CN105251374A - Preparation method of nano-scale surface defect seed crystal induced SAPO-34 molecular sieve membrane - Google Patents
Preparation method of nano-scale surface defect seed crystal induced SAPO-34 molecular sieve membrane Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 40
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000007547 defect Effects 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000006703 hydration reaction Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 16
- 235000012489 doughnuts Nutrition 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 29
- 238000000926 separation method Methods 0.000 abstract description 18
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000012510 hollow fiber Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000000713 high-energy ball milling Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002775 capsule Substances 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a nano-scale surface defect seed crystal induced SAPO-34 molecular sieve membrane, which comprises the steps of crushing an SAPO-34 molecular sieve into seed crystals with the particle size of 50 nm-2 mu m by using a high-energy ball mill, adding water to form a suspension, and adding HPC under ultrasonic stirring until the mass concentration reaches 0.05% to obtain a liquid crystal; putting the membrane support body into a liquid crystal, dipping, lifting, drying, and calcining at 400 ℃ for 4h to obtain a support body loaded with seed crystals; in a molar ratio of Al2O3∶P2O5∶SiO2∶TEAOH∶DPA∶H2And O = 1.0: 0.45: 1.2: 1.6: 100, putting the synthetic mother liquor into the support, carrying out hydration reaction at 180 ℃ for 12-24 h, heating to 400 ℃ at 0.8K/min, preserving heat for 10h, cooling to 25 ℃ at 0.8K/min, drying and calcining to obtain the hollow fiber SAPO-34 molecular sieve membrane. The method has simple process, low cost and less equipment investment, is suitable for industrial production, and the prepared SAPO-34 membrane molecular sieve membrane has higher gas separation efficiency and separation selectivity to CH4/CO2The separation selectivity of the method is greatly superior to that of the SAPO-34 molecular sieve membrane prepared by seed crystals without crushing treatment.
Description
Technical field
Inoranic membrane isolation technics has high efficiency, low energy consumption and take up an area the features such as few, and at present, inoranic membrane isolation technics is used widely in industrial gasses process, seepage slope and environmental protection etc.
Background technology
Inoranic membrane isolation technics has high efficiency, low energy consumption and take up an area the features such as few, and at present, inoranic membrane isolation technics is used widely in the fields such as industrial gasses process, seepage slope and environmental protection.
Molecular screen membrane is the important component part of inoranic membrane, and it has rule and homogeneous pore passage structure, has good catalysis and separation efficiency, particularly molecular screen membrane and is removing the CO in natural gas
2isolation technics in have splendid application prospect.The CO in natural gas is removed about molecular screen membrane
2existing a large amount of report, comprises T, DDR, MFI, Y, AlPO-18, SAPO-34 equimolecular sieve membrane.But except SAPO-34 molecular screen membrane, other molecular screen membrane can not meet high gas permeability and high separation selectivity mostly simultaneously.
SAPO-34 is the aluminium silicophosphate type molecular sieve with CHA configuration, and have three-dimensional 8 identical ring structure ducts, its pore size is 0.38nm, between CO
2(0.33nm) and CH
4(0.38nm) between.Meanwhile, SAPO-34 molecular sieve is for CO
2there is stronger Preferential adsorption effect, be more suitable for CH compared to other molecular screen materials
4/ CO
2separation, be that natural gas removes CO
2separation membrane first-selected in technique.At present, the report about SAPO-34 molecular screen membrane preparation technology is a lot, but in published report, the synthesis temperature of the SAPO-34 molecular screen membrane that preparation is fine and close is general higher, is generally 200 DEG C-220 DEG C; If reduction synthesis temperature, then needing to increase synthesis number of times could obtain compact film.People (NandiniDasetal.CeramicsInternational, 2012 (38): the 333 – 340) reports such as such as NandiniDas, synthesis temperature is 170 DEG C, and synthesis 120h, need synthesize 4 times and just can obtain fine and close SAPO-34 rete.Zhu Guangshan etc. disclose the method preparing SAPO-34 film on macropore stainless (steel) wire in CN200810050714.8, synthesis temperature 180 DEG C, and generated time reaches 15 days, and the film of first time synthesis, its CO
2/ CH
4separation selectivity only has 12.5.The people such as Zhang Baoquan (BaoquanZhangetal.MaterialsLetters, 2013 (91): 195 – 197) use the mode of heating using microwave, synthesize 4h, prepared high performance SAPO-34 molecular screen membrane at 180 DEG C.Although microwave process for synthesizing can shorten generated time greatly, reduce synthesis temperature, building-up process needs by microwave heating equipment, is not suitable for large industrialized preparation.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of Nanoscale Surface defect crystal seed induction doughnut SAPO-34 molecular screen membrane, this method adopts lower film synthesis temperature and less synthesis number of times, prepare the high strength with high compact film and have high separability can SAPO-34 molecular screen membrane.
Method of the present invention comprises step:
(1) high energy ball mill is adopted SAPO-34 sieve particle to be broken for the fine powder of 50nm ~ 2 μm, stand-by as crystal seed;
(2) added water by described crystal seed fine powder and be mixed with the molecular sieve suspension that mass content is 0.5-1%, under ultrasonic wave stirs, the mass concentration adding HPC in HPC solution to suspension reaches 0.05%, obtains crystal seed liquid; Immerse in crystal seed liquid by the flat board of drying or doughnut supporter, after Best-Effort request, dry, 400 DEG C of calcining 4h, obtain the supporter that load has crystal seed;
(3) take mol ratio as Al
2o
3: P
2o
5: SiO
2: TEAOH:DPA:H
2the proportional arrangement film synthesis mother liquid of O=1.0:1.0:0.45:1.2:1.6:100=1.0:1.0:0.45:1.2:1.6:100, put into the supporter of load crystal seed, after 180 DEG C of hydration reaction 12 ~ 24h, with the ramp to 400 of 0.8K/min DEG C, insulation 10h, then be cooled to 25 DEG C with the speed of 0.8K/min, take out supporter, dry and calcine, obtaining product doughnut SAPO-34 molecular screen membrane.Above-mentioned TEAOH is tetraethyl ammonium hydroxide, and DPA is di-n-propylamine;
TEAOH in above-mentioned steps (3) is tetraethyl ammonium hydroxide, and DPA is di-n-propylamine, lower same.
Described SAPO-34 sieve particle is the fine powder of 0.3 μm through high energy ball mill pulverizing, stand-by as crystal seed.
The described hydration reaction time is 18h.
Described supporter is doughnut four-way aluminium oxide or zirconia support.
Nanoscale SAPO-34 molecular sieve after the present invention adopts high-energy ball milling process is induced as crystal seed, molecular sieve after high-energy ball milling process, its surface topography generation significant change, particle diameter diminishes, and the crystal structure of crystal seed changes, in building-up process, the crystal structure destroyed more is conducive to improving seeded growth speed, and the crystal seed simultaneously after high-energy ball milling process has both larger specific area, can contact more fully with synthesis liquid, improve combined coefficient, can synthesis cycle be shortened.Thus can, under lower synthesis temperature, only need single sintering can obtain high fine and close SAPO-34 molecular sieve rete; Under same synthesis condition, the rete that this method synthesizes is more fine and close.The more important thing is, the SAPO-34 molecular screen membrane that this method adopts Nanoscale Surface defect crystal seed to make can improve gas separaion efficiency, proves by experiment, especially to CH
4/ CO
2separation selectivity be greatly better than the SAPO-34 molecular screen membrane that untreated crystal seed makes, improve CH
4/ CO
2separative efficiency.In sum, preparation technology of the present invention is simple, and preparation cost is low, can reduce equipment investment, good repeatability, is applicable to suitability for industrialized production.The gas separaion efficiency that the SAPO-34 membrane molecule sieve membrane tool made is higher and high separation selectivity.
Accompanying drawing explanation
Fig. 1 is X-ray line diffraction (XRD) curve map of SAPO-34 molecular sieve.
Fig. 2 is SEM (SEM) figure of the SAPO-34 molecular sieve of 1 μm without the particle diameter of high-energy ball milling process.
Fig. 3 is SEM (SEM) figure of the SAPO-34 molecular sieve of 0.3 μm through the particle diameter of high-energy ball milling process.
Fig. 4 is surface Scanning Electron microscope (SEM) micro-structure diagram of the SAPO-34 molecular screen membrane being 0.3 μm of Nanoscale Surface defect crystal seed Induced synthesis with particle diameter.
Fig. 5 is section microscope (SEM) micro-structure diagram of the SAPO-34 molecular screen membrane being 0.3 μm of Nanoscale Surface defect crystal seed Induced synthesis with particle diameter.
Surface Scanning Electron microscope (SEM) micro-structure diagram of Fig. 6 to be particle diameter be SAPO-34 molecular screen membrane of the crystal seed Induced synthesis without high energy ball mill process of 1 μm.
Fig. 7 is section microscope (SEM) micro-structure diagram of the SAPO-34 molecular screen membrane being the crystal seed Induced synthesis without high energy ball mill process of 1 μm with particle diameter.
Fig. 8 is surface Scanning Electron microscope (SEM) micro-structure diagram of the crystal seed Induced synthesis SAPO-34 molecular screen membrane without high energy ball mill process being 0.3 μm with particle diameter.
Fig. 9 is the section microstructure of the SAPO-34 molecular screen membrane being the crystal seed Induced synthesis without high energy ball mill process of 0.3 μm with particle diameter.
Detailed description of the invention
In following embodiment, the initial molecule sieve particle for 1 μm of seed feedstock and two kinds of specifications of 0.3 μm synthesizes by laboratory.In Fig. 1, upper two curves are respectively 0.3 μm of particle diameter molecular sieve of laboratory synthesis and X-ray line diffraction (XRD) curve of 1 μm of particle diameter molecular sieve, next curve is the SAPO-34 zeolites collection of illustrative plates of International Molecular sieve association, by contrasting with SAPO-34 zeolites peak, what confirm the molecular sieve of two kinds of specifications of laboratory synthesis gained is SAPO-34 molecular sieve.
embodiment 1
Step 1:
Be the SAPO-34 molecular sieve high energy ball mill break process 3h of 1 μm by average grain diameter, the molecular sieve particle diameter after process is 0.3 μm, as molecular sieve crystal seed, stand-by.Fig. 2 is the Electronic Speculum figure of the molecular sieve of 1 μm without the particle diameter of high energy ball mill process, and showing molecular sieve is sheet-like morphology.And after high energy ball mill process, the pattern of molecular sieve becomes the amorphous as Fig. 3 from the sheet of Fig. 2.
Step 2:
Add water crystal seed stirring, be mixed with the crystal seed suspension that mass content is 0.5%, HPC is added under ultrasonic wave stirs, mass content to HPC reaches 0.05%, adopts the mode of conventional Best-Effort request, takes out after aluminium oxide four-way doughnut supporter is flooded 15s in crystal seed liquid, 80 ° of C are dried, 400 DEG C of calcining 4h, during calcining, heating rate and rate of temperature fall are 1K/min, obtain the four-way doughnut supporter being coated with crystal seed.
Step 3:
General mole consists of Al
2o
3: P
2o
5: SiO
2: TEAOH:DPA:H
2o=1.0:1.0:0.45:1.2:1.6:100 is made into film synthesis mother liquid, at room temperature stir 48h, to be coated with in the doughnut support film synthesis mother liquid of crystal seed, enter baking oven, keep 180 DEG C, after synthesis 18h, take out washing, Muffle furnace is entered after drying, with the ramp to 400 of 0.8K/min DEG C calcining 10h, the template that SAPO-34 molecular screen membrane contains under high temperature air atmosphere is removed, and is cooled to room temperature subsequently with the speed of 0.8K/min, obtained product SAPO-34 molecular screen membrane of the present invention.
Fig. 4 shows the surface microstructure that employing particle diameter is the crystal seed synthesis SAPO-34 molecular screen membrane after the high energy ball mill process of 0.3 μm, and can find out in figure that supporting body surface is covered by SAPO-34 crystal, molecular sieve intergrowth is tight.
Fig. 5 shows the section microstructure of the SAPO-34 molecular screen membrane synthesized by the present embodiment, and can find out in figure that coating growth is tight, thicknesses of layers is 7 μm.
embodiment 2
Step 1:
Be averaged the SAPO-34 molecular sieve without high energy ball mill process that particle diameter is 1 μm, stand-by as crystal seed.
Step 2:
By embodiment 1 step 2 method, add water crystal seed stirring, will stir and be made into the crystal seed suspension of 0.5wt%, and under ultrasonic agitation, adding that HPC reaches to its mass content is 0.05%.The mode of same employing Best-Effort request, is placed on aluminium oxide four-way doughnut supporter after flooding 15s in crystal seed liquid and takes out, dry and calcine, obtaining the carrier support being coated with crystal seed.
Step 3:
With the step 3 of embodiment 1, obtained product SAPO-34 molecular screen membrane.
Fig. 6 shows and adopts particle diameter to be the surface microstructure of the SAPO-34 molecular screen membrane obtained without the crystal seed of high energy ball mill process of 1 μm, can find out in figure that supporting body surface is covered by SAPO-34 crystal, it is comparatively tight that molecular sieve exchanges growth, but compactness extent is less than Fig. 4 of embodiment 1.
Fig. 7 shows the section microstructure of the SAPO-34 molecular screen membrane synthesized by the present embodiment, and can find out in figure that coating growth is tight, thicknesses of layers is 6 μm.
embodiment 3
Step 1: be averaged the SAPO-34 molecular sieve without high energy ball mill process that particle diameter is 0.3 μm, stand-by as crystal seed.
Step 2:
By embodiment 1 step 2 method, add water crystal seed stirring, is made into the crystal seed suspension of 1wt%; Subsequently under ultrasonic agitation, adding that HPC reaches to its mass content is 0.05%.The mode of same employing Best-Effort request, takes out after supporter is flooded 15s in crystal seed liquid, dries and calcines (operating condition is with embodiment 1), obtaining the carrier of load crystal seed.
Step 3: with the step 3 of embodiment 1, obtained product SAPO-34 molecular screen membrane.
Fig. 8 shows the surface microstructure of the crystal seed synthesis film of 0.3 μm adopted without high energy ball mill process, and can find out in figure that supporting body surface is covered by SAPO-34 crystal seed, it is comparatively tight that molecular sieve exchanges growth.
Fig. 9 shows the section microstructure of the crystal seed synthesis film of 0.3 μm adopted without high energy ball mill process, and can find out in figure that coating growth is tight, thicknesses of layers is 6 μm.
embodiment 4
Step 1:
Be the SAPO-34 molecular sieve high energy ball mill process 6h of 1 μm by average grain diameter, the average grain diameter of gained molecular sieve fine powder is 0.1 μm, stand-by as crystal seed.
Step 2:
By the method for embodiment 1 step 2, add water crystal seed stirring, is made into the crystal seed suspension of 0.5wt%; Subsequently under ultrasonic agitation, adding that HPC reaches to its mass content is 0.05%.Adopt the mode of Best-Effort request, take out after supporter is flooded 15s in crystal seed liquid, dry and calcine, obtain the carrier of load crystal seed.
Step 3: with the step 3 of embodiment 1, obtained product SAPO-34 molecular screen membrane.
embodiment 5
Step 1:
Be the SAPO-34 molecular sieve high energy ball mill process 6h of 1 μm by average grain diameter, the average grain diameter of gained molecular sieve fine powder is 0.3 μm, stand-by as crystal seed.
Step 2:
By the method for embodiment 1 step 2, add water crystal seed stirring, is made into the crystal seed suspension of 1wt%; Subsequently under ultrasonic agitation, adding that HPC reaches to its mass content is 0.05%.Adopt the mode of Best-Effort request, take out after supporter is flooded 15s in crystal seed liquid, dry and calcine, obtain the carrier of load crystal seed.
Step 3: with the step 3 of embodiment 1, obtained product SAPO-34 molecular screen membrane.
embodiment 6
Step 1:
Be the molecular sieve high energy ball mill process 3h of 1 μm by average grain diameter, obtain the SAPO-34 molecular sieve crystal seed that average grain diameter is 0.3 μm.
Step 2:
By the method for embodiment 1 step 2, add water crystal seed stirring, is made into the crystal seed suspension of 2wt%; Subsequently under ultrasonic agitation, adding that HPC reaches to its mass content is 0.05%.Adopt the mode of Best-Effort request, take out after supporter is flooded 15s in crystal seed liquid, dry and calcine, obtain the carrier of load crystal seed.
Step 3: with the step 3 of embodiment 1, obtained product SAPO-34 molecular screen membrane.
Step 3:
With the step 3 of embodiment 1, obtained product SAPO-34 molecular screen membrane.
embodiment 7
Step 1:
Be the molecular sieve high energy ball mill process 3h of 1 μm by average grain diameter, obtain the SAPO-34 molecular sieve crystal seed that average grain diameter is 0.3 μm.
Step 2:
By the method for embodiment 1 step 2, add water crystal seed stirring, is made into the crystal seed suspension of 0.5wt%; Subsequently under ultrasonic agitation, adding that HPC reaches to its mass content is 0.05%.Adopt the mode of Best-Effort request, take out after supporter is flooded 15s in crystal seed liquid, dry and calcine, obtain the carrier of load crystal seed.
Step 3: except generated time changes 6h into, all the other conditions, with the step 2 in embodiment 1, obtain product SAPO-34 molecular screen membrane.
embodiment 8
Except generated time in step 3 changes into except 12h, all the other conditions, with embodiment 1, obtain product SAPO-34 molecular screen membrane.
embodiment 9
Except generated time in step 3 changes into except 24h, all the other conditions, with embodiment 1, obtain product SAPO-34 molecular screen membrane.
example 10the gas separating property test of SAPO-34 molecular screen membrane
Gas separating property is evaluated by gas permeability P and separation selectivity α.Gas permeability P=V/ (S × P), V are infiltration gas (CO
2or CH
4) flow, unit mol/s; S is effective film area, unit m
2; P is transmembrane pressure, unit Pa.Separation selectivity α=P
cO2/ P
cH4, i.e. CO
2with CH
4the ratio of permeability.
Gas separaion test is carried out to the film prepared by the various embodiments described above as follows: at 25 DEG C, the charging of four-way doughnut SAPO-34 molecular screen membrane assembly is CO
2/ CH
4mol ratio is the mist of 1:1, feed side pressure 0.2MPa, and per-meate side is atmospheric pressure.Per-meate side flow soap bubble flowmeter records, and per-meate side gas composition is recorded by Shimadzu gas-chromatography (GC-2014).
Preparation condition and the gas separaion result of the SAPO-34 molecular screen membrane synthesized by embodiment 1 ~ 9 are as shown in table 1.
Table 1
Table 1 represents, the film that embodiment 1 is made, and its separation selectivity is the highest; Embodiment 2,3 all adopts the original crystal seed without high-energy ball milling process, the separation selectivity making film obviously reduces, but embodiment 2 adopts the film of small particle diameter (0.3 μm) JZPD capsule, its separation selectivity slightly can be better than the film that embodiment 3 adopts Large stone (1 μm) JZPD capsule.Embodiment 4 because of the crystal seed particle diameter after ball-milling treatment meticulous, the separation selectivity of its film forming can be significantly less than embodiment 1.Embodiment 5,6 all adopts 0.3 μm of crystal seed after the high-energy ball milling process identical with embodiment 1, and just crystal seed suspension concentration increases, and the too high meeting of visible crystal seed suspension concentration makes the separating property of film decline.Embodiment 7,8,9 adopts different generated times to investigate the performance of film forming, by contrast, in embodiment 7, the generated time film forming separation selectivity of 6 hours can be the poorest, the generated time 2 of embodiment 8 and embodiment 9 is respectively 12 hours and 24 hours, compared to 18 in embodiment 1 hour, the separation selectivity of its film forming declines to some extent, and therefore generated time is good with 18 hours.
CO in table 1
2the resistance to mass tranfer that the thickness of self wall of permeability and supporter is brought is relevant, and the present invention adopts high-intensity hollow fiber four-way aluminium oxide (also can use zirconia) supporter, reduces support body layer resistance to mass tranfer.
Claims (4)
1. the preparation method of a Nanoscale Surface defect crystal seed induction SAPO-34 molecular screen membrane
,it is characterized in that comprising step:
(1) high energy ball mill is adopted SAPO-34 sieve particle to be broken for the fine powder of 50nm ~ 2 μm, stand-by as crystal seed;
(2) added water by described crystal seed fine powder and be mixed with the molecular sieve suspension that mass content is 0.5-1%, under ultrasonic wave stirs, the mass concentration adding HPC in HPC solution to suspension reaches 0.05%, obtains crystal seed liquid; Immerse in crystal seed liquid by the flat board of drying or doughnut supporter, after Best-Effort request, dry, 400 DEG C of calcining 4h, obtain the supporter that load has crystal seed;
(3) take mol ratio as Al
2o
3: P
2o
5: SiO
2: TEAOH:DPA:H
2the proportions film synthesis mother liquid of O=1.0:1.0:0.45:1.2:1.6:100, put into the supporter of load crystal seed, after 180 DEG C of hydration reaction 12 ~ 24h, with the ramp to 400 of 0.8K/min DEG C, insulation 10h, then be cooled to 25 DEG C with the speed of 0.8K/min, take out supporter, dry and calcine, obtaining product doughnut SAPO-34 molecular screen membrane.
2. the preparation method of Nanoscale Surface defect crystal seed induction SAPO-34 molecular screen membrane according to claim 1
,it is characterized in that described SAPO-34 sieve particle is broken for the fine powder of 0.3 μm through high energy ball mill, stand-by as crystal seed.
3. the preparation method of Nanoscale Surface defect crystal seed induction SAPO-34 molecular screen membrane according to claim 1 and 2
,it is characterized in that the described hydration reaction time is 18h.
4. the preparation method of Nanoscale Surface defect crystal seed induction SAPO-34 molecular screen membrane according to claim 3
,it is characterized in that described supporter is doughnut four-way aluminium oxide or zirconia support.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771683A (en) * | 2016-04-26 | 2016-07-20 | 南京工业大学 | Method for improving stability of SAPO-34 molecular sieve membrane in water vapor environment |
| CN105921033A (en) * | 2016-05-27 | 2016-09-07 | 南京工业大学 | Method for preparing CHA molecular sieve membrane in clear liquid |
| CN106938850A (en) * | 2017-04-14 | 2017-07-11 | 南京工业大学 | Method for preparing SAPO-34 molecular sieve membrane |
| CN107008157A (en) * | 2017-04-18 | 2017-08-04 | 南京工业大学 | SAPO-56 molecular sieve membrane and preparation method thereof |
| CN110002462A (en) * | 2019-04-30 | 2019-07-12 | 青岛科技大学 | The synthetic method and gained MTO catalyst of SAPO-34 type molecular sieve with hollow structure |
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| CN105771683A (en) * | 2016-04-26 | 2016-07-20 | 南京工业大学 | Method for improving stability of SAPO-34 molecular sieve membrane in water vapor environment |
| CN105771683B (en) * | 2016-04-26 | 2019-02-19 | 南京工业大学 | Method for improving stability of SAPO-34 molecular sieve membrane in water vapor environment |
| CN105921033A (en) * | 2016-05-27 | 2016-09-07 | 南京工业大学 | Method for preparing CHA molecular sieve membrane in clear liquid |
| CN106938850A (en) * | 2017-04-14 | 2017-07-11 | 南京工业大学 | Method for preparing SAPO-34 molecular sieve membrane |
| CN107008157A (en) * | 2017-04-18 | 2017-08-04 | 南京工业大学 | SAPO-56 molecular sieve membrane and preparation method thereof |
| CN107008157B (en) * | 2017-04-18 | 2019-07-19 | 南京工业大学 | SAPO-56 molecular sieve membrane and preparation method thereof |
| CN110002462A (en) * | 2019-04-30 | 2019-07-12 | 青岛科技大学 | The synthetic method and gained MTO catalyst of SAPO-34 type molecular sieve with hollow structure |
| CN110255579A (en) * | 2019-06-19 | 2019-09-20 | 正大能源材料(大连)有限公司 | Metal-modified hollow SAPO-34 molecular sieve of one kind and its preparation method and application |
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