CN212356645U - Separation membrane for groundwater pollution remediation - Google Patents
Separation membrane for groundwater pollution remediation Download PDFInfo
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- CN212356645U CN212356645U CN202020373612.6U CN202020373612U CN212356645U CN 212356645 U CN212356645 U CN 212356645U CN 202020373612 U CN202020373612 U CN 202020373612U CN 212356645 U CN212356645 U CN 212356645U
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Abstract
The utility model discloses a separation membrane preparation method for groundwater pollution remediation, the characterized in that of membrane: the hydrophilic membrane is a hydrophilic/hydrophobic separation membrane with a Janus structure, and the hydrophilic layer (zwitterionic polypeptide), the adhesion layer (dopamine) and the hydrophobic layer (PVDF membrane) are arranged from top to bottom in sequence. The preparation method of the hydrophilic/hydrophobic separation membrane with the Janus structure is simple, has a good separation effect on the separation of groundwater non-aqueous phase liquid, and has strong reusability, good feasibility and good practicability.
Description
Technical Field
The utility model relates to a groundwater nonaqueous phase liquid pollution handles field particularly, relates to a be used for prosthetic separation membrane of groundwater pollution.
Background
In recent years, the pollution of non-aqueous phase liquids (NAPLs) in groundwater caused by oil overflow, chemical leakage and the like is more and more emphasized, after the NAPLs are leaked, the NAPLs can be diffused and migrated in a long time, and the groundwater is polluted for a long time, so that the pollution to human health and natural environment is more extensive. Therefore, effective treatment of NAPLs in groundwater is an urgent problem to be solved in terms of human health and environmental protection.
At present, the surfactant enhanced extraction-treatment technology can effectively control NAPLs pollution zones in underground water and remove NAPLs pollution sources. Due to the addition of surfactants in this technique, part of the NAPLs are present in the groundwater and soil pores in the form of emulsions. The non-aqueous phase liquid emulsion needs to be separated after being pumped out. Conventional methods include gravity settling, centrifugation, flotation, and the like. These separation methods often have problems of low separation efficiency, high investment cost, large energy consumption, etc., and the treatment effect is not ideal.
In contrast, the microfiltration membrane technology is an ideal emulsion separation method due to the characteristics of low cost, low energy consumption, high efficiency and the like. However, most microfiltration separation membranes are organic polymer membranes, and due to the hydrophobic nature of the membranes, the water flux is very small, making it difficult to separate emulsions efficiently. In addition, macromolecular organic matters such as emulsion liquid drops, underground water humic acid and the like are very easy to adhere to the surface of the membrane, so that the service life and the reutilization property of the membrane are greatly reduced. Therefore, it is necessary to change the surface properties of the membrane, to improve its separation ability and reusability.
The Janus (in roman myth, it is a bisexual mythical) membrane refers to a membrane with two-sided structure or chemical composition different, and has dual properties such as positive/negative electricity, hydrophilic/hydrophobic, polar/nonpolar and the like, and is one of the leading and hot research directions in the field of material science. For example, the patent CN107529450A discloses a preparation method and application of a Janus double-layer ion imprinted composite membrane; the patent CN107794596A discloses a red fluorescent bi-anisotropic conductive Janus structure film and a preparation method thereof. The Janus hydrophilic/hydrophobic separation membrane has different chemical infiltration properties on two sides of the membrane, so that the non-aqueous phase liquid emulsion or water can only permeate the separation membrane in one direction under the drive of surface chemical potential. At present, no patent report is found on the hydrophilic/hydrophobic separation membrane with the Janus structure. In particular, no patent report is found on a hydrophilic/hydrophobic separation membrane having a Janus structure, which is applied to groundwater non-aqueous phase liquid emulsion separation.
Disclosure of Invention
An object of the utility model is to provide a be used for prosthetic separation membrane of groundwater pollution, this kind of membrane has very good effect to the separation of groundwater non-aqueous phase liquid emulsion, and repeatedly usable.
The structure of the groundwater non-aqueous phase liquid emulsion separation membrane with Janus structure is shown in figures 1-4. As shown in fig. 1, the above-described separation membrane includes a hydrophilic layer, an adhesive layer, and a hydrophobic layer. As shown in FIG. 2, the pore size of the hydrophilic layer is 0.1 to 0.4 μm. As shown in FIG. 3, the pore diameter of the hydrophobic layer film is 0.4 to 1 micron. As shown in fig. 4, the hydrophilic layer surface has a hydrophilic characteristic, the hydrophobic layer surface has a hydrophobic characteristic, and the inner surface of the membrane pores has a hydrophilic characteristic.
A preparation method of a separation membrane for groundwater pollution remediation is realized by the following technical scheme, and is characterized by comprising the following steps:
1) the polyvinylidene fluoride (PVDF) film is flatly laid in a groove of a self-made device (the structure is shown in figure 5), an annular silica gel sealing gasket is placed in the groove, and then the groove is sealed by a cylindrical cover (two ends are hollow).
2) Weighing 20-60 mg of dopamine hydrochloride, adding the dopamine hydrochloride into 20mL of 10mM Tris solution (pH8.5), and preparing into 1-3 mg/mL dopamine solution.
3) Adding the dopamine solution prepared in the step 2) into the automatic device in the step 1), and soaking for 1-6 hours at 15-35 ℃. And pouring out the upper solution, and washing with 20mL of water for 2-3 times to obtain the PVDF film with the adhesive layer.
4) 10-30 mg of zwitterionic polypeptide is weighed and added into 20mL of 10mM Tris solution (p8.5) to prepare a polypeptide solution with the concentration of 0.5-1.5 mg/mL.
The zwitterionic polypeptide in the step 4) is one of HS-VVEKE (sulfhydryl-valine-glutamic acid-lysine-glutamic acid), HS-VVEKEKE (sulfhydryl-valine-glutamic acid-lysine-glutamic acid) and CRRERE (cysteine-arginine-glutamic acid).
5) Pouring the polypeptide solution prepared in the step 4) into the self-made container containing the PVDF film with the adhesive layer in the step 3), and soaking for 2-6 hours at 15-35 ℃. And pouring out the upper solution, and washing with 20mL of water for 2-3 times to obtain the hydrophilic/hydrophobic separation membrane with the Janus structure.
The utility model discloses a beneficial effect:
1) the membrane preparation process is simple, the hydrophilic modification effect is obvious, and the upper surface is changed from hydrophobicity (120.6 degrees) to strong hydrophilicity (8.2 degrees).
2) The membrane has a Janus structure, one surface is hydrophilic, and the other surface is hydrophobic, so that in the separation process of the groundwater non-aqueous phase liquid emulsion, water can only permeate from one side of the hydrophilic layer to one side of the hydrophobic layer, and emulsion micro-droplets are intercepted on one side of the hydrophilic layer, thereby realizing the efficient separation of the emulsion.
3) The hydrophilic layer of the membrane is polypeptide micromolecules, the blockage of membrane pores can not be caused, and the pure water flux is controlled by 0Lm before modification-2h-1Increased to 9900 +/-562 Lm after modification-2h-1And is biodegradable and environment-friendly.
4) The membrane separation effect is good, the retention rate is high, the separation membrane has good separation effect on NPALs-containing emulsions of different systems, and the flux can be kept at 2000Lm-2h-1Above, the retention rate can be ensured to be above 97%.
5) The anti-pollution performance of the membrane is good, the membrane can be repeatedly used for many times, and after the membrane is repeatedly used for 5 times, the flux can still be recovered to be more than 90% of the first flux.
Drawings
FIG. 1 is a front view of a separation membrane having a Janus structure; wherein: 1-hydrophilic layer, 2-adhesive layer, 3-hydrophobic layer.
FIG. 2 top view of a hydrophilic layer of a separation membrane with Janus structure
FIG. 3 top view of hydrophobic layer of separation membrane with Janus structure
FIG. 4 is a sectional view of a separation membrane having a Janus structure
FIG. 5 is an apparatus for preparing a separation membrane having a Janus structure; wherein: 4-cylindrical cover, 5-annular gasket, 6-groove circular (for placing membrane element)
Detailed Description
The present invention and the preparation method and application of the present invention will be described in detail with reference to the following examples.
The structure of the groundwater non-aqueous phase liquid emulsion separation membrane with Janus structure is shown in figures 1-4. As shown in fig. 1, the above-described separation membrane includes a hydrophilic layer 1, an adhesive layer 2, and a hydrophobic layer 3. As shown in FIG. 2, the pore size of the hydrophilic layer 1 is 0.1-0.4 μm. As shown in FIG. 3, the pore diameter of the hydrophobic layer 3 is 0.4 to 1 μm. As shown in fig. 4, the surface of the hydrophilic layer 1 has a hydrophilic characteristic, the surface of the hydrophobic layer 3 has a hydrophobic characteristic, and the inner surface of the pore of the membrane has a hydrophilic characteristic.
Example 1
A preparation method of a separation membrane for groundwater pollution remediation comprises the following steps:
1) the polyvinylidene fluoride (PVDF) film is flatly laid in a groove of a self-made device (the structure is shown in figure 5), an annular silica gel sealing gasket is placed in the groove, and then the groove is sealed by a cylindrical cover (two ends are hollow).
2) 20mg of dopamine hydrochloride was weighed and added to 20mL of 10mM Tris solution (pH8.5) to prepare a dopamine solution having a concentration of 1 mg/mL.
3) Adding the dopamine solution prepared in the step 2) into the self-made device in the step 1), and soaking for 1 hour at 15 ℃. The upper solution was then decanted and washed 2 times with 20mL of water to produce a PVDF membrane having an adhesive layer.
4) 10mg of HS-VVEKE (mercapto-valine-glutamic acid-lysine-glutamic acid) was weighed and added to 20mL of 10mM Tris solution (pH8.5) to prepare a polypeptide solution having a concentration of 0.5 mg/mL.
5) Pouring the polypeptide solution prepared in the step 4) into the self-made container containing the PVDF film with the adhesive layer in the step 3), and soaking for 2 hours at 15 ℃. The upper solution was then decanted and washed 2 times with 20mL of water to produce a hydrophilic/hydrophobic separation membrane having a Janus structure.
Example 1 measurement of emulsion separation Effect of separation Membrane having Janus Structure in groundwater non-aqueous phase liquid emulsion separation application
3 typical groundwater NAPLS contaminants (stearic acid, n-hexane, diesel) and surfactant SDS were selected to prepare water samples for a total of 3 water samples.
The specific preparation process is as follows: according to the volume ratio of 1: 100, respectively taking NAPLs pollutants and water, adding a surfactant according to the concentration of 0.2mg/mL, and emulsifying the mixed solution by an emulsifying machine at the rotating speed of 20000rpm for 15 minutes.
And (3) emulsion separation process: opening a circulating vacuum water pump to pump off air in the filter flask, pouring 50mL of emulsion sample after the vacuum value is stable, recording the time of the water sample passing through the membrane, and calculating the flux; and measuring the content of organic matters in the water sample and the filtrate by using the TOC, thereby calculating the interception rate of NAPLs.
The flux at the time of separation and the retention of NAPLs for the different emulsions are shown in table 1.
TABLE 1 flux and rejection of various NAPLs emulsions
| NAPLs | Flux (Lm)-2h-1) | Retention (%) |
| Stearic acid | 2537±264 | 97.51 |
| N-hexane | 2168±223 | 98.61 |
| Diesel oil | 6017±312 | 97.47 |
The higher flux of the emulsion in either system indicates that the separation membrane has a high efficiency for emulsion separation.
The concentration of NAPLs in the filtrate was quite low after the filtration of the emulsions of different systems through the separation membrane, which indicates that the filtration of NAPLs-containing emulsions through the separation membrane is very effective.
Example 1 determination of the Recycling Effect of the separation Membrane having Janus Structure prepared in groundwater non-aqueous liquid emulsion separation application
A recycling test of the separation membrane was performed, as represented by a diesel emulsion containing SDS, to evaluate the recyclability of the separation membrane.
The specific operation is as follows: and opening a vacuum water pump to pump off air in the filter flask, pouring a proper amount of sewage sample after the vacuum value is stable, recording the time of sewage passing through the membrane, calculating the flux at the moment, repeating the process, respectively calculating the flux, taking out the membrane, cleaning with absolute ethyl alcohol and ultrapure water, putting the membrane back into the filter device, and repeating the process. The total was performed 5 times.
The flux changes during the 5 recycling experiments are shown in table 2, from which it can be seen that the initial flux of the separation membrane does not change much after each washing and the final flux of the membrane decreases, but not too much, at each filtration. Therefore, we can conclude that the separation membrane has excellent recyclability.
TABLE 20.09 MPa Change in flux upon repeated five filtrations of the emulsion
| Number of experiments | Initial flux (Lm)-2h-1) | Final flux (Lm)-2h-1) |
| 1 | 7134 | 3672 |
| 2 | 6945 | 3620 |
| 3 | 7216 | 3403 |
| 4 | 7012 | 3181 |
| 5 | 7325 | 2943 |
Example 2
A preparation method of a separation membrane for groundwater pollution remediation comprises the following steps:
1) the polyvinylidene fluoride (PVDF) film is flatly laid in a groove of a self-made device (the structure is shown in figure 5), an annular silica gel sealing gasket is placed in the groove, and then the groove is sealed by a cylindrical cover (two ends are hollow).
2) 40mg of dopamine hydrochloride was weighed and added to 20mL of 10mM Tris solution (pH8.5) to prepare a 2mg/mL dopamine solution.
3) Adding the dopamine solution prepared in the step 2) into the self-made device in the step 1), and soaking for 3 hours at 25 ℃. The upper solution was then poured out and washed 3 times with 20mL of water to produce a PVDF membrane having an adhesive layer.
4) 20mg of HS-VVEKEEKE (mercapto-valine-glutamic acid-lysine-glutamic acid) was weighed and added to 20mL of 10mM Tris solution (pH8.5) to prepare a polypeptide solution having a concentration of 1.0 mg/mL.
5) Pouring the polypeptide solution prepared in the step 4) into the self-made container containing the PVDF film with the adhesive layer in the step 3), and soaking for 4 hours at the temperature of 25 ℃. The upper solution was then decanted and washed 3 times with 20mL of water to produce a hydrophilic/hydrophobic separation membrane having a Janus structure.
Example 2 measurement of emulsion separation Effect of the separation Membrane having Janus Structure prepared in groundwater non-aqueous phase liquid emulsion separation application
3 typical groundwater NAPLS contaminants (stearic acid, n-hexane, diesel) and surfactant SDS were selected to prepare water samples for a total of 3 water samples.
The specific preparation process is as follows: according to the volume ratio of 1: 100, respectively taking NAPLs pollutants and water, adding a surfactant according to the concentration of 0.2mg/mL, and emulsifying the mixed solution by an emulsifying machine at the rotating speed of 20000rpm for 15 minutes.
And (3) emulsion separation process: opening a circulating vacuum water pump to pump off air in the filter flask, pouring 50mL of emulsion sample after the vacuum value is stable, recording the time of the water sample passing through the membrane, and calculating the flux; and measuring the content of organic matters in the water sample and the filtrate by using the TOC, thereby calculating the interception rate of NAPLs.
The flux at the time of separation and the retention of NAPLs for the different emulsions are shown in table 3.
TABLE 3 flux and rejection of various NAPLs emulsions
| NAPLs | Flux (Lm)-2h-1) | Retention (%) |
| Stearic acid | 3247±141 | 98.52 |
| N-hexane | 2564±201 | 97.22 |
| Diesel oil | 5087±142 | 97.21 |
Example 3
A preparation method of a separation membrane for groundwater pollution remediation comprises the following steps:
1) the polyvinylidene fluoride (PVDF) film is flatly laid in a groove of a self-made device (the structure is shown in figure 5), an annular silica gel sealing gasket is placed in the groove, and then the groove is sealed by a cylindrical cover (two ends are hollow).
2) 60mg of dopamine hydrochloride was weighed and added to 20mL of 10mM Tris solution (pH8.5) to prepare a dopamine solution having a concentration of 3 mg/mL.
3) Adding the dopamine solution prepared in the step 2) into the self-made device in the step 1), and soaking for 6 hours at 35 ℃. The upper solution was then poured out and washed 3 times with 20mL of water to produce a PVDF membrane having an adhesive layer.
4) 30mg of CRRERE (cysteine-arginine-glutamic acid) was weighed and added to 20mL of 10mM Tris solution (pH8.5) to prepare a polypeptide solution having a concentration of 1.5 mg/mL.
5) Pouring the polypeptide solution prepared in the step 4) into the self-made container containing the PVDF film with the adhesive layer in the step 3), and soaking for 6 hours at the temperature of 35 ℃. The upper solution was then decanted and washed 3 times with 20mL of water to produce a hydrophilic/hydrophobic separation membrane having a Janus structure.
Example 3 measurement of emulsion separation Effect of the separation Membrane having Janus Structure in groundwater non-aqueous phase liquid emulsion separation application
3 typical groundwater NAPLS contaminants (stearic acid, n-hexane, diesel) and surfactant SDS were selected to prepare water samples for a total of 3 water samples.
The specific preparation process is as follows: according to the volume ratio of 1: 100, respectively taking NAPLs pollutants and water, adding a surfactant according to the concentration of 0.2mg/mL, and emulsifying the mixed solution by an emulsifying machine at the rotating speed of 20000rpm for 15 minutes.
And (3) emulsion separation process: opening a circulating vacuum water pump to pump off air in the filter flask, pouring 50mL of emulsion sample after the vacuum value is stable, recording the time of the water sample passing through the membrane, and calculating the flux; and measuring the content of organic matters in the water sample and the filtrate by using the TOC, thereby calculating the interception rate of NAPLs.
The flux at the time of separation and the retention of NAPLs for the different emulsions are shown in table 4.
TABLE 4 flux and rejection of various NAPLs emulsions
| NAPLs | Flux (Lm)-2h-1) | Retention (%) |
| Stearic acid | 2247±242 | 98.01 |
| N-hexane | 3105±130 | 97.94 |
| Diesel oil | 5987±225 | 98.65 |
Claims (6)
1. A separation membrane for groundwater contamination remediation, the membrane characterized by: the hydrophilic layer, the adhesion layer, the dopamine and the hydrophobic layer, namely the polyvinylidene fluoride membrane are sequentially arranged from top to bottom; the pore size of the hydrophilic layer membrane is 0.1-0.4 micron, the pore size of the hydrophobic layer membrane is 0.4-1 micron, the surface of the hydrophilic layer has hydrophilic characteristics, the surface of the hydrophobic layer has hydrophobic characteristics, the inner surface of the membrane pore has hydrophilic characteristics, and the separation membrane is a hydrophilic/hydrophobic separation membrane with a Janus structure.
2. The separation membrane of claim 1, characterized by a polyvinylidene fluoride membrane as a substrate.
3. The separation membrane of claim 1, wherein the polyvinylidene fluoride membrane is modified with dopamine.
4. The separation membrane of claim 1, wherein the zwitterionic polypeptide is one of mercapto-valine-glutamic acid-lysine-glutamic acid, mercapto-valine-glutamic acid-lysine-glutamic acid, and cysteine-arginine-glutamic acid.
5. The separation membrane of any one of claims 1 to 4, which is used for groundwater non-aqueous phase liquid emulsion separation.
6. The separation membrane of claim 4, wherein: the groundwater non-aqueous phase liquid is one of stearic acid, normal hexane and diesel oil.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111137952A (en) * | 2020-03-23 | 2020-05-12 | 中新瑞美(天津)环保科技有限公司 | Preparation method of separation membrane for groundwater pollution remediation |
| CN113617062A (en) * | 2021-07-05 | 2021-11-09 | 暨南大学 | Self-driven oil-water separation composite Janus membrane material and preparation method and application thereof |
| CN113926316A (en) * | 2021-11-23 | 2022-01-14 | 江苏巨澜纳米科技有限公司 | Leak-proof humidifying composite hollow fiber membrane, preparation method and application thereof |
| CN115228305A (en) * | 2022-06-20 | 2022-10-25 | 深圳高性能医疗器械国家研究院有限公司 | Janus film and preparation method thereof |
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2020
- 2020-03-23 CN CN202020373612.6U patent/CN212356645U/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111137952A (en) * | 2020-03-23 | 2020-05-12 | 中新瑞美(天津)环保科技有限公司 | Preparation method of separation membrane for groundwater pollution remediation |
| CN113617062A (en) * | 2021-07-05 | 2021-11-09 | 暨南大学 | Self-driven oil-water separation composite Janus membrane material and preparation method and application thereof |
| CN113926316A (en) * | 2021-11-23 | 2022-01-14 | 江苏巨澜纳米科技有限公司 | Leak-proof humidifying composite hollow fiber membrane, preparation method and application thereof |
| CN113926316B (en) * | 2021-11-23 | 2024-01-26 | 江苏巨澜纳米科技有限公司 | Leakage-proof humidifying composite hollow fiber membrane, preparation method and application thereof |
| CN115228305A (en) * | 2022-06-20 | 2022-10-25 | 深圳高性能医疗器械国家研究院有限公司 | Janus film and preparation method thereof |
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