CN108927015A - A kind of preparation method of big flux ultrafiltration membrane - Google Patents
A kind of preparation method of big flux ultrafiltration membrane Download PDFInfo
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- CN108927015A CN108927015A CN201810940214.5A CN201810940214A CN108927015A CN 108927015 A CN108927015 A CN 108927015A CN 201810940214 A CN201810940214 A CN 201810940214A CN 108927015 A CN108927015 A CN 108927015A
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- kaolin
- nanometer sheet
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- big flux
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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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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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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- Inorganic Chemistry (AREA)
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Abstract
The present invention provides a kind of preparation methods of big flux ultrafiltration membrane, include the following steps: that the urea liquid of kaolin and saturation stirs evenly, and drying obtains intercalated compound, and intercalated compound, which is added in HCl solution, carries out ultrasound, obtain kaolin nanometer sheet solution；Kaolin nanometer sheet solution is adjusted to PH > 9 with PH regulator, obtains kaolin nanometer sheet dispersion liquid；Kaolin nanometer sheet is loaded to cellulose acetate micro-filtration film surface by the method for stacked in multi-layers by the kaolin nanometer sheet dispersion liquid and cationic polyacrylamide that will be obtained.Its initial flux of kaolin ultrafiltration membrane prepared by the present invention is ten times of polyvinylidene fluoride ultrafiltration film initial flux; substantially reduce the decaying of membrane flux; reduce fouling membrane; improve service life; improve water treatment efficiency; the stability of kaolin ultrafiltration membrane in water is improved, method is simple to operation and is easy to scale use, is conducive to promote.
Description
Technical field
The invention belongs to ultrafiltration membrane technique fields, more particularly, to a kind of preparation method of big flux ultrafiltration membrane.
Background technique
Membrane technology is a kind of water treatment technology of simple and effective, in environmentally friendly water treatment field using more and more extensive, and
Gradually become one of the basis of world's strategy of sustainable development.Membrane technology is widely used in each neck with its wide applicability
The water process in domain.However, the complexity of film preparation process and high cost are the significant obstacles that membrane technology promotes and applies.It can use
Have much in the material for preparing film, wherein main with inorganic, ceramic material and Organic and polymer materials material.Due to it is inorganic,
Cost is relatively high when ceramic material is used to prepare film and brittleness is big, and mechanical strength is small, so Organic and polymer materials material in recent years
It is widely used in preparing film and is used for the treatment of the natural organic matter in the water of surface.For example, graphene oxide and poly- in recent years
Vinylidene fluoride is widely used in preparing stable microfiltration membranes, ultrafiltration membrane, nanofiltration membrane to handle the natural organic matter in water.However
The preparation process is complicated, at high cost and not environmentally.So finding new material or new preparation method to reduce cost and simplification
Preparation process is imperative.
Summary of the invention
In view of this, the present invention is directed to propose a kind of preparation method of big flux ultrafiltration membrane, preparation method is simple, at low cost
And there is preferable filter effect, long service life.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of big flux ultrafiltration membrane, includes the following steps:
Step 1: kaolin and the urea liquid of saturation are stirred under the revolving speed of 200r at 55-70 DEG C with dispersion machine
80h, drying obtain intercalated compound, and intercalated compound, which is added in HCl solution, carries out ultrasound, and it is molten to obtain kaolin nanometer sheet
Liquid；
Step 2: kaolin nanometer sheet solution is adjusted to PH > 9 with PH regulator, so that negative electricity on kaolin nanometer sheet band
Repulsion to increase between nanometer sheet prevents from removing resulting nanometer sheet to reassemble again, is carried out again with high-speed mixer later
Stirring five minutes, since the PH of solution after the suction-operated for a period of time of kaolin nanometer sheet can be reduced, so needing later again
PH > 9 are adjusted, then are stirred five minutes with high-speed mixer, kaolin nanometer sheet dispersion liquid is obtained；
Step 3: by the obtained kaolin nanometer sheet dispersion liquid and cationic polyacrylamide in step 2, pass through layer
Kaolin nanometer sheet is loaded to cellulose acetate micro-filtration film surface by the folded method of layer heap.
Further, kaolin 40-50g is mixed with the urea liquid of the saturation of 50-100ml.
Further, the molecular weight of cationic polyacrylamide > 7,000,000, the solubility of cationic polyacrylamide are 0.1-
10mg/L。
Further, PH regulator is one or both of NaOH or KOH.
Further, the load number of plies of kaolin nanometer sheet is 1-300 layers in step 3.
Further, kaolin nanometer sheet is single layer kaolin nanometer sheet or multilayer kaolin nanometer sheet in step 1.
Further, the concentration of HCl is 1M, ultrasonic 8-15min in step 1.
Further, the aperture of cellulose acetate microfiltration membranes is 0.45um in step 3.
Cationic polyacrylamide is purchased from: fine chemistry industry research institute is recovered in Tianjin.
Compared with the existing technology, the preparation method of big flux ultrafiltration membrane of the present invention has the advantage that
The preparation method of big flux ultrafiltration membrane of the present invention, its initial flux of the kaolin ultrafiltration membrane of preparation are poly- inclined
Ten times of difluoroethylene ultrafiltration membrane initial flux, and the decaying of membrane flux can also be substantially reduced, fouling membrane is reduced, film is improved
Service life, improve water treatment efficiency；Cationic polyacrylamide crosslinking agent enhances kaolin nanometer sheet by electrostatic interaction
Between binding force, improve the stability of kaolin ultrafiltration membrane in water, the method for the present invention is simple to operation and is easy to scale
It uses, is conducive to promote.
Detailed description of the invention
Fig. 1: 0.45um acetate fiber micro-filtration film surface using cationic polyacrylamide as crosslinking agent, use stacked in multi-layers
Method loads the scanning electron microscope diagram of 50 layers of kaolin nanometer sheet；
Fig. 2: the BET figure of the kaolin ultrafiltration membrane of 10 layers of kaolin nanometer sheet of load.
Fig. 3: the BET figure of business polyvinylidene fluoride ultrafiltration film.
Fig. 4: with the kaolin ultrafiltration membrane and business polyvinylidene fluoride ultrafiltration film of the kaolin nanometer sheet for having loaded 10 layers
BSA (bovine serum albumin), the 300mL 10mg/L of filter 23 00mL BIT lake, 300mL ZGC river, 300mL 10mg/L
HA (humic acid), 300mL 10mg/L SA (sodium alginate) solution are come the initial flux figure of film when obtaining filtering organic solution；
Fig. 5: CPAM and Al is added3+The zeta potential energy diagram of kaolin nanometer sheet afterwards；
Fig. 6: CPAM and Al is added3+Luminosity Dispersion Analysis (PDA) figure of kaolin nanometer sheet afterwards；
Fig. 7: with kaolin ultrafiltration membrance filter 300mL BIT lake, the 300mL of the kaolin nanometer sheet for having loaded 10 layers
ZGC river, the BSA (bovine serum albumin) of 300mL 10mg/L, 300mL 10mg/L HA (humic acid), 300mL 10mg/L
SA (sodium alginate) solution is come the relative flux figure of film when obtaining filtering organic solution；
Fig. 8: business polyvinylidene fluoride ultrafiltration film filter 23 00mL BIT lake, 300mL ZGC river, 300mL
BSA (bovine serum albumin), 300mL 10mg/L HA (humic acid), 300mL 10mg/L SA (sodium alginate) solution of 10mg/L
Come the relative flux figure of film when obtaining filtering organic solution.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to examples and drawings, the present invention will be described in detail.
50g kaolin is stirred under the revolving speed of 200r at 65 DEG C with dispersion machine in the urea liquid that 80ml is saturated
The intercalated compound that drying obtains is added in the HCl that concentration is 1M ultrasound ten minutes at 60 DEG C later, obtains height by 80h
Ridge soil nanometer sheet solution, is adjusted to PH > 9 with NaOH for kaolin nanometer sheet solution later, then be stirred with high-speed mixer
It five minutes, readjusts PH > 9 again later and is stirred five minutes with high-speed mixer to obtain the dispersion of kaolin nanometer sheet again
Liquid.
Taking out kaolin solution later and being diluted to concentration is 50mg/L as stock solution.Take out the deposit of two parts of 50ml
CPAM is added in liquid portion, and Al is added in portion3+And it is tested with luminosity separating apparatus and records flocculation index value (FI value).
CPAM is added in the stock solution portion for further taking out two parts of 50ml, and Al is added in portion3+And with zeta current potential and grain size analysis
Instrument is tested and records zeta potential value.
As shown in Figure 5 and Figure 6, Fig. 5 shows the Al needed when zeta potential is equal to zero3+Amount be nearly the 100 of CPAM
Times；Fig. 6 shows as the same amount of CPAM and Al of addition3+When, the FI value after CPAM is added is bigger.By Fig. 5 and Fig. 6
CPAM is more preferably more suitable for making adhesive to the adhesivity of kaolin nanometer sheet.
The cationic polyacrylamide (CPAM) that 1mL 100ppm molecular weight is 8,000,000-1,500 ten thousand is dripped into acetic acid fibre
It ties up and pours out the ultrapure washing for using 5mL again after rocking 60s in plain microfiltration membranes twice, the kaolin that 2mL 0.3g/L is added later exists
Filters pressing is carried out under the conditions of 0.1MPa, the rear ultrapure washing with 5mL three times, has just loaded one in cellulose acetate microfiltration membranes at this time
Layer kaolin, unloads 10 layers under such, uses 200mL ultrapure water film afterwards.
It is filtered with the kaolin ultrafiltration membrane and business polyvinylidene fluoride ultrafiltration film of the kaolin nanometer sheet for having loaded 10 layers
300mL BIT lake, 300mL ZGC river, the BSA (bovine serum albumin) of 300mL 10mg/L, 300mL 10mg/L HA
(humic acid), 300mL 10mg/L SA (sodium alginate) solution, while data are acquired with electronic balance connection data display equipment,
To come the initial flux figure of film when obtaining filtering organic solution.
As shown in figure 4, its initial flux of the kaolin ultrafiltration membrane of preparation is about that polyvinylidene fluoride ultrafiltration film initially leads to
Ten times of amount.
It is filtered with the kaolin ultrafiltration membrane and business polyvinylidene fluoride ultrafiltration film of the kaolin nanometer sheet for having loaded 10 layers
300mL BIT lake, 300mL ZGC river, the BSA (bovine serum albumin) of 300mL 10mg/L, 300mL 10mg/L HA
(humic acid), 300mL 10mg/L SA (sodium alginate) solution, while data are acquired with electronic balance connection data display equipment,
To come the relative flux figure of film when obtaining filtering organic solution.
As shown in Figure 7 and Figure 8, the kaolin ultrafiltration membrane of the preparation journey that its relative flux reduces after filter 23 00mL solution
Degree is less than business polyvinylidene fluoride ultrafiltration film.
Initial flux is characterization: the treatment effeciency of film i.e. film can handle the amount of waste water within the unit time.
Relative flux is characterization: the contamination resistance of film is this is because the duct of film can be by waste water in the treatment of waste water
Pollutant, which is blocked, causes the pollution of film so as to cause the decline of relative flux.
Faster (i.e. curve is steeper) of relative flux decline indicates that the contamination resistance of film is poorer.
Simultaneously with electronic balance connection data display equipment acquire data, thus come obtain filtering organic solution when film it is opposite
Flux pattern.It is as shown in Figure 7 and Figure 8: the kaolin ultrafiltration membrane of the preparation degree that its relative flux reduces after filter 23 00mL solution
It is less than business polyvinylidene fluoride ultrafiltration film.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of big flux ultrafiltration membrane, characterized by the following steps:
Step 1: kaolin and the urea liquid of saturation are sufficiently stirred, and drying obtains intercalated compound, and intercalated compound is added to
Ultrasound is carried out in HCl solution, obtains kaolin nanometer sheet solution；
Step 2: kaolin nanometer sheet solution is adjusted to PH > 9 with PH regulator, obtains kaolin nanometer sheet dispersion liquid；
Step 3: by the obtained kaolin nanometer sheet dispersion liquid and cationic polyacrylamide in step 2, pass through heap layer by layer
Kaolin nanometer sheet is loaded to cellulose acetate micro-filtration film surface by folded method.
2. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: kaolin 40-50g and 50-
The urea liquid of the saturation of 100ml mixes.
3. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: cationic polyacrylamide
Molecular weight > 7,000,000, the solubility of cationic polyacrylamide are 0.1-10mg/L.
4. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: PH regulator be NaOH or
One or both of KOH.
5. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: kaolin nanometer in step 3
The load number of plies of piece is 1-300 layers.
6. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: kaolin nanometer in step 1
Piece is single layer kaolin nanometer sheet or multilayer kaolin nanometer sheet.
7. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: kaolin and full in step 1
The urea liquid of sum stirs 70-80h under the revolving speed of 200r with dispersion machine at 55-70 DEG C.
8. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: the concentration of HCl in step 1
For 1M, ultrasonic 8-15min.
9. the preparation method of big flux ultrafiltration membrane according to claim 1, it is characterised in that: cellulose acetate in step 3
The aperture of microfiltration membranes is 0.45um.
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| CN201810940214.5A CN108927015A (en) | 2018-08-17 | 2018-08-17 | A kind of preparation method of big flux ultrafiltration membrane |
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| CN201810940214.5A CN108927015A (en) | 2018-08-17 | 2018-08-17 | A kind of preparation method of big flux ultrafiltration membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832636A (en) * | 2022-05-03 | 2022-08-02 | 北京工业大学 | Preparation method of low-cost and large-area clay-based separation membrane for water treatment |
| CN115584171A (en) * | 2022-10-12 | 2023-01-10 | 福建省荔松新型材料有限公司 | High-weather-resistance coil steel coating and preparation method thereof |
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| CN101734677A (en) * | 2008-11-05 | 2010-06-16 | 北京化工大学 | Method for stripping laminated inorganic material |
| WO2014004479A2 (en) * | 2012-06-25 | 2014-01-03 | Massachusetts Institute Of Technology | Porous film |
| WO2018044298A1 (en) * | 2016-08-31 | 2018-03-08 | South Dakota Board Of Regents | Multilayer thin film nanocomposite membranes prepared by molecular layer-by-layer assembly |
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2018
- 2018-08-17 CN CN201810940214.5A patent/CN108927015A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734677A (en) * | 2008-11-05 | 2010-06-16 | 北京化工大学 | Method for stripping laminated inorganic material |
| WO2014004479A2 (en) * | 2012-06-25 | 2014-01-03 | Massachusetts Institute Of Technology | Porous film |
| WO2018044298A1 (en) * | 2016-08-31 | 2018-03-08 | South Dakota Board Of Regents | Multilayer thin film nanocomposite membranes prepared by molecular layer-by-layer assembly |
Non-Patent Citations (1)
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| HONG, JS ET AL.: "Role of clays in fouling-resistant clay-embedded polyelectrolyte multilayer membranes for wastewater effluent treatment", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832636A (en) * | 2022-05-03 | 2022-08-02 | 北京工业大学 | Preparation method of low-cost and large-area clay-based separation membrane for water treatment |
| CN115584171A (en) * | 2022-10-12 | 2023-01-10 | 福建省荔松新型材料有限公司 | High-weather-resistance coil steel coating and preparation method thereof |
| CN115584171B (en) * | 2022-10-12 | 2023-07-11 | 福建省荔松新型材料有限公司 | High-weather-resistance coil steel coating and preparation method thereof |
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