CN106276946B - A kind of synthetic method of RHO-SAPO molecular sieves and its application - Google Patents
A kind of synthetic method of RHO-SAPO molecular sieves and its application Download PDFInfo
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- CN106276946B CN106276946B CN201510318894.3A CN201510318894A CN106276946B CN 106276946 B CN106276946 B CN 106276946B CN 201510318894 A CN201510318894 A CN 201510318894A CN 106276946 B CN106276946 B CN 106276946B
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Abstract
This application discloses a kind of synthetic methods of RHO SAPO molecular sieves, this method in synthetic system by adding in RHO SAPO presomas, it can simply, efficiently obtain the RHO SAPO molecular sieve products of high-purity, and it by the grain size and addition of modulation RHO SAPO presomas, can realize that the grain size of RHO SAPO molecular sieve products is controllable in the range of 50nm~1 μm.Synthesized RHO SAPO molecular sieves are used as the catalyst of synthesizing cyclic carbonate ester, and reaction condition is mild, and cyclic carbonate ester high income, products obtained therefrom is easily isolated purification.
Description
Technical field
This application involves a kind of preparation methods of RHO-SAPO molecular sieves, belong to Zeolite synthesis field.
Background technology
Silicoaluminophosphamolecular molecular sieves (SAPO-n) be U.S. combinating carbide company (UCC) exploitation in 1984 it is a series of by
PO2 +、AlO2 -And SiO2Tetrahedron be total to vertex connect and compose Three-dimensional Open skeleton structure molecular screen material (USP 4,440,
871).The P of part or substitute P and Al atom sites simultaneously in Si atom same order elements neutrality aluminum phosphate skeleton structures, make skeleton
Net negative electrical charge is generated, causes Bronsted acidity, so as to assign the performances such as SAPO molecular sieve catalysis and gas adsorbing separation.
The structure species of silicoaluminophosphamolecular molecular sieves are various, including having SAPO-5, SAPO-37 and the SAPO- of 12 ring macropores
40, the SAPO-11 and SAPO-41 with 10 ring mesoporous and SAPO-34, SAPO-18 and the SAPO-35 with 8 ring apertures etc..
The SAPO molecular sieve with the big basket structure of aperture wherein using SAPO-34 molecular sieves as representative was concerned in recent years.SAPO-34
Molecular sieve has CHA structure type, and double 6 yuan of rings are piled into the elliposoidal cage and three dimensional intersection in 8 yuan of rings aperture of band according to ABC modes
Pore passage structure, aperture about 0.38 × 0.38nm, size about 1.0 × 0.67 × 0.67nm of cage.The molecular sieve is fitted since it has
Suitable pore passage structure, medium partially strong Acidity and high hydrothermal stability has been successfully applied to MTG, MTO and DeNOx and had waited
Journey.
Recently, the Chinese Academy of Sciences Dalian Chemistry and Physics Institute reports a series of synthesis of SAPO molecular sieves with RHO molecular sieve structures
And its application (Chem.Mater.2011,23,1406-1413；Microporous Mesoporous Mater.2011,144,
112-119；Chemsuschem, 2013,6,911-918).RHO framework of molecular sieve structure connects shape by α cages by double octatomic rings
Into category cubic system, main aperture road is made of double octatomic rings.The molecular sieve be have simultaneously 8 yuan of rings apertures (0.36nm ×
0.36nm) and the big basket structures of α.
The RHO-SAPO molecular sieve crystals granularity that the synthetic method reported is obtained in the micron-scale, and form modulation
It has difficulties, the RHO-SAPO molecular sieve siliconoxide mass contents of hydro-thermal method and rotating crystal method synthesis are coagulated 13% or so dry
Compose the silicone contents of the RHO-SAPO molecular sieves obtained in method and amine thermal synthesis method 20% or so (Chemsuschem,
2013,6,911-918).
In view of this, it is necessary to a kind of simple, efficient RHO-SAPO Zeolite synthesis method be provided, obtaining high-purity
RHO-SAPO sieve samples while, can realize that RHO-SAPO molecular sieve grain sizes are controllable within the specific limits.
The content of the invention
According to the one side of the application, a kind of synthetic method of RHO-SAPO molecular sieves is provided, this method is by closing
RHO-SAPO presomas are added in architectonical, can simply, efficiently obtain the RHO-SAPO zeolite products of high-purity, and
Can by the grain size and addition of modulation RHO-SAPO presomas, realize RHO-SAPO zeolite products grain size 50nm~
It is controllable in the range of 1 μm.
The synthetic method of the RHO-SAPO molecular sieves, which is characterized in that including at least following steps：
A) silicon source, phosphorus source, silicon source, organic amine template R and water are mixed, obtains the mixture with following mol ratio
I：
Al∶P∶Si∶R∶H2O=0.5~1.5: 0.5~2.0: 0.05~2: 0.5~5: 20~100；
B) RHO-SAPO presomas are added in into the mixture I that the step a) is obtained, stirs evenly, obtains mixture
II；
C) when by mixtures II obtained by step b), crystallization 12~72 is small under 150~240 DEG C of crystallization temperature；
D) after treating step c) crystallization, solid product separating, washing, drying is to get the RHO-SAPO molecular sieves.
Preferably, the mol ratio described in step a) in mixture I is：
Al∶P∶Si∶R∶H2O=1: 0.7~1.5: 0.1~1: 1~2: 30~70.
As a kind of embodiment, RHO-SAPO presomas described in step b) are by RHO-SAPO molecular sieves through mechanical grinding
At least one of mill, acid treatment, alkali process method handle to obtain.RHO-SAPO molecular sieves for processing can be by known
The RHO-SAPO molecular sieves that conventional method synthesizes or the RHO-SAPO molecules synthesized using the application method
Sieve.
As a kind of embodiment, RHO-SAPO presomas described in step b) directly use nanometer RHO-SAPO molecules
Sieve.Nanometer RHO-SAPO molecular sieves can be the RHO-SAPO molecules with nanoscale synthesized using the application method
Sieve.
Preferably, the average grain diameter of RHO-SAPO presomas described in step b) is 100nm~500nm.Further preferably
Ground, the average grain diameter of RHO-SAPO presomas described in step b) are 150nm~500nm.
Preferably, the grain size of RHO-SAPO molecular sieves obtained by step d) is in 50nm~1 μm.
Preferably, the addition of RHO-SAPO presomas is dry basis in mixture I in mixtures II described in step b)
The 1%~100% of amount.It is further preferred that the addition of RHO-SAPO presomas is mixed in mixtures II described in step b)
Close 5%~50% of butt weight in object I.It is further preferred that RHO-SAPO forerunner in mixtures II described in step b)
The addition of body is 10%~50% of butt weight in mixture I.
In the application, it can be realized by the average grain diameter and addition for changing RHO-SAPO presomas RHO-SAPO points final
The size tunable of son sieve product.
As a kind of embodiment, the average grain diameter of RHO-SAPO presomas is 50nm~500nm, and addition is mixture
The 5%~100% of butt weight in I, the average grain diameter of gained RHO-SAPO zeolite products is 50nm~1 μm.
As a kind of embodiment, the average grain diameter of RHO-SAPO presomas is 150nm~500nm, and addition is mixing
The 5%~30% of butt weight in object I, the average grain diameter of gained RHO-SAPO zeolite products is 50nm~800nm.
As a kind of embodiment, the average grain diameter of RHO-SAPO presomas is 50nm~200nm, and addition is mixture
The 5%~15% of butt weight in I, the average grain diameter of gained RHO-SAPO zeolite products is 50nm~200nm.
Preferably, crystallization temperature is 180~220 DEG C in step c), when crystallization time is 24~48 small.
Preferably, silicon source described in step a) in aluminium salt, activated alumina, aluminum alkoxide, metakaolin at least
It is a kind of.
Preferably, phosphorus source described in step a) is selected from least one of orthophosphoric acid, metaphosphoric acid, phosphate, phosphite.
Preferably, silicon source described in step a) is in Ludox, active silica, positive esters of silicon acis, metakaolin
It is at least one.
Preferably, organic amine template R described in step a) be selected from diethylamine, triethylamine, tetraethyl ammonium hydroxide,
At least one of quinoline, diisopropylamine, diethanol amine, triethanolamine, N, N- dimethylethanolamines, N, N- diethyl ethylene diamines.
According to the another aspect of the application, a kind of catalyst for acid catalyzed reaction is provided, which is characterized in that according to upper
At least one of RHO-SAPO molecular sieves of either method synthesis are stated to obtain after roasting in 400~700 DEG C of air.
According to the another aspect of the application, a kind of catalyst for synthesizing cyclic carbonate ester is provided, which is characterized in that according to
At least one of RHO-SAPO molecular sieves of any of the above-described method synthesis obtain after being roasted in 400~700 DEG C of air.It is preferred that
Ground, the synthesizing cyclic carbonate ester are that carbon dioxide passes through cycloaddition reaction synthesizing cyclic carbonate ester with oxygenatedchemicals.
The advantageous effect that the application can generate includes but not limited to：
(1) the application provide RHO-SAPO molecular sieves synthetic method, can simply, inexpensively, be efficiently obtained small crystalline substance
Grain RHO-SAPO sieve samples, and can RHO- be realized by the grain size and addition of modulation RHO-SAPO presomas
The grain size of SAPO molecular sieve product is controllable in the range of 50nm~1 μm.
(2) catalyst for synthesizing cyclic carbonate ester that the application provides, for carbon dioxide cycloaddition synthesis ring carbon acid
The reaction of ester, without solvent, other auxiliary agents and co-catalyst, reaction condition is mild, and cyclic carbonate ester high income, products obtained therefrom is easy to
Separating-purifying.
Description of the drawings
Fig. 1 is sample 3#Electron scanning micrograph.
Specific embodiment
The application is described in detail with reference to embodiment, but the application is not limited to these embodiments.
In the case of not doing specified otherwise, the test condition of the application is as follows：
Granulometry uses laser particle size method, in the Nano90- nanometer laser Li Du ＆Zeta constant-current titrations of Malvern company
It is measured on analyzer.
Sample material phase analysis analyzes (XRD) using X-ray powder diffraction, using Dutch Panaco (PANalytical)
It is measured on X ' the Pert PRO X-ray diffractometers of company, Cu targets, K α radiation sourceVoltage 40KV, electric current
40mA。
Sample composition is analyzed using x-ray fluorescence spectrometry (XRF), in the Magix-601 of PHILIPS Co. (Philips)
It is measured in type x-ray fluorescence spectrometry instrument.
SEM morphology analysis uses Scientific Instrument Factory of C.A.S's SU8020 types and TM3000 scanning electron microscope.
RHO-SAPO presomas are prepared using Mechanical Crushing method, are carried out on QM-3SP2 planetary ball mills.
The computational methods of sample yield are：The ÷ of product quality × 75% (inorganic matter butt quality+RHO- in Primogel
SAPO forerunner's weight) × 100%.
1 sample 1 of embodiment#~sample 4#Preparation
The preparation of RHO-SAPO presomas：
Using document Chem.Mater.2011, the method in 23,1406-1413, synthesis obtains large-sized RHO-SAPO
Molecular sieve.The large-sized RHO-SAPO molecular sieves of gained are placed in ball mill, in compactedness 20%, the item of 500 revs/min of rotating speed
When ball milling 12 is small under part, RHO-SAPO presomas are obtained.
The preparation of RHO-SAPO molecular sieves：
By boehmite, phosphoric acid (85wt%), ethyl orthosilicate, triethylamine and water according to molar ratio Al: P: Si: R:
H2O=0.5: 0.7: 0.05: 2: 30 ratio mixing, obtains mixture I；Then RHO-SAPO presomas are added in into mixture I,
The addition of RHO-SAPO presomas is the 1% of mixture I butt weight, after mixing, obtains mixtures II.By mixture
II is moved in stainless steel autoclave, crystallization 72h at 150 DEG C.After crystallization, solid product is centrifuged, is washed, 100
To get the RHO-SAPO molecular sieves after being dried in DEG C air, sample 1 is denoted as#.It weighs and sample 1 is calculated#Yield be
70wt%.
Sample 2#~sample 4#Preparation process and sample 1#It is identical, preparation condition, proportion scale and the crystalline substance of specific presoma
Change condition, sample yield and grain size are shown in Table 1.
2 sample 5 of embodiment#~sample 8#Preparation
Sample 5#~sample 8#Specific preparation process and sample 1#It is identical, the difference is that, embodiment 1 is respectively adopted
In obtained sample 1#, sample 4#, sample 2#With sample 4#As sample 5#, sample 6#, sample 7#With sample 8#Before
Drive body；In addition, sample 5#~sample 8#Proportion scale and crystallization condition, sample yield and grain size be shown in Table 1.
Table 1
1 sample D1 of comparative example#Preparation
Specific preparation process and sample 1#It is identical, the difference is that, change RHO-SAPO presomas into phase homogenous quantities not
Through ball milling, the big grain size RHO-SAPO molecular sieves prepared according to literature method, gained sample is denoted as sample D1#。
2 sample D2 of comparative example#Preparation
Specific preparation process and sample 1#It is identical, the difference is that, it is added without RHO-SAPO presomas, gained sample note
For sample D2#。
3 sample 1 of embodiment#~sample 8#XRF analysis
Using XRF to sample 1#~sample 8#Composition analyzed, the silica alumina ratio of sample is shown in Table 1 data.
4 sample 1 of embodiment#~sample 8#Morphology analysis
Using scanning electron microscope to sample 1#~sample 8#Pattern analyzed.The results show that sample 1#~sample 8#It is equal
To have well-regulated polyhedron, epigranular.Show the particle diameter distribution of sample uniformly and with high-crystallinity and purity.With sample
3#For Typical Representative, stereoscan photograph is as shown in Figure 1.
5 sample 1 of embodiment#~sample 8#XRD analysis
To sample 1#~sample 8#, sample D1#With sample D2#Carry out XRD analysis.The results show that with sample 1#For typical generation
Table, XRD data results are shown in Table 2.Sample 2#~sample 8#XRD data results and table 2 it is close, i.e., peak position is identical with shape,
It is fluctuated according to the variation peak relative peak intensities of synthesis condition in the range of ± 10%, it is with RHO pure phase knots to show synthetic product
The SAPO molecular sieve of structure, sample crystallinity are high.
Sample D1#With sample D2#XRD the results show that sample D1#With sample D2#It is RHO-SAPO and SAPO-34 points
The mixed phase of son sieve.Illustrate the use of nanoscale RHO-SAPO molecular sieve precursors, have and promote RHO-SAPO Crystallization of Zeolite
Effect.Without using presoma, pure phase RHO-SAPO molecular sieves can not be synthesized under the same conditions.
Table 2
6 catalytic performance test of embodiment
Sample 1 is respectively adopted#, sample 2#, sample 5#With sample 6#As catalyst, for CO2With the ring of epoxychloropropane
The reaction of addition synthesizing cyclic carbonate ester.It concretely comprises the following steps：The sample of 0.2g is sequentially added in 100mL stainless steel autoclaves
With 2mL epoxychloropropane, CO is passed through2, when reaction 4 is small under conditions of pressure 800Mpa, 120 DEG C.Reaction product is by gas phase color
Spectrum analysis (Varian3800, fid detector, capillary column PoraPLOT Q-HT), the results are shown in tables 3.
Epoxychloropropane conversion ratio=(molal quantity of epoxychloropropane in molal quantity-product of epoxychloropropane in raw material)
Molal quantity × 100% of epoxychloropropane in ÷ raw materials
In cyclic carbonate ester yield=product in the molal quantity ÷ raw materials of cyclic carbonate ester epoxychloropropane molal quantity × 100%
The sample being prepared it can be seen from 3 data of table according to the application method is used for CO as catalyst2With ring
The reaction of the cycloaddition synthesizing cyclic carbonate ester of oxygen chloropropane shows good catalytic performance, and without solvent, other auxiliary agents
And co-catalyst, reaction condition is mild, and cyclic carbonate ester high income, products obtained therefrom is easily isolated purification.
Table 3
The above is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (9)
1. a kind of synthetic method of RHO-SAPO molecular sieves, which is characterized in that including at least following steps：
A) silicon source, phosphorus source, silicon source, organic amine template R and water are mixed, obtains the mixture I with following mol ratio：
Al:P:Si:R:H2O=0.5~1.5:0.5~2.0:0.05~2:0.5~5:20~100；
B) RHO-SAPO presomas are added in into the mixture I that the step a) is obtained, stirs evenly, obtains mixtures II；
C) when by mixtures II obtained by step b), crystallization 12~72 is small under 150~240 DEG C of crystallization temperature；
D) after treating step c) crystallization, solid product separating, washing, drying is to get the RHO-SAPO molecular sieves；
RHO-SAPO presomas described in step b) by RHO-SAPO molecular sieves through in mechanical lapping, acid treatment, alkali process extremely
A kind of few method handles to obtain.
2. synthetic method according to claim 1, which is characterized in that the mol ratio described in step a) in mixture I
For：
Al:P:Si:R:H2O=1:0.7~1.5:0.1~1:1~2:30~70.
3. synthetic method according to claim 1, which is characterized in that RHO-SAPO presomas is averaged described in step b)
Grain size is 150nm~500nm.
4. synthetic method according to claim 1, which is characterized in that described in step b) in mixtures II before RHO-SAPO
The addition of body is driven as 1%~100% of butt weight in mixture I.
5. synthetic method according to claim 1, which is characterized in that the average grain diameter of RHO-SAPO presomas in step b)
For 50nm~500nm, addition is 1%~100% of butt weight in mixture I, RHO-SAPO molecular sieves obtained by step d)
Average grain diameter be 50nm~1 μm.
6. synthetic method according to claim 1, which is characterized in that the average grain diameter of RHO-SAPO presomas in step b)
For 150nm~200nm, addition is 5%~15% of butt weight in mixture I, RHO-SAPO molecular sieves obtained by step d)
Average grain diameter be 50nm~200nm.
7. synthetic method according to claim 1, which is characterized in that crystallization temperature is 180~220 DEG C in step c), brilliant
When the change time is 24~48 small.
8. a kind of catalyst for acid catalyzed reaction, which is characterized in that closed according to any one of claim 1 to 7 the method
Into at least one of RHO-SAPO molecular sieves obtained after being roasted in 400~700 DEG C of air.
9. a kind of catalyst for synthesizing cyclic carbonate ester, which is characterized in that according to any one of claim 1 to 7 the method
At least one of RHO-SAPO molecular sieves of synthesis.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5989518A (en) * | 1998-12-29 | 1999-11-23 | Uop Llc | Process for synthesizing and controlling the particle size and particle size distribution of a molecular sieve |
| CN101269820A (en) * | 2007-03-21 | 2008-09-24 | 中国石油化工股份有限公司 | Silicon aluminium phosphate molecular sieve and synthesizing process |
| CN101468810A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Composition containing silicoaluminophosphate molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5989518A (en) * | 1998-12-29 | 1999-11-23 | Uop Llc | Process for synthesizing and controlling the particle size and particle size distribution of a molecular sieve |
| CN101269820A (en) * | 2007-03-21 | 2008-09-24 | 中国石油化工股份有限公司 | Silicon aluminium phosphate molecular sieve and synthesizing process |
| CN101468810A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Composition containing silicoaluminophosphate molecular sieve |
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