CN108246124B - Preparation method of PVDF (polyvinylidene fluoride) membrane with catalytic self-cleaning function - Google Patents
Preparation method of PVDF (polyvinylidene fluoride) membrane with catalytic self-cleaning function Download PDFInfo
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- CN108246124B CN108246124B CN201711358164.1A CN201711358164A CN108246124B CN 108246124 B CN108246124 B CN 108246124B CN 201711358164 A CN201711358164 A CN 201711358164A CN 108246124 B CN108246124 B CN 108246124B
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention relates to the technical field of membrane separation materials, in particular to a preparation method of a PVDF membrane with a catalytic self-cleaning function. The invention grafts 4-aminopyridine on a PVDF main chain through a covalent bond, and then prepares a Fenton-like modifier through N element axial coordination metal phthalocyanine on a pyridine ring. The modifier is blended with PVDF powder, and the PVDF composite membrane is prepared by a non-solvent induced phase inversion technology. The composite membrane prepared by the method not only improves the hydrophilicity, the pore diameter, the void ratio and the negative charge of the PVDF membrane, but also improves the permeation flux and the pollution resistance of the PVDF membrane, and in addition, the PVDF membrane is endowed with the catalytic self-cleaning capability.
Description
Technical Field
The invention relates to the technical field of membrane separation materials, in particular to a preparation method of a PVDF membrane with a catalytic self-cleaning function.
Background
Polyvinylidene fluoride (PVDF) is a high molecular polymer material with the advantages of excellent weather resistance, heat resistance, acid and alkali resistance, easily controlled film forming process conditions, good mechanical property and the like. Therefore, the method is widely applied to the preparation of ultrafiltration membranes. But the PVDF material has low surface energy and strong hydrophobicity, which causes the problems of the PVDF film in the water treatment process: in the membrane bioreactor process or the oil/water system separation process, organic pollutants such as protein or oil stain and the like are easily adsorbed on the surface or in pores of the membrane, so that serious membrane pollution is caused. Thereby leading to the reduction of the membrane permeation flux and the increase of the transmembrane pressure difference; the increase in running cost and the reduction in membrane life.
Currently, the research on the anti-pollution performance of the PVDF membrane mainly focuses on hydrophilic modification. The hydrophilic purpose is achieved by doping inorganic nano particles or hydrophilic polymers and modifying in the membrane preparation process. The modification method has obvious effect and is easy to realize industrial production. However, the problem exists that the nano-grade inorganic substance has high surface area due to the particle volume effect, so that the agglomeration phenomenon is easy to occur, and further the modification effect is limited; the doped hydrophilic polymer, although simple in preparation process, causes elution or loss of the hydrophilic polymer during preparation or use of the membrane due to poor compatibility between the hydrophilic polymer and the hydrophobic PVDF.
The preparation method comprises the steps of grafting 4-aminopyridine on the surface of PVDF powder through a covalent bond, and then carrying out axial coordination on metal phthalocyanine (metal phthalocyanine) through N elements on a pyridine ring, so that the metal phthalocyanine is grafted onto the PVDF powder; and finally preparing the PVDF composite membrane with catalytic self-cleaning function by a blending method according to different doping proportions. The PVDF membrane process prepared by the method can effectively overcome the problems of agglomeration of nano inorganic matters, elution of hydrophilic polymers and the like. The main chain of the grafted metal phthalocyanine is PVDF, and the PVDF powder has a chemical structure similar to that of the film-making bulk PVDF powder, so that the PVDF powder has good compatibility. In addition, the metal phthalocyanine with a catalytic function is grafted, after the membrane is polluted and blocked, the polluted membrane is immersed in a hydrogen peroxide solution for a period of time, and the metal phthalocyanine axially activates the hydrogen peroxide to generate hydroxyl radicals with the oxidation potential of 2.8 ev. The hydroxyl free radicals can degrade pollutants adsorbed or deposited on the surface or in the pore diameter of the membrane into small molecular acid, even into carbon dioxide and water, without selectivity, thereby achieving the purpose of catalyzing the self-cleaning membrane.
Disclosure of Invention
Aiming at the problem that the modifying agent in the current blending modification method is agglomerated or eluted in the membrane preparation process, so that the modification effect cannot be achieved or is reduced, the invention provides a PVDF composite membrane with anti-pollution and catalytic self-cleaning functions, which is prepared by grafting a metal phthalocyanine catalyst with a catalytic function and stable chemical properties onto the surface of PVDF powder by a grafting-coordination technology and then doping the PVDF powder with the metal phthalocyanine catalyst according to a certain proportion.
The technical solution for realizing the purpose of the invention is as follows: a preparation method of a PVDF film with a catalytic self-cleaning function comprises the following steps:
step (1), performing alkalization treatment on PVDF: dispersing PVDF powder into 10 wt% potassium hydroxide aqueous solution, adding a small amount of ethanol in the dispersing process, and stirring while adding until the powder is completely wet; then stirring for 30min at 70 ℃, carrying out suction filtration and washing for several times, and carrying out vacuum drying at 60 ℃ to obtain light yellow alkalized PVDF powder, wherein the reaction process is as follows:
through the comparative test of the inventor, potassium hydroxide has obvious difference relative to alkaline matters such as sodium hydroxide, so other alkaline matters do not have the difference effect of the potassium hydroxide in the application;
step (2), grafting 4-aminopyridine on the alkalized PVDF powder: dispersing the PVDF powder obtained in the step (1) into 1 wt% sodium bicarbonate water solution, refluxing at 120 ℃ and dropwise adding a certain amount of 4-aminopyridine in the process of strong stirring; after the dropwise addition is finished, continuously stirring for 4h at 120 ℃, and performing vacuum drying at 60 ℃ to obtain reddish brown PVDF powder grafted with 4-aminopyridine, wherein the reaction process is as follows:
the sodium bicarbonate used in the step is compared with sodium carbonate and the like, and shows certain superiority which cannot be directly observed from the characteristics of the substances, and has obvious difference with the effect obtained by the substances such as the sodium carbonate and the like;
step (3), preparation of a modifier: dispersing the PVDF powder obtained in the step (2) into tetrahydrofuran, then dropwise adding a tetrahydrofuran solution in which metal phthalocyanine is dissolved, reacting for 12 hours at 70 ℃ after dropwise adding, performing suction filtration, washing for several times by using tetrahydrofuran until washing liquor is colorless, and performing vacuum drying at 40 ℃ to obtain light green modifier powder, wherein the reaction process is as follows:
in the present application, it is very important to control the temperature of the reaction, which directly affects the purity of the product and the molecular structure of the obtained substance, so for the purpose of the present application, the temperature adopted in the present application is relatively mild, but the use time is long, and the control of the condition is also the effect obtained after a great deal of comparison;
step (4), preparing the PVDF composite membrane with catalytic self-cleaning function: and (3) doping the modifier obtained in the step (3) into PVDF powder according to a certain proportion, wherein the modifier powder is added into the PVDF powder according to 1 wt% of the total weight of the casting solution, then adding the mixed powder into a casting solution, stirring at 60 ℃ until the mixed powder is completely dissolved, continuously stirring for 12 hours at 60 ℃, defoaming for 6 hours at room temperature under negative pressure, uniformly coating the casting solution on polyester non-woven fabric by using an automatic film scraper, standing the scraped film in the air for 30 seconds, and then putting the scraped film into deionized water at 35 ℃ to obtain the catalytic self-cleaning PVDF composite film.
Preferably, the PVDF composite membrane obtained in the preparation method has a catalytic self-cleaning process: when the composite membrane prepared in the step (4) is used for filtering protein or organic pollutants, and the membrane is seriously polluted and blocked, the membrane is soaked in hydrogen peroxide solution with a certain concentration for a period of time, or hydrogen peroxide solution with a certain concentration is added into a membrane component for a period of time, the pollutants on the surface of the membrane or in the pore diameter of the membrane are degraded, and the permeation flux of the membrane is recovered.
Preferably, the amount of the 4-aminopyridine used in step (2) of the above preparation method is 60 wt% of the mass of the alkalized PVDF powder.
Preferably, in step (3) of the above production method, the metal phthalocyanine is all of metal phthalocyanine and metal phthalocyanine derivatives such as iron phthalocyanine, copper phthalocyanine, cobalt phthalocyanine and the like, and more preferably, the metal phthalocyanine is iron phthalocyanine.
Preferably, in the step (4) of the preparation method, the modifying agent is doped into the PVDF powder in a proportion of 0.1-50%. The proportion of the modifier doped into the PVDF powder is 0.5-5% as a better choice.
Preferably, in the step 5 of the preparation method, the concentration of the hydrogen peroxide is 0.01-1 mol/L, and the dipping time is 1-180 min. More preferably, the concentration of the hydrogen peroxide is 0.01-0.1 mol/L, and the dipping time is 10-120 min. The hydrogen peroxide has strong oxidizability, so that the hydrogen peroxide has important effects on the protection film and the service life by controlling certain concentration and soaking time.
The invention has the following beneficial effects:
the metal phthalocyanine is a compound formed by connecting four symmetrical isoindole units with a central metal through an imine bridge bond and coordinating the four isoindole units with the central metal, and is a conjugated aromatic macrocyclic structure with 18 pi electrons, the structure of the compound is similar to that of porphyrin, and the compound has good physical and chemical stability. The metal phthalocyanine has good acid resistance, alkali resistance and chemical corrosion resistance, has oxidation or visible light activity, and is a catalyst with higher chemical stability and thermal stability. The invention grafts 4-aminopyridine on a PVDF main chain through a covalent bond, and then prepares a Fenton-like modifier through N element axial coordination metal phthalocyanine on a pyridine ring. The PVDF composite membrane with the catalytic self-cleaning function, which is prepared by blending the modifier with PVDF powder and by a non-solvent induced phase transition (NIPS) technology, has the following characteristics:
(1) the PVDF film with catalytic self-cleaning function is prepared through mixing nanometer inorganic matter with catalytic performance (such as TiO)2、SiO2、ZnO、Al2O3And carbon nanotube, etc.) directly mixed with PVDF powder, and then the composite film is prepared by the NIPS method. The method is easy to cause the problems of uneven dispersion of the nano inorganic substance and agglomeration of the nano inorganic substance, thereby leading the composite membrane to have poor catalytic performance. The metal phthalocyanine with the Fenton-like catalytic function is modified on the PVDF through a grafting-coordination technical method, and then the problems of uneven dispersion, agglomeration and poor compatibility of the metal phthalocyanine are effectively solved by utilizing the similarity of chemical structures among the PVDF.
(2) The method modifies the metal phthalocyanine on the PVDF by a grafting-coordination technical means, and effectively solves the problem of metal phthalocyanine overflow in the preparation or application process of the composite membrane by utilizing the characteristics of similarity of chemical structures and good compatibility among the PVDF.
(3) The composite membrane prepared by the method not only improves the hydrophilicity, the aperture, the void ratio and the negative charge of the PVDF membrane, but also improves the permeation flux and the pollution resistance of the PVDF membrane; and moreover, the PVDF membrane is endowed with catalytic self-cleaning capability.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which are not intended to limit the scope of the present disclosure in any way.
Example 1
Step 1, adding PVDF powder not doped with a modifier into a casting film solvent, stirring at 60 ℃ until the PVDF powder is completely dissolved, continuously stirring for 12 hours at 60 ℃, then defoaming for 6 hours under negative pressure, uniformly coating the casting film liquid on polyester non-woven fabric by using an automatic film scraping machine, standing the scraped film in air for 30 seconds, and then putting the film into deionized water at 35 ℃ to obtain a PVDF original film.
Example 2
Step 1, dispersing 6g of PVDF powder into 300mL of 10 wt% potassium hydroxide aqueous solution, adding 30mL of 95% ethanol in the dispersing process, and stirring while adding until the powder is completely wet; then stirring for 30min at 70 ℃, carrying out suction filtration and washing for several times, and carrying out vacuum drying at 60 ℃ to obtain light yellow alkalized PVDF powder;
step 2, dispersing 5g of PVDF powder obtained in the step 1 into sodium bicarbonate aqueous solution with the concentration of 1 wt%, and then dropwise adding a certain amount of 3g of 4-aminopyridine in the process of strong stirring at 120 ℃; after the dropwise addition is finished, continuously stirring for 4h at 120 ℃, and carrying out vacuum drying at 60 ℃ to obtain reddish brown PVDF powder grafted with 4-aminopyridine;
3, dispersing 3g of PVDF powder obtained in the step 2 into tetrahydrofuran, then dropwise adding a tetrahydrofuran solution in which metal phthalocyanine is dissolved (0.3 g of iron phthalocyanine is dissolved in 50ml of tetrahydrofuran), reacting at 70 ℃ for 12 hours after dropwise adding is finished, carrying out suction filtration, washing with tetrahydrofuran for several times until washing liquor is colorless, and carrying out vacuum drying at 40 ℃ to obtain light green modifier powder;
and 4, doping the modifier obtained in the step 3 into PVDF powder according to 1 wt% of the total weight of the casting solution, then adding the mixed powder into N, N-dimethylacetamide according to the solid content of 15 wt%, stirring at 60 ℃ until the mixed powder is completely dissolved, continuously stirring for 12 hours at 60 ℃, defoaming for 6 hours at room temperature under negative pressure, uniformly coating the casting solution on polyester non-woven fabric by using an automatic film scraper, standing the scraped film in the air for 30 seconds, and then putting the film into deionized water at 35 ℃ to obtain the catalytic self-cleaning PVDF composite film.
And 5, filtering 1g/L bovine serum albumin aqueous solution for 1h by using the composite membrane prepared in the step 4, soaking the polluted membrane in 0.02mol/L hydrogen peroxide aqueous solution for 90min, testing the permeation flux of the membrane by using deionization, and calculating the anti-pollution and catalytic self-cleaning performance of the membrane.
Example 3
And doping 2 wt% of a modifier into PVDF powder to prepare a PVDF composite membrane, and inspecting the pollution resistance and the catalytic self-cleaning performance of the membrane.
Example 4
3 wt% of modifier is doped into PVDF powder to prepare a PVDF composite membrane, and the pollution resistance and the catalytic self-cleaning performance of the membrane are inspected.
Example 5
And doping 4 wt% of modifier into PVDF powder to prepare a PVDF composite membrane, and inspecting the pollution resistance and the catalytic self-cleaning performance of the membrane.
Example results discussion one:
the composite membrane prepared by the invention has the following conditions and processes for testing the protein separation performance and the anti-pollution performance: the invention adopts a cross-flow permeation experiment, firstly pre-pressing the membrane for 30 minutes in deionized water under 0.15MPa, and then testing the pure water flux (J) of the membrane in the deionized water under 0.1MPaW1) Then, 1g/L Bovine Serum Albumin (BSA) aqueous solution (J) was filtered at 0.1MPap) The pH of the solution was about 7.4, the membrane was tested for anti-fouling performance, then rinsed with deionized water at 0.1MPa for 30min, and finally the pure water flux (J) was tested at 0.1MPaW2) The recovery rate of (c).
The separation performance and the anti-pollution performance of the composite membrane prepared by the invention are evaluated as follows:
water flux (J) is defined as: under certain operating conditions, the volume (V) of water per unit membrane area (A) permeated per unit time (t) is expressed in L/m2H. The specific calculation formula is as follows:
JW1and JW2For testing the pure water flux (J) for a period of 1 hourW1Represents the pure water flux of the membrane before the protein solution flux test, and JW2Pure water flux after membrane cleaning was required for the protein solution flux test).
The retention rate (R) of the composite membrane for BSA protein is calculated as follows:
CPand CPThe concentrations of the proteins in the permeate and feed were measured at 280nm using an ultraviolet-visible spectrophotometer.
Water flux recovery Rate (FR)w) Total pollution parameter (R)t) Reversible contamination parameter (R)r) And irreversible fouling parameter (R)ir) The equal parameters are used for evaluating the anti-pollution performance of the membrane, and the specific calculation formula is as follows:
table 1. examples 1-5 compare the separation performance and anti-contamination performance of composite membrane protein solutions:
and (3) comparing the results: the composite membrane prepared in example 2 has excellent anti-pollution performance and rejection rate.
Example results discussion two:
the composite membrane prepared by the invention has the following conditions and processes for testing the oil-water emulsion separation performance and the catalytic self-cleaning anti-pollution capacity: the invention adopts a cross-flow permeation experiment, firstly pre-pressing the membrane for 30 minutes in deionized water under 0.15MPa, and then testing the pure water flux (J) of the membrane in the deionized water under 0.1MPaW1) (ii) a Followed by filtering a 0.5g/L soybean oil simulated oil-water emulsion (J) at 0.1MPap) Testing the oil-water separation performance and the catalytic self-cleaning capacity of the membrane; rinsing with deionized water at 0.1MPa for 30min, and measuring pure water flux (J) at 0.1MPaW2) Recovery Rate (FRR)1) (ii) a The membrane was then immersed in 0.02mol/L hydrogen peroxide for 30min and the pure water flux (J) was again measured at 0.1MPaW3) Recovery Rate (FRR)2)。
The formula for calculating the retention rate (R) of the composite membrane to the oil-water emulsion is as follows:
TOCPand TOCPThe concentrations of the oil in the permeate and the oil in the feed liquid are measured by a total organic carbon meter.
Table 2 shows that examples 1 to 5 compare the oil-water separation performance and the catalytic self-cleaning capacity of the composite membrane:
and (3) comparing the results: experimental results show that the more modifier is doped, the stronger the catalytic self-cleaning capability of the membrane is.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. A preparation method of a PVDF film with a catalytic self-cleaning function is characterized by comprising the following steps:
step (1), dispersing PVDF powder into 10 wt% potassium hydroxide aqueous solution, wherein the dosage of the PVDF powder is 2 wt% -5 wt% of the mass of the potassium hydroxide aqueous solution; adding ethanol in the dispersing process, wherein the dosage of the ethanol is 8-12 wt% of the potassium hydroxide aqueous solution; then stirring for 30min at 70 ℃, carrying out suction filtration and washing for several times, and carrying out vacuum drying at 60 ℃ to obtain light yellow alkalized PVDF powder;
step (2), dispersing the alkalized PVDF powder obtained in the step (1) into a 1 wt% sodium bicarbonate aqueous solution, then refluxing at 120 ℃ and dropwise adding 4-aminopyridine in the process of strong stirring, wherein the using amount of the 4-aminopyridine is 50 wt% -70 wt% of the mass of the alkalized PVDF powder; then keeping stirring for 4h at 120 ℃, and vacuum drying at 60 ℃ to obtain reddish brown grafted 4-aminopyridine PVDF powder;
step (3), dispersing the grafted 4-aminopyridine PVDF powder obtained in the step (2) into tetrahydrofuran, then dropwise adding a tetrahydrofuran solution in which metal phthalocyanine is dissolved, after dropwise adding, refluxing at 70 ℃ and strongly stirring for 12 hours, carrying out suction filtration and washing with tetrahydrofuran for several times until washing liquor is colorless, and carrying out vacuum drying at 40 ℃ to obtain light green modifier powder; wherein the mass concentration of the metal phthalocyanine in the tetrahydrofuran solution of the metal phthalocyanine is 0.2-1.0 percent; the metal phthalocyanine is iron phthalocyanine and copper phthalocyanine;
and (4) doping the modifier powder obtained in the step (3) into PVDF powder, wherein the modifier powder is added into the PVDF powder according to 1 wt% of the total weight of the membrane casting solution, then adding the mixed powder into a membrane casting solvent, stirring at 60 ℃ until the mixed powder is completely dissolved, continuously stirring for 12 hours at 60 ℃, defoaming for 6 hours at room temperature under negative pressure, uniformly coating the membrane casting solution on polyester non-woven fabric by adopting an automatic membrane scraping machine, standing the scraped membrane in the air for 30 seconds, and then putting the scraped membrane into deionized water at 35 ℃ to obtain the catalytic self-cleaning PVDF composite membrane.
2. The method according to claim 1, wherein the 4-aminopyridine is used in an amount of 60 wt% based on the mass of the alkalized PVDF powder in the step (2).
3. The method according to claim 1, wherein the metal phthalocyanine is iron phthalocyanine.
4. The method according to claim 1, wherein the cleaning of the PVDF composite membrane obtained in step (4) is: the membrane is immersed in hydrogen peroxide solution with certain concentration for a period of time, or hydrogen peroxide solution with certain concentration is added into the membrane component for a period of time, pollutants on the surface of the membrane and in the pore diameter of the membrane are degraded, and the permeation flux of the membrane is recovered.
5. The preparation method according to claim 4, wherein the concentration of the hydrogen peroxide is 0.01-1 mol/L, and the dipping time is 1-180 min.
6. The preparation method according to claim 5, wherein the concentration of the hydrogen peroxide is 0.01-0.1 mol/L, and the dipping time is 10-120 min.
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| CN110975626B (en) * | 2019-12-09 | 2022-03-08 | 西安建筑科技大学 | Preparation method of photo-Fenton catalytic self-cleaning super-hydrophilic PVDF ultrafiltration membrane |
| CN115245751A (en) * | 2021-12-21 | 2022-10-28 | 浙江理工大学 | Preparation method of catalytic self-cleaning ceramic membrane |
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