CN101920170B - High-flux molecular sieve alcohol permeable membrane and preparation method thereof - Google Patents
High-flux molecular sieve alcohol permeable membrane and preparation method thereof Download PDFInfo
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- CN101920170B CN101920170B CN201010249630A CN201010249630A CN101920170B CN 101920170 B CN101920170 B CN 101920170B CN 201010249630 A CN201010249630 A CN 201010249630A CN 201010249630 A CN201010249630 A CN 201010249630A CN 101920170 B CN101920170 B CN 101920170B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000012528 membrane Substances 0.000 title claims abstract description 76
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- 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 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012510 hollow fiber Substances 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 235000012489 doughnuts Nutrition 0.000 claims description 37
- 239000013078 crystal Substances 0.000 claims description 22
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 6
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 22
- 238000000926 separation method Methods 0.000 abstract description 21
- 238000000855 fermentation Methods 0.000 abstract description 6
- 230000004151 fermentation Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005373 pervaporation Methods 0.000 abstract 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 50
- 238000001704 evaporation Methods 0.000 description 16
- 230000008020 evaporation Effects 0.000 description 16
- 238000001764 infiltration Methods 0.000 description 16
- 230000008595 infiltration Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052863 mullite Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 235000014666 liquid concentrate Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol 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
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a high-flux molecular sieve alcohol permeable membrane which consists of a support body and a membrane layer, wherein the support body is made of an yttrium-stabilized zirconia porous material, the membrane layer is a Silicalite-1 molecular sieve membrane, the average pore diameter of the support body is 0.1-5 mu m, and the porosity is 10-75%. The invention also discloses a preparation method of the hollow fibrous alcohol permeable membrane. The alcohol permeable membrane has excellent separation performance, improves the permeation flux by 3-20 times when being used for an ethanol/water system, has higher separation factor and good repeatability, particularly has better effect when being formed by a hollow fiber support body, is used in the fields of pervaporation, gas separation and the like, and particularly has important significance in the industrial application of ethanol fermentation liquor concentration.
Description
Technical field
The present invention relates to a kind of permeable membrane, particularly a kind of high flux molecular-sieve alcohol permselective membrane and preparation method thereof belongs to the inoranic membrane field.
Background technology
Ethanol can effectively substitute the part fossil fuel as a kind of cleaning, regenerative resource efficiently, therefore receives the great attention of countries in the world.At present, production of fuel ethanol mainly adopts the biomass ferment method, and countries such as Brazil, the U.S., China have all realized the large-scale production of alcohol fuel.Difference based on living beings and zymotechnique; The concentration of alcohol that the biomass ferment method obtains is generally 1～15%; Because ethanol has had strong inhibitory effects to the fermentation of bacterium, therefore, must in time isolate the ethanol in the zymotic fluid; Could realize the continuous, lasting of sweat, enhance productivity.
Infiltration evaporation is as the membrane separation technique of a new generation; In organic solvent minor amount of water remove and water in have tangible technology and economic advantages aspect a small amount of organic separation, have occupation area of equipment little, simple to operate, be prone to and advantage such as other PROCESS COUPLING.Infiltrating and vaporizing membrane is applied in two embrane method production of fuel ethanol technologies; Can isolate the ethanol in the biomass ferment liquid online, continuously, thereby reduce the inhibitory action of bacterium to fermentation, infiltrating and vaporizing membrane can also remove the water in the ethanol simultaneously; Make absolute ethyl alcohol, have a good application prospect.
At present, passing through that pure type membrane material flux is low, separating property is poor, is the technical bottleneck of two embrane method fuel ethanol production technologies.Simple organosilicon system film separation is too low, also is difficult to satisfy industrial requirements through a large amount of modifications with modifying; Inoranic membrane, particularly Silicalite-1 molecular screen membrane are a kind of total silicon molecular screen membranes, and the crystals electrostatic field is very little, have very strong hydrophobic performance, also possess good heat endurance simultaneously.At present, countries such as the U.S., Japan, China all are devoted to the practical application in alcohol/separated form water of Silicalite-1 molecular screen membrane, but Silicalite-1 molecular screen membrane flux still is difficult to satisfy large-scale commercial Application.
People such as Sano (Chem.Lett., 1992,2413-2414) reported synthetic Silicalite-1 molecular screen membrane on the stainless steel supporter for the first time, be applied to 60 ℃ of ethanol (5vol%)/water infiltration evaporation, separation factor reaches 58, but its flux has only 0.76Kgm
-2H
-1In addition, the stainless steel supporter prepares in the molecular screen membrane process, and rete is easy to generate cracking, therefore is difficult to make the thin molecular screen membrane of rete.People such as Lin Xiao (Chem.Commun., 2000,1889-1890) on the mullite supporter, synthesized the Silicalite-1 molecular screen membrane, be applied to 60 ℃ of ethanol/water systems, flux reaches 2.55Kgm
-2H
-1, separation factor is 72, is the best Silicalite-1 molecular screen membrane of reporting at present of performance.It is supporter that patent documentation CN101653702A has reported with the porous mullite, adopts super-dilute synthetic fluid (H
2O/SiO
2=500～2000) synthetic Silicalite-1 molecular screen membrane, (infiltration evaporation of system of 5wt%/95wt%), permeation flux and separation factor are respectively 1.45Kgm to be applied to 60 ℃ of ethanol/waters
-2H
-1With 80; People such as Chen Pei (CN200810150717.9; Chin.J.Chem. be supporter, 27 (2009) 1692-1696), utilize to contain the synthetic liquid of zirconium and prepared zirconium-silicon molecular sieve film with the mullite; (during the system of 5wt%/95wt%), its permeation flux and separation factor are respectively 1.01Kgm to be used for 60 ℃ of ethanol/waters
-2H
-1With 73.People such as V.Sebastian (J.Membr.Sci..355 (2010) 28-35) utilize microwave process for synthesizing at α-Al
2O
3Synthesized the Silicalite-1 molecular screen membrane on the capillary supporter, flux is 1.5Kgm
-2H
-1, separation factor is 54 (feed composition: ethanol/water=3wt%/97wt%; Feeding temperature: 45 ℃).According to bibliographical information, Silicalite-1 molecular screen membrane flux is generally on the low side, and its reason possibly be: molecular screen membrane prepares in the process, and the aluminium element in mullite or the alumina support infiltrates the Silicalite-1 framework of molecular sieve, has reduced its hydrophobic performance; The thickness of Silicalite-1 molecular screen membrane is thicker.
Summary of the invention
The object of the present invention is to provide a kind of high-throughout molecular-sieve alcohol permselective membrane, to satisfy ethanol/water system infiltration evaporation industrial application requirements.The present invention also provides the preparation method of this molecular-sieve alcohol permselective membrane.
This molecular-sieve alcohol permselective membrane is made up of supporter and rete, and wherein supporter is yttrium stable zirconium oxide (being called for short a YSZ down) porous material, and rete is the Silicalite-1 molecular screen membrane, and the average pore size of support body material is 0.1～5 μ m, and porosity is 10～75%.
Said supporter shape can be single tube, multichannel, flat board or hollow fiber.
Said supporter is the YSZ doughnut, and doughnut (pipe) external diameter is 0.75～3mm, and internal diameter is 0.55～2.8mm.
The optimum aperture of YSZ doughnut supporter is 0.1～5 μ m.
Alcohol permselective membrane of the present invention is to support the Silicalite-1 molecular screen membrane by the yttrium stable zirconium oxide porous supporting body to constitute; Because supporter does not contain aluminium element; Can effectively avoid mixing the separating property decline that the Silicalite-1 framework of molecular sieve causes because of hetero atom aluminium; Make the molecular sieve rete have the good hydrophobic performance, thereby the thickness of molecular sieve rete can reduce greatly, the rete resistance to mass tranfer reduces; Particularly the wall of doughnut supporter is very thin, and the resistance to mass tranfer of supporter also further reduces, and more helps processing high-throughout molecular screen membrane.Infiltration evaporation experiment proof; Alcohol permselective membrane of the present invention has excellent separating property, when using it for the ethanol/water system, can use it for fields such as infiltration evaporation, gas separation; Permeation flux has improved 3～20 times than bibliographical information value, still has higher separation factor and good repeatability simultaneously.Be that the alcohol permselective membrane effect of the present invention that constitutes of supporter is better particularly with the YSZ doughnut, significant in the commercial Application that alcohol fermentation liquid concentrates.
It is the preparation method of the high flux molecular-sieve alcohol permselective membrane of YSZ doughnut that the present invention provides a kind of supporter, comprises following steps:
(1), preparation YSZ doughnut supporter
After polyvinylpyrrolidone added the N-N-methyl-2-2-pyrrolidone N-, add polyether sulfone again, be stirred to abundant dissolving, add the YSZ powder then in batches; The mass ratio of YSZ powder and polyether sulfone, N-N-methyl-2-2-pyrrolidone N-, polyvinylpyrrolidone is 4～11: 1: 3～15: 0.05～0.50.After raw material fully stirred, it is moved in stainless steel storage tank, then it is extruded into hollow fiber, after the drying at room temperature, make the doughnut supporter at 1200～1600 ℃ of following sintering.
(2), preparation Silicalite-1 molecular sieve crystal seed
Raw material SiO
2, TPAOH, NaOH and water is 1: 0.1～0.6: 0.05～0.2: 5～23 to be mixed into solution with mol ratio; At the synthetic 3～24h of 60～170 ℃ of following hydro-thermals; Make the Silicalite-1 sieve particle; Water is washed till neutrality, adds water then and is made into the crystal seed suspension that concentration is 10wt%.
(3) apply crystal seed
YSZ doughnut supporter is soaked in water (but heated and boiled) a period of time, after the oven dry with its sealed at both ends; With hydroxypropyl cellulose and deionized water crystal seed suspension is diluted, then pH is adjusted to 3～4.YSZ doughnut supporter is immersed in the crystal seed suspension after the dilution, dries the back 400～600 ℃ of calcinings down, to remove organic matters such as TPAOH, hydroxypropyl cellulose.
(4) the crystal seed diauxic growth is processed the Silicalite-1 molecular screen membrane
TPAOH, positive tetraethyl orthosilicate and deionized water according to 1: 2～6: 300～1500 mixed in molar ratio, are stirred aging 6～24h, be made into the diauxic growth mother liquor.Supporter sealed at both ends with scribbling crystal seed in the step (3) places this diauxic growth mother liquor, and at 160～190 ℃ of reaction 6～40h, water is washed till pH=7, and dry back is 400～600 ℃ of calcinings down.
Better scheme is that in the secondary mother liquid of step (4), the mol ratio of TPAOH, positive tetraethyl orthosilicate and water is 1: 3～4: 450～700;
The synthetic temperature of hydro-thermal is 170～185 ℃ in the step (4);
The yttrium stable zirconium oxide doughnut supporter of step (1) is soaked in water and heated and boiled.
It is supporter that said method makes with porous YSZ material, and Silicalite-1 total silicon molecular screen membrane is the hollow fiber alcohol permselective membrane of the present invention of separating layer, is suitable for the commercial Application that alcohol fermentation liquid concentrates.
Description of drawings
The YSZ doughnut supporting body surface electromicroscopic photograph of Fig. 1-1400 ℃ following sintering.
The YSZ doughnut supporter section electromicroscopic photograph of Fig. 2-1400 ℃ following sintering.
The YSZ doughnut supporting body surface electromicroscopic photograph of Fig. 3-coating crystal seed.
The Silicalite-1 molecular screen membrane surface electromicroscopic photograph that Fig. 4-YSZ doughnut supports.
The Silicalite-1 molecular screen membrane section electromicroscopic photograph that Fig. 5-YSZ doughnut supports.
Fig. 6-doughnut molecular screen membrane of the present invention is used for the device flow chart of ethanol/water system infiltration evaporation test.
Specific embodiment
The preparation of molecular-sieve alcohol permselective membrane of the present invention is described through embodiment below, but the protection domain of this patent is not limited to embodiment.
The preparation of embodiment 1 porous YSZ hollow fiber supporter
Polyvinylpyrrolidone is added in the N-N-methyl-2-2-pyrrolidone N-, add polyether sulfone after the dissolving again, be stirred to abundant dissolving, add yttrium stable zirconium oxide powder (commercially available, as to contain 3～8% moles of yittrium oxide) then in batches; Yttrium stable zirconium oxide and polyether sulfone, N-N-methyl-2-2-pyrrolidone N-, polyvinylpyrrolidone are 10: 1: 4.87 by mass ratio: 0.08.After raw material fully stirred, it is moved in stainless steel storage tank, be extruded into hollow fiber then, after the drying at room temperature, under 1200～1600 ℃, sinter the supporter of YSZ hollow fiber into.
The aperture and the porosity of YSZ doughnut supporter are as shown in table 1: along with the rising of sintering temperature, average pore size reduces gradually, porosity reduces.Fig. 1 is the surperficial electromicroscopic photograph of the YSZ doughnut supporter of 1400 ℃ of following sintering, can find out, YSZ doughnut supporting body surface porous and pore-size distribution be homogeneous comparatively; Fig. 2 is the section electromicroscopic photograph of the YSZ doughnut supporter of 1400 ℃ of following sintering, and can find out: the external diameter of doughnut supporter is about 1.6mm, and wall thickness is about 0.4mm.
The aperture and the porosity of table 1YSZ hollow fiber supporter
Adopt homemade nanoscale Silicalite-1 sieve particle as crystal seed, crystal seed suspension is diluted, then pH is adjusted to 3～4 with hydroxypropyl cellulose (HPC) and deionized water.Selecting average pore size for use is 0.67 μ m, and porosity is that 56% YSZ doughnut is a supporter, in crystal seed suspension, floods 3～5s, dries the back 450 ℃ of calcinings down.(Fig. 3) can find out from electromicroscopic photograph: supporting body surface is coated with Silicalite-1 molecular sieve crystal seed equably.
Get concentration and be 1M TPAOH 5.66ml, analyze pure tetraethyl orthosilicate 4ml and the 52.5ml deionized water mixes (being that three's mol ratio is 1: 3.2: 560), make the diauxic growth mother liquor; The supporter that has applied crystal seed is placed this mother liquor, at the synthetic 8h of 180 ℃ of following hydro-thermals; Water is washed till neutrality, dries the back and calcines 8h down at 450 ℃, to remove the organic matters such as TPAOH in the molecular sieve pore passage, obtains the Silicalite-1 molecular screen membrane that the YSZ doughnut supports, high flux molecular-sieve alcohol permselective membrane promptly of the present invention.
The surperficial electromicroscopic photograph of the Silicalite-1 molecular screen membrane that Fig. 4 supports for the YSZ doughnut, can find out: Silicalite-1 molecular screen membrane surface is perfect to be fallen into; The section electromicroscopic photograph of the Silicalite-1 molecular screen membrane that Fig. 5 supports for the YSZ doughnut, can find out: thicknesses of layers only has about 3 μ m.
Embodiment 3 is the synthetic Silicalite-1 molecular screen membrane of supporter with the YSZ doughnut
The mol ratio of control TPAOH, positive tetraethyl orthosilicate and water is: 1: 4: 692, and at 180 ℃ of following hydro-thermal Synthetic 2 4h.All the other conditions are identical with embodiment 2.
Embodiment 4 is the synthetic Silicalite-1 molecular screen membrane of supporter with the YSZ doughnut
Control hydro-thermal generated time is 32h, and is synthetic at twice: at first, synthetic 16h cleans film to neutral with deionized water oven dry, roasting; Then, synthetic more under the same conditions 16h, all the other conditions are all identical with embodiment 2.
Adopt the doughnut molecular sieve film pervasion vapourizing unit shown in the accompanying drawing 6 to investigate the separating property of alcohol permselective membrane of the present invention to the ethanol/water system, contain ethanol 5wt% in the system, water 95wt% carries out performance test to the alcohol permselective membrane of embodiment 2～4, and feeding temperature is 60 ℃.
Among Fig. 6, be ethanol/water solution in the material fluid bath 3; Magnetic force heating stirrer 1 is heated to the feed liquid in the material fluid bath 3 predetermined temperature and stirs certain hour, makes feed concentration and uniformity of temperature profile.The sealing of doughnut molecular screen membrane 2 one ends, the other end is connected with emulsion tube, is connected with valve group 5 with vacuum meter 4 through three-way pipe, links to each other with cold-trap 6,7 through valve group 5; Above system links to each other with vavuum pump 9 through drying tower 8.In the experimentation, vavuum pump 9 makes system held vacuum below 200Pa, and the ethanol in the material fluid bath 3 sees through doughnut molecular screen membrane 2 of the present invention, under suction function, gets into cold-trap 6 or 7, rapid condensation and collection under liquid nitrogen temperature.Drying tower 8 prevents that in order to protection vavuum pump 9 liquid gets in the pump under the fortuitous event.The effect of vacuum meter 4 is through electronic sensor detection system vacuum.Cold-trap 6 and 7 one are subsequent use.Record each alcohol permselective membrane that embodiment 2～embodiment 4 makes infiltration evaporation permeation flux and separation factor data such as table 2 to ethanol/water=5wt%/95wt% system.
Table 2 alcohol permselective membrane infiltration evaporation performance (ethanol/water=5wt%/95wt%)
Comparative example 1
Professor Kita of Japan Yamaguchi university utilizes the original position hydrothermal synthesis method on mullite supports, to prepare the Silicalite-1 molecular screen membrane.Be applied to organic matter/water infiltration evaporation and separate, the 5wt%/separation factor of 95wt% ethanol/water under 60 ℃ reaches 106, and flux is 0.9Kgm
-2H
-1(selecting from AlChE J., 49 (2003), 11).Silicalite-1 molecular screen membrane of the present invention, separation factor is lower than this report value, but its permeation flux is more than 8 times of reported values, has more practical value.
Comparative example 2
Professor Chen Xiangshu of Jiangxi Normal University adopts dilute synthetic fluid on the mullite supporter, to prepare the Silicalite-1 molecular screen membrane; (5wt%/95wt%) the infiltration evaporation experiment of system, its permeation flux and separation factor are respectively up to 1.71Kgm in the time of 60 ℃ to be applied to ethanol/water
-2H
-1With 66 (selecting from CN 101648712A, 2009).Alcohol permselective membrane of the present invention is used for the infiltration evaporation experiment, and the separation factor under the same terms is a little less than this report, but permeation flux is 4 times of reported values, so the present invention has more industrial application value.
Comparative example 3
Bibliographical information is at α-Al
2O
3Prepared the Silicalite-1 molecular screen membrane on the supporter, (5wt%/95wt%) the infiltration evaporation experiment of system, its permeation flux and separation factor are respectively 1.9Kgm in the time of 85 ℃ to be applied to ethanol/water
-2H
-1With 23 (select from Microporous Mesoporous Mater., 127 (2010), 96-103).Alcohol permselective membrane of the present invention is used for the infiltration evaporation experiment, and separation factor and permeation flux more are applicable to the alcohol fermentation liquid concentration technique all far above reported values.
Comparative example 4
1994, people such as Sano were that template has been synthesized the Silicalite-1 molecular screen membrane with TPAOH on the porous stainless steel supporter, were applied to 5wt%/95wt% ethanol/water system, and infiltration evaporation flux and separation factor are respectively 0.8Kgm in the time of 60 ℃
-2H
-1With 60 (select from J.Membr.Sci., 95 (1994), 221-228).Compare with this report, alcohol permselective membrane of the present invention has very high permeation flux.
Claims (5)
1. a high-throughout molecular-sieve alcohol permselective membrane is made up of supporter and rete, and it is characterized by supporter is the yttrium stable zirconium oxide porous material, and the yttrium stable zirconium oxide average pore size is 0.1～5 μ m, and porosity is 10～75%; Rete is the Silicalite-1 molecular screen membrane, and said yttrium stable zirconium oxide supporter shape is a hollow fiber, and the doughnut external diameter is 0.75～3mm, and internal diameter is 0.55～2.8mm.
2. the preparation method of a high-throughout molecular-sieve alcohol permselective membrane according to claim 1 comprises following steps:
(1), preparation doughnut supporter
With raw material yttrium stable zirconium oxide powder, polyether sulfone, N-N-methyl-2-2-pyrrolidone N-and polyvinylpyrrolidone by mass ratio 4～11: 1: 3～15: 0.05～0.50 mixes, and it is spun into hollow fiber, drying at room temperature
After, at 1200～1600 ℃ of following sintering, make the doughnut supporter;
(2), preparation Silicalite-1 molecular sieve crystal seed
With raw material SiO
2, TPAOH, NaOH and water 1: 0.1～0.6: 0.05～0.2: 5～23 is mixed into solution to rub; At the synthetic 3～24h of 60～170 ℃ of following hydro-thermals; Make the Silicalite-1 sieve particle, water is washed till neutrality, adds the crystal seed suspension that water is made into 10wt% then;
(3), apply crystal seed
With hydroxypropyl cellulose and deionized water dilution crystal seed suspension, then pH is adjusted to 3～4; Yttrium stable zirconium oxide doughnut supporter is soaked in water, dries; After its sealed at both ends, in the crystal seed suspension of dilution, flood, make crystal seed be compound to the doughnut supporting body surface; Dry the back 400～600 ℃ of calcinings down, remove organic matter TPAOH and hydroxypropyl cellulose;
(4), the crystal seed diauxic growth is processed the Silicalite-1 molecular screen membrane
TPAOH, positive tetraethyl orthosilicate and deionized water by 1: 2～6: 300～1500 mixed in molar ratio, are stirred, aging 6～24h, the diauxic growth mother liquor; Supporter sealed at both ends with scribbling crystal seed in the step (3) places this diauxic growth mother liquor, and behind 160～190 ℃ of following hydrothermal synthesis reaction 6～40h, water washes to pH=7, and dry back is 400～600 ℃ of calcinings down.
3. the preparation method of high-throughout molecular-sieve alcohol permselective membrane according to claim 2 is characterized by in the secondary mother liquid of step (4), and the mol ratio of TPAOH, positive tetraethyl orthosilicate and water is 1: 3～4: 450～700.
4. the preparation method of high-throughout molecular-sieve alcohol permselective membrane according to claim 2 is characterized by that the synthetic temperature of said hydro-thermal is 170～185 ℃ in the step (4).
5. according to the preparation method of claim 2 or 3 or 4 described high-throughout molecular-sieve alcohol permselective membranes, the yttrium stable zirconium oxide doughnut supporter that it is characterized by step (1) is soaked in water and heated and boiled.
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| CN102580568B (en) * | 2012-03-13 | 2015-04-22 | 南京工业大学 | Batch preparation method of hollow fiber molecular sieve membrane |
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| CN106378013B (en) | 2016-11-10 | 2020-02-07 | 南京工业大学 | Preparation method and application of hierarchical pore molecular sieve membrane |
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| CN108126533B (en) * | 2017-12-13 | 2020-10-27 | 浙江大学 | Method for preparing porous ceramic support body by adding molecular sieve and in-situ hydro-thermal synthesis of molecular sieve membrane |
| CN109569316A (en) * | 2018-12-05 | 2019-04-05 | 广西大学 | A kind of preparation method of Silicalite-1 molecular screen membrane |
| CN113634138B (en) * | 2021-08-23 | 2023-01-24 | 华东理工大学 | Dynamic hydrothermal synthesis hollow fiber outer wall SUZ-4 type molecular sieve pervaporation membrane and method for removing methanol by using solvent thereof |
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