CN112023724B - Modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof - Google Patents
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- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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Abstract
The invention discloses a preparation method of a modified polyvinylidene fluoride ultrafiltration membrane, and relates to the technical field of water treatment. The preparation method of the modified polyvinylidene fluoride ultrafiltration membrane comprises the following steps: (1) reversely placing the polyvinylidene fluoride ultrafiltration membrane in an ultrafiltration device, and pouring the uniformly dispersed suction filtration liquid; wherein the suction filtration liquid comprises nano ferroferric oxide particles and dilute hydrochloric acid; (2) and (3) applying pressure to the polyvinylidene fluoride ultrafiltration membrane, carrying out suction filtration, after the suction filtration is finished, cleaning the unfixed nano ferroferric oxide particles on the surface of the polyvinylidene fluoride ultrafiltration membrane, and airing to obtain the modified polyvinylidene fluoride ultrafiltration membrane. The modified polyvinylidene fluoride ultrafiltration membrane prepared by the method has good hydrophilicity, super-adsorption performance and high interception effect, and the surface of the membrane has pollution resistance and long service life.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a modified polyvinylidene fluoride ultrafiltration membrane and a preparation method thereof.
Background
With the rapid development of economic society and the rapid development of industrial production, the production amount of industrial water and wastewater in China is rapidly increased. However, the available water resources in China are very limited, and industrial wastewater must be purified and recycled to make up for the defect of insufficient water resources.
At present, the domestic sewage treatment industry is developed vigorously. The membrane separation technology is a method which takes a membrane as a separation medium, applies certain propelling force on two sides of the membrane, and selectively measures an original object through the membrane so as to achieve the separation purpose. With the accumulation of basic theoretical research and the development of modern scientific technology, industrial application of membranes has been realized. Particularly, the ultrafiltration membrane separation technology is widely applied to the field of water treatment due to the advantages of low operation pressure, no phase change in the separation process, low energy consumption, wide application range, high separation efficiency, small occupied area, high automation degree and the like. The use of the ultrafiltration membrane is influenced by membrane flux, membrane interception and membrane pollution, and the membrane performance and the service life of the membrane are influenced.
Recently, nanotechnology has been rapidly developed from academic research and has begun to gradually realize commercial potential. The nanotechnology concept has enabled new breakthrough in new water treatment membrane performance and new functionalities, such as high permeability, catalytic reactivity and resistance to fouling. Therefore, in order to realize the feasibility of market promotion, the preparation method aims to prepare the low-resistance high-adsorption membrane with reliable performance, reusability, high performance and pollution resistance under easier conditions, and reduce the use cost of the water treatment membrane.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a modified polyvinylidene fluoride ultrafiltration membrane with high hydrophilicity, high adsorption and pollution resistance and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a modified polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
(1) reversely placing the polyvinylidene fluoride ultrafiltration membrane in an ultrafiltration device, and pouring the uniformly dispersed suction filtration liquid; wherein the filtrate comprises nano ferroferric oxide particles and dilute hydrochloric acid;
(2) and (3) applying pressure to the polyvinylidene fluoride ultrafiltration membrane, carrying out suction filtration, after the suction filtration is finished, cleaning the unfixed nano ferroferric oxide particles on the surface of the polyvinylidene fluoride ultrafiltration membrane, and airing to obtain the modified polyvinylidene fluoride ultrafiltration membrane.
Preferably, in the step (1), the preparation method of the polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
(a) dissolving polyvinylidene fluoride in a solvent, introducing inert gas, stirring and heating to obtain a homogeneous phase solution;
(b) vacuum degassing the homogeneous solution prepared in the step (a) to obtain a casting liquid, scraping the casting liquid onto cloth, and soaking the cloth in a coagulating bath to obtain a nascent PVDF ultrafiltration membrane;
(c) and (c) curing the primary PVDF ultrafiltration membrane obtained in the step (b) in deionized water, and drying to obtain the PVDF ultrafiltration membrane.
Preferably, in the step (a) of the preparation method of the polyvinylidene fluoride ultrafiltration membrane, the stirring speed is 400-600rpm, the stirring time is 10-14h, the heating temperature is 70-90 ℃, and the solvent is triethyl phosphate.
Preferably, in the step (b) of the preparation method of the polyvinylidene fluoride ultrafiltration membrane, the cloth is non-woven fabric, the coagulating bath is a mixed solution of triethyl phosphate and water, and the mass ratio of the triethyl phosphate to the water in the coagulating bath is as follows: water 5: 5.
preferably, in the step (1), the polyvinylidene fluoride ultrafiltration membrane is a hydrophilic multistage porous polyvinylidene fluoride ultrafiltration membrane, and the back surface of the prepared polyvinylidene fluoride ultrafiltration membrane is a non-woven fabric.
By adding a good solvent triethyl phosphate into the coagulating bath, the PVDF membrane casting solution is induced to be separated from the delayed liquid, so that a PVDF ultrafiltration membrane with a mesoporous structure is formed, the interception and capture capacity of the membrane on a nano catalyst can be enhanced, and the stable solidification effect of the membrane on a nano metal or metal oxide catalyst is improved.
Preferably, in the filtrate obtained in the step (1) of the preparation method of the modified polyvinylidene fluoride ultrafiltration membrane, the concentration of nano ferroferric oxide is 1-10g/L, and the concentration of dilute hydrochloric acid is 0.1-0.2 mol/L; the grain diameter of the nano ferroferric oxide is 10-40 nm.
Preferably, in the filtrate obtained in the step (1) of the preparation method of the modified polyvinylidene fluoride ultrafiltration membrane, the concentration of the nano ferroferric oxide is 10g/L, and the concentration of the dilute hydrochloric acid is 0.1 mol/L.
When the concentration of the dilute hydrochloric acid in the filtrate is 0.1mol/L, the dispersion effect on the nano ferroferric oxide in the solution is better, the dispersion is more uniform, and the structure of the membrane surface cannot be damaged; when the concentration of the nano ferroferric oxide (10-20nm) in the filtrate is 1-10g/L, the nano ferroferric oxide solution has better dispersion effect and more uniform dispersion, and the nano ferroferric oxide of the polyvinylidene fluoride ultrafiltration membrane has higher loading capacity.
Preferably, the pressure applied in the step (2) of the preparation method of the modified polyvinylidene fluoride ultrafiltration membrane is 0.17-0.2 bar.
Preferably, in the step (2) of the preparation method of the modified polyvinylidene fluoride ultrafiltration membrane, the single suction filtration time is 5-10min, and the total suction filtration time is 15-30 min.
When the single suction filtration time exceeds 10min, the nano ferroferric oxide particles in the solution are only accumulated on the surface of the membrane and are easy to fall off, and no actual particle loading effect exists. And the filtration for the first 10min can firmly load the small-particle nano ferroferric oxide in the membrane.
Meanwhile, the invention also provides the modified polyvinylidene fluoride ultrafiltration membrane with hydrophilicity, high adsorption and pollution resistance, which is prepared by the preparation method.
In addition, the invention also provides application of the modified polyvinylidene fluoride ultrafiltration membrane in wastewater treatment.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified polyvinylidene fluoride ultrafiltration membrane is obtained by treating a polyvinylidene fluoride ultrafiltration membrane through a suction filtration device and improving the components and the content of a filtrate, the surface of the modified polyvinylidene fluoride ultrafiltration membrane becomes rougher to form an obvious oxidized hydrophilic layer structure, and the surface of the modified polyvinylidene fluoride ultrafiltration membrane is less than 30 ℃ and has good hydrophilicity;
(2) when the surface of the modified polyvinylidene fluoride ultrafiltration membrane is used for separating humic acid, the modified polyvinylidene fluoride ultrafiltration membrane has super-adsorption performance and high interception effect, and has very long service life.
Drawings
FIG. 1 is an SEM image of the preparation surface and the section of a modified polyvinylidene fluoride ultrafiltration membrane in an embodiment of the invention; wherein (a) is an SEM image of the surface of the polyvinylidene fluoride ultrafiltration membrane before modification; (b) is SEM picture of section of polyvinylidene fluoride ultrafiltration membrane before modification; (c) is SEM picture of the surface of the modified polyvinylidene fluoride ultrafiltration membrane; (d) is SEM picture of section of modified polyvinylidene fluoride ultrafiltration membrane;
FIG. 2 shows nano ferroferric oxide (Fe)3O4NPs), modified front polyvinylidene fluoride ultrafiltration membrane (PPS-PVDF) and modified rear polyvinylidene fluoride ultrafiltration membrane (SC-PPS-PVDF @ Fe)3O4) XRD spectrum of (1).
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
The preparation method of the modified polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
the preparation method of the polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
(a) dissolving PVDF in triethyl phosphate at 70 ℃, and stirring for 10 hours under nitrogen at a mechanical stirring speed of 400rpm to obtain a homogeneous solution;
(b) vacuum degassing the homogeneous solution prepared in the step (a), removing micro bubbles in the homogeneous solution to obtain a casting liquid, scraping the casting liquid onto a non-woven fabric, and quickly soaking the non-woven fabric in a coagulating bath VPhosphoric acid triethyl ester：VWater (W)5: 5, soaking for 20s to obtain a primary PVDF ultrafiltration membrane;
(c) and (c) curing the primary PVDF ultrafiltration membrane obtained in the step (b) in deionized water, and drying to obtain the PVDF ultrafiltration membrane.
Secondly, preparing the modified polyvinylidene fluoride ultrafiltration membrane, which comprises the following steps:
(1) reversely placing the polyvinylidene fluoride ultrafiltration membrane prepared in the first step into an ultrafiltration device, and pouring the uniformly dispersed suction filtration liquid; wherein the suction filtration liquid comprises nano ferroferric oxide particles with the mass concentration of 1g/L and the particle size of 10-20nm and dilute hydrochloric acid with the mass concentration of 0.1 mol/L;
(2) applying pressure to the polyvinylidene fluoride ultrafiltration membrane at 0.17bar, carrying out suction filtration for 5min, and cleaning the nano ferroferric oxide particles which are not fixed on the surface of the polyvinylidene fluoride ultrafiltration membrane after the suction filtration is finished;
(3) repeating the step (2) for three times, finally, cleaning the unfixed nano ferroferric oxide particles on the surface of the polyvinylidene fluoride ultrafiltration membrane, and airing to prepare the modified polyvinylidene fluoride ultrafiltration membrane A.
Example 2
The preparation method of the modified polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
the preparation method of the polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
(a) dissolving PVDF in triethyl phosphate at 80 ℃, and stirring for 12 hours under nitrogen at a mechanical stirring speed of 500rpm to obtain a homogeneous solution;
(b) vacuum degassing the homogeneous solution prepared in the step (a), removing micro bubbles in the homogeneous solution to obtain a casting liquid, scraping the casting liquid onto a non-woven fabric, and quickly soaking the non-woven fabric in a coagulating bath VPhosphoric acid triethyl ester：VWater (W)5: 5, soaking for 30s to obtain a primary PVDF ultrafiltration membrane;
(c) and (c) curing the primary PVDF ultrafiltration membrane obtained in the step (b) in deionized water, and drying to obtain the PVDF ultrafiltration membrane.
Secondly, preparing the modified polyvinylidene fluoride ultrafiltration membrane, which comprises the following steps:
(1) reversely placing the polyvinylidene fluoride ultrafiltration membrane prepared in the first step into an ultrafiltration device, and pouring the uniformly dispersed suction filtration liquid; wherein the suction filtration liquid comprises nano ferroferric oxide particles with the mass concentration of 5g/L and the particle size of 15-30nm and dilute hydrochloric acid with the mass concentration of 0.15 mol/L;
(2) applying pressure to the polyvinylidene fluoride ultrafiltration membrane at 0.18bar, carrying out suction filtration for 7min, and cleaning the nano ferroferric oxide particles which are not fixed on the surface of the polyvinylidene fluoride ultrafiltration membrane after the suction filtration is finished;
(3) and (3) repeating the step (2) for four times, finally, cleaning the unfixed nano ferroferric oxide particles on the surface of the polyvinylidene fluoride ultrafiltration membrane, and airing to obtain the modified polyvinylidene fluoride ultrafiltration membrane B.
Example 3
The preparation method of the modified polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
the preparation method of the polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
(a) dissolving PVDF in triethyl phosphate at 90 ℃, and stirring for 14 hours under nitrogen at a mechanical stirring speed of 600rpm to obtain a homogeneous solution;
(b) vacuum degassing the homogeneous solution prepared in the step (a), removing micro bubbles in the homogeneous solution to obtain a casting liquid, and scraping the casting liquid toQuickly soaking the non-woven fabric in a coagulating bath VPhosphoric acid triethyl ester：VWater (W)5: 5, soaking for 40s to obtain a primary PVDF ultrafiltration membrane;
(c) and (c) curing the primary PVDF ultrafiltration membrane obtained in the step (b) in deionized water, and drying to obtain the PVDF ultrafiltration membrane.
Secondly, preparing the modified polyvinylidene fluoride ultrafiltration membrane, which comprises the following steps:
(1) reversely placing the polyvinylidene fluoride ultrafiltration membrane prepared in the first step into an ultrafiltration device, and pouring the uniformly dispersed suction filtration liquid; wherein the suction filtration liquid comprises nano ferroferric oxide particles with the mass concentration of 10g/L and the particle size of 20-40nm and dilute hydrochloric acid with the mass concentration of 0.2 mol/L;
(2) applying pressure to the polyvinylidene fluoride ultrafiltration membrane at 0.2bar, carrying out suction filtration for 10min, and cleaning the nano ferroferric oxide particles which are not fixed on the surface of the polyvinylidene fluoride ultrafiltration membrane after the suction filtration is finished;
(3) repeating the step (2) for five times, finally, cleaning the unfixed nano ferroferric oxide particles on the surface of the polyvinylidene fluoride ultrafiltration membrane, and airing to prepare the modified polyvinylidene fluoride ultrafiltration membrane C.
Comparative example
The comparative example was polyvinylidene fluoride ultrafiltration membrane D prepared in example 2.
The modified polyvinylidene fluoride ultrafiltration membrane prepared in the embodiment and the polyvinylidene fluoride ultrafiltration membrane prepared in the comparative example are subjected to a humic acid test at the same time, and the test method comprises the following steps:
respectively placing an unmodified polyvinylidene fluoride ultrafiltration membrane and a modified polyvinylidene fluoride ultrafiltration membrane in an ultrafiltration cup, respectively carrying out dead-end filtration on 100ml of 10ppm and 100ppm humic acid solutions under the pressure of 1bar, and calculating the retention rate; and (3) placing the membrane after the experiment into deionized water, soaking for 5min, stirring, and calculating the elution rate.
The results are shown in Table 1
TABLE 1 humic acid solution rejection
The results show that, as shown in table 1, the retention rate and elution rate of the modified polyvinylidene fluoride ultrafiltration membrane on humic acid solution are obviously higher than those of the unmodified polyvinylidene fluoride ultrafiltration membrane, and the modified polyvinylidene fluoride ultrafiltration membrane has excellent pollution resistance and effectively prolongs the service life of the membrane. As can be seen from figure 1, the modified polyvinylidene fluoride ultrafiltration membrane has the advantages that the surface becomes rougher, the micro-nano structure is reduced, and the adsorption sites of the membrane surface on humic acid are reduced. And an obvious oxidized hydrophilic layer structure is formed on the surface of the modified polyvinylidene fluoride ultrafiltration membrane, so that the strength of a hydration layer on the surface of the membrane is effectively enhanced, the adhesion of humic acid and the surface of the membrane is reduced, and the pollution resistance of the membrane is successfully improved. And the surface of the modified polyvinylidene fluoride ultrafiltration membrane is less than 30 ℃, so that the modified polyvinylidene fluoride ultrafiltration membrane has good hydrophilicity and can still maintain higher membrane flux under the condition of reducing the membrane porosity.
The modified polyvinylidene fluoride ultrafiltration membrane SC-PPS-PVDF @ Fe prepared by the invention3O4Scanning electron micrographs of (c, d) and unmodified polyvinylidene fluoride ultrafiltration membrane PPS-PVDF (a, b) are shown in FIG. 1, and it can be seen from FIGS. 1 (a, b) that the top surface of the PPS-PVDF membrane is composed of fused microspheres and the micropores on the surface are uniformly arranged. As shown in FIG. 1(c, d), SC-PPS-PVDF @ Fe is obtained after nano ferroferric oxide is loaded3O4The change of the surface cortex of the membrane is small, the nano ferroferric oxide is combined with the microspheres to reduce the porosity in the membrane, meanwhile, the nano ferroferric oxide is clearly combined with the microspheres from the front surface SEM picture 1(c), and the nano ferroferric oxide can be mainly concentrated below the surface cortex of the membrane from the picture 1(d) to form a compact nano ferroferric oxide layer, which indicates that the nano ferroferric oxide is anchored in the PPS-PVDF membrane.
The nanometer ferroferric oxide (Fe) prepared by the invention3O4-NPs), modified front polyvinylidene fluoride ultrafiltration membrane (PPS-PVDF) and modified rear polyvinylidene fluoride ultrafiltration membrane(SC-PPS-PVDF@Fe3O4) The XRD spectrum of the compound is shown in figure 2. From FIG. 2, Fe can be seen3O4The NPs mainly peak at 30, 35, 43, 53, 57, 63 with independent and narrow peak pattern, and we can see the Fe loaded3O4the-NPs are very pure. For PPS-PVDF, we see XRD peak positions mainly in the interval 15 to 30, while SC-PPS-PVDF @ Fe3O4Fe is added on the basis of PPS-PVDF peak type3O4The peak pattern of-NPs, and maintaining the independent and narrow peak pattern, it can be seen that Fe3O4The NPs are successfully firmly bonded to the PPS-PVDF.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. A preparation method of the modified polyvinylidene fluoride ultrafiltration membrane is characterized by comprising the following steps:
(1) reversely placing the polyvinylidene fluoride ultrafiltration membrane in an ultrafiltration device, and pouring the uniformly dispersed suction filtration liquid; wherein the filtrate comprises nano ferroferric oxide particles and dilute hydrochloric acid;
(2) applying pressure to the polyvinylidene fluoride ultrafiltration membrane, carrying out suction filtration, cleaning the unfixed nano ferroferric oxide particles on the surface of the polyvinylidene fluoride ultrafiltration membrane after the suction filtration is finished, and airing to obtain a modified polyvinylidene fluoride ultrafiltration membrane; in the step (2), the applied pressure is 0.17-0.2 bar; in the step (2), the time of single suction filtration is 5-10min, and the total suction filtration time is 15-30 min;
in the step (1), the preparation method of the polyvinylidene fluoride ultrafiltration membrane comprises the following steps:
(a) dissolving polyvinylidene fluoride in triethyl phosphate, introducing inert gas, stirring and heating to obtain a homogeneous phase solution; in the step (a), the stirring speed is 400-600rpm, the stirring time is 10-14h, and the heating temperature is 70-90 ℃;
(b) vacuum degassing the homogeneous solution obtained in the step (a) to obtain a casting liquid, scraping the casting liquid onto cloth, and soaking the non-woven fabric in a coagulating bath to obtain a nascent PVDF ultrafiltration membrane; the coagulating bath is a mixed solution of triethyl phosphate and water, and the mass ratio of the triethyl phosphate to the water in the coagulating bath is as follows: water = 5: 5;
(c) curing the primary PVDF ultrafiltration membrane obtained in the step (b) in deionized water, and drying to obtain the PVDF ultrafiltration membrane;
in the filtrate obtained in the step (1), the concentration of the nano ferroferric oxide is 1-10g/L, and the concentration of the dilute hydrochloric acid is 0.1-0.2 mol/L; the grain diameter of the nano ferroferric oxide is 10-40 nm.
2. The preparation method of the modified polyvinylidene fluoride ultrafiltration membrane of claim 1, wherein in the filtrate obtained in the step (1), the concentration of nano ferroferric oxide is 10g/L, and the concentration of dilute hydrochloric acid is 0.1 mol/L.
3. A modified polyvinylidene fluoride ultrafiltration membrane prepared by the preparation method of any one of claims 1-2.
4. The modified polyvinylidene fluoride ultrafiltration membrane of claim 3, applied to wastewater treatment.
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| CN108479429A (en) * | 2018-05-31 | 2018-09-04 | 中国科学院城市环境研究所 | It is a kind of to utilize nanometer Fe3O4The preparation method of modified PVDF microfiltration membranes and its utilization |
| CN108837711B (en) * | 2018-06-20 | 2021-06-11 | 华南师范大学 | Preparation method and application of nanoparticle modified PVDF flat membrane |
| CN108786487A (en) * | 2018-07-06 | 2018-11-13 | 武汉科技大学 | A kind of preparation and its application of functional form ultrafiltration membrane |
| CN110772993B (en) * | 2019-09-20 | 2023-12-05 | 浙江工业大学 | Method for preparing graphene oxide/modified titanium dioxide composite nanofiltration membrane through multi-effect coupling and application of graphene oxide/modified titanium dioxide composite nanofiltration membrane in dye desalination |
| CN111467963B (en) * | 2020-03-16 | 2022-02-25 | 淮阴师范学院 | Polyvinylidene fluoride/Fe3O4-attapulgite composite ultrafiltration membrane and preparation method thereof |
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