CN115739051A - Hydrophobic membrane and preparation method and application thereof - Google Patents
Hydrophobic membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN115739051A CN115739051A CN202211525041.3A CN202211525041A CN115739051A CN 115739051 A CN115739051 A CN 115739051A CN 202211525041 A CN202211525041 A CN 202211525041A CN 115739051 A CN115739051 A CN 115739051A
- Authority
- CN
- China
- Prior art keywords
- membrane
- solution
- hydrophobic
- hydrophobic membrane
- zno
- 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 126
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 15
- 229930195729 fatty acid Natural products 0.000 claims abstract description 15
- 239000000194 fatty acid Substances 0.000 claims abstract description 15
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000012510 hollow fiber Substances 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000004280 Sodium formate Substances 0.000 claims description 7
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 7
- 235000019254 sodium formate Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 53
- 238000005886 esterification reaction Methods 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 3
- 150000001263 acyl chlorides Chemical group 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 37
- 239000007788 liquid Substances 0.000 description 34
- 230000004907 flux Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a hydrophobic membrane, a preparation method thereof and application thereof in membrane absorption. Firstly, a ZnO array is prepared on the surface of the membrane in a solvothermal mode, so that a micro-nano structure is formed, and the hydrophobicity of the membrane is improved. Then, the intrinsic hydrophobic property of the material is changed through esterification reaction between acyl chloride groups on the fatty acid chloride and hydroxyl groups of ZnO, so that the hydrophobicity of the membrane is further improved, and the membrane absorbs and captures CO 2 . The invention has the advantages that the prepared hydrophobic membrane has good anti-wetting property, thereby greatly reducing the mass transfer resistance and having good market application prospectAnd (5) landscape.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a hydrophobic membrane, a preparation method thereof and application thereof in membrane absorption.
Background
CO, a major greenhouse gas 2 Accumulation in the atmosphere leads to global warming. Capturing and storing CO 2 And separating it from other gasesThe need for separation is increasing. Absorption, adsorption, cryogenic techniques and membrane techniques are the separation of CO 2 But the traditional separation process has the defects of overflow, foaming, entrainment, high cost and the like. Although gas-liquid absorption in chemical solvents is considered as the best technology for capturing carbon dioxide, the direct gas-liquid contact absorption technology has the disadvantages of high cost, high energy consumption and the like. Compared with the traditional method, the membrane separation process has the advantages of low energy consumption, less environmental pollution, easy industrial production and the like, and is easy to widely apply. However, pure gas separation membranes require a strict pore size design and are difficult to industrially produce continuously. To solve these problems, a new gas-liquid membrane contactor (GLMC) technology has been used in the separation process of mixed gases. GLMC presents a huge potential for application to solve some problems associated with continuous production and industrial use, and can greatly improve the separation efficiency of mixed gases.
In recent years, CO 2 The trapped gas-liquid film contact absorption technology has received increasing attention for process intensification. Gas-liquid membrane contact absorption is a non-dispersive absorption process, and mass transfer is achieved through a gas-liquid contactor (a membrane contactor). A membrane contactor is a device that directly contacts two different fluids without dispersing one phase into the other, thereby achieving mass transfer of a particular substance. The gas mixture flows on one side of the hydrophobic microporous membrane and the liquid absorbent membrane flows on the other side. Acid gas (CO) 2 ) From the gas phase into the gas-liquid interface and then absorbed by the liquid phase (alkaline absorbent). Compared with the traditional liquid absorption, the membrane contactor can provide a higher interface contact area for raw material gas and absorbent, although the existence of the membrane provides additional mass transfer resistance for gas-liquid membrane contact absorption. Compared with the traditional gas-liquid absorption method, the GLMC also has the advantages of flexible operation, easy amplification, low energy consumption, low cost and the like. The gas phase and the liquid phase are separated in a gas-liquid membrane contactor. The membrane acts as a medium for increasing the gas-liquid contact area and is not selective for separating gases. The morphology of the membrane is such that it influences the CO absorption process 2 One of the key factors of mass transfer. However, due to CO 2 Penetration of the liquid absorbent through the porous membrane is limited by the liquid-filled pores, the membrane gasAbsorption is susceptible to membrane wetting, thereby significantly reducing the performance of membrane absorption.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a hydrophobic membrane and a membrane absorption application thereof. The hydrophobic membrane contactor provided by the invention is used for CO 2 The absorption rate is high and the absorption flux is high.
To solve this problem, the membrane is modified, and increasing the hydrophobicity of the membrane is the most common method. In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a hydrophobic membrane, which is prepared by the following method:
(1) Preparing a ZnO array: dissolving zinc salt, 2-methylimidazole and anhydrous sodium formate in a mass ratio of 1-10-5:1 (preferably 5; vertically placing the hollow fiber membrane in the clarified solution, reacting at 50-100 ℃ for 6-24 h (preferably at 80 ℃ for 12 h), naturally cooling to room temperature, washing the obtained membrane with ZnO by using methanol (for several times until the redundant ZnO on the surface is removed), and drying to obtain a membrane with a ZnO array;
(2) Hydrophobic grafting: dissolving fatty acid chloride in an amide solvent A to obtain a solution A; dissolving organic amine in an amide solvent B to obtain a solution B; immersing the film with the ZnO array in the step (1) into the solution A preheated to 40-80 ℃ (preferably 60 ℃), fully soaking the film (the general required time is 0.5-4 h, in the embodiment of the invention is 1 h), then dropwise adding the solution B preheated to 40-80 ℃ (preferably 60 ℃) under stirring (600 rpm in the embodiment of the invention), after dropwise adding, sealing the obtained mixed solution at 40-80 ℃ and reacting for 0.5-4 h (preferably 60 ℃) for 1h, washing the obtained grafted film with ethanol (for a plurality of times), and drying (drying in a vacuum oven at 40 ℃ overnight) to obtain the hydrophobic film; the mass ratio of the fatty acid chloride to the organic amine is 1-10: 1 (preferably 6.87.
Further, in the step (1), the zinc salt is one or a mixture of more than two of zinc chloride, zinc nitrate and zinc acetate, and preferably zinc nitrate.
Further, the hollow fiber membrane in the step (1) is a PP membrane, a PTFE membrane, a PES membrane or a PS, preferably a PTFE membrane.
Further, the volume of the methanol in the step (1) is 100-1000mL/g (preferably 250 mL/g) based on the mass of the 2-methylimidazole.
Further, in the step (2), the organic amine is one or a mixture of more than two of Triethylamine (TEA), ethylenediamine and diethylenetriamine, and Triethylamine (TEA) is preferred.
Further, the fatty acid chloride in the step (2) is one or a mixture of two of palmitoyl chloride and stearoyl chloride, preferably palmitoyl chloride.
Preferably, the amide solvent A and the amide solvent B in the step (2) are both DMF; the volume of the amide-based solvent A in the step (2) is 2 to 100mL/g (preferably 16 mL/g) based on the mass of the fatty acid chloride; the volume of the amide solvent B is 2-100mL/g (preferably 13.7 mL/g) based on the mass of the organic amine. The amide solvent functions to dissolve the reactants.
The invention also provides a method for absorbing CO by using the hydrophobic membrane 2 The use of (1).
Compared with the prior art, the invention has the beneficial effects that:
(1) The micro-nano structure ZnO array is constructed on the film, so that the anti-wettability of the film is improved, and the micro-nano structure ZnO array is applied to film absorption for capturing CO for the first time 2 。
(2) The fatty acid chloride is modified, so that the free energy of the membrane material is reduced, the hydrophobicity of the membrane is further improved, the wetting behavior of the membrane is effectively relieved, and the mass transfer behavior of the membrane is indirectly enhanced.
(3) The invention synchronously implements modification from the perspective of material structure and intrinsic chemical property, synergistically strengthens the anti-wettability of the film and ensures that the film has CO resistance 2 Has good film absorption performance.
Drawings
FIG. 1 is a schematic view of hydrophobic membrane preparation.
FIG. 2 is a schematic diagram of CO absorption by a membrane contactor 2 And (4) a flow chart.
FIG. 3 is a schematic fluid flow diagram within a membrane contactor.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples, and variations and implementations are included within the technical scope of the present invention without departing from the content and scope of the present invention.
Example 1:
(1) Preparing a ZnO array: weighing 1g of zinc nitrate, 0.4g of 2-methylimidazole and 0.2g of anhydrous sodium formate, dissolving in 100mL of methanol, and carrying out ultrasonic treatment until the solution is completely clear. A PTFE membrane (Nanjing Zhongkegai New Membrane science and technology Co., ltd., pore diameter 0.02-0.5 μm, inner diameter 0.4mm, outer diameter 0.8 mm) was placed vertically in the clear solution and reacted at 80 ℃ for 12 hours. And naturally cooling to room temperature after the reaction is finished, taking out the film with the ZnO, washing the film in methanol for several times until redundant ZnO on the surface is removed, and drying to obtain the film with the ZnO array.
(2) Hydrophobic grafting: the modification is accomplished by an esterification reaction between the acid chloride groups on the fatty acid chloride and the hydroxyl groups of the ZnO. The organic amine acts as an HCl remover, completing the reaction. During grafting, solution A was prepared by dissolving 2.5g of palmitoyl chloride in 40mL of DMF, and solution B was prepared by adding 0.5mL of TEA (0.364 g) to 5mL of DMF. The two solutions were heated to 60 ℃ in a water bath, respectively, and then the membrane was immersed in solution a for 1h to ensure adequate contact of the membrane surface with the reagents. Thereafter, the prepared solution B was dropwise added to the solution a under stirring at 600 rpm. The reaction flask was then sealed and placed in an oven at 60 ℃ for 1 hour. After the reaction was complete, the membrane was washed several times with pure ethanol and then dried overnight in a vacuum oven at 40 ℃.
The prepared hydrophobic modified hollow fiber membrane is applied to membrane absorption as follows:
the prepared hydrophobic membrane contactor CO 2 The removal experiment, the mixed gas passes through the tube side, and the absorption liquid flows to CO on the shell side in a reverse flow mode 2 The gas is absorbed (fig. 3). With CO 2 /N 2 The mixed gas is a simulated gas in which CO 2 The concentration was 20v/v%. The testing temperature is 25 ℃, and the absorption liquid is dissolved in 1mol/L monoethanolamine waterThe flow rate of the absorption solution was 100mL/min.
Membrane contactor CO 2 Absorption flux of 5.4X 10 -3 mol m -2 s -1 。
Example 2:
(1) Preparing a ZnO array: weighing 1g of zinc nitrate, 0.4g of 2-methylimidazole and 0.2g of anhydrous sodium formate, dissolving in 100mL of methanol, and carrying out ultrasonic treatment until the solution is completely clear. A PTFE membrane (Nanjing Zhongkegai New Membrane science and technology Co., ltd., pore diameter 0.02-0.5 μm, inner diameter 0.4mm, outer diameter 0.8 mm) was placed vertically in the clear solution and reacted at 80 ℃ for 12 hours. And naturally cooling to room temperature after the reaction is finished, taking out the film with the ZnO, washing the film in methanol for several times until the redundant ZnO on the surface is removed, and drying to obtain the film with the ZnO array.
(2) Hydrophobic grafting: the modification is accomplished by an esterification reaction between the acid chloride groups on the fatty acid chloride and the hydroxyl groups of the ZnO. The organic amine acts as an HCl remover, completing the reaction. During grafting, solution A was prepared by dissolving 2.5g of stearoyl chloride in 40mL of DMF, and solution B was prepared by adding 0.5mL of TEA in 5mL of DMF. The two solutions were heated to 60 ℃ in a water bath, respectively, and then the membrane was immersed in solution a for 1h to ensure adequate contact of the membrane surface with the reagents. Thereafter, the solution B was dropwise added to the solution a under stirring at 600 rpm. The reaction flask was then sealed and placed in an oven at 60 ℃ for 1 hour. After the reaction was complete, the membrane was washed several times with pure ethanol and then dried overnight in a vacuum oven at 40 ℃.
The prepared hydrophobic modified hollow fiber membrane is applied to membrane absorption as follows:
the prepared hydrophobic membrane contactor CO 2 The removal experiment, the mixed gas passes through the tube side, and the absorption liquid flows to CO on the shell side in a reverse flow mode 2 The gas is absorbed. With CO 2 /N 2 The mixed gas is a simulated gas in which CO 2 The concentration was 20v/v%. The testing temperature is 25 ℃, the absorption liquid is 1mol/L monoethanolamine aqueous solution, and the flow rate of the absorption liquid is 100mL/min.
Membrane contactor CO 2 Absorption flux of 3.7X 10 -3 mol m -2 s -1 。
Example 3:
(1) Preparing a ZnO array: weighing 1g of zinc nitrate, 0.4g of 2-methylimidazole and 0.2g of anhydrous sodium formate according to the mass ratio, dissolving in 100mL of methanol, and carrying out ultrasonic treatment until the solution is completely clear. A PTFE membrane (Nanjing Zhongkegai New Membrane science and technology Co., ltd., pore diameter 0.02-0.5 μm, inner diameter 0.4mm, outer diameter 0.8 mm) was placed vertically in the clear solution and reacted at 80 ℃ for 12 hours. And naturally cooling to room temperature after the reaction is finished, taking out the film with the ZnO, washing the film in methanol for several times until the redundant ZnO on the surface is removed, and drying to obtain the film with the ZnO array.
(2) Hydrophobic grafting: the modification is accomplished by an esterification reaction between the acid chloride groups on the fatty acid chloride and the hydroxyl groups of the ZnO. The organic amine acts as an HCl remover, completing the reaction. During grafting, solution A was prepared by dissolving 2.5g of palmitoyl chloride in 40mL of DMF, and solution B was prepared by adding 0.5mL of TEA (0.364 g) to 5mL of DMF. The two solutions were heated to 60 ℃ in a water bath, respectively, and then the membrane was immersed in solution a for 1h to ensure adequate contact of the membrane surface with the reagents. Thereafter, the prepared solution B was dropwise added to the solution a under stirring at 600 rpm. The reaction flask was then sealed and placed in an oven at 60 ℃ for 1 hour. After the reaction was complete, the membrane was washed several times with pure ethanol and then dried overnight in a vacuum oven at 40 ℃.
The prepared hydrophobic modified hollow fiber membrane is applied to membrane absorption as follows:
the prepared hydrophobic membrane contactor CO 2 In the desorption experiment, the mixed gas flows through the tube pass, and the absorption liquid flows in a reverse direction to CO in the shell pass 2 The gas is absorbed. With CO 2 /N 2 The mixed gas is a simulated gas in which CO 2 The concentration was 20v/v%. The testing temperature is 25 ℃, and the absorption liquid adopts 1mol/L K 2 CO 3 The flow rate of the absorbing solution of the aqueous solution is 100mL/min.
Membrane contactor CO 2 Absorption flux of 3.8 × 10 -3 mol m -2 s -1 。
Example 4:
(1) Preparing a ZnO array: weighing 1g of zinc nitrate, 0.4g of 2-methylimidazole and 0.2g of anhydrous sodium formate according to the mass ratio, dissolving in 100mL of methanol, and carrying out ultrasonic treatment until the solution is completely clear. A PTFE membrane (Nanjing Zhongkegai New Membrane science and technology Co., ltd., pore diameter 0.02-0.5 μm, inner diameter 0.4mm, outer diameter 0.8 mm) was placed vertically in the clear solution and reacted at 80 ℃ for 12 hours. And naturally cooling to room temperature after the reaction is finished, taking out the film with the ZnO, washing the film in methanol for several times until redundant ZnO on the surface is removed, and drying to obtain the film with the ZnO array.
(2) Hydrophobic grafting: the modification is accomplished by an esterification reaction between the acid chloride groups on the fatty acid chloride and the hydroxyl groups of the ZnO. The organic amine acts as an HCl remover, completing the reaction. During grafting, solution A was prepared by dissolving 2.5g of palmitoyl chloride in 40mL of DMF, and solution B was prepared by adding 0.5mL of TEA in 5mL of DMF. The two solutions were heated to 60 ℃ in a water bath, respectively, and then the membrane was immersed in solution a for 1h to ensure adequate contact of the membrane surface with the reagents. Thereafter, the prepared solution B was dropwise added to the solution a under stirring at 600 rpm. The reaction flask was then sealed and placed in an oven at 60 ℃ for 1 hour. After the reaction was complete, the membrane was washed several times with pure ethanol and then dried overnight in a vacuum oven at 40 ℃.
The prepared hydrophobic modified hollow fiber membrane is applied to membrane absorption as follows:
the prepared hydrophobic membrane contactor CO 2 In the desorption experiment, the mixed gas flows through the tube pass, and the absorption liquid flows in a reverse direction to CO in the shell pass 2 The gas is absorbed. With CO 2 /N 2 The mixed gas is a simulated gas in which CO 2 The concentration was 20v/v%. The testing temperature is 25 ℃, the absorption liquid adopts 1mol/L diethanolamine aqueous solution, and the flow rate of the absorption liquid is 100mL/min.
Membrane contactor CO 2 Absorption flux of 4.6X 10 -3 mol m -2 s -1 。
Comparative example 1:
(1): preparing a ZnO array: weighing 1g of zinc nitrate, 0.4g of 2-methylimidazole and 0.2g of anhydrous sodium formate, dissolving in 100mL of methanol, and carrying out ultrasonic treatment until the solution is completely clear. A PTFE membrane (Nanjing Zhongkegai New Membrane science and technology Co., ltd., pore diameter 0.02-0.5 μm, inner diameter 0.4mm, outer diameter 0.8 mm) was placed vertically in the clear solution and reacted at 80 ℃ for 12 hours. And naturally cooling to room temperature after the reaction is finished, taking out the film with the ZnO, washing the film in methanol for several times until the redundant ZnO on the surface is removed, and drying to obtain the film with the ZnO array.
The prepared hydrophobic modified hollow fiber membrane is applied to membrane absorption as follows:
the prepared hydrophobic membrane contactor CO 2 In the desorption experiment, the mixed gas flows through the tube pass, and the absorption liquid flows in a reverse direction to CO in the shell pass 2 The gas is absorbed. With CO 2 /N 2 The mixed gas is a simulated gas in which CO 2 The concentration was 20v/v%. The testing temperature is 25 ℃, the absorption liquid is 1mol/L monoethanolamine aqueous solution, and the flow rate of the absorption liquid is 100mL/min.
Membrane contactor CO 2 Absorption flux of 2.3X 10 -3 mol m -2 s -1 。
Comparative example 2:
(1)Fe 2 O 3 preparing an array: weighing 1g ferrous sulfate and 5 mu L HCl, dissolving in 25mL and 75mL acetonitrile mixed solution, and carrying out ultrasonic treatment until the solution is completely clear. A PTFE membrane (Nanjing Zhongkegai New Membrane science and technology Co., ltd., pore diameter 0.02-0.5 μm, inner diameter 0.4mm, outer diameter 0.8 mm) was placed vertically in the clear solution and reacted at 100 ℃ for 4 hours. Naturally cooling to room temperature after the reaction is finished, and taking out the Fe growing on the Fe 2 O 3 The film of (1) is washed several times in methanol until the surface has an excess of Fe 2 O 3 Removing the Fe, and drying to obtain the Fe-containing iron alloy 2 O 3 A membrane of an array.
(2) Hydrophobic grafting: the modification is carried out by acid chloride groups on the fatty acid chloride and Fe 2 O 3 The esterification reaction between the hydroxyl groups of (b) is completed. The organic amine acts as an HCl remover, completing the reaction. During grafting, solution A was prepared by dissolving 2.5g of palmitoyl chloride in 40mL of DMF, and solution B was prepared by adding 0.5mL of TEA to 5mL of DMF. Heating the two solutions to 60 deg.C in water bath, and mixingThe membrane was immersed in solution a for 1h to ensure adequate contact of the membrane surface with the reagents. Thereafter, the prepared solution B was dropwise added to the solution a under stirring at 600 rpm. The reaction flask was then sealed and placed in an oven at 60 ℃ for 1 hour. After the reaction was complete, the membrane was washed several times with pure ethanol and then dried overnight in a vacuum oven at 40 ℃.
The prepared hydrophobic modified hollow fiber membrane is applied to membrane absorption as follows:
the prepared hydrophobic membrane contactor CO 2 The removal experiment, the mixed gas passes through the tube side, and the absorption liquid flows to CO on the shell side in a reverse flow mode 2 The gas is absorbed. With CO 2 /N 2 The mixed gas is a simulated gas in which CO 2 The concentration was 20v/v%. The testing temperature is 25 ℃, the absorption liquid is 1mol/L monoethanolamine aqueous solution, and the flow rate of the absorption liquid is 100mL/min.
Membrane contactor CO 2 Absorption flux of 4.1X 10 -3 mol m -2 s -1 。
Comparative example 3:
the raw PTFE membrane is used in membrane absorption as follows:
the prepared hydrophobic membrane contactor CO 2 The removal experiment, the mixed gas passes through the tube side, and the absorption liquid flows to CO on the shell side in a reverse flow mode 2 The gas is absorbed. With CO 2 /N 2 The mixed gas is a simulated gas in which CO 2 The concentration was 20v/v%. The testing temperature is 25 ℃, the absorption liquid is 1mol/L monoethanolamine aqueous solution, and the flow rate of the absorption liquid is 100mL/min. Membrane contactor CO 2 Absorption flux of 0.7X 10 -3 mol m -2 s -1 。
Claims (10)
1. A hydrophobic membrane is characterized in that the hydrophobic membrane is prepared by the following method:
(1) Preparing a ZnO array: dissolving zinc salt, 2-methylimidazole and anhydrous sodium formate in a mass ratio of 1-10: 1-5:1 in methanol to obtain a clear solution; vertically placing the hollow fiber membrane in the clarified solution, reacting at 50-100 ℃ for 6-24 h, naturally cooling to room temperature, washing the obtained membrane with ZnO by using methanol, and drying to obtain a membrane with a ZnO array;
(2) Hydrophobic grafting: dissolving fatty acid chloride in an amide solvent A to obtain a solution A; dissolving organic amine in an amide solvent B to obtain a solution B; immersing the film with the ZnO array in the step (1) into the solution A preheated to 40-80 ℃ for full infiltration, then dropwise adding the solution B preheated to 40-80 ℃ while stirring, after dropwise adding, sealing the obtained mixed solution at 40-80 ℃ for reaction for 0.5-4 h, washing the obtained grafted film with ethanol, and drying to obtain the hydrophobic film; the mass ratio of the fatty acid chloride to the organic amine is 1-10: 1.
2. the hydrophobic membrane of claim 1, wherein: the zinc salt in the step (1) is one or a mixture of more than two of zinc chloride, zinc nitrate and zinc acetate.
3. The hydrophobic membrane of claim 1, wherein: the hollow fiber membrane in the step (1) is a PP membrane, a PTFE membrane, a PES membrane or a PS membrane.
4. The hydrophobic membrane of claim 1, wherein: the volume of the methanol in the step (1) is 100-1000mL/g based on the mass of the 2-methylimidazole.
5. The hydrophobic membrane of claim 1, wherein: in the step (2), the organic amine is one or a mixture of more than two of triethylamine, ethylenediamine and diethylenetriamine.
6. The hydrophobic membrane of claim 1 wherein: in the step (2), the fatty acid chloride is one or a mixture of two of palmitoyl chloride and stearoyl chloride.
7. The hydrophobic membrane of claim 1 wherein: in the step (2), the amide solvent A and the amide solvent B are DMF.
8. The volume of the amide solvent A in the step (2) is 2-100mL/g based on the mass of the fatty acid chloride.
9. The hydrophobic membrane of claim 1, wherein: the volume of the amide solvent B in the step (2) is 2-100mL/g based on the mass of the organic amine.
10. The hydrophobic membrane of claim 1 in absorbing CO 2 The use of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211525041.3A CN115739051A (en) | 2022-11-30 | 2022-11-30 | Hydrophobic membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211525041.3A CN115739051A (en) | 2022-11-30 | 2022-11-30 | Hydrophobic membrane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115739051A true CN115739051A (en) | 2023-03-07 |
Family
ID=85341630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211525041.3A Pending CN115739051A (en) | 2022-11-30 | 2022-11-30 | Hydrophobic membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115739051A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007099396A2 (en) * | 2005-06-07 | 2007-09-07 | Foamix Ltd. | Antibiotic kit and composition and uses thereof |
| US20150053611A1 (en) * | 2013-08-23 | 2015-02-26 | Nanyang Technological University | Hydrophobic organic-inorganic composite hollow fiber membrane and method of forming the same |
| CN107198891A (en) * | 2017-06-20 | 2017-09-26 | 浙江工业大学 | super-hydrophobic metal organic framework array and preparation method and application thereof |
| CN108976669A (en) * | 2018-08-13 | 2018-12-11 | 赵焕 | A kind of hydrophobic pvc material and preparation method thereof |
| CN109310147A (en) * | 2016-07-11 | 2019-02-05 | 菲利普莫里斯生产公司 | Hydrophobicity capsule |
| CN110559889A (en) * | 2019-08-29 | 2019-12-13 | 浙江工业大学 | Hollow nano-particle composite nanofiltration membrane and preparation method and application thereof |
| CN110903590A (en) * | 2019-12-16 | 2020-03-24 | 重庆理工大学 | Wettability-controllable surface and preparation method and application thereof |
| KR20200130592A (en) * | 2019-05-10 | 2020-11-19 | 금오공과대학교 산학협력단 | Substrate including Superhydrophobic Hybrid Structure based on ZnO and Manufacturing Method therof |
| CN114849497A (en) * | 2022-04-11 | 2022-08-05 | 华南理工大学 | Fibril-like self-repairing anti-pollution ZnO/MXene base membrane and preparation method and application thereof |
-
2022
- 2022-11-30 CN CN202211525041.3A patent/CN115739051A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007099396A2 (en) * | 2005-06-07 | 2007-09-07 | Foamix Ltd. | Antibiotic kit and composition and uses thereof |
| US20150053611A1 (en) * | 2013-08-23 | 2015-02-26 | Nanyang Technological University | Hydrophobic organic-inorganic composite hollow fiber membrane and method of forming the same |
| CN109310147A (en) * | 2016-07-11 | 2019-02-05 | 菲利普莫里斯生产公司 | Hydrophobicity capsule |
| CN107198891A (en) * | 2017-06-20 | 2017-09-26 | 浙江工业大学 | super-hydrophobic metal organic framework array and preparation method and application thereof |
| CN108976669A (en) * | 2018-08-13 | 2018-12-11 | 赵焕 | A kind of hydrophobic pvc material and preparation method thereof |
| KR20200130592A (en) * | 2019-05-10 | 2020-11-19 | 금오공과대학교 산학협력단 | Substrate including Superhydrophobic Hybrid Structure based on ZnO and Manufacturing Method therof |
| CN110559889A (en) * | 2019-08-29 | 2019-12-13 | 浙江工业大学 | Hollow nano-particle composite nanofiltration membrane and preparation method and application thereof |
| CN110903590A (en) * | 2019-12-16 | 2020-03-24 | 重庆理工大学 | Wettability-controllable surface and preparation method and application thereof |
| CN114849497A (en) * | 2022-04-11 | 2022-08-05 | 华南理工大学 | Fibril-like self-repairing anti-pollution ZnO/MXene base membrane and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张从阳等: "CO2膜分离技术研究进展", 《广东化工》, vol. 42, no. 12, pages 73 - 74 * |
| 李慧等: "ZnO纳米棒阵列膜在低功率UV照射下润湿性可逆转换机制研究", 《功能材料》, vol. 48, no. 5, pages 5159 - 5163 * |
| 杨波等: "新型膜吸收技及其在电厂烟气CO2脱除中的应用", 《热力发电》, vol. 41, no. 08, pages 108 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104785129B (en) | Ammonized hollow fiber membrane substrate and application of ammonized hollow fiber membrane substrate to preparation of metal-organic framework membrane | |
| CN111408357B (en) | Biomass intelligent fiber-based amphoteric multifunctional adsorption material and preparation method and application thereof | |
| CN110141935B (en) | Functionalized ionic liquid phase change system for carbon dioxide capture and application | |
| CN110124616A (en) | A kind of modification biological charcoal and its method of modifying and application | |
| CN114522669A (en) | Integral solid amine adsorbent and preparation method thereof | |
| CN110732308A (en) | Preparation method of MOFs-based solid acid ammonia gas adsorbent | |
| US11607646B2 (en) | Process for CO2 capture from gaseous streams | |
| CN115739051A (en) | Hydrophobic membrane and preparation method and application thereof | |
| CN109400891A (en) | A kind of cadmium Base Metal organic frame and its preparation method and application | |
| CN108311109A (en) | A kind of molasses adsorbing material and its preparation method and application | |
| CN105645514B (en) | The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process | |
| KR100424863B1 (en) | A method for separation of carbon dioxide using a polyvinylidene difluoride hollow fiber membrane contactor | |
| CN110354631A (en) | A kind of preparation method and applications of the compound viscose of ionic liquid-active carbon | |
| CN110314667A (en) | A kind of preparation and its application of metal organic polymer material | |
| CN111715078A (en) | Sandwich graphene oxide hollow fiber membrane with fixed interlamellar spacing and preparation method and application thereof | |
| CN114768479A (en) | Eutectic solvent for efficiently absorbing carbon dioxide gas and preparation method and application thereof | |
| CN111559745A (en) | Adsorb CO2Preparation and modification method of solid material GO | |
| CN109012089A (en) | A method of carbon dioxide is trapped using potassium hydroxide and potassium carbonate | |
| CN104689791B (en) | Preparation and modification methods for solid material Zr-CN for adsorbing CO2 | |
| CN113786810A (en) | Preparation method and application of amine modified hydrophobic activated carbon fiber adsorbent | |
| CN112915966A (en) | Preparation method and application of polyaniline-based activated carbon | |
| CN113350977A (en) | Coupling membrane separation device for absorbing and separating acid gas from mixed gas | |
| CN107754558A (en) | A kind of NHD desulfurization concentrating method | |
| CN106362684A (en) | Nitrogenous carbon nanofiber material used for adsorption separation of carbon dioxide and preparing method thereof | |
| CN108380180A (en) | A kind of mineral acid intercalation graphene oxide CO2The preparation method of sorbing material |
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 |