CN113385045A - Super-hydrophobic hollow fiber membrane and preparation method, application and application method thereof - Google Patents
Super-hydrophobic hollow fiber membrane and preparation method, application and application method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 135
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 88
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002033 PVDF binder Substances 0.000 claims abstract description 45
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 45
- 238000001035 drying Methods 0.000 claims abstract description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000008347 soybean phospholipid Substances 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 claims description 14
- 235000010469 Glycine max Nutrition 0.000 claims description 13
- 244000068988 Glycine max Species 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000003904 phospholipids Chemical class 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 230000036571 hydration Effects 0.000 claims description 10
- 238000006703 hydration reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 4
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000006115 defluorination reaction Methods 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000693 micelle Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 235000021190 leftovers Nutrition 0.000 abstract description 2
- 150000004668 long chain fatty acids Chemical class 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 229940083466 soybean lecithin Drugs 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000004519 grease Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- -1 feed Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- 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
- B01D69/08—Hollow fibre membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/10—Phosphatides, e.g. lecithin
- C07F9/103—Extraction or purification by physical or chemical treatment of natural phosphatides; Preparation of compositions containing phosphatides of unknown structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a super-hydrophobic hollow fiber membrane and a preparation method, application and an application method thereof. The preparation steps are as follows: (1) the PVDF hollow fiber membrane is hydrolyzed and defluorinated in ammonia or organic amine aqueous solution, and hydroxyl is introduced on a molecular chain; (2) further carrying out esterification reaction with long-chain fatty acid to realize grafting of long-chain alkyl; (3) and finally, washing and drying by using n-hexane to obtain the super-hydrophobic modified membrane. The synthetic method is simple and easy to operate, and the solvent resistance and the separation performance of the membrane are further improved by grafting the long-chain alkyl. The prepared super-hydrophobic hollow fiber membrane can efficiently separate and enrich soybean phospholipids with high added value in the oil leftovers, the product purity reaches more than 85%, and the purification factor is not less than 3.5.
Description
Technical Field
The invention particularly relates to a super-hydrophobic hollow fiber membrane and a preparation method, application and application method thereof.
Background
Soybean oil always occupies the main position (about 40 percent) in the grease consumption structure of China, and the edible oil consumption of China continues to keep rigid growth along with the improvement of the income of the national economy. Based on the background, the significance of further extending the soybean processing industrial chain and improving the processing level is more remarkable, and higher requirements on deep processing of soybeans and improvement of the utilization rate of raw materials are provided. The hydration degummed oil residue is one of byproducts in the current soybean processing process, and contains a plurality of functional components with high added values, such as free fatty acid, sterol, phospholipid and the like, wherein soybean Phospholipid (PL) is listed as a safe and multipurpose natural food additive by countries in the world, and is widely applied to industries of food, medicine, feed, cosmetics and the like.
The content of soybean phospholipid in the hydration degummed oil residue is up to 40-50%, and the current production process of soybean phospholipid taking the hydration degummed oil residue as a raw material at home and abroad mainly comprises the steps of centrifugal separation, colloid decoloration, plate-and-frame filtration, concentration, drying and the like. However, due to the difference in technology and equipment, domestic soybean phospholipids still have the defects of deep color, low purity, poor transparency and the like, and the quality of the soybean phospholipids is far behind that of similar products abroad, and the soybean phospholipids have to be used as feed-grade concentrated phospholipids. Compared with the traditional process, the membrane separation technology has the advantages of low energy consumption, modularization, high efficiency and the like, and the application example of the membrane separation technology in the field of the oil industry is available abroad in the 80 th century. The method is still in the research stage at home, mainly uses an inorganic membrane, and although the inorganic membrane has better organic solvent resistance, the strong hydrophilicity and the adsorbability of the inorganic membrane easily cause the adsorption of polar groups such as phospholipid on the surface of the membrane, thereby causing the blockage of membrane pores and the pollution of the membrane. The polymer membrane used in the grease industry needs to have high permeability and organic solvent resistance, the research in this respect in China is still in the lagging stage, and only patents CN101838285A, CN106518906A and CN107319100A report that commercial membrane materials (including microfiltration, ultrafiltration and nanofiltration membranes) such as acetate fiber membrane (CA) and polysulfone membrane (PS) are used for separation and purification of soybean phospholipid. However, the membrane material still has the defects of poor separation performance, poor solvent resistance and the like, so that the special membrane material suitable for purifying the soybean lecithin is still far from the original design.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a super-hydrophobic hollow fiber membrane and a preparation method, application and an application method thereof.
The technical scheme for solving the problems comprises the following steps: a preparation method of a super-hydrophobic hollow fiber membrane is obtained by taking polyvinylidene fluoride (PVDF) with the membrane aperture of 2-50nm as a material and performing a modification process, wherein the modification process comprises two steps of hydrolysis and esterification grafting, and the reaction formula is as follows:
further, the modification process comprises the following steps:
step (1) PVDF defluorination reaction: immersing a PVDF hollow fiber membrane into an organic amine aqueous solution with a certain concentration, and reacting for a period of time at constant temperature;
step (2): washing the PVDF membrane prepared in the step (1) by using deionized water, and drying at 60 ℃;
and (3): immersing the PVDF membrane dried in the step (2) into fatty acid, and carrying out esterification reaction at a certain temperature;
and (4): and (4) washing and drying the esterified PVDF membrane in the step (3) by using n-hexane to obtain the super-hydrophobic hollow fiber membrane.
Further, the organic amine used in the step (1) is one or more of ammonia, ethylamine, diethylamine, triethylamine, ethylenediamine and n-propylamine, and the concentration is 20-30 wt%.
Further, the reaction temperature in the step (1) is 40-100 ℃, and the reaction time is 12-48 h.
Further, the fatty acid in the step (3) is one or more of n-capric acid, lauric acid, myristic acid, palmitic acid and stearic acid.
Further, the reaction temperature in the step (3) is 120-160 ℃, and the time is 2-6 h.
A super-hydrophobic hollow fiber membrane is obtained by adopting the preparation method.
Furthermore, the grafting rate of the super-hydrophobic hollow fiber membrane is 1-10%, and the super-hydrophobic hollow fiber membrane has good hydrophobicity and self-cleaning capability.
An application of a super-hydrophobic hollow fiber membrane in the high-efficiency purification of soybean phospholipid in soybean hydration degummed oil residue.
An application method of a super-hydrophobic hollow fiber membrane in the high-efficiency purification of soybean phospholipids in soybean hydrated degumming oil residues comprises the following steps:
(a) adding water-saturated n-hexane or cyclohexane solvent into the soybean hydration degumming oil residue, wherein the volume of the solvent is 2-5 times of the volume of the oil residue, and stirring and mixing to ensure that the phospholipid and the water form a reverse micelle with a water-in-oil core;
(b) and (3) filtering and separating the mixture by using the positive pressure super-hydrophobic hollow fiber membrane prepared by the method.
Further, the mixture in the step (b) can be supplemented with water with the volume of 0.5-3% of the volume of the mixture, the operating pressure of the super-hydrophobic hollow fiber membrane filtration is 1-1.5MPa, and the operating temperature is from room temperature to 60 ℃.
Further, the liquid on the side which is not penetrated in the step (b) is collected, and the solvent and the water in the liquid are removed by low-temperature distillation and drying means, so that the purified soybean phospholipid product is obtained.
Furthermore, the flux of the super-hydrophobic hollow fiber membrane can reach 500-1000L/(m)2H), the purity of the finally obtained dried phospholipid product reaches more than 85 percent, and the purification factor is not less than 3.5.
The invention has the following beneficial effects: the hollow fiber membrane is hydrolyzed and defluorinated in ammonia or organic amine water solution, and hydroxyl is introduced to a molecular chain; then, the long-chain alkyl is subjected to esterification reaction with long-chain fatty acid to realize grafting of the long-chain alkyl; and finally, washing and drying by using n-hexane to obtain the super-hydrophobic modified membrane. The synthesis method is simple and easy to operate, and the solvent resistance and the separation performance of the membrane are further improved by grafting long-chain alkyl. The prepared super-hydrophobic hollow fiber membrane can efficiently separate and enrich soybean phospholipids with high added value in the oil leftovers, the product purity reaches more than 85%, and the purification factor is not less than 3.5.
Drawings
FIG. 1 is a schematic structural view of a positive pressure hollow fiber membrane filtration device according to the present invention.
Detailed Description
The present invention will be further described with reference to the following embodiments. Examples 1 to 10 relate to a method for preparing a superhydrophobic hollow fiber membrane, and examples 11 to 15 relate to a method for applying a superhydrophobic hollow fiber membrane.
Example 1
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing a PVDF hollow fiber membrane into 25 wt% ammonia water solution, reacting for 15h at 50 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and immersing the dried PVDF membrane into molten stearic acid, reacting for 3 hours at 140 ℃, cleaning and drying by using normal hexane after the reaction is finished, and finally obtaining the super-hydrophobic hollow fiber membrane with the grafting rate of 5.4%.
Example 2
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing a PVDF hollow fiber membrane into a 22 wt% ethylenediamine solution, reacting for 36h at 70 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and immersing the dried PVDF membrane into molten n-capric acid, reacting for 6h at 130 ℃, washing and drying by using n-hexane after the reaction is finished, wherein the grafting rate of the finally prepared super-hydrophobic hollow fiber membrane is 7.8%.
Example 3
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing a PVDF hollow fiber membrane into 28 wt% triethylamine solution, reacting for 12h at 90 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and immersing the dried PVDF membrane into molten stearic acid, reacting for 2 hours at 150 ℃, cleaning and drying by using normal hexane after the reaction is finished, and finally obtaining the super-hydrophobic hollow fiber membrane with the grafting rate of 6.7%.
Example 4
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing the PVDF hollow fiber membrane into 21 wt% of ethylamine solution, reacting for 22h at 75 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and immersing the dried PVDF membrane into molten lauric acid, reacting for 3.5h at 120 ℃, cleaning and drying by using n-hexane after the reaction is finished, wherein the grafting rate of the finally prepared super-hydrophobic hollow fiber membrane is 4.2%.
Example 5
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing the PVDF hollow fiber membrane into 27 wt% triethylamine solution, reacting for 35h at 85 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and (3) immersing the dried PVDF membrane into molten myristic acid, reacting for 4 hours at 160 ℃, cleaning and drying by using normal hexane after the reaction is finished, and finally obtaining the super-hydrophobic hollow fiber membrane with the grafting rate of 7.4%.
Example 6
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing the PVDF hollow fiber membrane into 20 wt% of n-propylamine solution, reacting for 16h at 50 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and (3) immersing the dried PVDF membrane into molten palmitic acid, reacting for 3 hours at 145 ℃, cleaning and drying by using n-hexane after the reaction is finished, and finally obtaining the super-hydrophobic hollow fiber membrane with the grafting rate of 2.6%.
Example 7
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing a PVDF hollow fiber membrane into a 25 wt% mixed solution of ethylenediamine and diethylamine, reacting for 26h at 95 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and (3) immersing the dried PVDF membrane into molten myristic acid, reacting for 5.5 hours at 140 ℃, cleaning and drying by using n-hexane after the reaction is finished, and finally, the grafting rate of the prepared super-hydrophobic hollow fiber membrane is 6.2%.
Example 8
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing the PVDF hollow fiber membrane into a 21 wt% mixed solution of amine and ethylamine, reacting for 15h at 55 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and immersing the dried PVDF membrane into a mixture of molten palmitic acid and stearic acid, reacting for 5 hours at 155 ℃, cleaning and drying by using n-hexane after the reaction is finished, and finally obtaining the super-hydrophobic hollow fiber membrane with the grafting rate of 6.6%.
Example 9
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing the PVDF hollow fiber membrane into a mixed solution of 29 wt% of triethylamine and diethylamine, reacting for 40h at 95 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and immersing the dried PVDF membrane into a molten mixture of myristic acid and lauric acid, reacting for 5.5 hours at 150 ℃, cleaning and drying by using n-hexane after the reaction is finished, and finally preparing the super-hydrophobic hollow fiber membrane with the grafting rate of 9.5%.
Example 10
The preparation method of the super-hydrophobic hollow fiber membrane comprises the following steps:
immersing a PVDF hollow fiber membrane into a mixed solution of 25 wt% of n-propylamine and triethylamine, reacting for 38 hours at 60 ℃, then washing the PVDF membrane with deionized water, and drying at 60 ℃; and (3) immersing the dried PVDF membrane into a mixture of molten n-decanoic acid and stearic acid, reacting for 6 hours at 125 ℃, washing and drying by using n-hexane after the reaction is finished, and finally obtaining the super-hydrophobic hollow fiber membrane with the grafting rate of 7.4%.
Example 11
The application method of the super-hydrophobic hollow fiber membrane comprises the following steps:
adding water-saturated n-hexane solvent 2.5 times of the volume of the soybean hydration degummed oil residue (the content of soybean lecithin after dehydration and solvent is 60%) and continuously adding 2.5 v/v% of water, stirring and mixing, filtering by a positive pressure hollow fiber membrane at 50 ℃ and 1.4MPa, wherein the hollow fiber membrane is prepared by the embodiment 2, and the membrane flux is 860L/(m2H); collecting the liquid on the non-permeation side, and removing the solvent by low-temperature distillation and drying means to finally obtain the dried phospholipid product with the purity of 89.8 percent and the purification factor of 5.9.
Example 12
The application method of the super-hydrophobic hollow fiber membrane comprises the following steps:
adding cyclohexane solvent which is 4 times of the volume of oil residue and is saturated by water into the dehydrated and solvent-degummed oil residue of the soybeans (the content of soybean lecithin is 60 percent after dehydration and solvent), continuously adding 0.8v/v percent of water, stirring and mixing, filtering by a positive pressure hollow fiber membrane at room temperature and under the condition of 1.3MPa, and obtaining the hollow fiber membrane by the preparation of example 3, wherein the membrane flux is 660L/(m L)2H); collecting the liquid on the non-permeation side, removing the solvent by low-temperature distillation and drying means, and finally obtaining the dried phospholipid productThe purity is more than 85.3 percent, and the purification factor is 3.9.
Example 13
The application method of the super-hydrophobic hollow fiber membrane comprises the following steps:
adding 4.5 times of water-saturated n-hexane solvent of the volume of the oil residue into the dehydrated and solvent-degummed soybean oil residue (the content of soybean lecithin is 60 percent after dehydration and solvent), continuously adding 2.8v/v percent of water, stirring and mixing, filtering by a positive pressure hollow fiber membrane at the temperature of 60 ℃ and the pressure of 1.4MPa, and preparing the hollow fiber membrane by the embodiment 5, wherein the membrane flux is 920L/(m2H); collecting the liquid on the non-permeation side, and removing the solvent by low-temperature distillation and drying means to finally obtain the dried phospholipid product with the purity of over 90.6 percent and the purification factor of 6.4.
Example 14
The application method of the super-hydrophobic hollow fiber membrane comprises the following steps:
adding 3.5 times of water-saturated n-hexane solvent of the volume of the oil residue into the dehydrated and solvent-degummed soybean oil residue (the content of soybean lecithin is 60 percent after dehydration and solvent), continuously adding 1.6v/v percent of water, stirring and mixing, filtering by a positive pressure hollow fiber membrane at 45 ℃ and 1.1MPa, and preparing the hollow fiber membrane by the embodiment 7, wherein the membrane flux is 730L/(m)2H); collecting the liquid on the non-permeation side, and removing the solvent by low-temperature distillation and drying means to obtain the final dried phospholipid product with the purity of more than 87.4 percent and the purification factor of 4.6.
Example 15
The application method of the super-hydrophobic hollow fiber membrane comprises the following steps:
adding a water-saturated mixed solvent of n-hexane and cyclohexane in an amount which is 5 times the volume of the soybean hydration degummed oil residue (the content of soybean lecithin after dehydration and solvent is 60 percent), continuously adding 1.4v/v percent of water, stirring and mixing, filtering by a positive pressure hollow fiber membrane at the temperature of 30 ℃ and the pressure of 1.5MPa, and preparing the hollow fiber membrane by the embodiment 8, wherein the membrane flux is 810L/(m2H); collecting the liquid on the non-permeation side, removing the solvent by low-temperature distillation and drying means, and finally obtaining the dried phospholipid product with the purity of more than 88.6 percent,the purification factor is greater than 5.2.
Examples 11-15 were performed in a positive pressure hollow fiber membrane filtration apparatus as shown in fig. 1, which is a prior art, and the specific structure thereof is not described in detail herein. The positive pressure hollow fiber membrane filtering device is internally provided with a super-hydrophobic hollow fiber filtering membrane, and the filtering device is pressurized by introducing compressed air.
Many other changes and modifications can be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not to be limited to the specific embodiments, but only by the scope of the appended claims.
Claims (12)
1. The preparation method of the super-hydrophobic hollow fiber membrane is characterized in that the super-hydrophobic hollow fiber membrane is obtained by taking polyvinylidene fluoride (PVDF) with the membrane aperture of 2-50nm as a material and performing a modification process, wherein the modification process comprises two steps of hydrolysis and esterification grafting, and the reaction formula is as follows:
2. the method for preparing the superhydrophobic hollow fiber membrane of claim 1, wherein the modification process comprises the steps of:
step (1) PVDF defluorination reaction: immersing a PVDF hollow fiber membrane into an organic amine aqueous solution with a certain concentration, and reacting for a period of time at constant temperature;
step (2): washing the PVDF membrane prepared in the step (1) by using deionized water, and drying at 60 ℃;
and (3): immersing the PVDF membrane dried in the step (2) into fatty acid, and carrying out esterification reaction at a certain temperature;
and (4): and (4) washing and drying the esterified PVDF membrane in the step (3) by using n-hexane to obtain the super-hydrophobic hollow fiber membrane.
3. The method for preparing the superhydrophobic hollow fiber membrane according to claim 2, wherein the organic amine used in the step (1) is one or more of ammonia, ethylamine, diethylamine, triethylamine, ethylenediamine and n-propylamine, and the concentration is 20-30 wt%.
4. The method for preparing the superhydrophobic hollow fiber membrane of claim 2, wherein the reaction temperature in the step (1) is 40-100 ℃ and the reaction time is 12-48 hours.
5. The method for preparing the superhydrophobic hollow fiber membrane according to claim 2, wherein the fatty acid in the step (3) is one or more of n-decanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid.
6. The method for preparing the superhydrophobic hollow fiber membrane of claim 2, wherein the reaction temperature in the step (3) is 120-160 ℃ and the reaction time is 2-6 h.
7. A superhydrophobic hollow fiber membrane obtained by the production method according to any one of claims 1 to 6.
8. The superhydrophobic hollow fiber membrane of claim 7, wherein the superhydrophobic hollow fiber membrane has a grafting ratio of 1-10%, and has good hydrophobicity and self-cleaning ability.
9. The superhydrophobic hollow fiber membrane of claim 7 is used for efficient purification of soybean phospholipids in soybean hydrated degumming oil residue.
10. The application method of the super-hydrophobic hollow fiber membrane in the soybean hydration deoiling foot for the high-efficiency purification of the soybean phospholipid of the soybean hydration deoiling foot, which is disclosed by claim 7, comprises the following steps:
(a) adding water-saturated n-hexane or cyclohexane solvent into the soybean hydration degumming oil residue, wherein the volume of the solvent is 2-5 times of the volume of the oil residue, and stirring and mixing to ensure that the phospholipid and the water form a reverse micelle with a water-in-oil core;
(b) the mixture is separated by filtration through the positive pressure superhydrophobic hollow fiber membrane prepared by claim 1.
11. The method of claim 10, wherein the mixture in (b) is supplemented with water in an amount of 0.5-3% by volume of the mixture, the operating pressure of the superhydrophobic hollow fiber membrane filtration is 1-1.5MPa, and the operating temperature is from room temperature to 60 ℃.
12. The method of using a superhydrophobic hollow fiber membrane according to claim 10, wherein the liquid on the side not permeated in (b) is collected and the solvent and water in the liquid are removed by low temperature distillation and drying to obtain a purified soybean phospholipid product.
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