CN106902647B - Method for improving pervaporation stability of MFI molecular sieve membrane - Google Patents
Method for improving pervaporation stability of MFI molecular sieve membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 13
- 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 13
- 238000005373 pervaporation Methods 0.000 title abstract 2
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000007853 buffer solution Substances 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 24
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 238000005538 encapsulation Methods 0.000 claims description 3
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 229960003638 dopamine Drugs 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 13
- 230000008595 infiltration Effects 0.000 description 12
- 238000001764 infiltration Methods 0.000 description 12
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 11
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 11
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 11
- 235000012489 doughnuts Nutrition 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 11
- 230000008020 evaporation Effects 0.000 description 11
- 229960004502 levodopa Drugs 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- -1 saturated alkyl methoxy silanes Chemical class 0.000 description 8
- 239000002390 adhesive tape Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- COGJUEPPUXTFJM-UHFFFAOYSA-N CO[SiH](OC)OC.FC(CC)(F)F Chemical compound CO[SiH](OC)OC.FC(CC)(F)F COGJUEPPUXTFJM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical class NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for improving the pervaporation stability of an MFI molecular sieve membrane, which adopts different modification sources to modify the surface of the molecular sieve membrane and reduces the contact between the surface of the membrane and a raw material liquid. Firstly, the membrane is subjected to a drying treatment, and secondly, the membrane is subjected to a treatment in a modification solution. And finally, cleaning the modified membrane and performing post-treatment. The molecular sieve membrane modified by the method has good separation selectivity and stability in a separation system, and the modification operation is simple and easy.
Description
Technical field
The invention belongs to inorganic field of membrane preparation, and in particular to a kind of to improve MFI molecular sieve film pervasion vaporization stability
Method.
Background technique
As petroleum resources are increasingly reduced, cost of winning and difficulty are higher and higher, and environmental pollution is got worse.Alcohol fuel
As a kind of renewable energy, has the characteristics that cleaning, efficient, coal and petroleum are far smaller than to the pollution of environment.It is current main
Alcohol fuel to be made by biomass ferments such as corn, cassava or celluloses, but since ethyl alcohol makees the inhibition of fermentation liquid
With industrially generally requiring and isolation technics such as distillation technique of low separation efficiency etc. high using traditional energy consumption for mass fraction
Generally below 10% ethyl alcohol is separated from fermentation liquid, and this separate mode at high cost and low efficiency can not expire
It the current growing social demand of foot and runs in the opposite direction with the green chemical industry theory nowadays advocated.Membrane separation technique is one
Emerging, efficient isolation technics has a series of features such as energy saving, environmentally protective, easy to operate.Infiltration evaporation membrane separation technique
As a kind of emerging efficient, energy-saving and environmental protection isolation technics, the extensive concern of researcher is caused.All-silica MFI molecular screen membrane
By its specific skeleton structure and extremely strong hydrophobic performance, excellent saturating alcohol is shown in ethanol/water separation system.
MFI molecular sieve has two-dimentional ten-ring duct, aperture.Xia etc. (J.Membr.Sci., 2016,498,324-335) is in α-
Al2O3High-throughput silicalite-1 film is prepared on doughnut, synthesized film is in separation 5wt.% ethanol/water system
When, flux 9.8kgm-2·h-1, separation factor 58.
But in prolonged ethanol water separation process, the stability of MFI molecular screen membrane will appear violent decline
Trend.Synthesis silicalite-1 divides under alkaline condition for Chezeau et al. (Zeolites, 1991,11,598-606) discovery
When son sieve particle, the Si atom in skeleton, which can lack, causes " defect silicon " to generate to generate Si- in molecular sieve surface and inside
OH.The presence of Si-OH may generate certain influence to the stability of molecular screen membrane.Kuhn et al. (J.Mem.Sci., 2009,
It 339,264-274) also studied influence of the second alcohol and water to MFI molecular screen membrane stability.The study found that in separation process, second
Alcohol can have an impact MFI molecular screen membrane, to block molecular sieve pore passage, decline membrane stability.However, there is no deeply examine
Wherein specific reaction and its destabilization mechanism are examined, does not also suggest that the method that can effectively solve the problem that MFI molecular screen membrane is unstable.
In recent years, dopamine was obtained because of the similar powerful absorption property of mussel and its easy performance from poly- self assembly
Extensive concern (Science, 2007,318,426-430).And Liu et al. people (J.Mater.Chem.A, 2015,3:4722-
4728) recycling of the super-hydrophobic film for bio-fuel is prepared using poly-dopamine base.Surface treatment can reduce MFI molecular sieve
The Si-OH quantity of film surface, and can effectively reduce contact of the ethanol/water with film surface.
Summary of the invention
A kind of raising MFI molecular sieve film pervasion vaporization is provided the purpose of the invention is to improve the deficiencies in the prior art
The method of stability, moditied processing method of the invention is easy to operate, mild condition, and MFI molecular screen membrane can be improved in infiltration vapour
There is long-time operation stability during changing.
The present invention adopts the following technical scheme: being modified using modification source on molecular screen membrane surface, molecular screen membrane is improved
To the repulsion performance of water.It is impregnated using simple, the MFI molecular screen membrane that hydroxyl is contained on surface is handled using modification source,
So that film surface is adhered to one layer of organic matter layer, improves its stability during infiltration evaporation.
The specific technical proposal of the invention is: a kind of method for improving MFI molecular sieve film pervasion vaporization stability, specific
Steps are as follows:
(1) MFI molecular screen membrane is placed in baking oven dry；
(2) buffer solution is prepared, modification source is added into buffer solution, modification source solution is obtained, at the sealing of film both ends
It after reason, is placed in the solution of modification source, controls Temperature Treatment；
(3) it after cleaning the MFI molecular screen membrane after modification with deionized water, is placed in baking oven dry.
Modification source is Dopamine hydrochloride, C in preferred steps (2)1-18Trifluoroalkanes trimethoxy silane, C1-18Three saturation alkane
Base chlorosilane, C1-18Three saturated alkyl methoxy silanes or C1-18Three saturated alkyl Ethoxysilanes.
Buffer solution is that phosphate aqueous solution, three (methylol) aminomethanes (TrisHCl) are water-soluble in preferred steps (2)
Liquid or tetraborate aqueous solution；The mass percentage of buffer solution is 0.1%~0.3%；More preferable content is 0.1wt%
~0.2wt%.
The mass content for modifying source in preferred steps (2) in the solution of modification source is 0.1%~0.3%；More preferable content is
0.1wt%~0.2wt%.
Encapsulation process method described in preferred steps (2) is tetrafluoroethene rubber belt sealing, tetrafluoro rubber stopper or sealant
Sealing.
Treatment temperature is 20~60 DEG C in preferred steps (2)；The processing time is respectively 6~for 24 hours.
Processing mode is to stand, stir or vibrate in preferred steps (2).
MFI molecular screen membrane is laboratory self-control, preparation step such as seminar's document report in the present invention
(Ind.Eng.Chem.Res.2012,51,12073-12080):
The MFI crystal seed that mass fraction is 0.1~1wt% is prepared with the HPC aqueous solution of deionized water and 0.5wt% to suspend
Liquid coats crystal seed (3~10s of dip time) in YSZ doughnut supporting body surface using dip-coating method.Coat the branch of crystal seed
Support body after the drying, roasts 4~8h at 400~550 DEG C.By TEOS, TPAOH and deionized water prepare mole group and become 0.1
~0.32SiO2: 1TPAOH:120~180H2The Synthesis liquid of O.The supporter for loading crystal seed is placed in presoma, 150~
4~10h of hydrothermal synthesis at 180 DEG C obtains MFI molecular screen membrane.Obtained MFI molecular screen membrane is placed at 400~550 DEG C and is roasted
4~8h is burnt, it is spare to remove template agent removing.
It is preferred that the carrier of above-mentioned MFI molecular screen membrane is α-Al2O3Chip supporter, α-Al2O3The support of single channel doughnut
Body, α-Al2O3Four-way doughnut supporter, the stable zirconium oxide of yttrium (YSZ) chip supporter, the stable zirconium oxide of yttrium
(YSZ) single channel doughnut supporter, the stable zirconium oxide of yttrium (YSZ) four-way doughnut supporter.
The utility model has the advantages that
Moditied processing is carried out to MFI molecular screen membrane using method of the invention, MFI molecular screen membrane surface after moditied processing
Hydroxyl tails off, and hydroxyl is reacted with modification source generates hydrophobic long chain alkyl group.Hydrophobic state is presented in molecular screen membrane surface, is seeping
In saturating vaporescence, the contact of material liquid with MFI molecular screen membrane surface can be effectively prevented, reduce silicone hydroxyl and raw material occurs instead
It answers, therefore improves stability of molecular screen membrane during infiltration evaporation.So far, MFI molecular screen membrane is modified
Processing is carried out under the high temperature conditions with improving the report majority of its infiltration evaporation stability.Key of the invention exists
In under mild conditions, MFI molecular screen membrane surface is handled, the method for improving its stability in ethanol/water system.
Detailed description of the invention
Fig. 1 is the surface contact angle test result of the molecular screen membrane in embodiment 1；
Fig. 2 is the surface contact angle test result of the molecular screen membrane in embodiment 4；
Fig. 3 is the long-time segregational stability test comparison result figure of the molecular screen membrane in embodiment 1 and embodiment 4；Its
Middle a is molecular screen membrane prepared by embodiment 4, and b is molecular screen membrane prepared by embodiment 1.
Specific embodiment
Embodiment 1
Step 1, the MFI crystal seed that mass fraction is 1wt% is prepared with the HPC aqueous solution of deionized water and 0.5wt% to suspend
Liquid.
Step 2, crystal seed is coated in YSZ supporting body surface using dip-coating method, after dry at 60 DEG C, at 500 DEG C
Roast 6h.
Step 3, the supporter for loading crystal seed is placed in presoma, the hydrothermal synthesis 6h at 180 DEG C, obtains MFI molecule
Sieve membrane.Obtained MFI molecular screen membrane is placed at 500 DEG C and roasts 6h, to remove template agent removing.
The contact angle of embodiment 1 is as shown in Figure 1, the contact angle of prepared MFI molecular screen membrane is as can be seen from Fig.
105 °, show good hydrophobicity.
Embodiment 2
Step 1, the MFI crystal seed that mass fraction is 0.5wt% is prepared with the HPC aqueous solution of deionized water and 0.5wt% to hang
Supernatant liquid.
Step 2, using dip-coating method in α-Al2O3Supporting body surface coats crystal seed, after dry at 60 DEG C, in 400 DEG C
Lower roasting 8h.
Step 3, the supporter for loading crystal seed is placed in presoma, the hydrothermal synthesis 10h at 160 DEG C, obtains MFI molecule
Sieve membrane.Obtained MFI molecular screen membrane is placed at 400 DEG C and roasts 8h, to remove template agent removing.
Embodiment 3
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into wherein, specifically uses polytetrafluoroethylene (PTFE) adhesive tape, film both ends are sealed, prevent processing solution from entering doughnut intracavitary to branch
Support body duct results in blockage, and is vertically statically placed in dopamine solution, 30 DEG C of processing 6h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 4
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into and wherein stands, 30 DEG C of processing are for 24 hours.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
The contact angle result of film prepared by the present embodiment is as shown in Fig. 2, the MFI molecular screen membrane after modification still has well
Hydrophobicity, contact angle be 103 °.The long-time segregational stability test chart of its molecular screen membrane before modification as shown in figure 3, (implement
Example 1) MFI molecular screen membrane (a) separating property constantly decline, and modify after (the present embodiment) MFI molecular screen membrane (b) show
Good stability.
Embodiment 5
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into wherein, 30 DEG C of stir process 6h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 6
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into wherein, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 7
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into wherein, 30 DEG C of oscillation treatment 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 8
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, sodium dihydrogen phosphate is added in deionized water and is configured to buffer solution (0.1wt%), then to buffer solution
Middle addition trifluoro propane trimethoxy silane obtains modification solution, and (wherein the mass concentration of trifluoro propane trimethoxy silane is
0.3%) it, will be put into wherein after the sealing of film both ends, 30 DEG C of stir process 12h.
Step 3, after hydride modified MFI molecular screen membrane being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 9
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into wherein, 40 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 10
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.3wt%), then into buffer solution
Dopamine hydrochloride is added to obtain dopamine solution hydrochloric acid (wherein the mass concentration of Dopamine hydrochloride is 0.1%), film both ends are close
It is honored as a queen and is put into wherein, specifically use polytetrafluoroethylene (PTFE) adhesive tape, film both ends are sealed, prevent processing solution from entering doughnut intracavitary
It results in blockage to supporter duct, is vertically statically placed in dopamine solution, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 11
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, sodium tetraborate is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into wherein, specifically uses polytetrafluoroethylene (PTFE) adhesive tape, film both ends are sealed, prevent processing solution from entering doughnut intracavitary to branch
Support body duct results in blockage, and is vertically statically placed in dopamine solution, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 12
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.2%), after the sealing of film both ends
It is put into wherein, specifically uses polytetrafluoroethylene (PTFE) adhesive tape, film both ends are sealed, prevent processing solution from entering doughnut intracavitary to branch
Support body duct results in blockage, and is vertically statically placed in dopamine solution, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 13
Step 1, the MFI molecular screen membrane in embodiment 1 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.3%), after the sealing of film both ends
It is put into wherein, specifically uses polytetrafluoroethylene (PTFE) adhesive tape, film both ends are sealed, prevent processing solution from entering doughnut intracavitary to branch
Support body duct results in blockage, and is vertically statically placed in dopamine solution, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 14
Step 1, the MFI molecular screen membrane in embodiment 2 is placed in baking oven dry.
Step 2, TrisHCl is added in deionized water and is configured to buffer solution (0.1wt%), then into buffer solution
Dopamine hydrochloride is added and obtains dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after the sealing of film both ends
It is put into wherein, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membrane of DOPA being cleaned with deionized water, 60 DEG C of dry 12h in baking oven.
Embodiment 15
Infiltration evaporation characterization is carried out to the MFI molecular screen membrane after MFI molecular screen membrane obtained and modification.The infiltration evaporation of film
Permeation flux F (kgm of the performance usually by penetrating per membrane area in the unit time-2·h-1) and two parameters of separation factor α
It measures, α is defined as follows:
Y in formulaeAnd ywRespectively indicate the mass fraction of per-meate side second alcohol and water, xeAnd xwRespectively indicate in raw material ethyl alcohol and
The mass fraction of water.The infiltration evaporation performance for the MFI molecular screen membrane that embodiment 2~12 is modified is as shown in table 1, operation temperature 60
DEG C, water content 95wt.%.
The 20h infiltration evaporation after infiltration evaporation performance and modification in 1 embodiment 3~14 of table before the modification of MFI molecular screen membrane
Performance comparison
Embodiment 16
Infiltration evaporation characterization is carried out to the MFI molecular screen membrane that embodiment 3 is modified.It is applied to operation temperature be 60 DEG C,
The separation of 5wt.% butanol/water system.It is operated by 48 hours infiltration evaporations, the MFI molecular screen membrane after being modified in embodiment 3
Permeation flux maintain as 0.6kgm-2·h-1Left and right, and it stablizes 26 or so the separation factor of butanol/water.
Claims (6)
1. a kind of method for improving MFI molecular sieve film pervasion vaporization stability, the specific steps of which are as follows:
(1) MFI molecular screen membrane is placed in baking oven dry；
(2) buffer solution is prepared, modification source Dopamine hydrochloride is added into buffer solution, modification source solution is obtained, by film both ends
It after encapsulation process, is placed in the solution of modification source, controls Temperature Treatment；
(3) it after cleaning the MFI molecular screen membrane after modification with deionized water, is placed in baking oven dry.
2. according to the method described in claim 1, it is characterized in that buffer solution is phosphate aqueous solution, three (hydroxyls in step (2)
Methyl) aminomethane aqueous solution or tetraborate aqueous solution；The mass percentage of buffer solution is 0.1%~0.3%.
3. according to the method described in claim 1, it is characterized in that the mass content in source is modified in step (2) in the solution of modification source
It is 0.1%~0.3%.
4. according to the method described in claim 1, it is characterized in that encapsulation process method described in step (2) is tetrafluoroethene
Rubber belt sealing, tetrafluoro rubber stopper or sealant sealing.
5. according to the method described in claim 1, it is characterized in that treatment temperature is 20~60 DEG C in step (2)；Handle the time
For 6~for 24 hours.
6. according to the method described in claim 1, it is characterized in that processing mode is to stand, stir or vibrate in step (2).
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| CN110280146B (en) * | 2019-06-14 | 2021-12-17 | 南京工业大学 | Method for repairing defects of molecular sieve membrane by using three-dimensional mesh organic flexible material |
| CN111346516B (en) * | 2020-03-12 | 2022-06-24 | 江西师范大学 | Modification method of T-shaped molecular sieve membrane, modified T-shaped molecular sieve membrane and application thereof |
| CN112915814B (en) * | 2021-02-06 | 2022-09-16 | 江西师范大学 | Novel membrane material for gas separation and preparation method thereof |
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| CN103007779A (en) * | 2012-12-05 | 2013-04-03 | 南京工业大学 | Preparation method of hollow fiber hydrogen permeable molecular sieve membrane |
| 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 |
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| CN103007779A (en) * | 2012-12-05 | 2013-04-03 | 南京工业大学 | Preparation method of hollow fiber hydrogen permeable molecular sieve membrane |
| 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 |
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