CN106693731A - Method for preparing high-throughput ultrafiltration membrane from nano calcium carbonate doped polysulfone - Google Patents
Method for preparing high-throughput ultrafiltration membrane from nano calcium carbonate doped polysulfone Download PDFInfo
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- CN106693731A CN106693731A CN201611260742.3A CN201611260742A CN106693731A CN 106693731 A CN106693731 A CN 106693731A CN 201611260742 A CN201611260742 A CN 201611260742A CN 106693731 A CN106693731 A CN 106693731A
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- membrane
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- polysulfones
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
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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
-
- 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
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparing a high-throughput ultrafiltration membrane from nano calcium carbonate doped polysulfone. The method comprises the steps of taking the polysulfone as a polymer membrane material and nano calcium carbonate as a doped particle to prepare membrane casting liquid, preparing a membrane by a nonsolvent-induced phase separation method, and treating with a hydrochloric acid aqueous solution at a certain concentration for a period of time to form the high-throughput ultrafiltration membrane. The prepared ultrafiltration membrane can be used for ultrafiltration and serve as a basement membrane for preparing a nanofiltration and reverse osmosis composite membrane. The throughput of the ultrafiltration membrane is greater than that of the pure polysulfone under the same pressure, and an entrapment rate of bovine serum albumin is not changed basically.
Description
Technical field
The invention belongs to technical field of membrane, and in particular to a kind of nano-calcium carbonate calcium analysis polysulfones prepares high-flux ultra-filtration membrane
Method.
Background technology
Ultrafiltration originates from 1748, is a kind of with pressure difference as motive force, by size sieving actoion, so as to reach separation
The membrane technology of effect.It is with low cost because its is easy to operate, it is not necessary to increase any chemical reagent, mild condition, useless
Water process, household water filter and Food industry etc. are used widely.
The core of hyperfiltration technique is milipore filter, and the key factor for evaluating ultrafiltration film properties has flux, rejection and antipollution.
Therefore key issue of lifting ultrafiltration film properties reduces the transmission resistance of water or improves hydrophily and lifts film
Flux.It is a kind of very simple and effectively adjusts by adds different organic or inorganic additives in casting solution
The means of membrane structure.Conventional inorganic additive includes the inorganic salts of some alkali metal or alkaline-earth metal, such as lithium chloride, chlorine
Change ammonium, sodium nitrate etc., it is considered that their mechanism of action and inorganic salts to the Swelling Capacity of polymeric material and hydration sun from
Son is relevant with the complexing power of some functional groups in polymer molecule, and ion pair is there occurs between metal ion and polymeric material
Pole is acted on so that polymeric material can be obtained in gel and more combine water, so as to improve porosity.But also reduce film
Intensity, and be easily washed off in the last handling process of film.Current another major class inorganic additive is mainly metal oxidation
Thing, including silica, titanium dioxide, zeolite molecular sieve etc., its left and right mechanism are mainly the hydrophily for increasing film, so as to improve
Flux, but due to the reunion of inorganic particulate, cause film defect many, and filling rate is low.
For organic additive, such as polyethylene glycol (PEG), PVP (PVP) etc., these water-soluble polymerics
The addition influence solvent of thing changes the dissolved state of polymer in casting solution, while also changing to the solvability of polymer
Mass transfer of the non-solvent in casting solution, accelerates the gel precipitation speed of film, causes instantaneous demixing, so as in the forming process of film
Contribute to pore-forming.Compared to inorganic additive, polymeric additive is not easy to be washed off in last handling process, but drilling is made
Lifting is limited.Further increasing addition can not improve film properties, and general consumption is between 2-7%.
In order to further lift drilling effect, Nano particles of calcium carbonate is doped into polysulfones matrix material by the present invention, then is led to
Peracid treatment obtains porosity milipore filter higher.By the method for this " sacrifice ", we have prepared porosity
Height, flux and rejection are all than larger milipore filter.
The content of the invention
For deficiency of the prior art, prepared it is an object of the invention to provide a kind of nano-calcium carbonate calcium analysis polysulfones high
The method of flux milipore filter.The milipore filter maintains rate and protein retention higher while flux is improved.
To achieve these goals, the present invention is adopted the technical scheme that：
A kind of method that nano-calcium carbonate calcium analysis polysulfones prepares high-flux ultra-filtration membrane, the high-flux ultra-filtration membrane is with polysulfones
Polymeric film material, is doping particle with nano-calcium carbonate, and casting solution proportioning is the polysulfones of 10-20wt%, 0.5-10wt%'s
Nano-calcium carbonate, remaining is solvent N-methyl pyrrolidones, and mixed substrate membrane containing nano-grade molecular sieve is prepared into using phase separation method, is passed through
1-2mol/L hydrochloric acid post processing 10-30min prepares high-flux ultra-filtration membrane, and the high-flux ultra-filtration membrane is used for ultrafiltration or conduct
Prepare the counterdie of nanofiltration and reverse osmosis composite membrane.
The polymeric film material is selected from one or more mixed of polysulfones, polyether sulfone, Kynoar, polyacrylonitrile
Compound.
Nano-calcium carbonate doping accounts for the 0.5-10wt% of casting solution gross weight in the casting solution.
The nano-calcium carbonate calcium ion particle diameter is in 30-100nm.
The structure of the high-flux ultra-filtration membrane is tubular membrane, hollow-fibre membrane or Flat Membrane.
Methods described step is as follows：
Step (1) weighs the polymeric film material of 10-20wt%, the nano-calcium carbonate of 0.5-10wt%, and remaining is solvent,
12h, deaeration 6h under subsequent negative pressure 60-85KPa are stirred at 80 DEG C ± 5 DEG C, casting solution is obtained, casting solution is prepared into correspondence knot
The milipore filter of structure；
Step (2) milipore filter is post-processed：The milipore filter that will be prepared in step (1), it is molten with the hydrochloric acid that concentration is 1-2mol/L
Liquid processes 10-30min, and then with deionized water rinsing, to eluate pH=7, prepared film is put into deionized water
It is standby.
The method that composite membrane is prepared with high-flux ultra-filtration membrane is as follows with the preparation process that it prepares composite nanometer filtering film：
M-phenylene diamine (MPD) is soluble in the aqueous phase in solvent, and pH value control is obtained into interface polymerization reaction aqueous phase solution in 7-11,
Its concentration is 1.5-4wt%；
Polysulfones basement membrane is taken, aqueous phase solution 0.5-3min described in single-contact obtains being adsorbed with the polysulfones basement membrane of m-phenylene diamine (MPD)
Adsorption plane；
Remove unnecessary aqueous phase solution；
Pyromellitic trimethylsilyl chloride is dissolved in oil phase solvent, interface polymerization reaction oil-phase solution is obtained, its concentration is 0.1-
0.3wt%；
The polysulfones basement membrane adsorption plane is contacted into the oil-phase solution reaction 0.5-2min；
NF membrane product is can obtain after 80 DEG C of heat treatment 5min.
Beneficial effect
The invention has the advantages that：The addition of Nano particles of calcium carbonate, then pore-forming is decomposed by last handling process, can be with
Raise the porosity of film, flux increases.As shown in figure 1, with the increase of loading, the open-celled structure of its bottom surface increases, oozes
Saturating resistance reduces, and the numerical value of membrane porosity is also given in table 1.The method preparation condition is gentle, and process is simple, it is adaptable to which industry is expanded
Big production.
Ultrafiltration membrane porosity prepared by the Different adding amount of table 1
| Nano-calcium carbonate calcium content (weight %) | 0 | 5 | 7.5 | 10 |
| Porosity (volume %) | 71.2±4.8 | 83.4±1.1 | 88.9±0.9 | 90.0±3.7 |
Brief description of the drawings
Fig. 1 is the bottom electron microscope of comparative example of the present invention 1；
Fig. 2 is the bottom electron microscope of the embodiment of the present invention 1；
Fig. 3 is the bottom electron microscope of the embodiment of the present invention 2；
Fig. 4 is the bottom electron microscope of the embodiment of the present invention 3；
Fig. 5 is the surface electron microscope of comparative example of the present invention 2；
Fig. 6 is the surface electron microscope of embodiment 4；
Fig. 7 is the surface electron microscope of embodiment 5.
Specific embodiment
Embodiment 1
5g calcium carbonate is added in 80g 1-METHYLPYRROLIDONEs (NMP), ultrasonic disperse 30min, is subsequently added 15g through dry
The polysulfones of dry treatment, 80 DEG C of oil bath heatings, is configured to uniform casting solution.Step 3, flat board film preparation：By casting solution through filtering,
After deaeration, uniformly scraped on clean glass plate with scraper, be transferred to inversion of phases film forming in water.It is put into after desolventizing
20min is soaked in 1.2mol/L hydrochloric acid solutions, taking-up deionized water rinsing to eluate pH=7, gained film is stored in deionization
It is standby in water.
Embodiment 2
Weigh nano-calcium carbonate 7.5g to be added in 80g NMP, ultrasonic disperse 30min, be then added thereto to 15g dryings
The polysulfones for the treatment of, 80 DEG C of oil bath heatings, is configured to uniform casting solution.Through filtering, after deaeration, clean glass is uniformly hung over scraper
In glass plate, inversion of phases film forming in water is then transferred to.It is put into after desolventizing in 1.2mol/L hydrochloric acid and soaks 20min.Taking-up spends
Ionized water is rinsed to eluate pH=7, standby.
Embodiment 3
Weigh nano-calcium carbonate 10g to be added in 80g NMP, ultrasonic disperse 30min, be then added thereto to 15g dryings
The polysulfones for the treatment of, 80 DEG C of oil bath heatings, is configured to uniform casting solution.Through filtering, after deaeration, clean glass is uniformly hung over scraper
In glass plate, inversion of phases film forming in water is then transferred to.It is put into after desolventizing in 1.2mol/L hydrochloric acid and soaks 20min.Taking-up spends
Ionized water is rinsed to eluate pH=7, standby.
Comparative example 1
15g polysulfones is dissolved in 85gNMP, with scraper striking film forming, is stored in after desolvation standby in deionized water.
Embodiment 1~3 as comparative example 1 comparison other, test condition：D=4.5cm, test pressure 0.1MPa, BSA
Concentration 1g/L. Data Comparison such as table 2 below：
The different calcium carbonate doping milipore filter performance comparisons of table 2
Embodiment 4~5
Embodiment 4 and 5 carries out interfacial polymerization with the counterdie prepared in embodiment 1 and 2 respectively, aqueous phase monomers m-phenylene diamine (MPD),
Concentration 2wt%, water phase processor time 2min；Organic phase monomer pyromellitic trimethylsilyl chloride, concentration 0.15wt%, the interfacial polymerization time is
1min, is stored in standby in deionized water after 80 DEG C of heat treatment 5min.
Comparative example 2
Using the milipore filter prepared in comparative example 1 as counterdie, interfacial polymerization conditions are consistent with embodiment 3 and 4.Test-strips
Part：Osmotic cell effective diameter 4.5cm, pressure 0.5MPa, sodium chloride concentration 0.01mol/L, Data Comparison such as table 3:
Composite membrane performance comparison prepared by the different counterdies of table 3
Knowable to Data Comparison, the compound membrane flux prepared by embodiment 4,5 is higher, and the retention to sodium chloride is also maintained at
Higher level.The composite film surface that comparison diagram 2 can be seen that prepared by embodiment 4,5 is more coarse, and effective filtration area increases
Greatly, while the resistance of supporting layer greatly reduces, thus flux increase.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate the application example, and simultaneously
The non-restriction to implementation method.For those of ordinary skill in the field, can also do on the basis of the above description
Go out the change or variation of other multi-forms.There is no need and unable to be exhaustive to all of implementation method.And thus drawn
Obvious change that Shen goes out or among changing still in the protection domain of the application type.
Claims (7)
1. a kind of method that nano-calcium carbonate calcium analysis polysulfones prepares high-flux ultra-filtration membrane, it is characterised in that：The high flux ultrafiltration
Film, with polysulfones as polymeric film material, is doping particle with nano-calcium carbonate, and casting solution proportioning is the polysulfones of 10-20wt%,
The nano-calcium carbonate of 0.5-10wt%, remaining is solvent N-methyl pyrrolidones, is prepared into using phase separation method mixed
Matrix membrane is closed, by preparing high-flux ultra-filtration membrane after 1-2mol/L HCl treatments 10-30min, the high-flux ultra-filtration membrane is used
In ultrafiltration or as the counterdie for preparing nanofiltration and reverse osmosis composite membrane.
2. the method for preparing high-flux ultra-filtration membrane according to claim 1, it is characterised in that polymeric film material choosing
From polysulfones, polyether sulfone, Kynoar, polyacrylonitrile one or more mixture.
3. it is according to claim 1 prepare high-flux ultra-filtration membrane method, it is characterised in that nano-sized carbon in the casting solution
Sour calcium analysis amount accounts for the 0.5-10wt% of casting solution gross weight.
4. the method for preparation high-flux ultra-filtration membrane according to claim 1, it is characterised in that the nano-calcium carbonate from
Seed footpath is in 30-100nm.
5. it is according to claim 1 prepare high-flux ultra-filtration membrane method, it is characterised in that the high-flux ultra-filtration membrane
Structure is tubular membrane, hollow-fibre membrane or Flat Membrane.
6. it is according to claim 1 prepare high-flux ultra-filtration membrane method, it is characterised in that methods described step is as follows：
Step (1) weighs the polymeric film material of 10-20wt%, the nano-calcium carbonate of 0.5-10wt%, and remaining is solvent, 80
12h, deaeration 6h under subsequent negative pressure 60-85KPa are stirred at DEG C ± 5 DEG C, casting solution is obtained, casting solution is prepared into counter structure
Milipore filter；
Step (2) milipore filter is post-processed：The milipore filter that will be prepared in step (1), is at the hydrochloric acid solution of 1-2mol/L with concentration
Reason 10-30min, then with deionized water rinsing, to eluate pH=7, prepared film is put into standby in deionized water.
7. the method that composite membrane is prepared with high-flux ultra-filtration membrane according to claim 1, it is characterised in that multiple with its preparation
The preparation process for closing NF membrane is as follows：
M-phenylene diamine (MPD) is soluble in the aqueous phase in solvent, and pH value control is obtained into interface polymerization reaction aqueous phase solution in 7-11, its is dense
It is 1.5-4wt% to spend；
Polysulfones basement membrane is taken, aqueous phase solution 0.5-3min described in single-contact obtains being adsorbed with the polysulfones basement membrane absorption of m-phenylene diamine (MPD)
Face；
Remove unnecessary aqueous phase solution；
Pyromellitic trimethylsilyl chloride is dissolved in oil phase solvent, interface polymerization reaction oil-phase solution is obtained, its concentration is 0.1-
0.3wt%；
The polysulfones basement membrane adsorption plane is contacted into the oil-phase solution reaction 0.5-2min；
NF membrane product is can obtain after 80 DEG C of heat treatment 5min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611260742.3A CN106693731A (en) | 2016-12-30 | 2016-12-30 | Method for preparing high-throughput ultrafiltration membrane from nano calcium carbonate doped polysulfone |
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| CN201611260742.3A CN106693731A (en) | 2016-12-30 | 2016-12-30 | Method for preparing high-throughput ultrafiltration membrane from nano calcium carbonate doped polysulfone |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654379A (en) * | 2018-05-07 | 2018-10-16 | 宁波大学 | Porous support layer and its preparation method methods and applications |
| CN109821428A (en) * | 2017-11-23 | 2019-05-31 | 上海江柘环境工程技术有限公司 | A kind of high throughput antibacterial ultrafiltration membrane and its preparation process |
| CN110152505A (en) * | 2019-06-10 | 2019-08-23 | 泰州禾益新材料科技有限公司 | A kind of preparation method of bilayer polysulfone hollow fibre ultrafiltration membrane |
| CN111701459A (en) * | 2020-07-01 | 2020-09-25 | 浙江工业大学 | Nitrogen-heterocycle-containing polyaryletherketone/sulfone ultra/micro-filtration membrane and structure regulation method thereof |
| CN112237850A (en) * | 2019-07-19 | 2021-01-19 | 中能科泰（北京）科技有限公司 | Membrane and preparation method and application thereof |
| CN114053889A (en) * | 2021-11-22 | 2022-02-18 | 暨南大学 | Membrane casting liquid for preparing ultrafiltration membrane for filtering vaccine and ultrafiltration membrane |
| CN114950153A (en) * | 2022-03-01 | 2022-08-30 | 泰州九润环保科技有限公司 | High-flux PEG/PVDF composite desulfurization membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
| CN103831017A (en) * | 2014-02-28 | 2014-06-04 | 成都新柯力化工科技有限公司 | Preparation method of high molecular ultra-filtration membrane |
-
2016
- 2016-12-30 CN CN201611260742.3A patent/CN106693731A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
| CN103831017A (en) * | 2014-02-28 | 2014-06-04 | 成都新柯力化工科技有限公司 | Preparation method of high molecular ultra-filtration membrane |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821428A (en) * | 2017-11-23 | 2019-05-31 | 上海江柘环境工程技术有限公司 | A kind of high throughput antibacterial ultrafiltration membrane and its preparation process |
| CN108654379A (en) * | 2018-05-07 | 2018-10-16 | 宁波大学 | Porous support layer and its preparation method methods and applications |
| CN110152505A (en) * | 2019-06-10 | 2019-08-23 | 泰州禾益新材料科技有限公司 | A kind of preparation method of bilayer polysulfone hollow fibre ultrafiltration membrane |
| CN112237850A (en) * | 2019-07-19 | 2021-01-19 | 中能科泰（北京）科技有限公司 | Membrane and preparation method and application thereof |
| CN112237850B (en) * | 2019-07-19 | 2023-06-06 | 中能科泰（北京）科技有限公司 | Membrane and preparation method and application thereof |
| CN111701459A (en) * | 2020-07-01 | 2020-09-25 | 浙江工业大学 | Nitrogen-heterocycle-containing polyaryletherketone/sulfone ultra/micro-filtration membrane and structure regulation method thereof |
| CN114053889A (en) * | 2021-11-22 | 2022-02-18 | 暨南大学 | Membrane casting liquid for preparing ultrafiltration membrane for filtering vaccine and ultrafiltration membrane |
| CN114053889B (en) * | 2021-11-22 | 2024-03-26 | 暨南大学 | Membrane casting solution for preparing ultrafiltration membrane for vaccine filtration and ultrafiltration membrane |
| CN114950153A (en) * | 2022-03-01 | 2022-08-30 | 泰州九润环保科技有限公司 | High-flux PEG/PVDF composite desulfurization membrane and preparation method thereof |
| CN114950153B (en) * | 2022-03-01 | 2023-10-31 | 泰州九润环保科技有限公司 | High-flux PEG/PVDF composite desulfurization membrane and preparation method thereof |
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Application publication date: 20170524 |