CN109126489B - Preparation method of small-interception-molecular-weight polysulfone ultrafiltration membrane - Google Patents
Preparation method of small-interception-molecular-weight polysulfone ultrafiltration membrane Download PDFInfo
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- CN109126489B CN109126489B CN201811155951.0A CN201811155951A CN109126489B CN 109126489 B CN109126489 B CN 109126489B CN 201811155951 A CN201811155951 A CN 201811155951A CN 109126489 B CN109126489 B CN 109126489B
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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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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Abstract
The invention discloses a preparation method of a small-interception-molecular-weight polysulfone ultrafiltration membrane, which comprises the following steps of 1) dissolving polysulfone and an additive into a solvent to obtain a membrane casting solution; 2) carrying out vacuum defoaming on the membrane casting solution, and preparing a polysulfone ultrafiltration membrane basement membrane on industrial equipment; 3) preparing a polyvinyl alcohol (PVA) aqueous solution; 4) adding a certain amount of concentrated sulfuric acid into a PVA aqueous solution, coating the PVA aqueous solution on the surface of the prepared ultrafiltration membrane, and then putting the ultrafiltration membrane into an oven for reaction; 5) and soaking the ultrafiltration membrane after reaction in pure water for cleaning to obtain the required ultrafiltration membrane. The invention prepares the composite membrane by reacting the surface of the polysulfone basal membrane with PVA, and adjusts the surface cortex and micropores of the membrane by changing the reaction conditions in the membrane preparation engineering to obtain the polysulfone ultrafiltration membrane with different molecular weight cut-off.
Description
Technical Field
The invention relates to a method for preparing a small-interception-molecular-weight polysulfone ultrafiltration membrane, belonging to the technical field of ultrafiltration membrane preparation.
Background
The ultrafiltration membrane is one of a total of novel chemical unit operations, and has the main functions of filtering, separating, concentrating and purifying biological products, medicines and food industries; also used in devices for preparing blood, waste water and ultrapure water, etc., and has wide application. The ultrafiltration membrane separation can replace the natural sedimentation, plate-and-frame filtration, vacuum drum, centrifugal separation, solvent extraction, resin purification, activated carbon decoloration and other processes in the traditional process. The process is operated at normal temperature, has no phase change and does not produce secondary pollution. Has very good advantages.
At present, researchers are very deep and comprehensive in research on ultrafiltration membranes, all types of ultrafiltration membranes exist, ultrafiltration membranes with various molecular weight cutoffs also exist in the market, but low molecular weight cutoff ultrafiltration membranes (the molecular weight cutoff is less than 5000) are few, and the flux is low. Therefore, it is desirable to develop ultrafiltration membranes with lower molecular cut-off. Research shows that the ultrafiltration membrane with low molecular cut-off can replace part of the nanofiltration membrane to a certain extent, so that the ultrafiltration membrane has wider application range. The patent discloses a method for preparing ultrafiltration membranes with different trapped molecular masses.
Disclosure of Invention
The invention aims to provide a method for preparing ultrafiltration membranes with different molecular weight cut-off.
Therefore, the technical scheme of the invention is as follows: a preparation method of a small-interception-molecular-weight polysulfone ultrafiltration membrane is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving polysulfone and an additive into a solvent to obtain a membrane casting solution;
2) carrying out vacuum defoaming on the membrane casting solution, and preparing a polysulfone ultrafiltration membrane basement membrane;
3) preparing 0.02-0.2wt% polyethylene glycol (PVA) aqueous solution;
4) adding a certain amount of concentrated sulfuric acid into a PVA aqueous solution, coating the PVA aqueous solution on the surface of the prepared ultrafiltration membrane, and then putting the ultrafiltration membrane into an oven for reaction;
5) and soaking the ultrafiltration membrane after reaction in pure water for cleaning to obtain the required ultrafiltration membrane.
The preparation method comprises the following steps:
and (2) dissolving polysulfone and trimesic acid (TMA) into a solvent to obtain a membrane casting solution, wherein the additive in the step 1) is trimesic acid (TMA).
The total mass percentage of the additive trimesic acid in the step 1) is 2%.
In the step 4), the content of concentrated sulfuric acid in the PVA aqueous solution is 0.01% (volume ratio).
The PVA mixed solution in the step 4) is uniformly coated on the surface of the polysulfone base membrane for about 1 minute.
And (3) putting the coated film in the step 4) into an oven for 10 minutes at the temperature of 60 ℃, 80 ℃ and 90 ℃.
Soaking the ultrafiltration membrane prepared in the step 5) in pure water for 12 hours.
The invention has the beneficial effects that: the preparation method is simple, and the raw materials are wide in source and low in cost; the ultrafiltration membrane is suitable for the field of membrane separation by modifying the surface of the membrane and controlling the process conditions for preparing the membrane so as to regulate and control the performance and the structure of the ultrafiltration membrane. According to SEM images of the plane of the membrane, the membrane has larger pores at the temperature of 60 ℃ and smaller pores at the temperatures of 80 ℃ and 90 ℃; the molecular weight cut-off of the composite membrane prepared at the temperature of 60 ℃ is more than 10000, and smaller molecules (800) can be cut off at the temperature of 90 ℃ and the PVA concentration of 0.02 wt%; temperature can affect reactions that occur at the membrane surface, thereby altering the membrane surface structure to affect membrane performance. The ultrafiltration composite membrane prepared by the coaction of the PVA content and the reaction temperature can intercept different molecular masses.
Drawings
The following detailed description is made with reference to the accompanying drawings and embodiments of the present invention
FIG. 1 shows the rejection of polysulfone composite ultrafiltration membrane (PVA0.02wt%) at different temperatures, S1 being 60 ℃, S2 being 80 ℃, S3 being 90 ℃;
FIG. 2 shows the rejection rates of polysulfone composite ultrafiltration membrane (PVA0.03wt%) at different temperatures, S4 being 60 ℃, S5 being 80 ℃, S6 being 90 ℃;
FIG. 3 shows the rejection rates of polysulfone composite ultrafiltration membrane (PVA0.05wt%) at different temperatures, S7 being 60 ℃, S8 being 80 ℃, S9 being 90 ℃;
FIG. 4 shows the retention rates of polysulfone composite ultrafiltration membrane (PVA0.1wt%) at different temperatures, S10 being 60 deg.C, S11 being 80 deg.C, S12 being 90 deg.C;
FIG. 5 shows the retention rates of polysulfone composite ultrafiltration membrane (PVA0.2wt%) at different temperatures, S13 60 deg.C, S14 80 deg.C, and S15 90 deg.C.
Detailed Description
The invention is further explained below with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
EXAMPLE 1 preparation of aqueous polyvinyl alcohol solution
(1) Preparing a PVA aqueous solution: 485g of pure water is weighed and heated by a heating stirrer, the temperature is controlled below 30 ℃, 15g of polyvinyl alcohol (PVA) is weighed and added into the weighed pure water, the mixture is stirred for one hour to ensure that the PVA is uniformly distributed in the pure water, then the mixture is heated and stirred, the temperature is controlled at 95 ℃, the solution is changed into colorless and transparent particles, namely the PVA water solution with the required content of 3 percent by weight, and the PVA water solution is reserved.
(2) And titrating the PVA aqueous solution by using iodine solution to check whether the solution is pure, and when the iodine solution is dropwise added, finding that the solution does not generate floccule, wherein the solution is available, and if not, preparing again.
Example 2 preparation of polysulfone Ultrafiltration composite Membrane
(1) The aqueous PVA solution prepared in example 1 was diluted to 0.02 wt% with pure water, and 75g of the diluted solution was weighed, to which 0.02ml of concentrated sulfuric acid was added for use.
(2) Selecting a polysulfone base film with a certain size, uniformly coating the solution prepared in the step (1) in the example 2 on the surface of the base film, and putting the base film into an oven after about 1 minute, wherein the temperature is controlled to be 60 ℃ and the time is 10 minutes.
(3) And the prepared composite membrane is immersed in pure water for 12 hours to obtain the required ultrafiltration membrane. The contact angle is 69.64 +/-3, the pure water flux is 74.096 +/-10, and the molecular weight is 10000 (the retention rate is 76.71%).
Example 3
The PVA concentration in step (1) in example 2 was diluted to 0.03% by weight, and the other steps were not changed. The contact angle is 73,7 +/-3, the pure water flux is 66.421 +/-10, and the molecular weight is 10000 (the retention rate is 65.02%).
Example 4
The PVA concentration in step (1) in example 3 was diluted to 0.05% by weight, and the other steps were not changed. The contact angle is 70.68 +/-3, the pure water flux is 39.69 +/-10, and the molecular weight is 10000 (the retention rate is 85.33%).
Example 5
The PVA concentration in step (1) in example 4 was diluted to 0.1% by weight, and the other steps were not changed. The contact angle was 71, 76. + -. 4, pure water flux 26.81. + -. 5, molecular weight 10000 (cut-off 87.87%).
Example 6
The PVA concentration in step (1) in example 5 was diluted to 0.2% by weight, and the other steps were not changed. The contact angle is 67.74 + -5, the pure water flux is 17.977 + -5, and the molecular weight is 10000 (the retention rate is 72.7%).
Example 7
The temperature in step (2) of example 2 was controlled to 80 ℃ and the other steps were not changed. The contact angle is 60.52 + -5, the pure water flux is 47.81 + -5, and the molecular weight is 10000 (the retention rate is 87.14%).
Example 8
The PVA concentration in step (1) in example 7 was diluted to 0.03% by weight, and the other steps were not changed. The contact angle is 61.06 + -5, the pure water flux is 33.818 + -5, and the molecular weight is 6000 (the retention rate is 89.58%).
Example 9
The PVA concentration in step (1) in example 8 was diluted to 0.05% by weight, and the other steps were not changed. The contact angle is 66.78 + -5, the pure water flux is 21.241 + -5, and the molecular weight is 6000 (the retention rate is 94.95%).
Example 10
The PVA concentration in step (1) in example 9 was diluted to 0.1% by weight, and the other steps were not changed. The contact angle is 59.76 + -5, the pure water flux is 5.65 + -3, and the molecular weight is 1000 (the retention rate is 95.04%).
Example 11
The PVA concentration in step (1) in example 3 was diluted to 0.2% by weight, and the other steps were not changed. The contact angle is 72.08 + -4, the pure water flux is 7.368 + -4, and the molecular weight is 1000 (the retention rate is 94.24%).
Example 12
The temperature in step (2) of example 2 was controlled to 90 ℃ and the other steps were not changed. The contact angle is 58.14 +/-3, the pure water flux is 43.634 +/-10, and the molecular weight is 6000 (the retention rate is 93.26%).
Example 13
The PVA concentration in step (1) in example 12 was diluted to 0.03% by weight, and the other steps were not changed. The contact angle is 72.62 +/-5, the pure water flux is 41.477 +/-10, and the molecular weight is 10000 (the retention rate is 96.25%).
Example 14
The PVA concentration in step (1) in example 13 was diluted to 0.05% by weight, and the other steps were not changed. The contact angle is 75.76 +/-3, the pure water flux is 25.341 +/-5, and the molecular weight is 6000 (the retention rate is 94.75%).
Example 15
The PVA concentration in step (1) in example 14 was diluted to 0.1% by weight, and the other steps were not changed. The contact angle is 65.88 + -3, the pure water flux is 8.17 + -5, and the molecular weight is 800 (the retention rate is 92.29%).
Example 16
The PVA concentration in step (1) in example 15 was diluted to 0.2% by weight, and the other steps were not changed. The contact angle is 77.5 + -5, the pure water flux is 3.537 + -3, and the molecular weight is 1000 (the retention rate is 89.5%).
Claims (3)
1. A preparation method of a small-interception-molecular-weight polysulfone ultrafiltration membrane is characterized by comprising the following steps:
the method comprises the following steps:
1) dissolving polysulfone and an additive into a solvent to obtain a membrane casting solution;
2) carrying out vacuum defoaming on the membrane casting solution, and preparing a polysulfone ultrafiltration membrane basement membrane;
3) preparing a polyvinyl alcohol (PVA) aqueous solution with the concentration of 0.02-0.2 wt%;
4) adding a certain amount of concentrated sulfuric acid into a PVA aqueous solution, coating the PVA aqueous solution on the surface of the prepared ultrafiltration membrane, and then putting the ultrafiltration membrane into an oven for reaction;
5) soaking the ultrafiltration membrane after reaction in pure water for cleaning to obtain the required ultrafiltration membrane;
wherein: in the step 1), the additive is trimesic acid (TMA), the total mass percentage of the trimesic acid in the membrane casting solution is 2%, and in the step 4), the coated membrane is placed in an oven for 10 minutes at 80 ℃ or 90 ℃.
2. The method of claim 1, wherein: in the step 4), the content of concentrated sulfuric acid in the PVA aqueous solution is 0.01 vol%.
3. The method of claim 1, wherein: in the step 5), the soaking time in pure water is 12 h.
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|---|---|---|---|---|
| CN1509804A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Method for preparing composite hollow fibre membrane |
| CN101073750A (en) * | 2007-03-30 | 2007-11-21 | 浙江大学 | Method for producing density and gradient sectional porous ultrafiltration membrane |
| CN102091538A (en) * | 2011-01-10 | 2011-06-15 | 杭州水处理技术研究开发中心有限公司 | Method for preparing polyvinyl alcohol nanofiltration membrane with high rejection coefficient |
| JP5397772B2 (en) * | 2010-01-13 | 2014-01-22 | 独立行政法人物質・材料研究機構 | Polymer self-supporting membrane and separation membrane using the same |
| CN106914156A (en) * | 2017-04-10 | 2017-07-04 | 浙江工业大学 | A kind of preparation method of Novel polyvinyl alcohol NF membrane |
| CN108159894A (en) * | 2018-01-17 | 2018-06-15 | 浙江工业大学 | A kind of preparation method of polyvinyl alcohol composite nanometer filtering film |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509804A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Method for preparing composite hollow fibre membrane |
| CN101073750A (en) * | 2007-03-30 | 2007-11-21 | 浙江大学 | Method for producing density and gradient sectional porous ultrafiltration membrane |
| JP5397772B2 (en) * | 2010-01-13 | 2014-01-22 | 独立行政法人物質・材料研究機構 | Polymer self-supporting membrane and separation membrane using the same |
| CN102091538A (en) * | 2011-01-10 | 2011-06-15 | 杭州水处理技术研究开发中心有限公司 | Method for preparing polyvinyl alcohol nanofiltration membrane with high rejection coefficient |
| CN106914156A (en) * | 2017-04-10 | 2017-07-04 | 浙江工业大学 | A kind of preparation method of Novel polyvinyl alcohol NF membrane |
| CN108159894A (en) * | 2018-01-17 | 2018-06-15 | 浙江工业大学 | A kind of preparation method of polyvinyl alcohol composite nanometer filtering film |
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