CN106902647A - 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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- CN106902647A CN106902647A CN201710198427.0A CN201710198427A CN106902647A CN 106902647 A CN106902647 A CN 106902647A CN 201710198427 A CN201710198427 A CN 201710198427A CN 106902647 A CN106902647 A CN 106902647A
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- molecular screen
- mfi molecular
- cushioning liquid
- membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 34
- 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
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 230000004048 modification Effects 0.000 claims abstract description 26
- 238000012986 modification Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical group 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
- 230000008569 process Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- -1 saturated alkyl chlorosilanes Chemical class 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 239000000203 mixture Substances 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
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 claims 1
- 229960003132 halothane Drugs 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 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 12
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 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 20
- 229960003638 dopamine Drugs 0.000 description 17
- 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
- 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
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 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
- 239000012530 fluid Substances 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
- 238000002360 preparation method Methods 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009738 saturating Methods 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
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000008859 change Effects 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
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000007654 immersion Methods 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
- 239000003921 oil Substances 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
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum 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
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- 230000001629 suppression Effects 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
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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 raising MFI molecular sieve film pervasions vaporization stability
Method.
Background technology
As petroleum resources is increasingly reduced, cost of winning and difficulty more and more higher, environmental pollution are increasingly serious.Alcohol fuel
As a kind of regenerative resource, with cleaning, it is efficient the features such as, its pollution to environment is far smaller than coal and oil.It is current main
Alcohol fuel is obtained by biomass ferments such as corn, cassava or celluloses, but because ethanol is made for the suppression of zymotic fluid
With industrially generally requiring mass fraction using traditional high energy consumption and the isolation technics such as distillation technique of low separation efficiency etc.
Generally below 10% ethanol is separated from zymotic fluid, and this high cost and the low separate mode of efficiency cannot expire
The current growing social demand of foot and run in the opposite direction with the green chemical industry theory nowadays advocated.Membrane separation technique is one
Emerging, efficient isolation technics, possesses a series of features such as energy-conservation, environmental protection, 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 sieves have two-dimentional ten-ring duct, its aperture.Xia etc. (J.Membr.Sci., 2016,498,324-335) α-
Al2O3High-throughout silicalite-1 films are prepared on doughnut, synthesized film is separating 5wt.% ethanol/water systems
When, flux is 9.8kgm-2·h-1, separation factor is 58.
But, in prolonged ethanol water separation process, the stability of MFI molecular screen membranes occurs violent decline
Trend.Chezeau et al. (Zeolites, 1991,11,598-606) has found silicalite-1 points of synthesis in the basic conditions
During son sieve particle, the Si atoms in skeleton can be lacked causes " defect silicon " to produce so as to produce Si- in molecular sieve surface and inside
OH.The presence of Si-OH may produce certain influence to the stability of molecular screen membrane.Kuhn et al. (J.Mem.Sci., 2009,
339,264-274) also studied influence of the second alcohol and water to MFI molecular screen membrane stability.Research finds, in separation process, second
Alcohol can produce influence to MFI molecular screen membranes, so as to block molecular sieve pore passage, decline membrane stability.However, not examining deeply
Wherein specific reaction and its destabilization mechanism are examined, the method that can effectively solve the problem that MFI molecular screen membranes are unstable is not suggested that yet.
In recent years, dopamine was obtained because being similar to the powerful absorption property of mussel and the performance from poly- self assembly of its simplicity
Extensive concern (Science, 2007,318,426-430).And Liu et al. (J.Mater.Chem.A, 2015,3:4722-
4728) super-hydrophobic film is prepared for the recovery of bio-fuel using poly-dopamine basic unit.Surface treatment can reduce MFI molecular sieves
The Si-OH quantity on film surface, and can effectively reduce the contact of ethanol/water and film surface.
The content of the invention
A kind of MFI molecular sieve film pervasions that improve are provided the invention aims to improve the deficiencies in the prior art to vaporize
The method of stability, moditied processing method of the invention is easy to operate, mild condition, can improve MFI molecular screen membranes in infiltration vapour
There is long-time operation stability during change.
The present invention is adopted the following technical scheme that：Modified on molecular screen membrane surface using modification source, improved molecular screen membrane
To the repulsion performance of water.Using simple immersion, the MFI molecular screen membranes for containing hydroxyl to surface using modification source are processed,
Make one layer of organic matter layer of film surface attachment, improve its stability during infiltration evaporation.
Concrete technical scheme of the invention is：A kind of method that raising MFI molecular sieve film pervasions vaporize stability, its is specific
Step is as follows：
(1) MFI molecular screen membranes are placed in baking oven and are dried；
(2) cushioning liquid is prepared, to modification source is added in cushioning liquid, modification source solution is obtained, at the sealing of film two ends
After reason, it is placed in the solution of modification source, controls Temperature Treatment；
(3) after the MFI molecular screen membranes after modification are cleaned with deionized water, it is placed in baking oven and dries.
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.
Cushioning liquid is that aqueous phosphatic, three (methylol) aminomethanes (TrisHCl) are water-soluble in preferred steps (2)
Liquid or the tetraborate aqueous solution；The weight/mass percentage composition of cushioning liquid is 0.1%~0.3%；More preferably 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 preferably content is
0.1wt%~0.2wt%.
Encapsulation process method described in preferred steps (2) is tetrafluoroethene rubber belt sealing, tetrafluoro rubber stopper or fluid sealant
Sealing.
Treatment temperature is 20~60 DEG C in preferred steps (2)；Process time is respectively 6~24h.
Processing mode is standing, stirs or vibrate in preferred steps (2).
MFI molecular screen membranes are laboratory self-control, preparation process such as seminar's document report in the present invention
(Ind.Eng.Chem.Res.2012,51,12073-12080)：
HPC solution mass fractions with deionized water and 0.5wt% are that the MFI crystal seeds of 0.1~1wt% suspend
Liquid, crystal seed (3~10s of dip time) is coated using dip-coating method in YSZ doughnuts supporting body surface.Coat the branch of crystal seed
Support body after the drying, at 400~550 DEG C be calcined 4~8h.By TEOS, TPAOH and deionized water preparation mole composition are 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 Synthesiss at 180 DEG C, obtains MFI molecular screen membranes.Roasted at obtained MFI molecular screen membranes are placed in into 400~550 DEG C
4~8h is burnt, it is standby to remove template agent removing.
It is preferred that the carrier of above-mentioned MFI molecular screen membranes is α-Al2O3Chip supporter, α-Al2O3Single channel doughnut is supported
Body, α-Al2O3Four-way doughnut supporter, zirconium oxide (YSZ) chip supporter of yttrium stabilization, the zirconium oxide of yttrium stabilization
(YSZ) single channel doughnut supporter, zirconium oxide (YSZ) four-way doughnut supporter of yttrium stabilization.
Beneficial effect：
Moditied processing is carried out to MFI molecular screen membranes using the method for the present invention, MFI molecular screen membranes surface after moditied processing
Hydroxyl tails off, and hydroxyl generates hydrophobic long chain alkyl group with the reaction of modification source.Molecular screen membrane surface is presented hydrophobic state, is oozing
In saturating vaporescence, the contact of material liquid and MFI molecular screen membranes surface can be effectively prevented, reduce silicone hydroxyl and occur instead with raw material
Should, therefore improve stability of the molecular screen membrane during infiltration evaporation.So far, MFI molecular screen membranes are modified
Treatment, is carried out under the high temperature conditions with the report majority for improving its infiltration evaporation stability.Key of the invention exists
In under mild conditions, MFI molecular screen membranes surface is processed, the method for improving its stability in ethanol/water system.
Brief description of the drawings
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 HPC solution mass fractions with deionized water and 0.5wt% are that the MFI crystal seeds of 1wt% suspend
Liquid.
Step 2, crystal seed is coated using dip-coating method in YSZ supporting body surfaces, after being dried at 60 DEG C, at 500 DEG C
Roasting 6h.
Step 3, the supporter for loading crystal seed is placed in presoma, the Hydrothermal Synthesiss 6h at 180 DEG C, obtains MFI molecules
Sieve membrane.Obtained MFI molecular screen membranes are placed at 500 DEG C and are calcined 6h, to remove template agent removing.
The contact angle of embodiment 1 is as shown in figure 1, the contact angle of MFI molecular screen membranes prepared as can be seen from Fig. is
105 °, show good hydrophobicity.
Embodiment 2
Step 1, the HPC solution mass fractions with deionized water and 0.5wt% are that the MFI crystal seeds of 0.5wt% hang
Supernatant liquid.
Step 2, using dip-coating method in α-Al2O3Supporting body surface coats crystal seed, after being dried 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 Synthesiss 10h at 160 DEG C, obtains MFI molecules
Sieve membrane.Obtained MFI molecular screen membranes are placed at 400 DEG C and are calcined 8h, to remove template agent removing.
Embodiment 3
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into wherein, it is specific to use polytetrafluoroethylene (PTFE) adhesive tape, film two ends are sealed, prevent processing solution from entering in doughnut chamber to branch
Support body duct results in blockage, and is vertically statically placed in dopamine solution, 30 DEG C for the treatment of 6h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 4
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into and wherein stands, 30 DEG C for the treatment of 24h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
The contact angle result of the film prepared by the present embodiment has good as shown in Fig. 2 the MFI molecular screen membranes after modification remain unchanged
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 membranes (a) separating properties constantly decline, and modify after (the present embodiment) MFI molecular screen membranes (b) show
Good stability.
Embodiment 5
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into wherein, 30 DEG C of stir process 6h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 6
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into wherein, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 7
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into wherein, 30 DEG C of oscillation treatment 12h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 8
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during sodium dihydrogen phosphate is added into deionized water, then to cushioning liquid
Middle addition trifluoro propane trimethoxy silane obtains modification solution, and (mass concentration of wherein trifluoro propane trimethoxy silane is
0.3%) it is put into wherein after, film two ends are sealed, 30 DEG C of stir process 12h.
Step 3, after hydride modified MFI molecular screen membranes are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 9
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into wherein, 40 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 10
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.3wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution hydrochloric acid (wherein the mass concentration of Dopamine hydrochloride is 0.1%), film two ends are close
It is honored as a queen and is put into wherein, it is specific to use polytetrafluoroethylene (PTFE) adhesive tape, film two ends are sealed, prevent processing solution from entering in doughnut chamber
Supporter duct is resulted in blockage, is vertically statically placed in dopamine solution, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 11
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during sodium tetraborate is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into wherein, it is specific to use polytetrafluoroethylene (PTFE) adhesive tape, film two ends are sealed, prevent processing solution from entering in doughnut chamber 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 membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 12
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.2%), after film two ends are sealed
It is put into wherein, it is specific to use polytetrafluoroethylene (PTFE) adhesive tape, film two ends are sealed, prevent processing solution from entering in doughnut chamber 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 membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 13
Step 1, the MFI molecular screen membranes in embodiment 1 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.3%), after film two ends are sealed
It is put into wherein, it is specific to use polytetrafluoroethylene (PTFE) adhesive tape, film two ends are sealed, prevent processing solution from entering in doughnut chamber 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 membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 14
Step 1, the MFI molecular screen membranes in embodiment 2 is placed in baking oven and is dried.
Step 2, cushioning liquid (0.1wt%) is configured to during TrisHCl is added into deionized water, then in cushioning liquid
Dopamine hydrochloride is added to obtain dopamine solution (wherein the mass concentration of Dopamine hydrochloride is 0.1%), after film two ends are sealed
It is put into wherein, 30 DEG C of stir process 12h.
Step 3, after the amine-modified MFI molecular screen membranes of DOPA are cleaned with deionized water, 60 DEG C dry 12h in baking oven.
Embodiment 15
Infiltration evaporation sign is carried out to the MFI molecular screen membranes after obtained MFI molecular screen membranes and modification.The infiltration evaporation of film
Performance is generally by the permeation flux F (kgm in the unit interval through per membrane area-2·h-1) and two parameters of separation factor α
To weigh, α is defined as follows：
Y in formulaeAnd ywThe mass fraction of per-meate side second alcohol and water, x are represented respectivelyeAnd xwRespectively represent raw material in ethanol and
The mass fraction of water.As shown in table 1, operation temperature is 60 to the infiltration evaporation performance of the MFI molecular screen membranes of the modification of embodiment 2~12
DEG C, water content be 95wt.%.
Infiltration evaporation performance before the modification of MFI molecular screen membranes and the 20h infiltration evaporations after modification in the embodiment 3~14 of table 1
Performance comparison
Embodiment 16
MFI molecular screen membranes to the modification of embodiment 3 carry out infiltration evaporation sign.It is applied to operation temperature for 60 DEG C,
The separation of 5wt.% butanol/water systems.Operated by the infiltration evaporations of 48 hours, the MFI molecular screen membranes after being modified in embodiment 3
Permeation flux to maintain be 0.6kgm-2·h-1Left and right, and its separation factor stabilization to butanol/water is 26 or so.
Claims (7)
1. a kind of method that raising MFI molecular sieve film pervasions vaporize stability, it is comprised the following steps that：
(1) MFI molecular screen membranes are placed in baking oven and are dried；
(2) prepare cushioning liquid, to modification source is added in cushioning liquid, obtain modification source solution, by film two ends encapsulation process after,
It is placed in the solution of modification source, controls Temperature Treatment；
(3) after the MFI molecular screen membranes after modification are cleaned with deionized water, it is placed in baking oven and dries.
2. method according to claim 1, it is characterised in that modification source is Dopamine hydrochloride, C in step (2)1-18Three fluothane
Hydrocarbon trimethoxy silane, C1-18Three saturated alkyl chlorosilanes, C1-18Three saturated alkyl methoxy silanes or C1-18Three saturated alkyls
Ethoxysilane.
3. method according to claim 1, it is characterised in that cushioning liquid is aqueous phosphatic, three (hydroxyls in step (2)
Methyl) the aminomethane aqueous solution or the tetraborate aqueous solution；The weight/mass percentage composition of cushioning liquid is 0.1%~0.3%.
4. method according to claim 1, it is characterised in that modify the mass content in source in step (2) in the solution of modification source
It is 0.1%~0.3%.
5. method according to claim 1, it is characterised in that the encapsulation process method described in step (2) is tetrafluoroethene
Rubber belt sealing, tetrafluoro rubber stopper or sealant sealing.
6. method according to claim 1, it is characterised in that treatment temperature is 20~60 DEG C in step (2)；Process time
Respectively 6~24h.
7. method according to claim 1, it is characterised in that in step (2) processing mode to stand, stirring or vibrate.
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| CN108031301A (en) * | 2017-12-28 | 2018-05-15 | 三明学院 | MAPS improved silicas filling PIM-1 composite membranes and preparation method thereof |
| CN110280146A (en) * | 2019-06-14 | 2019-09-27 | 南京工业大学 | Method for repairing defects of molecular sieve membrane by using three-dimensional mesh organic flexible material |
| CN111346516A (en) * | 2020-03-12 | 2020-06-30 | 江西师范大学 | Modification method of T-shaped molecular sieve membrane, modified T-shaped molecular sieve membrane and application thereof |
| CN112915814A (en) * | 2021-02-06 | 2021-06-08 | 江西师范大学 | Novel membrane material for gas separation and preparation method thereof |
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| CN108031301A (en) * | 2017-12-28 | 2018-05-15 | 三明学院 | MAPS improved silicas filling PIM-1 composite membranes and preparation method thereof |
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| CN110280146A (en) * | 2019-06-14 | 2019-09-27 | 南京工业大学 | Method for repairing defects of molecular sieve membrane by using three-dimensional mesh organic flexible material |
| 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 |
| CN111346516A (en) * | 2020-03-12 | 2020-06-30 | 江西师范大学 | Modification method of T-shaped molecular sieve membrane, modified T-shaped molecular sieve membrane and application thereof |
| CN112915814A (en) * | 2021-02-06 | 2021-06-08 | 江西师范大学 | Novel membrane material for gas separation and preparation method 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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