CN104743574B - A kind of preparation method of 44 micro porous molecular sieve of high-purity SAPO - Google Patents
A kind of preparation method of 44 micro porous molecular sieve of high-purity SAPO Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of 44 micro porous molecular sieve of high-purity SAPO, mixture gel is obtained by raw material of phosphorus source, silicon source, silicon source, composite mould plate agent and water, by mixture gel closed crystallization, gained crystallization product washing, dry, roasting remove composite mould plate agent, obtain 44 micro porous molecular sieves of SAPO, composite mould plate agent used is R1 and R2, and the R1 is ethylenediamine（EDA）, diethylenetriamine（DETA）, triethylene tetramine（TETA）, TEPA（TEPA）Or pentaethylene hexamine（PEHA）, the R2 be N, N, N ', 1,6 hexamethylene diamine of N ' tetramethyls（TMHD）.The present invention uses organic amine composite mould plate agent, promotes the formation of SAPO 44, by the adjustment of the amount of being used for, it is only necessary to which one time crystallization is obtained 44 molecular sieves of highly purified SAPO, and preparation process is easily operated, cycle is short, is easy to industrial applications.
Description
Technical field
The present invention relates to a kind of preparation method of SAPO-44 micro porous molecular sieves, and in particular to a kind of high-purity SAPO-44 is micro-
The preparation method of porous molecular sieve, belongs to technical field of molecular sieve preparation.
Background technology
Silicoaluminophosphamolecular molecular sieves（SAPO-n）Be U.S. combinating carbide company exploitation, by SiO2、PO2 +And AlO2 -Three kinds
The microporous crystals that tetrahedron is constituted, wherein n represent different crystal structures.The structure species of SAPO series are numerous, according to which
The size in aperture can be divided into the large aperture molecular sieve more than 50 nm（Such as SAPO-5）, between the middle pore diameter mol of 2-50 nm
Sieve（Such as SAPO-11）With the small-bore molecular sieve less than 2 nm（Such as SAPO-34, SAPO-44）Deng.Good pore passage structure makes
SAPO-n molecular sieves have excellent selective activization, can be used in many hydrocarbon conversion reactions as catalyst, or conduct
Adsorbent separating mixture.
The basic structural unit of SAPO-44 molecular sieves is double hexatomic rings, and these pair of hexatomic ring is connected by part four-membered ring,
The three-dimensional open-framework with octatomic ring is defined, belongs to pinhole type molecular sieve.SAPO-44 molecular sieves are except possessing good heat
Outside stability, also with acid and ion exchangeable, this makes which be used widely in various fields.Due to its unique duct
Structure and acidity, have been widely used in all kinds of catalytic reactions, including oxidation, acid catalysiss and isomerization reaction etc..
United States Patent (USP) US4440871A discloses a kind of hydrothermal synthesis method of SAPO-44, the method with aqueous silicon solution,
Phosphoric acid, aluminum isopropylate. and organic formwork agent cyclohexylamine are raw material, are reacted 52 hours at 200 DEG C, and SAPO-44 is obtained, and gained is produced
In thing, SAPO-44 occurs as principal phase, it is impossible to obtain highly purified SAPO-44 molecular sieves.Patent WO99/19254
（CN1278780A）Also disclose that a kind of synthetic method of SAPO-44, the method also with cyclohexylamine as template, resulting product
Thing is substantially SAPO-44, but also has dephasign.In order to improve the purity of SAPO-44, patent CN201210363833.5 and
CN201310499121.0 using composite mould plate agent, through different temperatures twice crystallization process synthesis SAPO-44, but these
Method increased preparation process, make the loaded down with trivial details of preparation process change.
The content of the invention
It is an object of the invention to provide a kind of preparation method of high-purity SAPO-44 micro porous molecular sieve, prepared by the method
Journey is easily operated, and the SAPO-44 micro porous molecular sieves purity of gained is high, without dephasign.
The present invention selects special composite mould plate agent, only crystallization of Jing that the higher SAPO-44 molecules of purity are obtained
Sieve, under the cooperation of preparation process and technological parameter, better, concrete technical scheme is as follows：
A kind of preparation method of high-purity SAPO-44 micro porous molecular sieve, with phosphorus source, silicon source, silicon source, composite mould plate agent and water
Mixture gel is obtained for raw material, mixture gel closed crystallization, the washing of gained crystallization product, dry, roasting are removed compound
Template, obtains SAPO-44 micro porous molecular sieves, and composite mould plate agent used is R1 and R2, and the R1 is ethylenediamine（EDA）, divinyl
Triamine（DETA）, triethylene tetramine（TETA）, TEPA（TEPA）Or pentaethylene hexamine（PEHA）, the R2 be N, N,
N ', N '-tetramethyl -1,6- hexamethylene diamines（TMHD）.
Inventor has found to play Synergistic using compound generation of the organic amine template to molecular sieve through numerous studies
Effect, can aid in the nucleation of gel, the more conducively generation of SAPO-44 micro porous molecular sieves.
In above-mentioned preparation method, the Al that composite mould plate agent is brought into silicon source2O3Mol ratio be：Al2O3：R1：R2=1：
0.27-0.9：2.0-3.0, preferably 1：0.5-0.6：2.4-2.6.
In above-mentioned preparation method, phosphorus source comes from phosphoric acid, phosphorous acid or phosphate.
In above-mentioned preparation method, source of aluminium comes from boehmite, boehmite or aluminum oxyhydroxide.
In above-mentioned preparation method, the silicon source comes from tetraethyl orthosilicate, Ludox or waterglass.
In above-mentioned preparation method, the consumption of silicon source, silicon source, phosphorus source and water meets following mol ratio：SiO2：Al2O3：P2O5：
H2O =0.5-1.0：1：1.0-1.5：30-70, preferred 0.7-0.8：1：1.2-1.3：35-50.
In above-mentioned preparation method, crystallization temperature is 150-250 DEG C, preferably 190-210 DEG C.
In above-mentioned preparation method, crystallization time be 48-108 hours, preferably 96 hours.
In above-mentioned preparation method, crystallization product in 450-650 DEG C of roasting, preferably in 550 DEG C of roastings.
In above-mentioned preparation method, roasting time be 4-8 hours, preferably 6 hours.
In above-mentioned preparation method, crystallization product is dried 6-24 hours at 80-120 DEG C.
In above-mentioned preparation method, crystallization product is dried 12 hours preferably at 100 DEG C.
In above-mentioned preparation method, when preparing mixture gel, the addition sequence of composite mould plate agent is highly purified to obtaining
SAPO-44 molecular sieves do not affect.
Highly purified molecular sieve, when from optimizing technology parameters, gained molecule can be obtained under above-mentioned process conditions
Sieve degree of crystallinity is more preferable.
The present invention uses organic amine composite mould plate agent, promotes the formation of SAPO-44, by the adjustment of the amount of being used for, only
Need a crystallization that highly purified SAPO-44 molecular sieves are obtained, preparation process is easily operated, cycle is short, be easy to industrialization to answer
With.Additionally, by the preferred of process conditions, the degree of crystallinity of molecular sieve can be improved so as to which application effect is more preferably.
Description of the drawings
The XRD spectra of 1 products therefrom of Fig. 1 embodiments.
The XRD spectra of 1 products therefrom of Fig. 2 comparative examples.
The XRD spectra of 2 products therefrom of Fig. 3 comparative examples.
The N of 1 products therefrom of Fig. 4 embodiments2Adsorption isothermal curve.
The XRD spectra of 3 products therefrom of Fig. 5 comparative examples.
Specific embodiment
Molecular sieve preparation method of the present invention, specifically includes following steps：
（1）By composite mould plate agent, phosphorus source, silicon source, silicon source, water mix homogeneously, mixture gel is obtained.
（2）Mixture gel is transferred in reactor, to 150-250 DEG C, constant temperature is brilliant at autogenous pressures for airtight heating
Change a period of time, after crystallization is complete, naturally cool to room temperature.
（3）Product centrifugation after crystallization, wash to it is neutral, be dried, dried solid product 450- in atmosphere
650 DEG C of roastings obtain SAPO-44 micro porous molecular sieves to remove composite mould plate agent completely, that is,.
Below, the specific example of several present invention is enumerated, following embodiments are only used for explaining the present invention, not to its content
Limited.
Embodiment 1
Use TEPA（TEPA）SAPO-44 is prepared with TMHD double templates, step is as follows：
1st, according to mol ratio SiO2：Al2O3：P2O5：TEPA：TMHD：H2O=0.75：1：1.25：0.54：2.5：50 weigh silicon
Colloidal sol, boehmite, phosphoric acid, TEPA, TMHD and water.
2nd, 0.8280g TEPA are dissolved in 7.2g deionized waters, sequentially add 2.3058g phosphoric acid, 1.0461g and intend thin water
Aluminum stone, 1.2267g Ludox and 3.4746g TMHD, continue stirring 12 hours.Reactant is transferred to into stainless steel cauldron
In, to 200 DEG C, thermostatic crystallization naturally cooled to room temperature after 96 hours to airtight heating at autogenous pressures.Centrifugation crystallization is produced
Repeatedly washing is precipitated to neutrality for thing deionized water, during product is put in drying baker 100 DEG C of dryings 12 hours, tube furnace
550 DEG C of roastings were obtained pressed powder after 6 hours.Products obtained therefrom Jing XRD diffraction analysis（Fig. 1）For pure SAPO-44 microporous moleculars
Sieve, without dephasign.The N of product2Adsorption isothermal curve as shown in figure 4, from fig. 4, it can be seen that the molecular sieve be micro porous molecular sieve, Jing
Its BET specific surface area is tested for 343 m2/g。
Embodiment 2
1st, according to mol ratio SiO2：Al2O3：P2O5：DETA：TMHD：H2O=0.8：1：1.2：0.6：2.5：50 weigh positive silicon
Acetoacetic ester, aluminum oxyhydroxide, phosphorous acid, DETA, TMHD and water.
2nd, 0.4952g DETA are dissolved in 7.2g deionized waters.Sequentially add 1.8522g phosphorous acid, 1.2307g hydroxyls
Aluminium oxide, 4.5357g tetraethyl orthosilicates and 3.4746gTMHD, continue stirring 12 hours.Reactant is transferred to into rustless steel high
In pressure kettle, to 210 DEG C, under pressure itself, thermostatic crystallization naturally cooled to room temperature after 96 hours to airtight heating.Deionized water
Repeatedly washing is precipitated to the aobvious neutrality of filtrate, 550 DEG C of roastings 6 during product is put in drying baker 100 DEG C of dryings 12 hours, tube furnace
Pressed powder is obtained after hour.Products obtained therefrom Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 3
Method according to embodiment 1 prepares SAPO-44, except for the difference that：Template used dose of R1 is pentaethylene hexamine（PEHA）.
Products obtained therefrom Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 4
Method according to embodiment 1 prepares SAPO-44, except for the difference that：Template used dose of R1 is triethylene tetramine（TETA）.
Products obtained therefrom Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 5
Method according to embodiment 1 prepares SAPO-44, except for the difference that：Template used dose of R1 is ethylenediamine（EDA）.Gained
Product Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 6
Method according to embodiment 1 prepares SAPO-44, and except for the difference that crystallization temperature is 150 DEG C, and the time is 108h.Gained
Product Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 7
Method according to embodiment 1 prepares SAPO-44, and except for the difference that crystallization temperature is 250 DEG C, and the time is 48h.Gained is produced
Product Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 8
Method according to embodiment 1 prepares SAPO-44, and the crystallization product baking temperature for except for the difference that obtaining is 80 DEG C, when
Between be 24h.Products obtained therefrom Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 9
Method according to embodiment 1 prepares SAPO-44, and the crystallization product baking temperature for except for the difference that obtaining is 120 DEG C, when
Between be 6h.Products obtained therefrom Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 10
Method according to embodiment 1 prepares SAPO-44, and except for the difference that calcining heat is 450 DEG C, and the time is 8h.Gained is produced
Product Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 11
Method according to embodiment 1 prepares SAPO-44, and except for the difference that calcining heat is 650 DEG C, and the time is 4h.Gained is produced
Product Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Embodiment 12
Method according to embodiment 1 prepares SAPO-44, and except for the difference that selected mol ratio is SiO2：Al2O3：P2O5：
TEPA：TMHD：H2O=0.5：1：1：0.54：2.5：30 weigh Ludox, boehmite, phosphoric acid, TEPA, TMHD and water.Institute
It is pure SAPO-44 micro porous molecular sieves to obtain product Jing XRD diffraction analysis, without dephasign.
Embodiment 13
Method according to embodiment 1 prepares SAPO-44, and except for the difference that selected mol ratio is SiO2：Al2O3：P2O5：
TEPA：TMHD：H2O=1：1：1.5：0.54：2.5：70 weigh Ludox, boehmite, phosphoric acid, TEPA, TMHD and water.Institute
It is pure SAPO-44 micro porous molecular sieves to obtain product Jing XRD diffraction analysis, without dephasign.
Embodiment 14
Method according to embodiment 1 prepares SAPO-44, and except for the difference that selected mol ratio is SiO2：Al2O3：P2O5：
TEPA：TMHD：H2O=0.75：1：1.25：0.9：2.0：50 weigh waterglass, boehmite, sodium phosphate, TEPA, TMHD and water.Institute
It is pure SAPO-44 micro porous molecular sieves to obtain product Jing XRD diffraction analysis, without dephasign.
Embodiment 15
Method according to embodiment 1 prepares SAPO-44, and except for the difference that selected mol ratio is SiO2：Al2O3：P2O5：
TEPA：TMHD：H2O=0.75：1：1.25：0.27：3.0：50 weigh Ludox, boehmite, phosphoric acid, TEPA, TMHD and
Water.Products obtained therefrom Jing XRD diffraction analysis is pure SAPO-44 micro porous molecular sieves, without dephasign.
Comparative example 1
Molecular sieve is prepared using the method for embodiment 1, except for the difference that：Only make template with single R1, prepare mixture and coagulate
During glue, according to mol ratio SiO2：Al2O3：P2O5：R1：H2O=0.75：1：1.25：0.54：50 weigh Ludox, boehmite,
Phosphoric acid, TEPA and water.
The XRD diffraction patterns of products obtained therefrom as shown in Fig. 2 it can be seen that the not pure SAPO-44 of product, except
Outside SAPO-44, also contain AlPO4And SiO2Composition.
Comparative example 2
Molecular sieve is prepared using the method for embodiment 1, except for the difference that：Only make template with single R2, prepare mixture and coagulate
During glue, according to mol ratio SiO2：Al2O3：P2O5：R2：H2O=0.75：1：1.25：2.5：50 weigh Ludox, boehmite,
Phosphoric acid, TMHD and water.
The XRD diffraction patterns of products obtained therefrom as shown in figure 3, it can be seen that the non-SAPO-44 molecular sieves of products obtained therefrom,
For SAPO-56.
Comparative example 3
Method according to embodiment 1 prepares molecular sieve, except for the difference that：SiO2：Al2O3：P2O5：TEPA：TMHD：H2O=
0.75：1：1.25：0.18：2.5：50.The XRD diffraction patterns of products therefrom are as shown in figure 5, it can be seen that products obtained therefrom
For non-pure SAPO-44 molecular sieves, the dephasign containing SAPO-56.
Claims (11)
1. a kind of preparation method of high-purity SAPO-44 micro porous molecular sieve, is characterized in that：With phosphorus source, silicon source, silicon source, compound die
Plate agent and water are that raw material is obtained mixture gel, by mixture gel closed crystallization, the washing of gained crystallization product, dry, roasting
Composite mould plate agent is removed, SAPO-44 micro porous molecular sieves are obtained, composite mould plate agent used is R1 and R2, and the R1 is ethylenediamine, diethyl
Alkene triamine, triethylene tetramine, TEPA or pentaethylene hexamine, the R2 be N, N, N ', N '-tetramethyl -1,6- hexamethylene diamines；
The Al that composite mould plate agent is brought into silicon source2O3Mol ratio be：Al2O3：R1：R2=1：0.27-0.9：2.0-3.0；
The consumption of silicon source, silicon source, phosphorus source and water meets following mol ratio：SiO2：Al2O3：P2O5：H2O =0.5-1.0：1：1.0-
1.5：30-70；
Crystallization temperature is 150-250 DEG C, and crystallization time is 48-108 hours.
2. preparation method according to claim 1, is characterized in that：The Al that composite mould plate agent is brought into silicon source2O3Mol ratio
For：Al2O3：R1：R2=1：0.5-0.6：2.4-2.6.
3. preparation method according to claim 1, is characterized in that：The consumption of silicon source, silicon source, phosphorus source and water meets following rubbing
You compare：SiO2：Al2O3：P2O5：H2O =0.7-0.8：1：1.2-1.3：35-50.
4. the preparation method according to any one of claim 1-3, is characterized in that：Crystallization temperature is 190-210 DEG C.
5. the preparation method according to any one of claim 1-3, is characterized in that：Crystallization product is in 450-650 DEG C of roasting.
6. preparation method according to claim 5, is characterized in that：Crystallization product is in 550 DEG C of roastings.
7. preparation method according to claim 1, is characterized in that：Crystallization time is 96 hours；Roasting time is that 4-8 is little
When.
8. preparation method according to claim 7, is characterized in that：Roasting time is 6 hours.
9. the preparation method according to any one of claim 1-3, is characterized in that：Phosphorus source comes from phosphoric acid, phosphorous
Acid or phosphate；Source of aluminium comes from boehmite, boehmite or aluminum oxyhydroxide；The silicon source comes from positive silicic acid second
Ester, Ludox or waterglass.
10. the preparation method according to any one of claim 1-3, is characterized in that：Crystallization product is done at 80-120 DEG C
Dry 6-24 hours.
11. preparation methoies according to claim 10, is characterized in that：Crystallization product is dried 12 hours at 100 DEG C.
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| EP3630681B1 (en) * | 2017-05-31 | 2022-03-16 | IFP Energies nouvelles | Direct synthesis of a sapo material with afx structure comprising copper and use of this material |
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| CN108557841B (en) * | 2018-07-05 | 2021-07-27 | 天津大学 | Preparation method for synthesizing CHA molecular sieve by using tetraethylenepentamine as template agent |
| CN115231591B (en) * | 2021-04-22 | 2023-08-04 | 中国石油化工股份有限公司 | Pure-phase small-grain SAPO-44 molecular sieve, and preparation method and application thereof |
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