CN108404686B - Preparation method of metal ion adsorption sewage separation membrane - Google Patents
Preparation method of metal ion adsorption sewage separation membrane Download PDFInfo
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- CN108404686B CN108404686B CN201810426980.XA CN201810426980A CN108404686B CN 108404686 B CN108404686 B CN 108404686B CN 201810426980 A CN201810426980 A CN 201810426980A CN 108404686 B CN108404686 B CN 108404686B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention relates to a preparation method of a metal ion adsorption sewage separation membrane. According to the invention, the characteristic that graphene oxide and polyphenol have more hydrophilic oxygen-containing functional groups and can generate chelation reaction with metal ions is utilized, so that the membrane can adsorb the metal ions while separating sewage. The metal ion adsorption sewage separation membrane prepared by the method can be repeatedly used after adsorption is finished by cleaning, so that secondary pollution is avoided, and valuable metals can be recovered.
Description
Technical Field
The invention relates to the technical field of membranes for water treatment, in particular to a preparation method of a metal ion adsorption sewage separation membrane.
Background
At present, the main methods for harmless treatment of wastewater containing metal ions include membrane separation, electrochemical precipitation, ion exchange, adsorption and biological treatment. Among them, the membrane separation technology has many advantages compared with other technologies, such as good selectivity, capability of separating molecular substances, normal temperature operation, no phase change, low energy consumption, and cost about 1/3-1/8 of evaporation concentration or freeze concentration. Therefore, the membrane separation technology has wide application prospect in the field of sewage treatment.
Polyvinylidene fluoride (PVDF) is used as a microfiltration membrane or ultrafiltration membrane material with good comprehensive performance, has the characteristics of high temperature resistance, radiation resistance, wear resistance, chemical corrosion resistance and the like, but cannot be directly used for metal ion adsorption. The blending is the simplest and most common membrane modification method, and compared with other methods, the blending modification has the advantages that the blending modification and the membrane forming are carried out synchronously, the process is simple, complicated post-treatment steps are not needed, the modifier can cover the membrane surface and the inner wall of the membrane hole at the same time, the damage of the membrane structure cannot be caused, and the like.
Graphene is continuously developed and utilized in the aspect of impurity removal by an adsorption method due to the huge specific surface area of graphene, and the derivative graphene oxide of the graphene has stronger adsorption capacity on metal ions due to the fact that a large number of oxygen-containing polar groups such as hydroxyl groups, epoxy groups, carboxyl groups and the like exist on two sides of a plane and an edge. However, the graphene oxide is small in size, and is dispersed in water after being used as an adsorbent to adsorb metal ions, so that the graphene oxide is not easy to remove in the later period, and secondary pollution of a water body is brought.
The polyphenol compounds comprise Tannin (Tannin, TA), Dopamine (DA), Pyrogallol (PG), catechol, epigallocatechin and the like, contain adjacent hydroxyl groups which can generate chelation and complexation with metal ions, and have good adsorption effect on the metal ions. In addition, the graphene oxide can be modified by oxidative coupling polymerization on the graphene oxide, so as to increase the volume of the compound, see chinese patents CN104098860A, CN107638816A, CN105944691A, and the like.
Based on the method, firstly, the graphene oxide is modified by using polyphenol compounds such as tannin and the like, and then the modified graphene oxide is mixed with PVDF powder to prepare the metal ion adsorption sewage separation membrane. A large amount of oxygen-containing polar groups such as carboxyl, phenolic hydroxyl, epoxy and the like contained in the film are utilized to carry out high-efficiency adsorption and desorption on low-concentration metal ions such as lead, copper and the like; in addition, the microporous structure and the hydrophilic functional group of the membrane are utilized, so that the membrane has a good blocking effect on large-particle pollutants and oily pollutants. Due to the interaction between the graphene oxide and the polyphenol compound, the volume of the compound is greatly increased, so that the compound can stably exist in the blending membrane and cannot be removed from the blending membrane in the adsorption and filtration processes, the compound can be repeatedly used, and the secondary pollution of the graphene oxide to a water body is prevented.
Disclosure of Invention
The invention aims to solve the problems of complex preparation process, poor performance and the like of an adsorption membrane in the prior art, and provides a preparation method of a metal ion adsorption sewage separation membrane. The separation membrane can be used for efficiently adsorbing metal ions in sewage, filtering and removing pollutants such as large granular substances, colloids and the like in water, valuable metal ions in the membrane material adsorbing the metal ions can be efficiently recovered after the membrane material is cleaned, and the separation membrane can be reused. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a metal ion adsorption sewage separation membrane comprises the following steps:
(a) ultrasonically dispersing graphene oxide in deionized water, adding a polyphenol compound, uniformly stirring, and carrying out solid-liquid separation after the reaction is finished to obtain polyphenol modified graphene oxide;
(b) ultrasonically dispersing the polyphenol modified graphene oxide in an organic solvent A, adding polyvinylidene fluoride and a pore-forming agent, and fully stirring to obtain a membrane casting solution;
(c) and pouring the membrane casting solution on a flat plate, blade-coating to form a membrane, then placing the membrane in the solution B for curing, finally taking out, washing and drying to obtain the metal ion adsorption sewage separation membrane.
In the scheme, the polyphenol compound is selected from one of tannin, dopamine, pyrogalloc acid, catechol and epigallocatechin, and the mass ratio of the added polyphenol compound to the graphene oxide is 10-20: 1.
In the scheme, the polyvinylidene fluoride is powder, and the average molecular weight of the polyvinylidene fluoride is 10-40 ten thousand.
In the above scheme, the pore-forming agent is polyvinylpyrrolidone K30.
In the above scheme, the organic solvent a is selected from one of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), and N-methylpyrrolidone (NMP).
In the above scheme, the solution B is selected from one of water, ethanol and octanol.
In the scheme, the mass fraction of the polyphenol modified graphene oxide in the casting solution is 1-2%, the mass fraction of the polyvinylidene fluoride is 10-15%, the mass fraction of the pore-forming agent is 0.5-2%, and the balance is the organic solvent A.
Further, the preparation method of the polyphenol modified graphene oxide specifically comprises the following steps: ultrasonically dispersing graphene oxide in deionized water, heating to 30-60 ℃, stirring for reacting for 8-16h, filtering by using a membrane with the aperture of 0.1-0.5 mu m, and washing, drying and grinding filter residues to obtain the graphene oxide membrane.
The method for preparing the casting solution comprises the following steps: ultrasonically dispersing the polyphenol modified graphene oxide in an organic solvent A, adding pre-dried polyvinylidene fluoride and a pore-making agent into a dispersion liquid under a protective atmosphere, stirring and reacting for 20-28h, and finally removing bubbles in vacuum for 4-8h to obtain the graphene oxide porous material.
Compared with the prior art, the invention has the following unexpected beneficial effects:
(1) the metal ion adsorption sewage separation membrane is prepared by adopting a method of blending polyphenol modified graphene oxide and polyvinylidene fluoride, wherein the polyphenol modified graphene oxide is uniformly dispersed in a flat membrane, and both the polyphenol modified graphene oxide and the flat membrane have hydrophilic oxygen-containing functional groups which can generate chelation with metal ions, so that the membrane can adsorb the metal ions while separating sewage;
(2) the large specific surface area and rich oxygen-containing functional groups contained in the graphene oxide and the polyphenol compound are fully utilized, the complexation effect on metal ions is remarkably improved, and the removal rate of the separation membrane on low-concentration metal ions can reach more than 95%;
(3) the polyphenol modified graphene oxide in the separation membrane stably exists in a flat membrane, can be repeatedly used after being cleaned after being subjected to adsorption treatment on sewage, and can efficiently recover valuable metal ions in the sewage;
(4) by utilizing the microporous structure of the membrane and the hydrophilic functional groups, the oily pollutants can be separated while metal ions are adsorbed;
(5) compared with CN107638816A, the graphene oxide is modified by polyphenol compounds, the volume of the graphene oxide is increased, so that the graphene oxide stably exists in a solution, the adsorbent is prevented from being separated from a blending film during direct blending, and then the graphene oxide is blended with polyvinylidene fluoride and directly formed into a film by a solution phase conversion method.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
The reagents used in the invention are all commonly available on the market. The adsorption efficiency of the metal ions was determined by the following method: the Pb (II) and Cu (II) solutions were diluted with standard 100mg/L stock solutions of Pb (II) and Cu (II), respectively, the pH of the solution was adjusted to 5 with NaOH and HCl, 10mL of a 10mg/L metal ion solution was filtered through the prepared adsorption membrane, the lower clear solution was then filtered through a 0.22 μm pore membrane, and the concentration of metal ions in the filtrate was measured by atomic absorption spectroscopy, and the calculation was performed according to the adsorption efficiency equation (1).
In the formula, E-metal ion adsorption efficiency, C0-initial concentration of metal ions, mg/L; c-concentration after adsorption of metal ions, mg/L.
The invention adopts the following method to determine the adsorption capacity of metal ions: taking an adsorption film prepared by a certain mass, placing the adsorption film into a conical flask, adding a metal ion solution with a certain volume and fixed concentration, oscillating for 12 hours in a constant-temperature oscillator at 30 ℃, testing the concentration of metal ions by using an atomic absorption spectrometer, and calculating according to an adsorption capacity formula (2).
In the formula, C0-initial concentration of metal ions, mg/L; ce-metal ion concentration at adsorption equilibrium, mg/L; vf-a metal ion volume; w-dry film quality.
The desorption rate is determined by the following method: washing the adsorption membrane after adsorption equilibrium with deionized water until the filtrate does not contain metal ions, mixing with a certain volume of 0.1M hydrochloric acid solution, oscillating in a constant temperature oscillator for a certain time, measuring the ion concentration in the solution, and calculating the desorption rate according to the formula (3).
Wherein eta-desorption rate, concentration of metal ions in the C-eluent, mg/L; v-eluent volume, L; q-adsorption capacity of membrane adsorbent before elution, mg/g; m-mass of the adsorption film.
The retention rate of the prepared adsorption membrane on Bovine Serum Albumin (BSA) is measured by adopting the following method for representing the separation effect on organic pollutants, and the specific process is as follows: BSA powder was dissolved in PBS buffer (pH 7.4) to prepare a BSA solution of 200mg/L, and the BSA solution was filtered through the prepared filter membrane to collect a permeate. And (3) measuring the absorbance of the penetrating fluid at 278nm by using an ultraviolet-visible spectrophotometer, and calculating the retention rate according to the formula (4).
Wherein, R-retention; cpThe mass concentration of the permeate BSA, mg/L; cfMass concentration of BSA in the feed solution, mg/L.
Example 1
Firstly, 100mg of graphene oxide is ultrasonically dispersed in 100mL of deionized water, 2g of tannin is added, the solution is heated to 50 ℃ and stirred to react for 12 hours, a product is filtered by a membrane with the pore diameter of 0.2 mu m, and then the product is cleaned, dried, ground and stored to obtain polyphenol modified graphene oxide (TA-GO).
2g ofTA-GO was ultrasonically dispersed in 84g DMF in N2Under protection, 12.5g of dried and pretreated PVDF powder (average molecular weight of 10-40 ten thousand) and 1.5g of hole-making agent polyvinylpyrrolidone K30 are slowly added into the dispersion liquid, the mixture is stirred and reacted for 24 hours to ensure that the casting solution is uniform and stable, and finally the casting solution is placed in a vacuum drying oven for defoaming for 6 hours.
Pouring the prepared casting solution on a glass plate, scraping out a flat membrane with uniform thickness by using a scraper, and then placing the flat membrane in a water coagulation bath for curing to form a membrane. Taking out, washing with deionized water for several times, and storing in deionized water or room temperature drying environment.
Example 2
Firstly, 100mg of graphene oxide is ultrasonically dispersed in 100mL of deionized water, then 2g of dopamine is added, the solution is heated to 50 ℃ and stirred for 12 hours, a product is filtered by a membrane with the pore diameter of 0.2 mu m, and then the product is cleaned, dried, ground and stored to obtain the dopamine modified graphene oxide (DA-GO).
1g DA-GO was ultrasonically dispersed in 84g DMF in N2And slowly adding 13.5g of dried and pretreated PVDF powder (average molecular weight is 10-40 ten thousand) and 1.5g of a pore-forming agent polyvinylpyrrolidone K30 into the dispersion under protection, stirring for reacting for 24 hours to ensure that the casting solution is uniform and stable, and finally placing the casting solution in a vacuum drying oven for defoaming for 6 hours.
Pouring the prepared casting solution on a glass plate, scraping out a flat membrane with uniform thickness by using a scraper, and then placing the flat membrane in a water coagulation bath for curing to form a membrane. Taking out, washing with deionized water for several times, and storing in deionized water or room temperature drying environment.
Example 3
Firstly, 100mg of graphene oxide is ultrasonically dispersed in 100mL of deionized water, 2g of pyrogallol is added, the solution is heated to 50 ℃ and stirred for 12 hours, the product is filtered by a membrane with the pore diameter of 0.2 mu m, and then the product is cleaned, dried, ground and preserved to obtain pyrogallol modified graphene oxide (PG-GO).
1.5g PG-GO was ultrasonically dispersed in 84g DMF in N213.5g of dried and pretreated PVDF powder (average molecular weight is 10-40 ten thousand) and 1g of pore-forming agent polyvinylpyrrolidone K30 are slowly added into the dispersion liquid under protection, and stirring is carried outAnd reacting for 24 hours to ensure that the casting solution is uniform and stable, and finally placing the casting solution in a vacuum drying oven for defoaming for 6 hours.
Pouring the prepared casting solution on a glass plate, scraping out a flat membrane with uniform thickness by using a scraper, and then placing the flat membrane in a water coagulation bath for curing to form a membrane. Taking out, washing with deionized water for several times, and storing in deionized water or room temperature drying environment.
Example 4
Firstly, 100mg of graphene oxide is ultrasonically dispersed in 100mL of deionized water, 2g of pyrogallol is added, the solution is heated to 50 ℃ and stirred for 12 hours, the product is filtered by a membrane with the pore diameter of 0.2 mu m, and then the product is cleaned, dried, ground and preserved to obtain pyrogallol modified graphene oxide (PG-GO).
2g PG-GO was ultrasonically dispersed in 84g DMF in N2And slowly adding 13g of dried and pretreated PVDF powder (average molecular weight is 10-40 ten thousand) and 1g of pore-forming agent polyvinylpyrrolidone K30 into the dispersion under protection, stirring for 24 hours to enable the casting solution to be uniform and stable, and finally placing the casting solution in a vacuum drying oven for defoaming for 6 hours.
Pouring the prepared casting solution on a glass plate, scraping out a flat membrane with uniform thickness by using a scraper, and then placing the flat membrane in a water coagulation bath for curing to form a membrane. Taking out, washing with deionized water for several times, and storing in deionized water or room temperature drying environment.
Example 5
Firstly, 100mg of graphene oxide is ultrasonically dispersed in 100mL of deionized water, 2g of tannin is added, the solution is heated to 50 ℃ and stirred for 12 hours, the product is filtered by a membrane with the pore diameter of 0.2 mu m, and then the product is cleaned, dried, ground and stored to obtain the tannin modified graphene oxide (TA-GO).
Ultrasonic dispersion of 1.5g TA-GO in 84.5g DMF in N2And slowly adding 13.5g of dried and pretreated PVDF powder (average molecular weight is 10-40 ten thousand) and 0.5g of pore-forming agent polyvinylpyrrolidone K30 into the dispersion under protection, stirring for reacting for 24 hours to ensure that the casting solution is uniform and stable, and finally placing the casting solution in a vacuum drying oven for defoaming for 6 hours.
Pouring the prepared casting solution on a glass plate, scraping out a flat membrane with uniform thickness by using a scraper, and then placing the flat membrane in a water coagulation bath for curing to form a membrane. Taking out, washing with deionized water for several times, and storing in deionized water or room temperature drying environment.
Example 6
Firstly, 100mg of graphene oxide is ultrasonically dispersed in 100mL of deionized water, 2g of dopamine is added, the solution is heated to 50 ℃ and stirred for 12 hours, a product is filtered by a membrane with the pore diameter of 0.2 mu m, and then the product is cleaned, dried, ground and stored to obtain the dopamine modified graphene oxide (DA-GO).
1g of DA-GO alkene was ultrasonically dispersed in 84g of DMF in N2And under protection, slowly adding 14g of dried and pretreated PVDF powder (average molecular weight of 10-40 ten thousand) and 1g of pore-forming agent polyvinylpyrrolidone K30 into the dispersion, stirring for 24 hours to enable the casting solution to be uniform and stable, and finally placing the casting solution in a vacuum drying oven for defoaming for 6 hours.
Pouring the prepared casting solution on a glass plate, scraping out a flat membrane with uniform thickness by using a scraper, and then placing the flat membrane in a water coagulation bath for curing to form a membrane. Taking out, washing with deionized water for several times, and storing in deionized water or room temperature drying environment.
The metal ion-adsorbing wastewater separation membranes obtained in examples 1 to 6 were subjected to the above-mentioned tests, and the comparative adsorption efficiency tables shown in Table 1 were obtained.
TABLE 1 comparison of adsorption efficiency of Metal ion-adsorbing Sewage separation membranes obtained in examples 1 to 6
As can be seen from table 1, the polyphenol-modified graphene oxide has a high adsorption efficiency of 95% or more to a low-concentration metal ion solution as an adsorbent. The separation membrane prepared by the method has a great application value for the treatment of the sewage containing metal ions in life.
TABLE 2 comparison table of desorption efficiency of the metal ion adsorption sewage separation membrane prepared in examples 1 to 6
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Desorption rate of lead ion | 95.4％ | 94.6％ | 93.3％ | 96.5％ | 95.2％ | 90.8％ |
| Copper ion desorption rate | 97.1％ | 96.4％ | 96.6％ | 98.3％ | 97.9％ | 95.7％ |
As can be seen from Table 2, the metal ion adsorption sewage separation membrane prepared by the method of the present invention has a high desorption rate of metal ions, and therefore, can be used for the recovery and application of valuable metal ions.
The metal ion adsorption sewage separation membrane prepared in example 5 was selected for the cleaning regeneration adsorption test, and the results are shown in table 3.
TABLE 3 TABLE 5 Table of relationship between the regeneration frequency and adsorption efficiency of the metal ion adsorption sewage separation membrane
As can be seen from table 3, the metal ion adsorption sewage separation membrane prepared by the method of the present invention has high adsorption efficiency on metal ions after being washed and regenerated for multiple times, which indicates that the polyphenol modified graphene oxide stably exists in the adsorption membrane, and does not separate from the adsorption membrane to cause secondary pollution to water, and is safer and more environmentally friendly.
TABLE 4 comparison table of the retention rates of the metal ion adsorption sewage separation membranes prepared in examples 1 to 6 on bovine serum albumin
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Retention rate | 60％ | 57％ | 61％ | 62％ | 61％ | 56％ |
As can be seen from Table 4, the metal ion adsorption sewage separation membrane prepared by the method has a good retention effect on bovine serum albumin, because the protein is a hydrophobic substance, and with the addition of the polyphenol modified graphene oxide, the improvement of the hydrophilicity of the membrane surface is not beneficial to the passing of the protein, so the protein retention rate is improved.
Claims (1)
1. A preparation method of a metal ion adsorption sewage separation membrane is characterized by comprising the following steps:
(a) ultrasonically dispersing graphene oxide in deionized water, adding a polyphenol compound, uniformly stirring, heating to 30-60 ℃, stirring, reacting for 8-16h, filtering by using a membrane with the aperture of 0.1-0.5 mu m, and washing, drying and grinding filter residues to obtain polyphenol modified graphene oxide;
(b) ultrasonically dispersing polyphenol modified graphene oxide in an organic solvent A, adding pre-dried powdery polyvinylidene fluoride and a pore-forming agent into a dispersion liquid under a protective atmosphere, stirring and reacting for 20-28h, and finally removing bubbles in vacuum for 4-8h to obtain a casting solution; the mass fraction of the polyphenol modified graphene oxide in the casting solution is 1-2%, the mass fraction of the polyvinylidene fluoride is 10-15%, the mass fraction of the pore-forming agent is 0.5-2%, and the balance is the organic solvent A;
(c) pouring the membrane casting solution on a flat plate, blade-coating to form a membrane, then placing the membrane in a solvent B for curing, finally taking out, washing and drying to obtain a metal ion adsorption sewage separation membrane;
wherein the polyphenol compound is selected from one of tannin, dopamine, pyrogalloc acid, catechol and epigallocatechin, and the mass ratio of the added amount of the polyphenol compound to the graphene oxide is 10-20: 1; the organic solvent A is selected from one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, the solvent B is selected from one of water, ethanol and octanol, and the pore-making agent is polyvinylpyrrolidone K30 specifically; the average molecular weight of the polyvinylidene fluoride is 10-40 ten thousand.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853755A (en) * | 1972-11-06 | 1974-12-10 | Du Pont | Osmosis efficiency from tannin treatment of non-porous semipermeable membranes having hydrous heavy metal coatings |
| CN103480347A (en) * | 2013-10-11 | 2014-01-01 | 天津汉晴环保科技有限公司 | Preparation method of composite flat membrane for adsorbing heavy metal ions and product thereof |
| CN107213803A (en) * | 2017-05-08 | 2017-09-29 | 武汉理工大学 | A kind of Kynoar film surface grafting coats composite modifying method |
| CN107626219A (en) * | 2017-10-30 | 2018-01-26 | 天津市金鳞水处理科技有限公司 | A kind of antipollution hollow-fibre membrane of heavy metal ion and organic dyestuff remove function |
| CN107638816A (en) * | 2017-11-14 | 2018-01-30 | 安徽大学 | A kind of dopamine helps the preparation method of scattered graphene oxide modified polyvinylidene fluoride ultrafiltration membrane |
| CN107715700A (en) * | 2017-11-24 | 2018-02-23 | 中国科学院烟台海岸带研究所 | A kind of high-salt wastewater processing corrosion resistant anti-soil film and its preparation method and application |
-
2018
- 2018-05-07 CN CN201810426980.XA patent/CN108404686B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853755A (en) * | 1972-11-06 | 1974-12-10 | Du Pont | Osmosis efficiency from tannin treatment of non-porous semipermeable membranes having hydrous heavy metal coatings |
| CN103480347A (en) * | 2013-10-11 | 2014-01-01 | 天津汉晴环保科技有限公司 | Preparation method of composite flat membrane for adsorbing heavy metal ions and product thereof |
| CN107213803A (en) * | 2017-05-08 | 2017-09-29 | 武汉理工大学 | A kind of Kynoar film surface grafting coats composite modifying method |
| CN107626219A (en) * | 2017-10-30 | 2018-01-26 | 天津市金鳞水处理科技有限公司 | A kind of antipollution hollow-fibre membrane of heavy metal ion and organic dyestuff remove function |
| CN107638816A (en) * | 2017-11-14 | 2018-01-30 | 安徽大学 | A kind of dopamine helps the preparation method of scattered graphene oxide modified polyvinylidene fluoride ultrafiltration membrane |
| CN107715700A (en) * | 2017-11-24 | 2018-02-23 | 中国科学院烟台海岸带研究所 | A kind of high-salt wastewater processing corrosion resistant anti-soil film and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Jing Ma等.Bio‐inspired method to fabricate poly‐dopamine/reduced graphene oxide composite membranes for dyes and heavy metal ion removal.《POLYMERS FOR ADVANCED TECHNOLOGIES》.2018,第29卷(第2期),第941-950页. * |
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