CN108529641A - A kind of zeolite molecular sieve and preparation method thereof with multistage pore canal - Google Patents

A kind of zeolite molecular sieve and preparation method thereof with multistage pore canal Download PDF

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CN108529641A
CN108529641A CN201810609223.6A CN201810609223A CN108529641A CN 108529641 A CN108529641 A CN 108529641A CN 201810609223 A CN201810609223 A CN 201810609223A CN 108529641 A CN108529641 A CN 108529641A
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molecular sieve
zeolite molecular
preparation
pore canal
ammonium
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CN108529641B (en
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梁洁
侯锐
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Beihang University
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    • 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
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • 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
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

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  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a kind of zeolite molecular sieve and preparation method thereof with multistage pore canal, belongs to zeolite molecular sieve synthetic technology field.Silicon source, silicon source and water are mixed evenly first for the preparation method, then organic quaternary ammonium salt template is added dropwise and constantly stirs to get aluminosilicate gels；Then the aluminosilicate gels are transferred in hydrothermal reaction kettle, hydrothermal crystallizing.Finally by hydrothermal crystallizing product centrifuge twice afterwards dry to get to the present invention zeolite molecular sieve.The zeolite molecular sieve that the present invention is prepared has multi-stage artery structure, is embodied in microporous mesoporous structure.Compared with prior art, the zeolite molecular sieve that the present invention obtains is a kind of novel zeolite molecular sieve, has some superiority in fields such as selective absorption, catalysis.

Description

A kind of zeolite molecular sieve and preparation method thereof with multistage pore canal
Technical field
The invention belongs to zeolite molecular sieve synthetic technology fields, are related to a kind of novel alumino-silicate with multistage pore canal The preparation method and its property representation of zeolite molecular sieve.
Background technology
Zeolite molecular sieve is due to having many advantages, such as higher thermal stability, uniform pore-size distribution, larger specific surface area It is widely used in the fields such as petrochemical industry, catalysis, environmental protection.Hydrothermal synthesis method is that synthesis zeolite is most effective at present Method.The method is specially to be mixed in a certain ratio silicon source, silicon source, organic formwork agent, mineralizer and solvent to be formed uniformly Gel pass through specific chemical reactive synthesis zeolite molecular sieve under certain temperature and pressure.
In the synthesis of zeolite molecular sieve, template often plays a crucial role.In recent years, in order to obtain novelty It is zeolite structured, people tend to select complicated, rigid organic quaternary ammonium salt ion as template.These are complicated Quaternary ammonium salt had both improved the synthesis cost of New-type Zeolite Molecular Sieves, also limited some zeolites with preferable property in practical work Application in industry.
Invention content
It is an object of the invention to prepare a kind of novel aluminosilicate zeolite molecular sieve with multistage pore canal and its Preparation method, specifically by using the simple quaternary ammonium salt template zeolite molecular sieve novel as Material synthesis.
To achieve the above object, the preparation method of a kind of novel zeolite molecular sieve with multistage pore canal of the invention, Specifically comprise the following steps：
(1) silicon source, silicon source and water are mixed evenly, then organic quaternary ammonium salt template is added dropwise and is stirred continuously Obtain aluminosilicate gels.Silicon source in the aluminosilicate gels, silicon source, the molar ratio of organic quaternary ammonium salt template and water are SiO2：Al2O3：Organic quaternary ammonium salt template：H2O=(0.65~0.95):(0.05~0.35):(0.2~0.75):(5~ 20)。
(2) aluminosilicate gels are transferred in hydrothermal reaction kettle, the hydrothermal crystallizing 3 under the conditions of 100~175 DEG C ~30 days.
(3) it is centrifuged after being cooled to room temperature (2) step products therefrom, obtained sediment is washed with deionized water It is centrifuged again after washing, can be obtained zeolite molecular sieve after dry.
Wherein, waterglass, unformed SiO may be selected in silicon source2In powder, Ludox and ethyl orthosilicate any one or Two or more, one or both of sodium metaaluminate, aluminium isopropoxide, aluminium oxide and amorphous hydroted alumina powder may be selected in silicon source More than, organic quaternary ammonium salt template can be 3-methyl cyclohexanol ammonium, dimethyl ethyl hexamethylene ammonium, diethylmethyl hexamethylene ammonium, diformazan Base cyclohexyl ammonium, diethylpropyl hexamethylene ammonium, trimethyl isopropyl ammonium, dimethyl ethyl isopropyl ammonium, diethylmethyl are different One or more of propyl ammonium, dimethyl propyl isopropyl ammonium or diethylpropyl isopropyl ammonium.
Preferred molar ratio is SiO in step (1)2：Al2O3：Organic quaternary ammonium salt template：H2O=(0.75~0.9): (0.05~0.15):(0.3~0.6):(10~20).
Preferred hydrothermal crystallizing temperature is 120~150 DEG C in step (2), and the time is 3~18 days.
The zeolite molecular sieve being prepared by the above method has multi-stage artery structure, is embodied in micropore- Meso-hole structure.
Compared with prior art, the present invention haing the following advantages：
(1) zeolite molecular sieve that the present invention obtains is a kind of novel zeolite molecular sieve, passes through its XRD spectrum and current state 238 kinds of existing molecular sieve Comparative results that border molecular sieve association is confirmed are it is found that finally obtained zeolite molecular sieve is a kind of complete New zeolite molecular sieve has good development prospect.
(2) New-type Zeolite Molecular Sieves prepared by the present invention are by the way that it is with multi-stage artery structure known to structural characterization, specifically Micropore-mesopore structure is shown as, there is some superiority in fields such as selective absorption, catalysis.
Description of the drawings
Fig. 1 is the XRD diffraction patterns for the zeolite molecular sieve that embodiment 1 is prepared.
Fig. 2 is the XRD diffraction patterns for the zeolite molecular sieve that embodiment 2 is prepared.
Fig. 3 is the XRD diffraction patterns for the zeolite molecular sieve that embodiment 3 is prepared.
Fig. 4 is the XRD diffraction patterns for the zeolite molecular sieve that embodiment 4 is prepared.
Fig. 5 is the N for the zeolite molecular sieve that embodiment 4 is prepared2Physical absorption balances isothermal chart.
Fig. 6 is the graph of pore diameter distribution for the zeolite molecular sieve that embodiment 4 is prepared.
Specific implementation mode
Below in conjunction with the accompanying drawings and embodiment carries out the present invention detailed complete narration, but the invention is not limited in realities Apply example.Those of ordinary skill in the art's obtained all other embodiment without making creative work, Belong to the range that the present invention is protected.
Embodiment 1
A kind of preparation method of the novel aluminosilicate zeolite molecular sieve with multistage pore canal, includes the following steps：
(1) by the unformed SiO of 0.306g2Powder, 0.07g amorphous hydroted alumina powder, 1.622g water and 1ml templates It is evenly stirred until to form aluminosilicate gels.Selected template is 3-methyl cyclohexanol ammonium.
(2) aluminosilicate gels are transferred in hydrothermal reaction kettle, the hydrothermal crystallizing 30 days under the conditions of 100 DEG C.
(3) be centrifuged after being cooled to room temperature product, obtained centrifugation product be washed with deionized after again It centrifuges, can be obtained zeolite molecular sieve after dry.
XRD as shown in Figure 1 is the results show that the zeolite molecular sieve prepared by embodiment 1 is located at characteristic peak 7.52 °, 8.84 °, 18.9 °, 20.92 ° and 22.96 °, N further is done to preparation-obtained zeolite molecular sieve product2Full micropore Physical absorption is tested, it was demonstrated that obtained zeolite molecular sieve has the multistage pore canal of micropore-mesopore, micro-pore diameter Mesopore diameter
Embodiment 2
A kind of preparation method of the novel aluminosilicate zeolite molecular sieve with multistage pore canal, includes the following steps：
(1) it is evenly stirred until 1.324g Ludox, 0.049g sodium metaaluminates, 1.622g water and 1ml templates to form silicon Aluminate gel.Selected template chooses dimethyl propyl hexamethylene ammonium.
(2) aluminosilicate gels are transferred in hydrothermal reaction kettle, the hydrothermal crystallizing 3 days under the conditions of 170 DEG C.
(3) it is once centrifuged after being cooled to room temperature product after hydrothermal crystallizing, obtained primary centrifugation product is used It is centrifugally separating to obtain secondary centrifuging product again after deionized water washing, zeolite point is can be obtained after secondary centrifuging product is dried Son sieve.
The zeolite molecular sieve has the multi-stage artery structure of micropore-mesopore, and XRD as shown in Figure 2 is as a result, the zeolite There is molecular sieve characteristic peak to be located at 7.52 °, 8.84 °, 18.9 °, 20.92 ° and 22.96 °.Further to preparation-obtained Zeolite molecular sieve product is N2Full micropore physical absorption test, obtained zeolite molecular sieve have the multi-stage porous of micropore-mesopore Road, micro-pore diameterMesopore diameter
Embodiment 3
(1) by 1.063g ethyl orthosilicates, 0.092g aluminium oxide, 1.567g water is evenly stirred until to be formed with 1ml templates Aluminosilicate gels.Selected template chooses trimethyl isopropyl ammonium.
(2) aluminosilicate gels are transferred in hydrothermal reaction kettle, the hydrothermal crystallizing 21 days under the conditions of 120 DEG C.
(3) it is centrifuged after being cooled to room temperature hydrothermal crystallizing product, obtained centrifugation product is washed with deionized water It is centrifuged again after washing, can be obtained zeolite molecular sieve after the drying of secondary centrifuging product.
XRD as shown in Figure 3 is the results show that the zeolite molecular sieve prepared by embodiment 1 is located at characteristic peak 7.52 °, 8.84 °, 18.9 °, 20.92 ° and 22.96 °, N further is done to preparation-obtained zeolite molecular sieve product2Full micropore Physical absorption is tested, and obtained zeolite molecular sieve has the multistage pore canal of micropore-mesopore, micro-pore diameterIt is mesoporous straight Diameter
Embodiment 4
(1) it is evenly stirred until 1.125g waterglass, 0.049g sodium metaaluminates, 1.135g water and 1ml templates to form silicon Aluminate gel.Selected template chooses dimethyl ethyl isopropyl ammonium.
(2) aluminosilicate gels are transferred in hydrothermal reaction kettle, the hydrothermal crystallizing 16 days under the conditions of 150 DEG C.
(3) it is centrifuged after being cooled to room temperature hydrothermal crystallizing product, after obtained product is washed with deionized It centrifuges again, can be obtained zeolite molecular sieve after dry.
XRD as shown in Figure 4 is the results show that the zeolite molecular sieve prepared by embodiment 1 is located at characteristic peak 7.52 °, 8.84 °, 18.9 °, 20.92 ° and 22.96 °, N further is done to preparation-obtained zeolite molecular sieve product2Full micropore Physical absorption is tested, and obtained zeolite molecular sieve has the multistage pore canal of micropore-mesopore, micro-pore diameterIt is mesoporous straight Diameter
The 238 kinds of existing molecular sieve XRD spectrums confirmed by comparison International Molecular sieve association are it has been confirmed that the present invention is real Apply example preparation zeolite molecular sieve be a kind of New-type Zeolite Molecular Sieves, characteristic peak be located at 7.52 °, 8.84 °, 18.9 °, 20.92 ° and 22.96 °, referring to Fig. 1~Fig. 4.
Fig. 5 show the N of the zeolite molecular sieve of the preparation of embodiment 42Physical absorption balances isothermal chart, the adsorption equilibrium isothermal Line belongs to I type thermoisopleth, should belong to microcellular structure, while hysteresis loop occurs at 0.7P ° -1P ° and understanding it with mesoporous property Matter, the zeolite molecular sieve is the novel molecular sieve of the multistage pore canal with micropore-mesopore in summary.
From fig. 6 it can be seen that the micropore of the zeolite molecular sieve synthesized by embodiment 4 is mainly distributed onIt is mesoporous main It is distributed in
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those familiar with the art in the technical scope disclosed by the present invention, all answer by the change or replacement that can be readily occurred in It is included within the scope of the present invention.Therefore, protection scope of the present invention should be with the scope of the claims It is accurate.

Claims (6)

1. a kind of preparation method of the zeolite molecular sieve with multistage pore canal, it is characterised in that：The preparation method is specifically wrapped Include following steps,
Step 1: silicon source, silicon source and water are mixed evenly, then organic quaternary ammonium salt template is added dropwise and is stirred continuously Obtain aluminosilicate gels；Silicon source in the aluminosilicate gels, silicon source, the molar ratio of organic quaternary ammonium salt template and water are SiO2:Al2O3:Organic quaternary ammonium salt template:H2O=(0.65~0.95):(0.05~0.35):(0.2~0.75):(5~ 20)。
Step 2: the aluminosilicate gels are transferred in hydrothermal reaction kettle, the hydrothermal crystallizing 3 under the conditions of 100~175 DEG C ~30 days；
Step 3: being centrifuged after step 2 products therefrom is cooled to room temperature, obtained sediment is washed with deionized water It is centrifuged again after washing, zeolite molecular sieve is obtained after dry.
2. a kind of preparation method of zeolite molecular sieve with multistage pore canal according to claim 1, it is characterised in that：Silicon Source selects waterglass, unformed SiO2In powder, Ludox and ethyl orthosilicate any one or it is two or more；Silicon source selects One or more of sodium metaaluminate, aluminium isopropoxide, aluminium oxide and amorphous hydroted alumina powder；Organic quaternary ammonium salt template Agent is 3-methyl cyclohexanol ammonium, dimethyl ethyl hexamethylene ammonium, diethylmethyl hexamethylene ammonium, dimethyl propyl hexamethylene ammonium, diethyl third The own ammonium of basic ring, trimethyl isopropyl ammonium, dimethyl ethyl isopropyl ammonium, diethylmethyl isopropyl ammonium, dimethyl propyl isopropyl One or more of base ammonium or diethylpropyl isopropyl ammonium.
3. a kind of preparation method of zeolite molecular sieve with multistage pore canal according to claim 1, it is characterised in that：Step In rapid one, molar ratio SiO2：Al2O3：Organic quaternary ammonium salt template：H2O=(0.75~0.9):(0.05~0.15):(0.3 ~0.6):(10~20).
4. a kind of preparation method of zeolite molecular sieve with multistage pore canal according to claim 1, it is characterised in that：Step In rapid two, hydrothermal crystallizing temperature is 120~150 DEG C, and the time is 3~18 days.
5. a kind of zeolite molecular sieve with multistage pore canal, it is characterised in that：The zeolite molecular sieve has multistage pore canal knot Structure is embodied in micropore-mesopore structure.
6. a kind of zeolite molecular sieve with multistage pore canal according to claim 5, it is characterised in that：The zeolite point Sub- sifter device has characteristic peak to be located at 7.52 °, 8.84 °, 13.92 °, 18.9 °, 20.92 ° and 22.96 °, micro- in zeolite molecular sieve Bore diaMesopore diameter
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110054197A (en) * 2019-04-11 2019-07-26 北京航空航天大学 Zeolite molecular sieve and preparation method thereof, radionuclide strontium adsorbing composition
WO2021203963A1 (en) * 2020-04-07 2021-10-14 Basf Se Zeolite of a new framework structure type and production thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102826564A (en) * 2012-08-14 2012-12-19 华南理工大学 Preparation method for Beta zeolite molecular sieve with hierarchical porous structure
CN103214003A (en) * 2013-04-09 2013-07-24 华南理工大学 Mesoporous Y-type zeolite molecular sieve and preparation method thereof
CN107572547A (en) * 2017-08-30 2018-01-12 天津大学 A kind of synthetic method of multilevel ordered mesoporous Si-Al molecular sieve

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102826564A (en) * 2012-08-14 2012-12-19 华南理工大学 Preparation method for Beta zeolite molecular sieve with hierarchical porous structure
CN103214003A (en) * 2013-04-09 2013-07-24 华南理工大学 Mesoporous Y-type zeolite molecular sieve and preparation method thereof
CN107572547A (en) * 2017-08-30 2018-01-12 天津大学 A kind of synthetic method of multilevel ordered mesoporous Si-Al molecular sieve

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110054197A (en) * 2019-04-11 2019-07-26 北京航空航天大学 Zeolite molecular sieve and preparation method thereof, radionuclide strontium adsorbing composition
WO2021203963A1 (en) * 2020-04-07 2021-10-14 Basf Se Zeolite of a new framework structure type and production thereof

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