CN107746065A - A kind of method for preparing the molecular screen membrane of high-performance SAPO 34 - Google Patents
A kind of method for preparing the molecular screen membrane of high-performance SAPO 34 Download PDFInfo
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- CN107746065A CN107746065A CN201711277867.1A CN201711277867A CN107746065A CN 107746065 A CN107746065 A CN 107746065A CN 201711277867 A CN201711277867 A CN 201711277867A CN 107746065 A CN107746065 A CN 107746065A
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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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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- 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
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- 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
Abstract
The invention discloses a kind of preparation method of the molecular screen membrane of high-performance SAPO 34, step includes the synthesis molecular sieve seeds of SAPO 34；Porous carrier outer surface is modified；By in the molecular sieve seed dip-coatings of SAPO 34 to modified porous carrier outer surface；The porous carrier for being coated with the molecular sieve seeds of SAPO 34 of preparation is placed in molecular sieve synthesis mother liquid, carries out hydrothermal crystallizing；Template agent removing is removed in high-temperature roasting, obtains the molecular screen membranes of SAPO 34.The present invention prepares the molecular screen membranes of SAPO 34 using silane coupler modified porous carrier, adds the adhesive force between carrier surface and zeolite crystal, not only greatly improves the synthesis repeatability of the molecular screen membranes of SAPO 34, and shortens the generated time of film.The film synthesized is to H2/CO2Separation selectivity is higher, while can also be applied to CO2/CH4And CO2/N2In being separated Deng gas.
Description
Technical field
The invention belongs to zeolite membrane material technical field, more particularly to one kind prepares the molecular screen membrane of high-performance SAPO -34
Method.
Background technology
With flourishing for economy, environmental problem and energy problem have become stop human society and realize sustainable development
The significant obstacle of exhibition.Greenhouse effects are on the rise now, as most important greenhouse gases CO2, largely it is present in flue
In gas and coal gas, environment is not only polluted, and reduce the efficiency of combustion of the energy.
In the past few decades, membrane separation technique emerges rapidly.Substantial amounts of research report shows that UF membrane has that energy consumption is low, if
Standby the advantages that investing the operation of low and continuity, in CO2There is huge application potential [Ind.Eng.Chem.Res.41 in removing field
(2002)1393].Membrane separation technique make use of one or more materials than other materials can faster film, so as to reach separation
Purpose containing two or more incoming mixtures.Molecular screen membrane has homogeneous aperture, high temperature resistant, anti-chemical solvent and can carried out
The advantages that ion exchange, therefore have huge answer in fields such as catalytic reaction, gas separation, infiltration evaporation separation and environmental protection
Use potentiality.
Zeolite is the crystalline microporous material for having on molecular level uniform pore size.When molecular sieve crystal symbiosis formed film,
Its selective absorption, gas mixing can effectively be sieved by possessing different diffusion rates and molecule screening function to being ignorant of material
Thing.The zeolite molecular sieve film for having 0.2~0.8nm holes size is the first choice of gas separation.Y, X, MOR, ZSM-5, SAPO-34 and
SSZ-13 has been prepared and separated for gas.
Silicoaluminophosphamolecular molecular sieves (SAPO-n) are important one in molecular sieves, substitute phosphorus oxygen four by silicon-oxy tetrahedron
What face body or aluminum-oxygen tetrahedron were formed.SAPO-34 molecular sieves have CHA types topological structure and the three-dimensional octatomic ring duct communicated,
Channel diameter 0.38nm, with CH4Kinetic diameter is similar, more than N2(0.36nm) and CO2The kinetic diameter of (0.33nm).Profit
There are different competitive Adsorption ability and diffusion rate for gas with SAPO-34 molecular screen membranes, CO can be efficiently separated2。
Secondary hydro-thermal method synthesis SAPO-34 molecular screen membranes are to use most methods at this stage, and wherein crystal seed coating is equal
One property is most important.Supporting body surface is modified and has coated homogeneity with carrier adhesive force and raising crystal seed to increase crystal seed
[J.memsci.350 (2010) 5] is reported in LAT types molecular screen membrane.
Supplement SAPO-34 molecular screen membranes and which shortage or urgently improved performance on application performance be present.
But there has been no the document report of support modification synthesis SAPO-34 molecular screen membranes at present.
The content of the invention
Present invention aims at improve the deficiencies in the prior art, there is provided a kind of method of the molecular screen membrane of high-performance SAPO -34.
It is as follows using technical scheme to reach above-mentioned purpose：
A kind of method for preparing the molecular screen membrane of high-performance SAPO -34, comprises the following steps：
1) preparation of crystal seed：Deionized water, silicon source, tetraethyl ammonium hydroxide TEAOH solution, silicon source are mixed with phosphoric acid and stirred
Mix aging and crystal seed reaction solution is made, under 170~210 DEG C of heating, crystallization 24~36 hours, centrifuge, wash, dry, obtain
SAPO-34 molecular sieve seeds；
2) porous carrier pre-processes：By porous carrier each ultrasonic 1~2 hour in deionized water, ethanol and acetone soln
6~12 were dried at 40~80 DEG C afterwards as a child, was then calcined 8~12 hours at 350~600 DEG C；
3) carrier surface modification：Step 2 gained porous carrier is placed in the toluene solution of silane coupler, and in nitrogen
React at 80~120 DEG C under conditions of protection 0.5~2 hour, be then dried in vacuo 24 hours；
4) coating of crystal seed：Step 1 gained SAPO-34 molecular sieves are placed in after step 3 gained porous carrier both ends are sealed
In the ethanol solution of crystal seed, the carrier of uniform load SAPO-34 crystal seeds is obtained after drying；
5) synthesis of SAPO-34 molecular screen membranes：By phosphoric acid, deionized water, silicon source, silicon source, tetraethyl ammonium hydroxide TEAOH
After being well mixed with di-n-propylamine DPA, aging 48~72 hours at 50 DEG C, molecular screen membrane synthesis mother liquid is formed；By step 4 institute
The carrier that SAPO-34 crystal seeds must be loaded is placed in the stainless steel cauldron equipped with synthesis mother liquid, the water under the conditions of 170~210 DEG C
Thermal crystallisation 6~10 hours, one layer of SAPO-34 molecular screen membrane is formed in porous carrier outer wall, then wash, dry；
6) template agent removing is removed in roasting：It is small that step 5 gained SAPO-34 molecular sieves membrane tube is calcined 4~8 at 450~600 DEG C
When, obtain the molecular screen membrane of high-performance SAPO -34.
By such scheme, crystal seed reaction liquid making method is as follows described in step 1：By deionized water and tetraethyl ammonium hydroxide
TEAOH solution mixes 3~5min, and addition silicon source, which is stirred at room temperature, causes it that silicon source, stirring 1~6 are added dropwise after hydrolyzing for 1~6 hour
After hour, phosphoric acid is slowly added dropwise, it is quick to stir aging 12~48 hours, obtain crystal seed reaction solution.
By such scheme, each component Al in molar ratio in crystal seed reaction solution described in step 12O3:P2O5:SiO2:TEAOH:H2O
For 1:(1~2):(0.3~0.6):(1~3):(55~150).
By such scheme, silicon source includes aluminium isopropoxide, aluminium hydroxide, Tributyl aluminate or aluminium chloride in step 1 and 5.
By such scheme, silicon source includes Ludox, tetraethyl orthosilicate, methyl silicate, sodium metasilicate or water in step 1 and 5
Glass.
By such scheme, silane coupler described in step 3 is 3- aminopropyl triethoxysilanes (APTES) or γ-first
Base acryloxypropyl trimethoxy silane (KH-570).
By such scheme, the molar fraction of silane coupler toluene solution described in step 3 is 1~4mmol/L.
By such scheme, the ethanol solution mass percent of SAPO-34 molecular sieve seeds described in step 4 for 0.2~
0.8%.
By such scheme, each component mol ratio presses Al in synthesis mother liquid described in step 52O3:P2O5:SiO2:TEAOH:
DPA:H2O is 1:(1~3):(0.2~0.6):(1~3):(1~3):(55~450).
By such scheme, the heating calcined described in step 6 and rate of temperature fall are no more than 2K/min.
The present invention has the beneficial effect that relative to prior art：
Using silane coupler to carrier surface modification, crystal and carrier surface adhesive force are added, is greatly improved
The compactness and uniformity of SAPO-34 molecular screen membranes, the synthesis repeatability of SAPO-34 molecular screen membranes is improved, and greatly
Synthesis crystallization time is shortened, saves and prepares cost.
The SAPO-34 molecular screen membrane favorable orientations prepared, in separation H2/CO2During mixture, H2Permeability be 10.92 ×
10-7mol·m-2·s-1·Pa-1, separation selectivity is more than 14.57 (test temperature is 25 DEG C, pressure 100kPa).
Brief description of the drawings
Fig. 1：X-ray powder diffraction (XRD) figure of SAPO-34 crystal seeds in embodiment 1；
Fig. 2：ESEM (SEM) figure of SAPO-34 crystal seeds in embodiment 1；
Fig. 3：The surface SEM figures (modification of APTES surfaces) of SAPO-34 films in embodiment 1；
Fig. 4：The section SEM figures (modification of APTES surfaces) of SAPO-34 films in embodiment 1；
Fig. 5：The surface SEM figures (modification of KH-570 surfaces) of SAPO-34 films in embodiment 2；
Fig. 6：The surface SEM figures (surface unmodified) of SAPO-34 films in embodiment 3.
Embodiment
Following examples, technical scheme is further explained, but not as limiting the scope of the invention.
Embodiment 1
The preparation of SAPO-34 crystal seeds：5.02g is added into 22.67g tetraethyl ammonium hydroxides solution (TEAOH, 25wt%)
Deionized water, 5min is stirred, weigh 7.97g aluminium isopropoxides and add in above-mentioned solution, be stirred at room temperature 2 hours, 2.31g is then added dropwise
4.45g phosphoric acid solutions (85wt%) are slowly added dropwise after 2 hours in Ludox (30wt%), stirring, quick stirring 24 hours.Formed
The mol ratio of colloidal sol each component be：1Al2O3:1~2P2O5:0.3~0.6SiO2:1~3TEAOH:55~150H2O.Using
Hydrothermal synthesis method, colloidal sol is added in the stainless steel cauldron of teflon lined, the hydrothermal crystallizing under 200 DEG C of synthesis temperatures
24 hours, SAPO-34 molecular sieve seeds are obtained after centrifuge washing.
Carrier surface modification：By porous carrier in deionized water, ethanol and acetone soln after each ultrasonic 1 hour at 60 DEG C
Lower drying 6 as a child, is then calcined 8 hours at 450 DEG C.Porous carrier after processing is placed in 2.56mmol/LAPTES first
In benzole soln, react at 110 DEG C under conditions of nitrogen protection 1 hour, be then dried in vacuo 24 hours.It will change by surface
Property after carrier seeding processing, be specially：The second of SAPO-34 molecular sieves will be placed in after modified porous carrier both ends sealing
In alcoholic solution, molecular sieve is coated on porous carrier using dip coating, the load of uniform load SAPO-34 crystal seeds is obtained after drying
Body.
The synthesis of SAPO-34 molecular screen membranes：4.47g phosphoric acid solutions (85wt%) are added in 44.00g deionized waters, stirred
Mixing 5min makes its mixing, then adds 8.00g aluminium isopropoxides, being stirred at room temperature 2 hours makes its hydrolysis；Then 1.162g is added dropwise
Ludox (30wt%), quick addition 11.39g tetraethyl ammonium hydroxides solution (TEAOH, 25wt%) after stirring 30min, quickly
50 DEG C of water-baths are transferred to after dropwise addition 1.98g di-n-propylamines solution (DPA) stirring 30min to be aged 4 days, obtain after stirring 30min
SAPO-34 molecular screen membrane presomas；The modified porous carrier for being coated with SAPO-34 crystal seeds in surface prepared by step (2) is put
In reactor, the sealing of carrier both ends, the molecular screen membrane presoma that addition synthesizes before, hydrothermal crystallizing 6 hours at 210 DEG C,
Porous carrier is taken out, with deionized water rinsing to neutrality, is put into 100 DEG C of baking ovens and is dried overnight, most after calcining 6 at 550 DEG C
Hour removes template (heating and rate of temperature fall are 1 DEG C/min), obtains SAPO-34 molecular screen membranes.
The XRD of crystal seed, as shown in figure 1, being pure SAPO-34 crystalline phases, no stray crystal, the SEM of crystal seed schemes, such as Fig. 2 institutes
Show.
Fig. 3 shows the surface microstructure of the SAPO-34 films synthesized on the modified more empty carriers in APTES surfaces.
Molecular sieve crystal compact growth, carrier surface are covered by one layer of SAPO-34 crystal.
Fig. 4 shows the section face microstructure of the SAPO-34 films synthesized on the modified more empty carriers in APTES surfaces.
Coating growth is continuously fine and close, and thickness is about 8 microns.
The gas separating property of film by equimolar than H2/CO2Mixed gas tests separating property.It is 25 DEG C in temperature,
Pressure difference is tested under the conditions of being 100kPa, and its separating resulting is shown in Table 1.
Embodiment 2
It is in step (2) that modifying agent used is KH-570, remaining step and embodiment 1 with the difference of embodiment 1
It is identical.
H2/CO2Gas separating method is same as Example 1, and test result is as shown in table 1.Fig. 5 is SAPO-34 points prepared
The surface SEM figures of sub- sieve membrane.Fig. 5 shows that carrier surface is completely covered by SAPO-34 crystal, molecular sieve crystal compact growth.
Embodiment 3
It is in step (2) that carrier surface is unmodified with the difference of embodiment 1, remaining step is same as Example 1.
H2/CO2Gas separating method is same as Example 1, and test result is as shown in table 1.Fig. 6 is SAPO-34 points prepared
The surface SEM figures of sub- sieve membrane.SAPO-34 molecular screen membranes prepared by Fig. 6 displays are defective, have crack between crystal, it will necessarily
Influence gas separation effect.
Embodiment 4
It is that the concentration of modifier A PTES toluene solutions used in step (2) is 4mmol/ with the difference of embodiment 1
L, remaining step are same as Example 1.
H2/CO2Gas separating method is same as Example 1, and test result is as shown in table 1.
Embodiment 5
H2/CO2Gas separating method is same as Example 1, and test result is as shown in table 1.
The concentration for being modifying agent KH-570 toluene solutions used in step (2) with the difference of embodiment 1 is
4mmol/L, remaining step are same as Example 1.
Table 1 is the H of SAPO-34 molecular screen membranes prepared by embodiment 1-52/CO2Gas separating resulting counts.It can therefrom see
Go out, after APTES and KH-570 are to carrier surface modification, either generated time, infiltration rate or H2/CO2Gas separation effect
All it is significantly better than unmodified case.
Table 1：The H of the SAPO-34 molecular screen membranes prepared in embodiment2/CO2Gas separating resulting.
Claims (10)
- A kind of 1. method for preparing the molecular screen membrane of high-performance SAPO -34, it is characterised in that comprise the following steps：1) preparation of crystal seed：Deionized water, silicon source, tetraethyl ammonium hydroxide TEAOH solution, silicon source and phosphoric acid are mixed old Change and crystal seed reaction solution is made, under 170~210 DEG C of heating, crystallization 24~36 hours, centrifuge, wash, dry, obtain SAPO-34 Molecular sieve seed；2) porous carrier pre-processes：By porous carrier in deionized water, ethanol and acetone soln after each ultrasonic 1~2 hour 6~12 were dried at 40~80 DEG C as a child, was then calcined 8~12 hours at 350~600 DEG C；3) carrier surface modification：Step 2 gained porous carrier is placed in the toluene solution of silane coupler, and protected in nitrogen Under conditions of react 0.5~2 hour at 80~120 DEG C, be then dried in vacuo 24 hours；4) coating of crystal seed：Step 1 gained SAPO-34 molecular sieve seeds are placed in after step 3 gained porous carrier both ends are sealed Ethanol solution in, dry after obtain the carrier of uniform load SAPO-34 crystal seeds；5) synthesis of SAPO-34 molecular screen membranes：By phosphoric acid, deionized water, silicon source, silicon source, tetraethyl ammonium hydroxide TEAOH and two After n-propylamine DPA is well mixed, aging 48~72 hours at 50 DEG C, molecular screen membrane synthesis mother liquid is formed；Will be negative obtained by step 4 The carrier for carrying SAPO-34 crystal seeds is placed in the stainless steel cauldron equipped with synthesis mother liquid, and hydro-thermal is brilliant under the conditions of 170~210 DEG C Change 6~10 hours, one layer of SAPO-34 molecular screen membrane is formed in porous carrier outer wall, then wash, dry；6) template agent removing is removed in roasting：Step 5 gained SAPO-34 molecular sieves membrane tube is calcined 4~8 hours at 450~600 DEG C, Obtain the molecular screen membrane of high-performance SAPO -34.
- 2. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that crystal seed described in step 1 It is as follows to react liquid making method：Deionized water and tetraethyl ammonium hydroxide TEAOH solution are mixed into 3~5min, add aluminium Source, which is stirred at room temperature, causes it that silicon source is added dropwise after hydrolyzing for 1~6 hour, after stirring 1~6 hour, phosphoric acid is slowly added dropwise, quickly stirs aging 12~48 hours, obtain crystal seed reaction solution.
- 3. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that crystal seed described in step 1 Each component Al in molar ratio in reaction solution2O3:P2O5:SiO2:TEAOH:H2O is 1:(1~2):(0.3~0.6):(1~3):(55 ~150).
- 4. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that silicon source in step 1 and 5 Including aluminium isopropoxide, aluminium hydroxide, Tributyl aluminate or aluminium chloride.
- 5. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that silicon source in step 1 and 5 Including Ludox, tetraethyl orthosilicate, methyl silicate, sodium metasilicate or waterglass.
- 6. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that silicon described in step 3 Alkane coupling agent is 3- aminopropyl triethoxysilanes or γ-methacryloxypropyl trimethoxy silane.
- 7. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that silicon described in step 3 The molar fraction of alkane coupling agent toluene solution is 1~4mmol/L.
- 8. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that described in step 4 The ethanol solution mass percent of SAPO-34 molecular sieve seeds is 0.2~0.8%.
- 9. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that closed described in step 5 Each component mol ratio presses Al into mother liquor2O3:P2O5:SiO2:TEAOH:DPA:H2O is 1:(1~3):(0.2~0.6):(1~ 3):(1~3):(55~450).
- 10. the method for preparing the molecular screen membrane of high-performance SAPO -34 as claimed in claim 1, it is characterised in that forged described in step 6 The heating of burning and rate of temperature fall are no more than 2K/min.
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| CN107746059A (en) * | 2017-09-15 | 2018-03-02 | 武汉理工大学 | A kind of preparation method of the hollow silica microsphere of surface silane-containing modification |
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| CN114715914B (en) * | 2022-04-06 | 2024-01-02 | 华南理工大学 | Method for removing organic structure guiding agent in SAPO-34 molecular sieve membrane pore canal at low temperature |
| CN116081957A (en) * | 2022-12-15 | 2023-05-09 | 中建材玻璃新材料研究院集团有限公司 | Porous film and preparation method and application thereof |
| CN116081957B (en) * | 2022-12-15 | 2024-04-16 | 中建材玻璃新材料研究院集团有限公司 | Porous film and preparation method and application thereof |
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Application publication date: 20180302 |