CN107158974B - High-strength hydrophilic nanofiltration membrane, preparation method thereof and application thereof in protein solution desalination process - Google Patents
High-strength hydrophilic nanofiltration membrane, preparation method thereof and application thereof in protein solution desalination process Download PDFInfo
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- CN107158974B CN107158974B CN201710360650.0A CN201710360650A CN107158974B CN 107158974 B CN107158974 B CN 107158974B CN 201710360650 A CN201710360650 A CN 201710360650A CN 107158974 B CN107158974 B CN 107158974B
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- 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
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- 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
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- 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
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Abstract
The invention relates to a high-strength hydrophilic nanofiltration membrane, a preparation method thereof and application thereof in a protein solution desalination process, and belongs to the technical field of membrane materials. The nanofiltration membrane provided by the invention utilizes the modifier containing polyhydroxy to form bonding with-SiO-of montmorillonite to form a cross-linked network structure, and meanwhile, the modifier also has hydrophobic genes and can form a better compatible structure with a base membrane, so that the bonding force between the montmorillonite and the base membrane is improved; because the montmorillonite has better ion exchange performance, when the nanofiltration membrane is applied to the protein solution desalination process, the nanofiltration membrane has better interception performance and pollution resistance to protein due to the hydrophilicity of the membrane, and has higher transmittance to inorganic salt due to the ion exchange performance of the montmorillonite.
Description
Technical Field
The invention relates to a high-strength hydrophilic nanofiltration membrane, a preparation method thereof and application thereof in a protein solution desalination process, and belongs to the technical field of membrane materials.
Background
Nanofiltration (nanofiltraction) is a novel pressure-driven membrane separation process developed in recent years, is a membrane separation technology between reverse osmosis and ultrafiltration, and is one of the hotspots of the research in the field of domestic outer membrane separation at present because of lower operation pressure, different selectivity to mono-and divalent ions, higher interception to small molecular organic matters, low equipment investment and low energy consumption [3 ]. The aperture range of the nanofiltration membrane is about 1-5 nanometers, and the molecular weight cut-off of the membrane is about 200-2000. The nanofiltration membrane is mostly a composite membrane, and a surface separation layer of the nanofiltration membrane is composed of polyelectrolyte, can intercept high-valence salt and permeate monovalent salt, can intercept organic matters with molecular weight of more than 100 and enable small-molecular organic matters to permeate the membrane, can separate like amino acid and protein, and realizes separation of organic matters with high relative molecular weight and low relative molecular weight, so that the nanofiltration membrane is widely applied to the fields of chemical industry, biochemistry, environmental protection and metallurgy, such as separation, concentration, refining, industrial wastewater treatment, drinking water preparation, material recovery and the like in food and pharmacy.
In recent years, with the large application of nanofiltration technology in water treatment, pharmacy, food and other industries, the demand of hydrophilic nanofiltration membranes is greatly increased. However, the hydrophilic nanofiltration membrane variety with commercial application value is very rare. Therefore, a new membrane preparation technology and a surface hydrophilic modification method become hot spots for developing nanofiltration membranes.
The method for carrying out hydrophilic modification on the surface of the nanofiltration membrane comprises the following steps: chemical grafting modification, physical modification (e.g., ultraviolet irradiation), inorganic particle doping. The inorganic particle doping method is a method in which hydrophilic inorganic particles are added to a film-forming material to improve the hydrophilicity of a film by the inorganic particles.
However, since the film-forming material is usually a polymer, its compatibility with inorganic particles is low, which easily results in low strength of the film material and easy damage during use.
Disclosure of Invention
The purpose of the invention is: provides a nanofiltration membrane with hydrophilicity, which has higher strength and is suitable for the concentration and separation process of protein due to the advantage of high hydrophilicity. The technical conception is as follows: bonding is formed between the modifier containing polyhydroxy and-SiO-of the montmorillonite to form a cross-linked network structure, and meanwhile, the modifier also has hydrophobic genes and can form a better compatible structure with the basement membrane, so that the bonding force between the montmorillonite and the basement membrane is improved; because the montmorillonite has better ion exchange performance, when the nanofiltration membrane is applied to the protein solution desalination process, the nanofiltration membrane has better interception performance and pollution resistance to protein due to the hydrophilicity of the membrane, and has higher transmittance to inorganic salt due to the ion exchange performance of the montmorillonite.
The technical scheme is as follows:
first aspect of the invention:
a preparation method of a high-strength hydrophilic nanofiltration membrane comprises the following steps:
step 1, preparation of aqueous phase solution: dispersing 1.2-2.5 parts by weight of montmorillonite into 80-90 parts by weight of deionized water, adding 0.2-0.5 part by weight of anionic surfactant, 2-4 parts by weight of anhydrous piperazine and 0.5-0.8 part by weight of compound shown in formula (I), and uniformly stirring by ultrasound to obtain an aqueous solution;
(I)；
step 2, preparing an oil phase solution: dissolving 5-12 parts by weight of trimesoyl chloride in 80-85 parts by weight of normal hexane, and uniformly mixing to obtain an oil phase solution;
step 3, interfacial polymerization: and (2) taking an ultrafiltration membrane as a base membrane, soaking the base membrane in the water phase solution, taking out, soaking in the oil phase solution, taking out, drying in a blast air box at 50-65 ℃, and then washing the surface with deionized water to obtain the high-strength hydrophilic nanofiltration membrane.
In the step 1, the anionic surfactant is one or a mixture of two of sodium dodecyl sulfate and sodium dodecyl sulfate.
In the step 3, the ultrafiltration membrane is made of polyether sulfone, polyvinylidene fluoride or polysulfone; the range of the molecular weight cut-off of the ultrafiltration membrane is 8-15 ten thousand.
In the step 3, the basement membrane is soaked in the aqueous phase solution for 3-10 min; soaking the base membrane in the oil phase solution for 3-10 min; the drying time is 30-60 min.
Second aspect of the invention:
the nanofiltration membrane directly obtained by the preparation method.
The third aspect of the present invention:
a desalting method for protein containing salt adopts the nanofiltration membrane to concentrate.
The protein is BSA; the salt is NaCl.
The operation parameters in the concentration process are as follows: the pressure is 0.5-2.5 Mpa, and the temperature is 10-30 ℃.
The montmorillonite is applied to simultaneously improving the protein retention rate of the nanofiltration membrane and the transmittance of inorganic salt.
Advantageous effects
The nanofiltration membrane provided by the invention utilizes the modifier containing polyhydroxy to form bonding with-SiO-of montmorillonite to form a cross-linked network structure, and meanwhile, the modifier also has hydrophobic genes and can form a better compatible structure with a base membrane, so that the bonding force between the montmorillonite and the base membrane is improved; because the montmorillonite has better ion exchange performance, when the nanofiltration membrane is applied to the protein solution desalination process, the nanofiltration membrane has better interception performance and pollution resistance to protein due to the hydrophilicity of the membrane, and has higher transmittance to inorganic salt due to the ion exchange performance of the montmorillonite.
Drawings
FIG. 1 is an infrared spectrum of the nanofiltration membrane prepared in example 3.
Detailed Description
Example 1
Step 1, preparation of aqueous phase solution: dispersing 1.2 parts of montmorillonite in 80 parts of deionized water according to parts by weight, adding 0.2 part of sodium dodecyl sulfate, 2 parts of anhydrous piperazine and 0.5 part of compound shown in formula (I), and uniformly stirring by ultrasonic to obtain an aqueous solution;
(I)；
step 2, preparing an oil phase solution: dissolving 5 parts of trimesoyl chloride in 80 parts of normal hexane by weight, and uniformly mixing to obtain an oil phase solution;
step 3, interfacial polymerization: and (2) taking a polyether sulfone ultrafiltration membrane as a base membrane (the range of molecular weight cut-off is 12 ten thousand), soaking the base membrane in an aqueous phase solution for 3min, taking out, soaking in an oil phase solution for 3min, taking out, drying in a blast air box at 50 ℃ for 30min, and then washing the surface with deionized water to obtain the high-strength hydrophilic nanofiltration membrane.
Example 2
Step 1, preparation of aqueous phase solution: dispersing 2.5 parts of montmorillonite in 90 parts of deionized water according to parts by weight, adding 0.5 part of sodium dodecyl sulfate, 4 parts of anhydrous piperazine and 0.8 part of compound shown in formula (I), and uniformly stirring by ultrasonic to obtain an aqueous solution;
(I)；
step 2, preparing an oil phase solution: dissolving 12 parts of trimesoyl chloride in 85 parts of normal hexane by weight, and uniformly mixing to obtain an oil phase solution;
step 3, interfacial polymerization: and (2) taking a polyether sulfone ultrafiltration membrane as a base membrane (the range of molecular weight cut-off is 12 ten thousand), soaking the base membrane in an aqueous phase solution for 10min, taking out, soaking in an oil phase solution for 10min, taking out, drying in a 65 ℃ blast air box for 60min, and then washing the surface with deionized water to obtain the high-strength hydrophilic nanofiltration membrane.
Example 3
Step 1, preparation of aqueous phase solution: dispersing 1.8 parts of montmorillonite in 85 parts of deionized water according to parts by weight, adding 0.3 part of sodium dodecyl sulfate, 3 parts of anhydrous piperazine and 0.6 part of compound shown in formula (I), and uniformly stirring by ultrasonic to obtain an aqueous solution;
(I)；
step 2, preparing an oil phase solution: dissolving 8 parts of trimesoyl chloride in 82 parts of normal hexane by weight, and uniformly mixing to obtain an oil phase solution;
step 3, interfacial polymerization: and (2) taking a polyether sulfone ultrafiltration membrane as a base membrane (the range of molecular weight cut-off is 12 ten thousand), soaking the base membrane in an aqueous phase solution for 5min, taking out, soaking in an oil phase solution for 5min, taking out, drying in a blast air box at 55 ℃ for 40min, and then washing the surface with deionized water to obtain the high-strength hydrophilic nanofiltration membrane.
The obtained nanofiltration membrane has surface infrared spectrum as shown in figure 1, wherein the surface infrared spectrum is 3436cm-1NH on the piperazine ring22929 cm-1And 1430 cm-1Is the vibration characteristic peak of the benzene ring; 1635 cm-1Is the-CONH-characteristic peak of the amide; 1222 cm-1Is the characteristic peak of the R-O-R' ether group of the modifier. It can be confirmed that a copolymerization network is formed between the modifier and piperazine, trimesoyl chloride and montmorillonite.
Comparative example 1
The difference from example 3 is that: in the preparation of the aqueous solution, the compound represented by the formula (I) is not added.
Comparative example 2
The difference from example 3 is that: in the preparation of the aqueous solution, montmorillonite was not added.
Characterization test
1. Measuring the tensile strength of the nanofiltration membrane by using a tensile testing machine;
2. measuring the pure water flux of the nanofiltration membrane under the condition of 0.5 Mpa;
3. filtration test of salt-containing protein solution
Preparing an aqueous solution containing 2wt% of Bovine Serum Albumin (BSA) and 3wt% of NaCl, and performing protein concentration and desalination tests by using the nanofiltration membrane, wherein in the filtering process, the feed liquid temperature is 25 ℃, the filtering pressure is 1.5Mpa, and the penetrating fluid returns to the feed liquid tank for circulation. The filtration time was 50min, and the retention rate for BSA and NaCl were measured.
The results are as follows:
as can be seen from the table, the composite nanofiltration membrane provided by the invention has higher strength and water flux; in example 3, compared to comparative example 1, the modifier with more hydroxyl groups is added to the aqueous solution, so that the hydroxyl groups can be crosslinked with-SiO-bonds of montmorillonite, and the effect of improving the tensile strength of the film is achieved; example 3 compared with comparative example 2, it can be seen that the addition of montmorillonite improves the permeability of NaCl by utilizing its ion exchange property, and the separation degree of protein and salt is improved by improving the retention rate of BSA due to the hydrophilicity of montmorillonite.
Claims (8)
1. A preparation method of a high-strength hydrophilic nanofiltration membrane is characterized by comprising the following steps:
step 1, preparation of aqueous phase solution: dispersing 1.2-2.5 parts by weight of montmorillonite into 80-90 parts by weight of deionized water, adding 0.2-0.5 part by weight of anionic surfactant, 2-4 parts by weight of anhydrous piperazine and 0.5-0.8 part by weight of compound shown in formula (I), and uniformly stirring by ultrasound to obtain an aqueous solution;
(I)；
step 2, preparing an oil phase solution: dissolving 5-12 parts by weight of trimesoyl chloride in 80-85 parts by weight of normal hexane, and uniformly mixing to obtain an oil phase solution;
step 3, interfacial polymerization: and (2) taking an ultrafiltration membrane as a base membrane, soaking the base membrane in the water phase solution, taking out, soaking in the oil phase solution, taking out, drying in a blast air box at 50-65 ℃, and then washing the surface with deionized water to obtain the high-strength hydrophilic nanofiltration membrane.
2. The method of claim 1, wherein in the step 1, the anionic surfactant is one or a mixture of sodium dodecyl sulfate and sodium dodecyl sulfate.
3. The method for preparing a high-strength hydrophilic nanofiltration membrane according to claim 1, wherein in the step 3, the ultrafiltration membrane is made of polyethersulfone, polyvinylidene fluoride or polysulfone; the range of the molecular weight cut-off of the ultrafiltration membrane is 8-15 ten thousand.
4. The method for preparing a high-strength hydrophilic nanofiltration membrane according to claim 1, wherein in the step 3, the basement membrane is soaked in the aqueous solution for 3-10 min; soaking the base membrane in the oil phase solution for 3-10 min; the drying time is 30-60 min.
5. A nanofiltration membrane directly obtained by the preparation method of any one of claims 1 to 4.
6. A method for desalting proteins containing salts, characterized in that the nanofiltration membrane of claim 5 is used for concentration.
7. The method for desalting a salt-containing protein according to claim 6, wherein said protein is BSA; the salt is NaCl.
8. The method for desalting salt-containing protein according to claim 6, wherein the operating parameters during said concentrating are: the pressure is 0.5-2.5 MPa, and the temperature is 10-30 ℃.
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| CN103157386A (en) * | 2011-12-16 | 2013-06-19 | 三星电子株式会社 | Semi-permeable separation membrane including coated nanoporous particles in a polymer matrix, and method of manufacturing the same |
| CN103635242A (en) * | 2011-07-01 | 2014-03-12 | 国际商业机器公司 | Thin film composite membranes embedded with molecular cage compounds |
| CN103897088A (en) * | 2012-12-28 | 2014-07-02 | 财团法人工业技术研究院 | Electrical particle, additive and filtering membrane |
| CN105358238A (en) * | 2013-07-04 | 2016-02-24 | 巴斯夫欧洲公司 | Multiple channel membranes |
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| WO2012166701A2 (en) * | 2011-05-27 | 2012-12-06 | Cornell University | Nanoparticle-functionalized membranes, methods of making same, and uses of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103635242A (en) * | 2011-07-01 | 2014-03-12 | 国际商业机器公司 | Thin film composite membranes embedded with molecular cage compounds |
| CN103157386A (en) * | 2011-12-16 | 2013-06-19 | 三星电子株式会社 | Semi-permeable separation membrane including coated nanoporous particles in a polymer matrix, and method of manufacturing the same |
| CN102886207A (en) * | 2012-10-23 | 2013-01-23 | 杭州水处理技术研究开发中心有限公司 | Preparation method of composite reverse osmosis membrane |
| CN103897088A (en) * | 2012-12-28 | 2014-07-02 | 财团法人工业技术研究院 | Electrical particle, additive and filtering membrane |
| CN105358238A (en) * | 2013-07-04 | 2016-02-24 | 巴斯夫欧洲公司 | Multiple channel membranes |
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