CN106669439B - Reverse osmosis membrane of stable against biological contamination and preparation method thereof - Google Patents
Reverse osmosis membrane of stable against biological contamination and preparation method thereof Download PDFInfo
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- CN106669439B CN106669439B CN201611234058.8A CN201611234058A CN106669439B CN 106669439 B CN106669439 B CN 106669439B CN 201611234058 A CN201611234058 A CN 201611234058A CN 106669439 B CN106669439 B CN 106669439B
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- reverse osmosis
- lignin
- osmosis membrane
- stable against
- biological contamination
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- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 66
- 238000011109 contamination Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920005610 lignin Polymers 0.000 claims abstract description 113
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 claims abstract description 66
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 claims abstract description 66
- 229940114124 ferulic acid Drugs 0.000 claims abstract description 66
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 235000001785 ferulic acid Nutrition 0.000 claims abstract description 66
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims description 48
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 32
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229940015043 glyoxal Drugs 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N Glyoxylic acid Natural products OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 8
- 244000005700 microbiome Species 0.000 abstract description 6
- 230000036541 health Effects 0.000 abstract description 4
- 231100000989 no adverse effect Toxicity 0.000 abstract description 4
- 240000006394 Sorghum bicolor Species 0.000 description 23
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 240000000111 Saccharum officinarum Species 0.000 description 19
- 235000007201 Saccharum officinarum Nutrition 0.000 description 19
- 230000000844 anti-bacterial effect Effects 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 235000015505 Sorghum bicolor subsp. bicolor Nutrition 0.000 description 10
- 239000010902 straw Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000295644 Staphylococcaceae Species 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MCPANHZWUBLTMU-UHFFFAOYSA-N chloro(trimethyl)silane hexane Chemical compound C[Si](Cl)(C)C.CCCCCC MCPANHZWUBLTMU-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940119526 coniferyl alcohol Drugs 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to reverse osmosis membrane technology fields more particularly to a kind of reverse osmosis membrane of stable against biological contamination and preparation method thereof.The reverse osmosis membrane of the stable against biological contamination include support film layer, and from it is described support one surface of film layer successively combine outward antipollution film layer, compact film；The antipollution film layer is made of the lignin that ferulic acid is grafted.The reverse osmosis membrane of the stable against biological contamination can effectively inhibit microorganism in the growth of film surface, improve the stable against biological contamination ability of film, and human health and environment are had no adverse effect, while still maintaining good water flux and salt rejection rate, therefore can be widely applied in water treatment field.
Description
Technical field
The present invention relates to the reverse osmosis membranes and its preparation side of reverse osmosis membrane technology field more particularly to a kind of stable against biological contamination
Method.
Background technique
With society rapid development, earth fresh water total content be no longer satisfied people life needed for, sea water desalination with
And water purification alleviates demand of the people to freshwater resources to a certain extent.Wherein, either sea water desalination or water purification industry,
Reverse osmosis membrane has become current most common film.
However, since the microorganisms such as bacterium adhere to and breed, making reverse osmosis membrane surface in the use process of reverse osmosis membrane
By biological pollution, decline so as to cause the permeance property of reverse osmosis membrane.Biological pollution becomes reverse osmosis membrane in use
One of main problem faced.Reduce the method for biological pollution first is that pre-processed to the Active Chlorine of water high concentration, remove
Go microorganism.However chlorine processing can generate harmful organic by-products, and the free chlorine in water is to the reverse osmosis of polyamide material
Permeable membrane has oxidative degradation.Another method is periodically to be cleaned using detergent to reverse osmosis membrane.However this method
The process for needing to stop water process will cause production capacity decline.
In recent years some patents disclose preparation stable against biological contamination reverse osmosis membrane method, for example, Patent No.
The United States Patent (USP) of US8875906B2 coats silver nanotube in film layer by supporting in PS membrane, reaches with stable against biological contamination
Effect；The United States Patent (USP) of Patent No. 20150224450A1 crosslinking curing in polyamide separating layer has zwitterionic carbon
Nanotube；The United States Patent (USP) of the Patent No. US6551536 then doped nano titanium dioxide particle in polyamide separating layer；And it is special
Benefit number is the United States Patent (USP) of US20140238939A1 in polyamide separating layer surface grafting doped quaternary ammonium salt class antibacterials.
The compound for having antibacterial action and inorganic particle used in these above-mentioned methods usually have certain toxicity, are not
Harmless and environment amenable material (M.Salwiczek et al, Trends Biotechnology, 2014 (32),
82-90；M.Cowan et al,Clinical Microbiology Reviews,1999(12)564-582).
Therefore, status is the problem of reverse osmosis membrane faces microbial contamination in use, by adding into reverse osmosis membrane
The mode of traditional Antimicrobial agent, although antimicrobial, added tradition in reverse osmosis membrane can be played the role of
Antimicrobial agent does not meet current environmentally protective requirement.
Summary of the invention
It is an object of the invention to have certain poison existing for Antimicrobial agent for existing add into reverse osmosis membrane
Property, it is unfriendly to human body and environment the problems such as, a kind of reverse osmosis membrane of stable against biological contamination is provided.
Meanwhile the present invention also correspondingly provides the preparation method of the reverse osmosis membrane of the stable against biological contamination.
To achieve the above object of the invention, the embodiment of the present invention uses the following technical solution:
A kind of reverse osmosis membrane of stable against biological contamination, the reverse osmosis membrane of the stable against biological contamination include support film layer, and from
The antipollution film layer for supporting one surface of film layer successively to combine outward, compact film；The antipollution film layer is connect by ferulic acid
The lignin of branch is constituted.
And the preparation method of the reverse osmosis membrane of above-mentioned stable against biological contamination, it at least includes the following steps:
Step S01. carries out grafting processing to natural lignin using ferulic acid；
The lignin that ferulic acid is grafted and crosslinking agent are configured to solution by step S02., and are coated on PS membrane and are supported film layer
One surface, is then dried, and forms antipollution film layer；
M-phenylenediamine solution, pyromellitic trimethylsilyl chloride solution are successively coated on the pollution-resistant membrane layer surface by step S03.,
Reaction is dried to obtain compact film, and by rinsing, drying process, obtains the reverse osmosis membrane of stable against biological contamination.
The reverse osmosis membrane for the stable against biological contamination that the above embodiment of the present invention provides joined natural antibacterial medicine in reverse osmosis membrane
Object ferulic acid and lignin are as antipollution film layer, and the lignin that ferulic acid is grafted is fixed on by the method by being chemically crosslinked
PS membrane supports film surface effectively microorganism can be inhibited in film surface by the high activity anti-microbial property of ferulic acid
Growth, improves the stable against biological contamination ability of film, and has no adverse effect to human health and environment, while still maintaining good
Water flux and salt rejection rate.
The preparation method of the reverse osmosis membrane for the stable against biological contamination that the above embodiment of the present invention provides, using ferulic acid to wooden
Element carries out grafting processing, and re-coating supports film surface in PS membrane, and is being applied by m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride
The lignin surface for having covered ferulic acid grafting carries out interface polymerization reaction, has obtained the antibiont that lignin is grafted comprising ferulic acid
The reverse osmosis membrane of pollution, the preparation method raw material sources are convenient, and process conditions are simple, and graft effect is good, and obtained antibiosis
The reverse osmosis membrane antibacterial effect of object pollution is good, nontoxic.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the preparation method process flow diagram of the reverse osmosis membrane of stable against biological contamination of the embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of reverse osmosis membrane of stable against biological contamination, including support film layer, and from the support
Antipollution film layer that one surface of film layer successively combines outward, compact film；The antipollution film layer is grafted wooden by ferulic acid
Element is constituted.
Wherein, in any one embodiment, the support film layer of the reverse osmosis membrane of stable against biological contamination is PS membrane support membrane
Layer.
In a preferred embodiment, in the antipollution film layer that the lignin of ferulic acid grafting is constituted, the grafting rate of ferulic acid
It is 15%~65%.Since lignin has apparent bactericidal effect to gram-positive bacterium, but to gramnegative bacterium
Bactericidal effect it is unobvious.Under the grafting rate, lignin and ferulic acid mutually act synergistically, common to improve to bacterium and fungi
Antibacterial effect.
In one embodiment, lignin is natural lignin, and natural lignin has from a wealth of sources, the spies such as green non-pollution
Point.
The lignin of ferulic acid grafting is crosslinking in the surface of support film layer by the effect of crosslinking agent.Crosslinking agent can be
Glyoxal or maleic acid.
It is further preferred that antipollution film layer with a thickness of 3 μm~5 μm.
The monomer lignin alcohol of lignin is formed as shown in the p- tonquinol of following formula (I), (II) coniferyl alcohol, (III) sinapinic alcohol,
General lignin is made of several monomers, and ferulic acid is grafted shown in the reaction such as formula (IV) of lignin.For convenience, at this
In reaction, only show that lignin participates in the part-structure of reaction, the structure use-R of lignin other parts is indicated, represented by R
Lignin other parts structure, can be the other parts structure of common lignin, due to belonging to common structure, this hair
Bright embodiment is omitted not to be described in detail.
Preferably, the compact film be aramid layer, the aramid layer by m-phenylene diamine (MPD), pyromellitic trimethylsilyl chloride polymerization and
At, by compact film realize antipollution film layer be further securely attached on support film surface.
The reverse osmosis membrane of stable against biological contamination provided in an embodiment of the present invention, grafting antibiotic property is stronger on lignin and structure
With natural antibiotics ferulic acid similar in monomer lignin alcohol, ferulic acid is grafted lignin as antipollution film layer, by ferulic acid
High activity anti-microbial property, can effectively inhibit microorganism in the growth of film surface, improve the stable against biological contamination ability of film, and
Human health and environment are had no adverse effect, while still maintaining good water flux and salt rejection rate.
Correspondingly, the present invention is on the basis of providing the reverse osmosis membrane of stable against biological contamination, it is further provided the antibiont
A kind of preparation method of the reverse osmosis membrane of pollution.
As shown in Figure 1, in one embodiment, the preparation method of the reverse osmosis membrane of the stable against biological contamination includes at least
Following steps:
Step S01. carries out grafting processing to natural lignin using ferulic acid；
The lignin that ferulic acid is grafted and crosslinking agent are configured to solution by step S02., and are coated on PS membrane and are supported film layer
One surface, is then dried, and forms antipollution film layer；
M-phenylenediamine solution, pyromellitic trimethylsilyl chloride solution are successively coated on the pollution-resistant membrane layer surface by step S03.,
Reaction is dried to obtain compact film, and by rinsing, drying process, obtains the reverse osmosis membrane of stable against biological contamination.
It wherein, can also include the extraction step of lignin the step of ferulic acid is grafted lignin before.
In a preferred embodiment, the extracting method of lignin is as follows:
1) sodium hydroxide solution of crops stalk powder and 2M after taking drying is mixed according to the mass ratio of 1:10
It closes, is heated 12 hours in 60 DEG C of baking ovens；
2) centrifugal treating is carried out to the mixed liquor after heating, centrifuge is separated 15 minutes with 5000 revs/min of revolving speed, taken
Supernatant；
3) pH value of supernatant is adjusted to 4.0 with the sulfuric acid of 5M, is placed 12 hours in 4 DEG C of environment, passes through centrifugation
Machine is separated 15 minutes with 5000 revs/min of revolving speed, collects the lignin being settled out；
4) collect lignin after drying, with 1% mass fraction be dissolved in the sodium hydroxide solution of 0.5M to
With.
The raw material for extracting lignin, can be the crops stems such as broomcorn straw, sugarcane stalk.
In a preferred embodiment, the graft reaction of step S01 at least includes the following steps:
(1) lignin liquor that mass percentage is 0.5~1.5% is provided, and the pH value of the lignin liquor is
5.5~6.5；
(2) it is by volume the solution in step (1): buffer=1:(15~20) ratio, it is added in Xiang Suoshu solution
The kaliumphosphate buffer of 100mM~110mM；
(3) ferulic acid, horseradish peroxidase are sequentially added into the solution of step (2), room temperature graft reaction 10~
In process of grafting, 0.3~0.6mL10% volume fraction is added into reaction mixture every 2~4min by 40min
Aqueous hydrogen peroxide solution, shown in specific graft reaction such as above formula (IV).
10~40min of graft reaction time may be implemented ferulic acid grafting rate and reach 15%~65%.
(4) it after graft reaction, is centrifuged, collecting reaction product, and according to reaction product with 1wt%~5wt%
It is scattered in deionized water, being then heated to 55~65 DEG C dissolves reactant, and it seals and is saved in 55~65 DEG C of environment, to
With.
Lignin liquor in step (1) can contain 0.5~1.5wt% for what the embodiment of the present invention was extracted using diluted acid
The sodium hydroxide solution pH value of lignin is adjusted to 5.5~6.5 and obtains.
Preferably, in step (3), lignin, ferulic acid, horseradish peroxidase are (45~55) according to mass ratio:
(380~400): (1~5) feeds intake.
In a preferred embodiment, the lignin of ferulic acid grafting grafting obtained is coated on support film layer (namely
PS membrane support film layer) a surface, need first by ferulic acid grafting lignin and crosslinking agent wiring solution-forming.
Specifically, process for preparation is as follows:
Crosslinking agent such as glyoxal or maleic acid are dissolved in deionized water, the crosslinking agent for obtaining 5wt%~15wt% is molten
Liquid；
The lignin that ferulic acid is grafted is mixed at 60 DEG C with crosslinking agent, lignin and crosslinking according to ferulic acid grafting
The mass ratio of agent is (8~10): 1 carries out mixed processing；
By the quick spin coating on a surface of support film layer of desk-top glue spreader, and the wooden of ferulic acid grafting will be coated with
Plain solution, which is placed in air, to carry out air-drying processing, it is ensured that the thickness of coating is between 3 μm~5 μm.
Preferably, the drying mode of step S02 preferably air-dries, and air-dries and can effectively avoid film layer generation fold.
In a preferred embodiment, in the m-phenylenediamine solution of step S03 m-phenylene diamine (MPD) mass fraction be 1.0%~
2.0%, after m-phenylenediamine solution is coated in the lignin coating surface of ferulic acid grafting, it is placed in air and air-dries 10~20min,
Then the pyromellitic trimethylsilyl chloride solution that mass fraction is 0.05%~0.1% is coated on air-dried surface again, passes through equal benzene three
Polymerization reaction occurs for formyl chloride and m-phenylene diamine (MPD), generates polyamide in antipollution film layer (i.e. the lignin layer of ferulic acid grafting) and causes
Close film layer.
It is further preferred that m-phenylenediamine solution is m-phenylene diamine (MPD) aqueous solution, pyromellitic trimethylsilyl chloride solution is equal benzene front three
The hexane solution of acyl chlorides.
After obtaining polyamide compact film, also use deionized water and mass fraction for 10% or so ethanol water
It is rinsed and film layer is placed in 5~10min of heat treatment in 100 DEG C, the stable against biological contamination of the embodiment of the present invention can be obtained
Reverse osmosis membrane.
The preparation method of the reverse osmosis membrane of stable against biological contamination provided in an embodiment of the present invention, using ferulic acid to lignin into
Row grafting processing, re-coating supports film surface in PS membrane, and passes through m-phenylene diamine (MPD) aqueous solution and pyromellitic trimethylsilyl chloride
Hexane solution carries out interface polymerization reaction on the lignin surface for being coated with ferulic acid grafting, has obtained being grafted comprising ferulic acid
The reverse osmosis membrane of the stable against biological contamination of lignin, the preparation method raw material sources are convenient, and process conditions are simple, and graft effect is good
It is good, and the reverse osmosis membrane antibacterial effect of obtained stable against biological contamination is good, it is nontoxic.
The reverse osmosis membrane of the stable against biological contamination of preparation of the embodiment of the present invention can be applied in water treatment field.It specifically includes
It can be applied in the fields such as sea water desalination, bitter desalination, pharmacy, biotechnology, sewage treatment.
The reverse osmosis membrane for the stable against biological contamination that embodiment provides in order to better illustrate the present invention, does below by embodiment
It is further to illustrate.
Embodiment 1
(1) extraction of lignin:
It is 24 hours dry at 60 DEG C after broomcorn straw is crushed；
Broomcorn straw powder after drying is mixed with the sodium hydroxide solution of 2M with the mass ratio of 1:10, in 60 DEG C of baking ovens
Middle heating 12 hours；Mixed liquor after heating is separated 15 minutes by centrifuge with 5000 revs/min of revolving speed, and supernatant is taken；
The pH value of supernatant is adjusted to 4.0 with the sulfuric acid of 5M, is placed 12 hours in 4 DEG C of environment, with centrifuge with
5000 revs/min of revolving speed separates 15 minutes, collects the lignin being settled out；
The lignin of collection is dissolved in the sodium hydroxide solution of 0.5M after drying, so that lignin in solution
Mass fraction is 1%.
(2) the grafting processing of ferulic acid:
With the sodium hydroxide solution containing 1wt% lignin in the hydrochloric acid regulating step (1) of 2M, make pH=6.0, then with
The buffer solution of potassium phosphate of 105mM is mixed according to the ratio that mass ratio is 1:19；
500mL mixed solution is taken, 1.940g ferulic acid, 5mg horseradish peroxidase are added into the mixed solution of 500mL
Enzyme starts to react in room temperature, and the aqueous hydrogen peroxide solution of 0.5mL10% volume fraction was added every 3 minutes, reacts 30 points
Clock；
After reaction, reaction solution is separated 15 minutes by centrifuge with 5000 revs/min of revolving speed, collects precipitating
Reaction product；
Deionized water is dispersed with 1% mass fraction by reaction product, 60 DEG C is heated to and reactant is dissolved, is sealed
It is stored in 60 DEG C of baking oven.
(3) coating processing of lignin:
Using glyoxal as solute, glyoxal is dissolved in deionized water, is configured to 10% cross-linking agent solution.It will connect
Lignin liquor after branch mixes at 60 DEG C with cross-linking agent solution, and the mass ratio for controlling lignin and crosslinking agent is 10:1.It is logical
The quick spin coating in PS membrane support film layer of desk-top glue spreader is crossed, is air-dried 15 minutes in air after the completion of coating, controls coating
With a thickness of 4 microns.
(4) interfacial polymerization is handled:
Mass fraction is coated in the PS membrane that (3) obtain for the aqueous solution of 1.5% m-phenylene diamine (MPD) to connect with ferulic acid
On the lignin coating surface of branch, air-dry 15 minutes in air；Then by the pyromellitic trimethylsilyl chloride of mass fraction 0.05%
Hexane solution is coated on polysulfones support membrane, and pyromellitic trimethylsilyl chloride polymerize with m-phenylene diamine (MPD) generates polyamide compact film.With
It is rinsed respectively with the ethanol water of deionized water and 10% mass fraction afterwards, and is heat-treated 10min at 100 DEG C, contained
The reverse osmosis membrane of the stable against biological contamination for the lignin for thering is ferulic acid to be grafted.
Embodiment 2
(1) extraction of lignin:
It is 24 hours dry at 60 DEG C after broomcorn straw is crushed；
The sodium hydroxide solution of broomcorn straw powder and 2M after taking drying carries out mixed processing with the mass ratio of 1:10,
It is placed in 60 DEG C of baking ovens and heats 12 hours；Mixed liquor after heating separates 15 by centrifuge with 5000 revs/min of revolving speed
Minute, take supernatant；
The pH value of supernatant is adjusted to 4.0 with the sulfuric acid of 5M, is placed 12 hours in 4 DEG C of environment, with centrifuge with
5000 revs/min of revolving speed separates 15 minutes, collects the lignin being settled out；
The lignin of collection is dissolved in deionized water after drying, so that the mass fraction of lignin is in solution
1%, 60 DEG C are heated to, and save in 60 DEG C of environment.
(2) coating processing of lignin:
Using glyoxal as solute, glyoxal is dissolved in deionized water, is configured to the cross-linking agent solution of 10wt%.It will
The lignin liquor that step (1) obtains mixes at 60 DEG C with cross-linking agent solution, and the mass ratio for controlling lignin and crosslinking agent is
10:1.Quick spin coating in film layer is supported in PS membrane by desk-top glue spreader, is air-dried 15 minutes in air after the completion of coating, control
Coating processed with a thickness of 4 microns.
(3) interfacial polymerization is handled:
Mass fraction is coated in the PS membrane that (2) obtain for the aqueous solution of 1.5% m-phenylene diamine (MPD) to apply with lignin
In layer surface, air-dry 15 minutes in air；Then the hexane solution of the pyromellitic trimethylsilyl chloride of mass fraction 0.05% is applied
It overlays on polysulfones support membrane, pyromellitic trimethylsilyl chloride polymerize with m-phenylene diamine (MPD) generates polyamide compact film.Then spend respectively from
The rinsing of the ethanol water of sub- water and 10% mass fraction, and it is heat-treated 10min at 100 DEG C, it obtains anti-containing lignin
The reverse osmosis membrane of biological pollution.
Embodiment 3
In addition to the graft reaction time of lignin and ferulic acid is changed to 15 minutes, other are same as Example 1.
Embodiment 4
In addition to the graft reaction time of lignin and ferulic acid is changed to 10 minutes, other are same as Example 1.
Embodiment 5
In addition to the graft reaction time of lignin and ferulic acid is changed to 40 minutes, other are same as Example 1.
Embodiment 6
In addition to broomcorn straw is changed to sugarcane stalk, other are same as Example 1.
Embodiment 7
In addition to broomcorn straw is changed to sugarcane stalk, other are same as Example 2.
Embodiment 8
In addition to the graft reaction time that broomcorn straw is changed to sugarcane stalk and lignin and ferulic acid is changed to 15 minutes,
Other are same as Example 1.
Embodiment 9
In addition to the graft reaction time that broomcorn straw is changed to sugarcane stalk and lignin and ferulic acid is changed to 10 minutes,
Other are same as Example 1.
Embodiment 10
In addition to the graft reaction time that broomcorn straw is changed to sugarcane stalk and lignin and ferulic acid is changed to 40 minutes,
Other are same as Example 1.
Comparative example 1
Mass fraction is coated in PS membrane for the aqueous solution of 1.5% m-phenylene diamine (MPD) to support in film layer, in air wind
It is 15 minutes dry.Then the hexane solution of the pyromellitic trimethylsilyl chloride of mass fraction 0.05% is coated on polysulfones support membrane；?
Three formyl chloride of benzene polymerize with m-phenylene diamine (MPD) generates polyamide compact film.Then respectively with deionized water and 10% mass fraction
Ethanol water rinsing, is heat-treated 10 minutes using at 100 DEG C, obtains polyamide composite reverse osmosis membrane.
In order to detect the performance for the diaphragm that Examples 1 to 10 and comparative example 1 obtain, every kind of diaphragm takes 5 progress antibiosis
The test of object pollution capacity and reverse osmosis aptitude tests.
(1) stable against biological contamination aptitude tests
Diaphragm (Examples 1 to 10 and comparative example 1) is immersed in golden staphylococci culture solution (CFU=10 respectively5/ml)
In, it is cultivated 24 hours at 37 DEG C.Number of bacteria, which is calculated, according to following formula 1 reduces percentage R:
R%=100 × (A-B)/A ... formula 1
Wherein A is the number of bacteria at 0 moment, and B is the number of bacteria after 24 hours, and (each example takes 5 block films to acquired results
The average value of built-in testing) it is shown in Table 1.
1 stable against biological contamination aptitude tests data of table
| Example | Lignin source | Ferulic acid grafting time min | Bacterium reduces percentage for 24 hours |
| Embodiment 1 | Sorghum lignin | 30 | 49.7% |
| Embodiment 2 | Sorghum lignin | 0 | 25.4% |
| Embodiment 3 | Sorghum lignin | 15 | 34.6% |
| Embodiment 4 | Sorghum lignin | 10 | 33.2% |
| Embodiment 5 | Sorghum lignin | 40 | 61.6% |
| Embodiment 6 | Sugarcane lignin | 30 | 45.1% |
| Embodiment 7 | Sugarcane lignin | 0 | 19.7% |
| Embodiment 8 | Sugarcane lignin | 15 | 29.6% |
| Embodiment 9 | Sugarcane lignin | 10 | 26.8% |
| Embodiment 10 | Sugarcane lignin | 40 | 55.2% |
| Comparative example 1 | N/A | N/A | 0 |
As known from Table 1, after lignin is grafted ferulic acid as antipollution film layer, the antibacterial ability of reverse osmosis membrane obtains obvious
It improves, after sorghum lignin is grafted ferulic acid, antibacterial ability improves 30%-142% compared to non-grafted sorghum lignin；
And after sugarcane lignin grafting ferulic acid, antibacterial ability equally improves nearly compared to the sugarcane lignin of non-grafted ferulic acid
36%-180%.Under equal conditions, the antibacterial effect that sorghum lignin is grafted ferulic acid is grafted asafoetide relative to sugarcane lignin
The effect of acid is preferable.The time of graft reaction is longer namely grafting rate is higher, and antibacterial ability is better.
(2) reverse osmosis aptitude tests
Diaphragm is taken to test on cross-current type diaphragm check-out console, test condition is 2000ppm NaCl aqueous solution, 225psi behaviour
Make pressure, 2 DEG C of temperature, pH=7；Acquired results (average value that each example takes 5 block film built-in testings) are shown in Table 2.
The reverse osmosis aptitude tests data of table 2
| Example | Lignin source | Ferulic acid grafting time min | Water flux (gfd) | Salt rejection rate (%) |
| Embodiment 1 | Sorghum lignin | 30 | 26.9 | 98.46 |
| Embodiment 2 | Sorghum lignin | 0 | 28.1 | 98.65 |
| Embodiment 3 | Sorghum lignin | 15 | 27.7 | 98.24 |
| Embodiment 4 | Sorghum lignin | 10 | 27.9 | 98.52 |
| Embodiment 5 | Sorghum lignin | 40 | 26.2 | 98.96 |
| Embodiment 6 | Sugarcane lignin | 30 | 24.8 | 97.27 |
| Embodiment 7 | Sugarcane lignin | 0 | 27.4 | 97.73 |
| Embodiment 8 | Sugarcane lignin | 15 | 25.1 | 96.91 |
| Embodiment 9 | Sugarcane lignin | 10 | 26.5 | 97.24 |
| Embodiment 10 | Sugarcane lignin | 40 | 24.1 | 97.65 |
| Comparative example 1 | N/A | N/A | 30.2 | 98.14 |
As known from Table 2, after natural lignin's grafting ferulic acid, with the lignin of non-grafted ferulic acid or not comprising wooden
For the reverse osmosis membrane of plain layer in terms of salt rejection rate, variation is little, it may be said that has little influence on salt rejection rate, water flux is declined slightly, and is connect
The time of branch reaction is longer, and water flux decline is more obvious, and when grafting time is more than 40min, grafting rate is more than 65%, therefore,
The embodiment of the present invention considers that the grafting rate of ferulic acid is less than or equal to 65%.
In summary the test of stable against biological contamination and reverse osmosis performance, it is seen that joined natural antibacterial in reverse osmosis membrane
Medicament ferulic acid and lignin are as antipollution film layer, and the method by being chemically crosslinked fixes the lignin that ferulic acid is grafted
Effectively microorganism can be inhibited in film surface by the high activity anti-microbial property of ferulic acid in PS membrane support film surface
Growth, improve the stable against biological contamination ability of film, and human health and environment had no adverse effect, while still maintaining good
Water flux and salt rejection rate.The data of antibacterial ability, water flux and salt rejection rate, the embodiment of the present invention in comprehensive consideration table 1, table 2
It is preferred that the grafting rate of ferulic acid is 15%~65%.
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
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of reverse osmosis membrane of stable against biological contamination, it is characterised in that: the reverse osmosis membrane of the stable against biological contamination includes support membrane
Layer, and from it is described support one surface of film layer successively combine outward antipollution film layer, compact film；The antipollution film layer by
The lignin of ferulic acid grafting is constituted.
2. the reverse osmosis membrane of stable against biological contamination as described in claim 1, it is characterised in that: the lignin of the ferulic acid grafting
In, the grafting rate of ferulic acid is 15%~65%.
3. the reverse osmosis membrane of stable against biological contamination as described in claim 1, it is characterised in that: the compact film is polyamide
Layer.
4. the reverse osmosis membrane of stable against biological contamination as described in claim 1, it is characterised in that: the support film layer is PS membrane
Layer.
5. the reverse osmosis membrane of stable against biological contamination as described in claim 1, it is characterised in that: the antipollution film layer with a thickness of
3 μm~5 μm.
6. a kind of preparation method of the reverse osmosis membrane of stable against biological contamination, at least includes the following steps:
Step S01. carries out grafting processing to natural lignin using ferulic acid；
The lignin that ferulic acid is grafted and crosslinking agent are configured to solution by step S02., and are coated on PS membrane and are supported one table of film layer
Then face is dried, form antipollution film layer；
M-phenylenediamine solution, pyromellitic trimethylsilyl chloride solution are successively coated on the pollution-resistant membrane layer surface by step S03., react,
It is dried, obtains compact film, and by rinsing, drying process, obtain the reverse osmosis membrane of stable against biological contamination.
7. the preparation method of the reverse osmosis membrane of stable against biological contamination as claimed in claim 6, it is characterised in that: the grafting processing
Method the following steps are included:
(1) provide mass percentage be 0.5~1.5% lignin liquor, and the pH value of the lignin liquor be 5.5~
6.5；
(2) it is in mass ratio the solution in step (1): buffer=1:(15~20) ratio, 100mM is added in Xiang Suoshu solution
The kaliumphosphate buffer of~110mM；
(3) ferulic acid and horseradish peroxidase are sequentially added into the solution of step (2), room temperature 10~40min of graft reaction,
In process of grafting, the peroxidating of 0.3~0.6mL10% volume fraction is added into reaction mixture every 2~4min
Aqueous solution of hydrogen；
(4) it after graft reaction, is centrifuged, collecting reaction product, and according to reaction product with 1wt%~5wt% dispersion
In deionized water, being then heated to 55~65 DEG C dissolves reactant, seals and saves in 55~65 DEG C of environment, for use.
8. the preparation method of the reverse osmosis membrane of stable against biological contamination as claimed in claim 6, it is characterised in that: the step S02
Solution in, be the lignin of ferulic acid grafting: crosslinking agent=(8~10): 1 ratio according to mass ratio, in Xiang Suoshu solution
Crosslinking agent is added；The crosslinking agent is glyoxal or maleic acid.
9. the preparation method of the reverse osmosis membrane of stable against biological contamination as claimed in claim 6, it is characterised in that: the m-phenylene diamine (MPD)
The mass fraction of solution is 1.0%~2.0%；The mass fraction of the pyromellitic trimethylsilyl chloride solution is 0.05%~0.1%.
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| CN1359288A (en) * | 1999-07-05 | 2002-07-17 | 伊迪亚股份公司 | Improved method for transport across adaptive semipermeable barriers |
| EP2677042A1 (en) * | 2011-02-18 | 2013-12-25 | Toray Industries, Inc. | Method for producing sugar solution |
| CN104053492A (en) * | 2011-11-28 | 2014-09-17 | 安尼基有限责任公司 | Method for reprocessing an aqueous solution containing lignin |
| CN106000135A (en) * | 2016-06-26 | 2016-10-12 | 仇颖莹 | Preparation method of anti-pollution composite filtering membrane |
| CN106076126A (en) * | 2016-08-17 | 2016-11-09 | 林春梅 | A kind of bio-based hemodialysis membrane and preparation method thereof |
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| CN1359288A (en) * | 1999-07-05 | 2002-07-17 | 伊迪亚股份公司 | Improved method for transport across adaptive semipermeable barriers |
| EP2677042A1 (en) * | 2011-02-18 | 2013-12-25 | Toray Industries, Inc. | Method for producing sugar solution |
| CN104053492A (en) * | 2011-11-28 | 2014-09-17 | 安尼基有限责任公司 | Method for reprocessing an aqueous solution containing lignin |
| CN106000135A (en) * | 2016-06-26 | 2016-10-12 | 仇颖莹 | Preparation method of anti-pollution composite filtering membrane |
| CN106076126A (en) * | 2016-08-17 | 2016-11-09 | 林春梅 | A kind of bio-based hemodialysis membrane and preparation method thereof |
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