CN109626393A - A kind of preparation method for the SUZ-4 that hedgehog is spherical - Google Patents
A kind of preparation method for the SUZ-4 that hedgehog is spherical Download PDFInfo
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- 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
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- 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
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Abstract
The object of the invention provides a kind of preparation method using cheap new type formwork agent synthesis SUZ-4 molecular sieve.Sial mixed glue solution is prepared first, is subsequently added into template ethylenediamine (EDA) and the mixing of ethylenimine (CHA) arbitrary proportion.It is then added to the growth of reaction kettle high temperature crystallization；Wherein crystallization temperature are as follows: 130 DEG C -170 DEG C, crystallization time are as follows: 2 days -5 days.Finally synthesize the spherical SUZ-4 molecular sieve of the hedgehog generated by cheap template.The method and process that SUZ-4 molecular sieve is synthesized involved in the present invention simply, is just gone, and not only greatly reduces the synthesis cost of the molecular sieve, the spherical SUZ-4 molecular sieve of hedgehog is also obtained.
Description
Technical field
The invention belongs to silicon, the technical fields of aluminum oxide molecular sieve, and in particular to the two kinds of moulds utilized inexpensively
Plate agent is mixed with the spherical SUZ-4 of hedgehog.
Technical background
1992, Britain's BP company first discovery simultaneously prepared SUZ-4 molecular sieve.Barri etc. is containing Si02,Al203,
It is template, synthesis that organic matter tetraethyl hydroxide, which is added, by (TEAOH) and quinuclidine in the Primogel of KOH and NaOH mixture
SUZ-4 molecular sieve is gone out.This is the synthesis for the first time of the molecular sieve, but the repeatability of the synthetic method is poor, in certain journey
The research and development of SUZ-4 molecular sieve is hindered on degree.
1999, the researchs such as Asensi improved the repeatability of SUZ-4 Zeolite synthesis, they are in 150 DEG C of temperature
It is lower that new Primogel has been used to match 21.2Si0 one by one2:Al203:7.9KOH:2.6TEAOH:498.6H20 (molar ratio),
In there is no NaOH and quinuclidine, this is because they think Na ion not and are the necessary species of SUZ-4 synthesis, and its presence
The generation of competition phase MOR can be induced；What quinuclidine equally nor is it necessary that, system still can be under the template action of TEAOH
Generate SUZ-4 molecular sieve.In this way, the repeatability of the route is good, composite result is reliable, and become that follow-up study uses always matches
Than the discovery of the novelty has greatly pushed the development of SUZ-4 Zeolite synthesis.
2000, Paik etc. used Et6-diquat-5 as template and has synthesized silica alumina ratio (Si/A1) larger (8.2)
SUZ-4 molecular sieve, they are it is thought that result caused by organic macromolecule.
So far, do not occurred synthesizing new type formwork agent the report of SUZ-4 Zeolite synthesis again.
The application is with reference to following documents and full text introduces.
[1]Barri,S.A.I.,“Crystalline(metallo)silicates and germanates-SUZ-4”,
US Pat.5118483(1992).
[2]Asensi,M.A.,Camblor,M.A.,Martinez,A.,“Zeolite SUZ-4:Re-producible
synthesis,physicochemical characterization and catalytic evaluation for the
skeletal isomerization of n-butenes”,Micropor.Mesopor.Mater.,28,427–436
(1999).
[3]W.C.Paik,C.H.Shin,S.B.Hong,J.Chem.Soc.,Chem.Commun.(2000)1609.
Summary of the invention
The present invention provides a kind of SUZ-4 molecular sieve spherical with hedgehog, and using described in new type formwork agent synthesis
The method of SUZ-4 molecular sieve.
The method for synthesizing the SUZ-4 molecular sieve using new type formwork agent includes: to prepare sial mixed glue solution first,
It is subsequently added into template ethylenediamine (EDA) and ethylenimine (CHA) mixing；It is then added to the growth of reaction kettle high temperature crystallization；Its
Middle crystallization temperature are as follows: 130 DEG C -170 DEG C, crystallization time are as follows: 2 days -5 days；Finally obtain the spherical SUZ-4 molecule of the hedgehog
Sieve.
Preferably, the preparation process of the silicon-aluminum sol includes: to add water to be mixed into a solution silicon source and KOH first, by
Silicon source and double template are mixed into b solution；Then a solution and b solution are sufficiently stirred to obtain uniform sial mixed sols.
Preferably, the silicon source is that one of silica solution, waterglass, white carbon black or arbitrary proportion mix, the aluminium
Source is that the silicon source is one of aluminium powder, boehmite, aluminium hydroxide, aluminium isopropoxide, aluminum nitrate, aluminum sulfate or appoints
The mixing of meaning ratio.
Preferably, the crystallization temperature is 140 DEG C -160 DEG C, crystallization time are as follows: 3 days -5 days.
Preferably, the molar ratio of double template ethylenediamine (EDA) and ethylenimine (CHA) is (1~10): (1~10).
Preferably, by crystallization product by washing, dry and roasting.Wherein drying temperature is 120 DEG C, the time 4 hours, roasting
Burning temperature is 550 DEG C, the time 6 hours.
Preferably, each raw material initial molar ratio in preparation method are as follows: Al2O3:SiO2:KOH:EDA:CHA:H2O=1:(15
~30): (5~20): (1~10): (1~10): (100~2500).
Compared with prior art, the invention is characterized in that: utilize relatively inexpensive ethylenediamine (EDA) and ethylenimine
(CHA) SUZ-4 molecular sieve is synthesized as double template, greatly reduced and production cost, be conducive to industrial mass production.And
And there is particularity using the SUZ-4 Molecular Sieve Morphology that double template is synthesized.Following example makes into one the present invention
The explanation of step.
Detailed description of the invention:
Fig. 1 is the XRD spectra of 1 synthetic sample of example.
Fig. 2 is the XRD spectra of 2 synthetic sample of example.
Fig. 3 is the scanning electron microscope (SEM) photograph of 2 synthetic sample of example.
Fig. 4 is the XRD spectra of 5 synthetic sample of example.
Fig. 5 is the XRD spectra of 7 synthetic sample of example.
Implementation method of the invention:
Embodiment 1
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30.01g silica solution (40%), 2.55g ethylenediamine, 6.01g cyclohexylamine are added 30g deionized water and mixed
It stirs evenly to form solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is shifted
Into 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample passes through
Washing, 120 DEG C of dryings, 550 DEG C of roasting 6h obtain SUZ-4 molecular sieve, crystallinity 85%.Its XRD spectra is shown in attached drawing 1.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:7EDA:10CHA:798H2O
Embodiment 2
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30.01g silica solution (40%), 2.19g ethylenediamine, 6.01g cyclohexylamine are added 30g deionized water and mixed
It stirs evenly to form solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is shifted
Into 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample passes through
Washing, 120 DEG C of dryings, 550 DEG C of roasting 6h obtain pure SUZ-4 molecular sieve, crystallinity 98%, and pass through x-ray fluorescence light
It is 15.6 that spectrum analysis instrument, which measures Si/Al,.Attached drawing 2 gives the XRD spectra of sample obtained by this example.Attached drawing 3 gives this example
The SEM of gained sample schemes.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:6EDA:10CHA:798H2O
Embodiment 3
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30.01g silica solution (40%), 1.82g ethylenediamine, 6.01g cyclohexylamine are added 30g deionized water and mixed
It stirs evenly to form solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is shifted
Into 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample passes through
Washing, 120 DEG C of dryings, 550 DEG C of roasting 6h, the sample spectrogram of the experiment is on an equal basis in example 2, and only crystallinity is 80%.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:5EDA:10CHA:798H2O
Embodiment 4
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30.01g silica solution (40%), 1.09g ethylenediamine, 6.01g cyclohexylamine are added 30g deionized water and mixed
It stirs evenly to form solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is shifted
Into 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample passes through
Washing, 120 DEG C of dryings, 550 DEG C of roasting 6h, the sample spectrogram of the experiment is on an equal basis in example 2, and only crystallinity is 74%.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:3EDA:10CHA:798H2O
Embodiment 5
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30.01g silica solution (40%), 3.28g ethylenediamine, 6.01g cyclohexylamine are added 30g deionized water and mixed
It stirs evenly to form solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is shifted
Into 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample passes through
Washing, 120 DEG C of dryings, 550 DEG C of roasting 6h, the characteristic peak of sample start the MOR that makes the transition.Attached drawing 4 gives sample obtained by this example
XRD spectra.Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:9EDA:10CHA:798H2O
Embodiment 6
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30.01g silica solution (40%), 3.64g ethylenediamine, 6.01g cyclohexylamine are added 30g deionized water and mixed
It stirs evenly to form solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is shifted
Into 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample passes through
Washing, 120 DEG C of dryings, 550 DEG C of roasting 6h, the sample spectrogram of the experiment is on an equal basis in example 5.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:10EDA:10CHA:798H2O
Embodiment 7
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30g deionized water is added in 30.01g silica solution (40%), 3.64g ethylenediamine to be mixed evenly to be formed
Solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is transferred to 170ml polytetrafluoro
In ethylene reaction kettle, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.For gained sample by washing, 120 DEG C dry
Dry, 550 DEG C of roasting 6h obtain pure SUZ-4 molecular sieve.The characteristic peak of sample is MFI series.Attached drawing 5 gives this example institute
Obtain the XRD spectra of sample.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:10EDA:0CHA:798H2O
Embodiment 8
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30g deionized water is added in 30.01g silica solution (40%), 6.01g cyclohexylamine to be mixed evenly to be formed
Solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is transferred to 170ml polytetrafluoro
In ethylene reaction kettle, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.For gained sample by washing, 120 DEG C dry
Dry, 550 DEG C of roasting 6h obtain the pure MFI spectrogram that obtains such as example 7.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:0EDA:10CHA:798H2O
Embodiment 9
The operating procedure of example 2 is repeated, the difference is that crystallization time is 3 days, the SUZ-4 molecular sieve knot synthesized
Brilliant degree is 85%.
Embodiment 10
The operating procedure of example 2 is repeated, the difference is that crystallization time is 5 days, the SUZ-4 molecular sieve knot synthesized
Brilliant degree is 100%.
Embodiment 11
The operating procedure of example 2 is repeated, the difference is that crystallization temperature is 130 DEG C, the SUZ-4 molecular sieve being synthesized
Crystallinity is 79%.
Embodiment 12
The operating procedure of example 2 is repeated, the difference is that crystallization temperature is 140 DEG C, the SUZ-4 molecular sieve being synthesized
Crystallinity is 86%.
Embodiment 13
The operating procedure of example 2 is repeated, the difference is that crystallization temperature is 160 DEG C, the result of synthetic sample is close in fact
Example 2, crystallinity is up to 100%.
Embodiment 14
The operating procedure of example 2 is repeated, the difference is that crystallization temperature is 170 DEG C, the SUZ-4 molecular sieve synthesized
Crystallinity is 88%.
Claims (8)
1. a kind of SUZ-4 Zeolite synthesis method that hedgehog is spherical, comprising: prepare sial mixed glue solution first, be subsequently added into mould
Plate agent ethylenediamine (EDA) and ethylenimine (CHA) mixing；It is then added to the growth of reaction kettle high temperature crystallization；Wherein crystallization temperature
Are as follows: 130 DEG C -170 DEG C, crystallization time are as follows: 2 days -5 days；Finally obtain the spherical SUZ-4 molecular sieve of the hedgehog.
2. synthetic method described in claim 1, it is characterised in that: the preparation process of the silicon-aluminum sol includes: first by aluminium
Source and KOH add water to be mixed into a solution, are mixed into b solution by silicon source and double template；Then a solution and b solution are sufficiently stirred
It mixes to obtain uniform sial mixed sols.
3. synthetic method as claimed in claim 2, it is characterised in that: the silicon source is aluminium powder, boehmite, hydroxide
One of aluminium, aluminium isopropoxide, aluminum nitrate, aluminum sulfate or arbitrary proportion mixing；The silicon source is silica solution, waterglass, white
One of carbon black or arbitrary proportion mixing.
4. synthetic method of any of claims 1 or 2, it is characterised in that: the crystallization temperature is 140 DEG C -160 DEG C, when crystallization
Between are as follows: 3 days -5 days.
5. synthetic method of any of claims 1 or 2, it is characterised in that: double template ethylenediamine (EDA) and ethylenimine (CHA)
Molar ratio be (1~10): (1~10).
6. synthetic method of any of claims 1 or 2, it is characterised in that further comprising the steps of: crystallization product process is washed,
Dry and roasting.Wherein drying temperature is 120 DEG C, the time 4 hours, and maturing temperature is 550 DEG C, the time 6 hours.
7. synthetic method described in claim 1 or 3, it is characterised in that: include Al in sial mixed glue solution2O3、SiO2And KOH,
Each raw material initial molar ratio in preparation method are as follows: Al2O3:SiO2:KOH:EDA:CHA:H2O=1:(15~30): (5~20): (1
~10): (1~10): (100~2500).
8. a kind of SUZ-4 molecular sieve that hedgehog is spherical, it is characterised in that: -7 any the methods synthesize according to claim 1
It arrives.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282068A (en) * | 2023-02-15 | 2023-06-23 | 山西大学 | Willow leaf-shaped K-SUZ-4 molecular sieve and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118483A (en) * | 1988-08-03 | 1992-06-02 | The British Petroleum Company P.L.C. | Crystalline (metallo) silicates and germanates-suz-4 |
| CN102241407A (en) * | 2011-04-29 | 2011-11-16 | 大连理工大学 | Preparation method of SUZ-4 molecular sieve |
| CN107285340A (en) * | 2017-08-02 | 2017-10-24 | 南京大学连云港高新技术研究院 | A kind of preparation method of the zeolite molecular sieves of SUZ 4 |
| CN108408735A (en) * | 2018-05-21 | 2018-08-17 | 太原理工大学 | A method of preparing SUZ-4 molecular sieves using silicon ash |
-
2019
- 2019-02-26 CN CN201910140480.4A patent/CN109626393B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118483A (en) * | 1988-08-03 | 1992-06-02 | The British Petroleum Company P.L.C. | Crystalline (metallo) silicates and germanates-suz-4 |
| CN102241407A (en) * | 2011-04-29 | 2011-11-16 | 大连理工大学 | Preparation method of SUZ-4 molecular sieve |
| CN107285340A (en) * | 2017-08-02 | 2017-10-24 | 南京大学连云港高新技术研究院 | A kind of preparation method of the zeolite molecular sieves of SUZ 4 |
| CN108408735A (en) * | 2018-05-21 | 2018-08-17 | 太原理工大学 | A method of preparing SUZ-4 molecular sieves using silicon ash |
Non-Patent Citations (3)
| Title |
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| P. VONGVORADIT ET AL.: "Fast Crystallization of SUZ-4 Zeolite with Hydrothermal Synthesis: Part I Temperature and Time Effect", 《PROCEDIA ENGINEERING》 * |
| STEPHEN L. LAWTON ET AL.: "Synthesis and Proposed Framework Topology of Zeolite SUZ-4", 《J. CHEM. SOC., CHEM. COMMUN.,》 * |
| 周华兰等: "Fe掺杂SUZ_4催化剂制备及其SCR反应活性", 《工业催化》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282068A (en) * | 2023-02-15 | 2023-06-23 | 山西大学 | Willow leaf-shaped K-SUZ-4 molecular sieve and preparation method thereof |
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