CN114522549A - Preparation method of SAPO-34/PVA pervaporation composite membrane - Google Patents
Preparation method of SAPO-34/PVA pervaporation composite membrane Download PDFInfo
- Publication number
- CN114522549A CN114522549A CN202210061113.7A CN202210061113A CN114522549A CN 114522549 A CN114522549 A CN 114522549A CN 202210061113 A CN202210061113 A CN 202210061113A CN 114522549 A CN114522549 A CN 114522549A
- Authority
- CN
- China
- Prior art keywords
- pva
- sapo
- membrane
- composite membrane
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000005373 pervaporation Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000004907 flux Effects 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005266 casting Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006136 alcoholysis reaction Methods 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 24
- 230000018044 dehydration Effects 0.000 abstract description 11
- 238000006297 dehydration reaction Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 abstract 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- 239000007788 liquid Substances 0.000 description 10
- 239000012466 permeate Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 101100204059 Caenorhabditis elegans trap-2 gene Proteins 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing 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
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a preparation method of a SAPO-34/PVA pervaporation composite membrane, belonging to the field of chemical separation. The preparation method of the pervaporation composite membrane provided by the invention comprises the steps of adding zeolite molecular sieve SAPO-34 into PVA membrane casting solution, coating the mixture on an ultrafiltration membrane, heating the mixture after solvent is volatilized to further crosslink and solidify the mixture, and obtaining the SAPO-34/PVA pervaporation composite membrane. The composite membrane prepared by the invention can improve the roughness of the membrane by adding SAPO-34, provides a preferential channel for water permeation at the same time, and obviously increases permeation flux when being used for organic solvent dehydration.
Description
Technical Field
The invention relates to the technical field of pervaporation membranes, in particular to a preparation method of an SAPO-34/PVA pervaporation composite membrane for ethanol dehydration.
Background
The fuel ethanol is a novel green fuel, has become the development focus of world renewable energy sources, and can be mixed with gasoline for use based on the relatively high octane number and the heat of vaporization, so that the fuel ethanol has wide application prospects. At present, fuel ethanol is mainly generated by fermenting second generation raw materials (agricultural residues and forest biomass), and ethanol prepared by a fermentation method is subjected to common rectification to obtain an ethanol solution with the mass fraction of 95%. Since the ethanol-water solution is an azeotropic mixture, a special dehydration method is required for further obtaining anhydrous ethanol.
In the world, the problems of energy shortage, resource shortage, environmental pollution and the like are more and more serious, and people in various countries seek a cleaner and green separation technology to replace the original traditional separation method. As a novel separation technology, membrane separation technology is receiving more and more attention due to its advantages of high separation efficiency, low energy consumption, simple operation, small pollution and the like.
Pervaporation membrane separation technology is a membrane separation process that combines membrane permeation and molecular scale evaporative separation. In the process of pervaporation, a separated mixture is placed on one side of a non-porous polymer membrane or a molecular-scale inorganic porous membrane, a separated component in a feed liquid is dissolved on the surface of the membrane, and then the separated component permeates the membrane through diffusion, and chemical potential difference is caused by vacuum or low pressure on the other side of the membrane, so that vaporization is generated on the other side. Under the action of adsorption and diffusion, some components in the feed liquid preferentially diffuse through the membrane, so that separation is realized. The following water permeable membrane polymers are commonly used: polyvinyl alcohol (PVA), Chitosan (CS), cellulose acetate, polyimide, polyacrylonitrile, and the like. PVA has good hydrophilicity, stable physical and chemical properties and good film forming property, the film realizes the dehydration of high-concentration ethanol industrially, and the current industrialized organic pervaporation dehydration film only contains PVA.
The industrial organic pervaporation membranes are all plate-frame membrane assemblies, the specific surface area is small, and in order to obtain higher permeation amount, the membrane assemblies need to be made larger, and the corresponding mass is larger. If the permeation flux of the membrane can be improved, the volume of the plate-frame type membrane component can be effectively reduced under the condition of unchanged treatment capacity.
The permeation flux of the PVA pervaporation membrane is improved, and an effective method is to carry out organic/inorganic hybridization.Hybridization refers to the preparation of a polymer separation membrane after mixing with a polymer as a main body and a filler as a disperse phase. The hybrid membrane has the advantages of realizing the synergistic effect of the two, enhancing the pervaporation performance of the membrane and improving the thermal stability and mechanical strength of the membrane. The SAPO-34 molecular sieve is prepared from PO4、AlO4And SiO4An ellipsoidal cage structure with eight-membered rings and four-membered rings and a three-dimensional channel structure which are connected together. SAPO-34 molecular sieve has good hydrophilicity with pore size of about 0.38 nm. The pore canal size is larger than the dynamic diameter of water molecules and smaller than the dynamic diameter of most organic molecules, so that the water molecule permeation can be facilitated. The incorporation of PVA into the membrane facilitates water permeation and thus increases the permeation flux of the membrane.
In addition, the incorporation of SAPO-34 into PVA increases the roughness of the pervaporation membrane, which in turn increases the surface area of the membrane, thereby increasing the permeate flux.
Disclosure of Invention
The invention aims to provide a preparation method of an SAPO-34/PVA pervaporation composite membrane, which can effectively improve the dehydration flux of an organic solvent.
In order to solve the technical problem, the preparation method of the SAPO-34/PVA pervaporation composite membrane comprises the following steps:
(1) preparing a casting solution: dissolving PVA in an acetic acid solution, adding SAPO-34 with certain mass, fully dispersing and mixing, adding a cross-linking agent, and uniformly stirring to obtain a membrane casting solution;
(2) preparing a composite membrane: and (2) taking an ultrafiltration membrane as a bottom membrane, uniformly coating the casting membrane solution obtained in the step (1) on the bottom membrane according to a certain thickness, volatilizing the solvent at room temperature, primarily curing, and then fully crosslinking through heat treatment to obtain the SAPO-34/PVA pervaporation composite membrane.
In the above production method, the degree of alcoholysis of the PVA used in the step (1) is 98 to 99 (mole%), and the average degree of polymerization (n) is 2400 to 2500.
In the preparation method, the mass fraction of the acetic acid solution used in the step (1) is 2-4%.
In the preparation method, the SAPO-34 used in the step (1) accounts for 1-20% of the mass of the PVA.
In the preparation method, the SAPO-34 subjected to high-temperature calcination is used in the step (1).
In the preparation method, the dosage of the glutaraldehyde used in the step (2) is 2-4% of the mass of the PVA.
In the preparation method, the ultrafiltration membrane used in the step (2) is polyacrylonitrile, polysulfone or polyethersulfone, and the pure water flux is 50-500L/m2 kg。
In the preparation method, the heat treatment temperature in the step (2) is 60-120 ℃.
In the preparation of the composite membrane, SAPO-34 is filled in PVA, and the composite membrane has the following functions:
1. the SAPO-34 molecular sieve is blended into PVA, so that the roughness of the membrane is increased, the surface area of the membrane is increased, and the flux is improved;
2. the SAPO-34 molecular sieve pore size can allow water to pass through smoothly, and is also favorable for improving the permeation flux of the membrane.
Hydroxyl groups on the surface of SAPO-34 can promote the crosslinking of PVA, so that the PVA is more compact and the permeation flux is reduced, therefore, before the SAPO-34 is used, the hydroxyl groups on the surface of the SAPO-34 are removed by calcining at high temperature.
The composite membrane is used for ethanol dehydration, and the separation performance of the composite membrane mainly has two indexes, namely permeation flux and separation factor.
1) Composite membrane permeate flux, which is used to characterize the rate at which a permeate component permeates through a membrane, is the amount of a mixture component that diffuses through the membrane per unit area of time and is defined by the formula:
where m is the mass of permeate passing through the membrane of area s over time Δ t.
2) The separation factor represents the separation effect of the composite membrane on ethanol and water, and is defined by the following formula:
wherein x isi、xjIs the composition of water and ethanol in the feed liquid, yi，yjIs composed of water and ethanol in penetrating fluid. The larger the separation factor a, the less ethanol in the permeate and the better the selectivity.
The composite membrane prepared by the invention has greatly increased permeation flux, and can effectively reduce the area of the separation membrane and the size of the membrane component, thereby reducing the equipment investment cost and having larger industrial application prospect.
Drawings
FIG. 1 is a diagram showing a device for testing the separation performance of a composite membrane according to the present invention, which separates water from a mixed liquid of water and ethanol by pervaporation. Wherein: 1. the device comprises a membrane chamber, 2, a cold trap, 3, a vacuum pump, 4, a feed liquid pump, 5, a feed liquid groove, 6 and a flowmeter.
FIG. 2 is a scanning electron microscope image of the surface of the composite film.
Detailed Description
The invention relates to a preparation method of an SAPO-34/PVA pervaporation composite membrane, which comprises the following steps:
(1) preparing a casting solution: dissolving PVA in an acetic acid solution, adding SAPO-34 with certain mass, fully dispersing and mixing, adding a cross-linking agent, and uniformly stirring to obtain a membrane casting solution;
(2) preparing a composite membrane: and (2) taking an ultrafiltration membrane as a bottom membrane, uniformly coating the membrane casting solution in the step (1) on the bottom membrane according to a certain thickness, volatilizing the solvent at room temperature, primarily curing, and then fully crosslinking through heat treatment to obtain the SAPO-34/PVA pervaporation composite membrane.
The alcoholysis degree of the PVA used in the step (1) is 98-99 (mole%), and the average polymerization degree (n) is 2400-2500.
The mass fraction of the acetic acid solution used in the step (1) is 2-4%.
The SAPO-34 used in the step (1) accounts for 1-20% of the mass of PVA.
The step (1) is implemented by using SAPO-34 subjected to high-temperature calcination.
The dosage of the glutaraldehyde used in the step (2) is 2-4% of the mass of PVA.
The ultrafiltration membrane used in the step (2) is made of polyacrylonitrile, polysulfone or polyethersulfone, and the pure water flux is 50-500L/m2 kg.
The heat treatment temperature in the step (2) is 60-120 ℃.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
FIG. 1 is a testing device for the separation performance of the composite membrane of the present invention, in which a polyvinyl alcohol composite membrane is fixed in a membrane chamber 1, a feed liquid tank 5 adopts an electric heating coil, the feed liquid is heated to a certain temperature, and is conveyed upstream of the membrane chamber 1 by a feed liquid pump 4 through a flow meter 6, and then flows back to the feed liquid tank 5. The downstream of the membrane chamber 1 is vacuumized by a vacuum pump 3, so that a certain pressure difference is kept between the upstream and the downstream of the pervaporation membrane in the membrane chamber 1. The components (mainly water) entering the pervaporation membrane upstream pass through the separating layers of the membrane and are desorbed downstream, the desorbed components pass through the cold trap 2, the water and solvent are frozen into solids, which remain in the cold trap 2, and a small amount of non-condensable gas is pumped away through the cold trap 2 by the vacuum pump 3. And analyzing the sample taken from the cold trap to obtain the separation factor and the flux of the pervaporation membrane.
Dissolving PVA in 2% acetic acid solution, adding SAPO-34 which is 20% by mass of PVA and is calcined at high temperature, fully mixing, adding cross-linking agent glutaraldehyde which is 2% by mass of PVA, and uniformly stirring to obtain a casting solution;
(1) the alcoholysis degree of the PVA is 98-99 (mole%), and the average polymerization degree is 2400-2500;
(2) uniformly coating the membrane casting solution obtained in the step (1) on a bottom membrane by using an ultrafiltration membrane as the bottom membrane, performing primary curing when a solvent is cured at room temperature, and then performing heat treatment to fully crosslink the film casting solution to obtain the SAPO-34/PVA pervaporation composite membrane;
the ultrafiltration membrane is made of polyacrylonitrile, and has pure water flux of 200L/m2 kg；
The heat treatment temperature is 90 ℃.
The prepared modified composite membrane is used for testing the dehydration performance of ethanol, and when the water content in the feed is 10 percent and the operation temperature is 69 ℃, the permeation flux is 864 g.m-2·h-1The separation factor was 63.
Example 2
(1) Dissolving PVA in 3% acetic acid solution, adding SAPO-34 which is 15% by mass of PVA and is calcined at high temperature, fully mixing, adding cross-linking agent glutaraldehyde which is 3% by mass of PVA, and uniformly stirring to obtain a casting solution;
the alcoholysis degree of the PVA is 98-99 (mole%), and the average polymerization degree is 2400-2500;
(2) preparing a composite membrane: uniformly coating the membrane casting solution obtained in the step (1) on a bottom membrane by using an ultrafiltration membrane as the bottom membrane, performing primary curing when a solvent is cured at room temperature, and then performing heat treatment to fully crosslink the film casting solution to obtain the SAPO-34/PVA pervaporation composite membrane;
the ultrafiltration membrane is made of polyether sulfone and has a pure water flux of 500L/m2 kg；
The heat treatment temperature is 100 ℃.
The prepared modified composite membrane is used for testing the dehydration performance of ethanol, and when the water content in the feed is 10 percent and the operation temperature is 69 ℃, the permeation flux is 1363 g.m-2·h-1The separation factor was 48.
Example 3
(1) Dissolving PVA in 4% acetic acid solution, adding SAPO-34 which is 5% by mass of PVA and is calcined at high temperature, fully mixing, adding cross-linking agent glutaraldehyde which is 4% by mass of PVA, and uniformly stirring to obtain a casting solution;
the alcoholysis degree of the PVA is 98-99 (mole%), and the average polymerization degree is 2400-2500;
(2) preparing a composite membrane: uniformly coating the membrane casting solution obtained in the step (1) on a bottom membrane by using an ultrafiltration membrane as the bottom membrane, performing primary curing when a solvent is cured at room temperature, and then performing heat treatment to fully crosslink the film casting solution to obtain the SAPO-34/PVA pervaporation composite membrane;
the ultrafiltration membrane is made of polysulfone, and the pure water flux is 200L/m2 kg；
The heat treatment temperature was 105 ℃.
The prepared modified composite membrane is used for testing the dehydration performance of ethanol, and when the water content in the feed is 10 percent and the operation temperature is 69 ℃, the permeation flux is 1080 g.m-2·h-1The separation factor was 41.
Comparative example:
(1) dissolving PVA in 2% acetic acid solution, adding cross-linking agent glutaraldehyde accounting for 2% of the mass of the PVA, and uniformly stirring to obtain a casting solution;
the alcoholysis degree of the PVA is 98-99 (mole%), and the average polymerization degree is 2400-2500;
(2) preparing a composite membrane: uniformly coating the membrane casting solution obtained in the step (1) on a bottom membrane by using an ultrafiltration membrane as the bottom membrane, performing primary curing when a solvent is cured at room temperature, and then performing heat treatment to fully crosslink the film casting solution to obtain a polyvinyl alcohol membrane;
the ultrafiltration membrane is made of polyacrylonitrile, and has pure water flux of 200L/m2 kg；
The heat treatment temperature is 90 ℃.
The prepared polyvinyl alcohol membrane is used for testing the ethanol dehydration performance, and when the water content in the feed is 10 percent and the operation temperature is 69 ℃, the permeation flux is 629g m-2·h-1The separation factor was 113.
Claims (8)
1. A preparation method of an SAPO-34/PVA pervaporation composite membrane is characterized by comprising the following steps:
(1) preparing a casting solution: dissolving PVA in an acetic acid solution, adding SAPO-34 with certain mass, fully dispersing and mixing, adding a cross-linking agent, and uniformly stirring to obtain a membrane casting solution;
(2) preparing a composite membrane: and (2) taking an ultrafiltration membrane as a bottom membrane, uniformly coating the membrane casting solution in the step (1) on the bottom membrane according to a certain thickness, volatilizing and primarily curing the solvent at room temperature, and then carrying out heat treatment to fully crosslink the solvent so as to obtain the SAPO-34/PVA pervaporation composite membrane.
2. The method for preparing the SAPO-34/PVA pervaporation composite membrane according to claim 1, wherein the alcoholysis degree of PVA used in the step (1) is 98-99 (mole%), and the average polymerization degree (n) is 2400-2500.
3. The method for preparing the SAPO-34/PVA pervaporation composite membrane according to claim 1, wherein the mass fraction of the acetic acid solution used in the step (1) is 2% -4%.
4. The method for preparing the SAPO-34/PVA pervaporation composite membrane according to claim 1, wherein the SAPO-34 used in the step (1) accounts for 1-20% of the mass of PVA.
5. The method for preparing SAPO-34/PVA pervaporation composite membrane according to claim 1, wherein the SAPO-34 subjected to high temperature calcination is used in the step (1).
6. The method for preparing the SAPO-34/PVA pervaporation composite membrane according to claim 1, wherein the amount of glutaraldehyde used in the step (2) is 2-4% of the mass of PVA.
7. The method for preparing SAPO-34/PVA pervaporation composite membrane according to claim 1, wherein the ultrafiltration membrane used in the step (2) is polyacrylonitrile, polysulfone or polyethersulfone, and has a pure water flux of 50-500L/m2 kg。
8. The method for preparing SAPO-34/PVA pervaporation composite membrane according to claim 1, wherein the temperature of the heat treatment in the step (2) is 60-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210061113.7A CN114522549A (en) | 2022-01-19 | 2022-01-19 | Preparation method of SAPO-34/PVA pervaporation composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210061113.7A CN114522549A (en) | 2022-01-19 | 2022-01-19 | Preparation method of SAPO-34/PVA pervaporation composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114522549A true CN114522549A (en) | 2022-05-24 |
Family
ID=81621156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210061113.7A Pending CN114522549A (en) | 2022-01-19 | 2022-01-19 | Preparation method of SAPO-34/PVA pervaporation composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114522549A (en) |
Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156740A (en) * | 1982-06-01 | 1992-10-20 | Gft Ingenieurburo Fur Industrieanlagenbau | Multi-layer membrane and the use thereof for the separation of liquid mixtures according to the pervaporation process |
| US20080141858A1 (en) * | 2006-12-18 | 2008-06-19 | Chunqing Liu | Gas Separations Using High Performance Mixed Matrix Membranes |
| CN101274767A (en) * | 2007-03-27 | 2008-10-01 | 中国科学院大连化学物理研究所 | Method for synthesizing ITQ-13 molecular sieve |
| US20080296527A1 (en) * | 2007-06-01 | 2008-12-04 | Chunqing Liu | Uv cross-linked polymer functionalized molecular sieve/polymer mixed matrix membranes |
| US20090149565A1 (en) * | 2007-12-11 | 2009-06-11 | Chunqing Liu | Method for Making High Performance Mixed Matrix Membranes |
| US20090149313A1 (en) * | 2007-12-11 | 2009-06-11 | Chunqing Liu | Mixed Matrix Membranes Containing Low Acidity Nano-Sized SAPO-34 Molecular Sieves |
| US20090155464A1 (en) * | 2007-12-12 | 2009-06-18 | Chunqing Liu | Molecular Sieve/Polymer Mixed Matrix Membranes |
| CN101524627A (en) * | 2009-03-27 | 2009-09-09 | 上海应用技术学院 | Preparing method of cross-linking polyvinyl alcohol permeation evaporating compound film |
| AU2012200036A1 (en) * | 2005-03-09 | 2012-02-02 | The Regents Of The University Of California | Nanocomposite membranes and methods of making and using same |
| US20120048109A1 (en) * | 2010-08-24 | 2012-03-01 | Chevron U. S. A. Inc. | Mixed Matrix Membranes |
| EP2668995A1 (en) * | 2012-05-31 | 2013-12-04 | Universita' Della Calabria | Method for preparing hydrophobic fluorinated mixed matrix membranes, said membranes, and separation methods using said membranes |
| CN103420393A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Method for removing templates from original powder of titanium silicalite, titanium silicalite and preparation method and applications thereof |
| CN103894074A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Novel hybrid membrane as well as preparation method and application thereof |
| US20140212940A1 (en) * | 2011-05-25 | 2014-07-31 | Bp P.L.C. | Membranes |
| CN106268332A (en) * | 2016-08-30 | 2017-01-04 | 淮阴师范学院 | The preparation method of polyvinyl alcohol/graphite phase carbon nitride pervaporation hybrid membrane |
| JP2018130719A (en) * | 2017-02-17 | 2018-08-23 | 三菱ケミカル株式会社 | Porous support-zeolite membrane composite body, method for producing rho type zeolite and separation method |
| CN109467100A (en) * | 2017-09-07 | 2019-03-15 | 中国石油化工股份有限公司 | The synthetic method and application of SAPO-34 molecular sieve |
| CN110354698A (en) * | 2019-07-05 | 2019-10-22 | 南京工业大学 | A kind of sulfonated polyethylene alcohol catalysis composite membrane and preparation method |
| CN110773121A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Boric acid modified molecular sieve and preparation method and application thereof |
| CN111249917A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Preparation method and application of SAPO-34 based mixed matrix membrane |
| CN111482092A (en) * | 2020-05-11 | 2020-08-04 | 中国矿业大学(北京) | Preparation method of SAPO-34/PDMS gas permeable membrane |
| CN111495196A (en) * | 2020-03-20 | 2020-08-07 | 中国矿业大学(北京) | Preparation method of polydopamine modified white carbon black polyvinyl alcohol pervaporation membrane |
| CN113856498A (en) * | 2021-10-26 | 2021-12-31 | 泰州九润环保科技有限公司 | Polyamide reverse osmosis membrane doped with polyamide modification layer coated molecular sieve |
| CN113924158A (en) * | 2019-06-17 | 2022-01-11 | 日本碍子株式会社 | Zeolite membrane complex, method for producing zeolite membrane complex, separation device, membrane-type reaction device, and separation method |
-
2022
- 2022-01-19 CN CN202210061113.7A patent/CN114522549A/en active Pending
Patent Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156740A (en) * | 1982-06-01 | 1992-10-20 | Gft Ingenieurburo Fur Industrieanlagenbau | Multi-layer membrane and the use thereof for the separation of liquid mixtures according to the pervaporation process |
| AU2012200036A1 (en) * | 2005-03-09 | 2012-02-02 | The Regents Of The University Of California | Nanocomposite membranes and methods of making and using same |
| US20080141858A1 (en) * | 2006-12-18 | 2008-06-19 | Chunqing Liu | Gas Separations Using High Performance Mixed Matrix Membranes |
| CN101274767A (en) * | 2007-03-27 | 2008-10-01 | 中国科学院大连化学物理研究所 | Method for synthesizing ITQ-13 molecular sieve |
| US20080296527A1 (en) * | 2007-06-01 | 2008-12-04 | Chunqing Liu | Uv cross-linked polymer functionalized molecular sieve/polymer mixed matrix membranes |
| US20090149565A1 (en) * | 2007-12-11 | 2009-06-11 | Chunqing Liu | Method for Making High Performance Mixed Matrix Membranes |
| US20090149313A1 (en) * | 2007-12-11 | 2009-06-11 | Chunqing Liu | Mixed Matrix Membranes Containing Low Acidity Nano-Sized SAPO-34 Molecular Sieves |
| US20090155464A1 (en) * | 2007-12-12 | 2009-06-18 | Chunqing Liu | Molecular Sieve/Polymer Mixed Matrix Membranes |
| CN101524627A (en) * | 2009-03-27 | 2009-09-09 | 上海应用技术学院 | Preparing method of cross-linking polyvinyl alcohol permeation evaporating compound film |
| US20120048109A1 (en) * | 2010-08-24 | 2012-03-01 | Chevron U. S. A. Inc. | Mixed Matrix Membranes |
| US20140212940A1 (en) * | 2011-05-25 | 2014-07-31 | Bp P.L.C. | Membranes |
| CN103420393A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Method for removing templates from original powder of titanium silicalite, titanium silicalite and preparation method and applications thereof |
| EP2668995A1 (en) * | 2012-05-31 | 2013-12-04 | Universita' Della Calabria | Method for preparing hydrophobic fluorinated mixed matrix membranes, said membranes, and separation methods using said membranes |
| CN103894074A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Novel hybrid membrane as well as preparation method and application thereof |
| CN106268332A (en) * | 2016-08-30 | 2017-01-04 | 淮阴师范学院 | The preparation method of polyvinyl alcohol/graphite phase carbon nitride pervaporation hybrid membrane |
| JP2018130719A (en) * | 2017-02-17 | 2018-08-23 | 三菱ケミカル株式会社 | Porous support-zeolite membrane composite body, method for producing rho type zeolite and separation method |
| CN109467100A (en) * | 2017-09-07 | 2019-03-15 | 中国石油化工股份有限公司 | The synthetic method and application of SAPO-34 molecular sieve |
| CN111249917A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Preparation method and application of SAPO-34 based mixed matrix membrane |
| CN113924158A (en) * | 2019-06-17 | 2022-01-11 | 日本碍子株式会社 | Zeolite membrane complex, method for producing zeolite membrane complex, separation device, membrane-type reaction device, and separation method |
| CN110354698A (en) * | 2019-07-05 | 2019-10-22 | 南京工业大学 | A kind of sulfonated polyethylene alcohol catalysis composite membrane and preparation method |
| CN110773121A (en) * | 2019-11-08 | 2020-02-11 | 四川大学 | Boric acid modified molecular sieve and preparation method and application thereof |
| CN111495196A (en) * | 2020-03-20 | 2020-08-07 | 中国矿业大学(北京) | Preparation method of polydopamine modified white carbon black polyvinyl alcohol pervaporation membrane |
| CN111482092A (en) * | 2020-05-11 | 2020-08-04 | 中国矿业大学(北京) | Preparation method of SAPO-34/PDMS gas permeable membrane |
| CN113856498A (en) * | 2021-10-26 | 2021-12-31 | 泰州九润环保科技有限公司 | Polyamide reverse osmosis membrane doped with polyamide modification layer coated molecular sieve |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Membranes for bioethanol production by pervaporation | |
| CN100569349C (en) | A kind of priority dealcoholization PDMS/PVDF multilayer complex films and preparation method thereof | |
| Dong et al. | High performance ceramic hollow fiber supported PDMS composite pervaporation membrane for bio-butanol recovery | |
| CN101703898B (en) | PDMS/PVDF pervaporation composite membrane, preparation method and application thereof | |
| US8496831B2 (en) | Dehydration processes using membranes with hydrophobic coating | |
| CN102743981B (en) | Preparation and application of sodium alginate pervaporation hybrid membrane | |
| Si et al. | A high-efficiency diffusion process in carbonized ZIF-8 incorporated mixed matrix membrane for n-butanol recovery | |
| Zheng et al. | The potential of pervaporation for biofuel recovery from fermentation: An energy consumption point of view | |
| CN102000516B (en) | Method for preparing polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite hollow fiber film | |
| CN112337319A (en) | Mixed-dimension assembled covalent organic framework composite membrane, preparation and application | |
| CN101269304A (en) | Method for preparing pervaporation membrane for separating alcohol-water system | |
| CN113896220B (en) | Cerium fluoride porous nanosheet adjusted mixed matrix membrane and preparation method and application thereof | |
| CN113351037A (en) | ZIF-8/PDMS mixed matrix pervaporation membrane and preparation method and application thereof | |
| CN112316741B (en) | Mixed matrix membrane of beaded MOF filled silicone rubber | |
| Gonçalves et al. | Developments in downstream butanol separation from acetone, butanol, and ethanol fermentation | |
| CN110152503A (en) | A kind of preparation method for the solvent resistant nanofiltration membrane that graphene oxide is compound with tool microporous polymer certainly | |
| CN114522549A (en) | Preparation method of SAPO-34/PVA pervaporation composite membrane | |
| CN112934004A (en) | Preparation method and application of cucurbituril/metal ion crosslinked graphene oxide composite membrane | |
| CN109012222B (en) | Preparation and application of composite membrane for producing alcohol compounds by purification biological method | |
| CN115253714B (en) | Mixed matrix membrane doped with molybdenum disulfide nanosheet modified material, and preparation method and application thereof | |
| CN101099924A (en) | Method for preparing chitosan/ZSM-5 molecular compound film | |
| Liu et al. | Performance of a pervaporation system for the separation of an ethanol-water mixture using fractional condensation | |
| CN115888441A (en) | Composite nanofiltration membrane and preparation method thereof | |
| KR101467906B1 (en) | Method of manufacturing pervaporation using metal ion complex | |
| CN107899438B (en) | Polyethyleneimine-polyacrylic acid-calcium oxalate/hydrolyzed polyacrylonitrile ultrathin composite membrane and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220524 |
|
| RJ01 | Rejection of invention patent application after publication |