large pore volume and processes for preparing the same |
| CN102452665A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing layered zeolite with MWW structure |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
-
2018
- 2018-04-27 CN CN201810396244.4A patent/CN108439425A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4581211A (en) * | 1982-10-04 | 1986-04-08 | Imperial Chemical Industries Plc | Zeolite EU-12 |
| CN101024499A (en) * | 2007-02-02 | 2007-08-29 | 华东理工大学 | Method for synthesizing MWW mole cular sieve |
| US20120095276A1 (en) * | 2010-10-13 | 2012-04-19 | Zhang Zhizhi | Nu-85 molecular sieve having a large pore volume and processes for preparing the same |
| CN102452665A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing layered zeolite with MWW structure |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
Non-Patent Citations (3)
| Title |
|---|
| ABRAHAM ARAYA ET AL.: "Synthesis, properties, and catalytic", 《ZEOLITES》 * |
| QUANLI KE ET AL.: "Targeted Synthesis of Ultrastable High-Silica RHO Zeolite Through", 《CHEMISTRY-AN ASIAN JOURNAL》 * |
| 杨继生: "《表面活性剂原理与应用》", 31 December 2012, 东南大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348661A (en) * | 2018-12-21 | 2020-06-30 | 株式会社模范 | ETL molecular sieve, metal modified ETL molecular sieve and application thereof in carbonylation reaction |
| CN112892242A (en) * | 2021-01-29 | 2021-06-04 | 江西师范大学 | High-flux mordenite molecular sieve membrane and preparation method and application thereof |
| CN112892242B (en) * | 2021-01-29 | 2022-08-02 | 江西师范大学 | High-flux mordenite molecular sieve membrane and preparation method and application thereof |
| WO2022190793A1 (en) * | 2021-03-10 | 2022-09-15 | 日本碍子株式会社 | Zeolite membrane complex, separation device, membrane reaction device, and method for manufacturing zeolite membrane complex |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI490167B (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| CN101249968B (en) | Method for synthesizing Beta molecular sieve by organic-free template | |
| US10646847B2 (en) | GIS-type zeolite | |
| JPH02221115A (en) | Zeolite and its manufacture | |
| JP6835869B2 (en) | Synthesis of molecular sieve SSZ-98 | |
| CN102712489A (en) | [Beta] zeolite and method for producing same | |
| CN108439425A (en) | A kind of ETL types molecular sieve and its manufacturing method | |
| JPH111319A (en) | Ers-10 zeolite and its production | |
| JP6968406B2 (en) | Method for manufacturing KFI-type zeolite | |
| CN107934982B (en) | A kind of macropore silicate molecular sieve and preparation method thereof | |
| CN104428248B (en) | The manufacture method of MAZ type zeolite | |
| JP2020066564A (en) | Rho type zeolite and manufacturing method therefor | |
| CN110300729A (en) | Molecular sieve SSZ-111, its synthesis and purposes | |
| CN109694090B (en) | SCM-13 molecular sieve and preparation method thereof | |
| CN105800644A (en) | Method for producing MTW-type zeolite | |
| JP4470003B2 (en) | High silica mordenite and its synthesis method | |
| JP6727884B2 (en) | ZSM-5 type zeolite having almond-like shape and method for producing the same | |
| CN111186846A (en) | ITH structure silicon-aluminum molecular sieve and preparation method thereof | |
| CN109911913A (en) | Prepare the method and BEA type molecular sieve of BEA type molecular sieve | |
| EP2837597B1 (en) | Method for producing pau zeolite | |
| JP7438733B2 (en) | STW type zeolite and its manufacturing method | |
| CN113830781B (en) | EUO molecular sieve and synthesis method and application thereof | |
| CN109694084A (en) | The preparation method of DOH zeolite molecular sieve | |
| JP5597867B2 (en) | Method for producing crystalline porous inorganic oxide material | |
| CN112537781B (en) | Molecular sieve with TON structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180824 |