CN110449047A - Positive nanofiltration membrane of a kind of high throughput towards biogas slurry purifying and preparation method thereof - Google Patents
Positive nanofiltration membrane of a kind of high throughput towards biogas slurry purifying and preparation method thereof Download PDFInfo
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- CN110449047A CN110449047A CN201910669678.1A CN201910669678A CN110449047A CN 110449047 A CN110449047 A CN 110449047A CN 201910669678 A CN201910669678 A CN 201910669678A CN 110449047 A CN110449047 A CN 110449047A
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- nanofiltration membrane
- quantum dot
- carbon quantum
- biogas slurry
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- 239000012528 membrane Substances 0.000 title claims abstract description 55
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 40
- 239000002002 slurry Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000001014 amino acid Nutrition 0.000 claims abstract description 21
- 150000001413 amino acids Chemical class 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 230000004907 flux Effects 0.000 claims abstract description 17
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims abstract description 5
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 5
- 239000004220 glutamic acid Substances 0.000 claims abstract description 5
- 210000002469 basement membrane Anatomy 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 12
- 238000012695 Interfacial polymerization Methods 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- ABFPKTQEQNICFT-UHFFFAOYSA-M 2-chloro-1-methylpyridin-1-ium;iodide Chemical compound [I-].C[N+]1=CC=CC=C1Cl ABFPKTQEQNICFT-UHFFFAOYSA-M 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 240000002853 Nelumbo nucifera Species 0.000 claims description 5
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 5
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims description 5
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims 4
- 229920001601 polyetherimide Polymers 0.000 claims 4
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 claims 1
- CCZWSTFVHJPCEM-UHFFFAOYSA-N 2-iodopyridine Chemical compound IC1=CC=CC=N1 CCZWSTFVHJPCEM-UHFFFAOYSA-N 0.000 claims 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004472 Lysine Substances 0.000 abstract description 4
- 230000010148 water-pollination Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 229920002873 Polyethylenimine Polymers 0.000 description 9
- 230000005611 electricity Effects 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010889 donnan-equilibrium Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000021232 nutrient availability Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D71/06—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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention proposes a kind of concept that biogas slurry purification process is carried out using high-throughput positive nanofiltration membrane.The modification that hydrophily carbon quantum dot carries out nanofiltration membrane is used in the present invention, while so that it is kept high-throughput, water flux increases 2.29 times.Modified nanofiltration membrane has very high retention for lysine, leucine and the glutamic acid in biogas slurry, reaches as high as 94.3%.Reach 2.45 simultaneously for the separation factor of amino acid and negative valency ion, has illustrated the purification process that there are the nanofiltration membrane of preparation very big potentiality to carry out biogas slurry.
Description
Technical field
Positive nanofiltration membrane of the high throughput that the present invention relates to a kind of towards biogas slurry purification process and preparation method thereof, belongs to film point
From field of material technology.
Background technique
Biogas slurry is by residue of the various organic matters such as people, animal excrement and crops tangerine stalk after anaerobic fermentation.Its
In contain a large amount of amino acid, be the raw material of liquid fertilizer.Its quick-acting nutritious ability is strong, and Nutrient availability is high, can quilt rapidly
Crop is absorbed and utilized, and can not only improve the yield and quality of crop, and have the degeneration-resistant effect of diseases prevention, is a kind of good organic
Liquid fertilizer.But since biogas slurry water content is high, volume is big, transport, the continuity of storage requirement difficulty and biogas slurry discharge and farmland
There are contradictions for the seasonality of fertilising, therefore still have quite large-scale biogas slurry to utilize due to direct emission because that can not dissolve in time, this
Can not only threat be generated to environment and human health, while be also a kind of serious wasting of resources.But simultaneously containing big in biogas slurry
The sulfate radical and chloride ion of amount, will affect the purity of the benefit materials in biogas slurry.If therefore amino acid in liquid can be carried out pure
Change recycling, by effective innoxious, recycling comprehensive utilization for realizing biogas slurry.
Membrane separation technique can not only effectively remove pollutant and obtain the permeate of high quality, but also can be realized nutrient
Concentration obtains the concentrate for being rich in nutriment.Nanofiltration (NF) be grow up the late 1980s one kind between reverse osmosis
Novel membrane separation technique between ultrafiltration thoroughly, membrane aperture is suitable for separating the dissolution group that size is about 1nm in 0.5-2nm or so
Point, therefore it is known as " nanofiltration ".Therefore the purification process for selecting suitable nanofiltration membrane to carry out biogas slurry has very big prospect.
Summary of the invention
The invention proposes a kind of nanofiltration membranes of high-throughput charged positive electricity towards biogas slurry purification process.Utilize carbon quantum dot pair
After nanofiltration membrane is modified, the water flux of film can be improved, by electrical selection, can achieve to amino acid in biogas slurry and bear
The separation of valence ion.
The first aspect of the invention provides:
A kind of nanofiltration membrane is sequentially compounding by basement membrane, carbon quantum dot middle layer and selection separating layer.
In one embodiment, the selection separating layer is by polyamide polymer.
In one embodiment, the selection separating layer has lotus electropositive.
In one embodiment, the material of the basement membrane is selected from polyether sulfone (PES), sulfonated polysulfone (SPSF), polyethers
Acid imide (PEI) etc..
The second aspect of the invention provides:
The preparation method of above-mentioned nanofiltration membrane, includes the following steps:
Step 1 provides basement membrane；
Step 2 coats carbon quantum dot middle layer on the surface of basement membrane；
Step 3 prepares interfacial polymerization layer by the method for interfacial polymerization in carbon quantum dot middle layer.
In one embodiment, the material of the basement membrane is selected from polyether sulfone (PES), sulfonated polysulfone (SPSF), polyethers
Acid imide (PEI) etc..
It in one embodiment, is to be dipped in basement membrane in the suspension containing carbon quantum dot to coat in step 2；Carbon
Concentration 2~6wt% of the quantum dot in suspension, the surface of carbon quantum dot have passed through Treatment with activating agent.
In one embodiment, activator is the chloro- 1- methylpyridinium iodide (CMPI) of 2-.
In one embodiment, step 3 is prepared into acyl chloride monomer by interfacial polymerization by amine monomers
It arrives.
In one embodiment, amine monomers are polyethyleneimine, concentration 1-3% of the amine monomers in water phase；Acyl chlorides
Class monomer is trimesoyl chloride, concentration 0.1-3% of the acyl chloride monomer in organic phase.
The third aspect of the invention provides:
Above-mentioned nanofiltration membrane is for the application in the separation to amino acid and inorganic salts in biogas slurry.
In one embodiment, the amino acid is selected from lysine, leucine or glutamic acid, the inorganic salts
Selected from Na2SO4 or NaCl.
In one embodiment, the nanofiltration membrane of high-throughput charged positive electricity for improve the separation to amino acid and inorganic salts because
Son.
In one embodiment, the water that the nanofiltration membrane of high-throughput charged positive electricity is used to improve in the separation process to biogas slurry is logical
Amount.
The fourth aspect of the invention provides:
Carbon quantum dot is as the middle layer of basement membrane and selection separating layer for improving in the flux in biogas slurry filter process
Using.
The fifth aspect of the invention provides:
The chloro- 1- methylpyridinium iodide (CMPI) of 2- is used to prepare the application in nanofiltration membrane.
In one embodiment, the chloro- 1- methylpyridinium iodide (CMPI) of the 2- is for living to carbon quantum dot
Change.
In one embodiment, the chloro- 1- methylpyridinium iodide (CMPI) of the 2- is for improving nanofiltration membrane to biogas slurry
Water flux in separation process.
Beneficial effect
The present invention has very high rejection for carbonium using positively charged nanofiltration membranes, lower for negative valency ion rejection rate
Mechanism, can amino acid in effectively catching biogas slurry, remove sulfate radical and chloride ion, carry out the purification process of biogas slurry.Except this it
After being modified outside due to carbon quantum dot to homemade nanofiltration membrane, the hydrophily of film is changed, it is logical to construct supper-fast ion
Road increases the water flux of film, greatly improves the performance of positively charged membrane.
Detailed description of the invention
Fig. 1 is the flux vs of nanofiltration membrane；
Fig. 2 is the rejection comparison of nanofiltration membrane；
Fig. 3 is XPS characterization result；
Fig. 4 is molecular cut off characterization result；
Fig. 5 is to characterize under condition of different pH to the separating property of amino acid and salt；
Fig. 6 is the characterization of Zeta potential；
Fig. 7 is the separating property characterization comparison of the positive nanofiltration membrane prepared and business negative electricity nanofiltration membrane to amino acid and salt；
Fig. 8 is the performance map of the positive nanofiltration membrane prepared and business negative electricity nanofiltration membrane to the concentration and separation of amino acid and salt.
Specific embodiment
The positive nanofiltration membrane of high throughput provided by the invention is successively multiple by basement membrane, carbon quantum dot middle layer, selection separating layer
It closes.
Wherein, basement membrane can be normal macromolecule member material, exist as supporting layer.For example, basement membrane can be used
The substances such as non-woven fabrics and polymeric membrane, material can select polyether sulfone (PES), polyacrylonitrile (PAN), Kynoar
(PVDF) etc..In one embodiment, above-mentioned polyethers sulfolane solution and solvent are prepared by mixing into casting solution, then on a glass
Blade coating comes out, and is immersed in the water and prepares porous asymmetric basement membrane by phase inversion.
Laminar is coated in membrane surface among carbon quantum dot, simultaneously because joined the effect of activating agent, so that its
In carboxyl can be reacted with the amino of polyethyleneimine in interfacial polymerization layer, reduce interfacial polymerization layer the degree of cross linking, from
And hole diameter enlargement.In addition, the hydrophily of carbon quantum dot itself can also construct the channel of ion fast strikethrough, increase the flux of film.
The polyamide separating layer of the lotus positive electricity is after above-mentioned operation.
The positively charged membrane being prepared has the ion of lotus positive electricity compared to having higher isoelectric point for negative electricity film
Very high rejection, such as lysine, leucine and glutamic acid.There is lower rejection, such as sulphur simultaneously for negative ion
Acid ion and chloride ion.Therefore just there is good effect using the separation that the positively charged membrane being prepared carries out amino acid and ion
Fruit.
Embodiment 1
1. the preparation of plate membrane
Polyether sulfone macromolecule polymer material is dissolved in organic solvent, is stirred overnight using blender, is taken off after a static night
Then bubble is scratched casting solution on a glass using scraper, inversion of phases processing film forming is carried out in water, at the film prepared
In deionized water, polyether sulfone basement membrane is obtained.
2. the preparation of carbon quantum dot middle layer
The aqueous solution for preparing carbon quantum dot first prepares the deionized water suspension containing 2wt% carbon quantum dot and 0.1g hydrogen is added
Then the chloro- 1- methylpyridinium iodide (CMPI) of 0.1g 2- is added for activating carbon quantum dot in sodium oxide molybdena regulation pH value.Stirring half
After a hour, basement membrane is immersed into 10min in carbon quantum dot solution, after removing extra solution, is obtained in uniform carbon quantum dot
Interbed.
3. selecting the preparation of layer
Respectively prepare 1wt% aq. polyethyleneimine (polyethyleneimine molecular weight is respectively 1.8K, 10K and 70K) and
Water phase and oily phase of the organic phase solution of the trimesoyl chloride of 0.1wt% as interface polymerization reaction, wherein pyromellitic trimethylsilyl chloride is molten
Using n-hexane as solvent, stirring can be used liquid after one hour.Aqueous phase solution is poured on film first, cleansing tissue is used after two minutes
Extra water phase is removed, is subsequently poured into organic phase, reacts 1min, after the solution for removing excess surface, the film prepared is placed on
It is saved in deionized water.
The film that this method is prepared is named as 2%CQDs/TFC film subsequent.
Reference examples 1
The difference from embodiment 1 is that not using carbon quantum dot as middle layer, interfacial polymerization is carried out directly on basement membrane,
Positively charged membrane is prepared.The film that this reference examples is prepared is named as TFC film subsequent.
Reference examples 2
The difference from embodiment 1 is that: in the preparation process of carbon quantum dot middle layer, the chloro- 1- methyl iodide of activator 2- is not added
For pyridine and sodium hydroxide.The film that this reference examples is prepared is named as Pure-2%CQDs/TFC film subsequent
Reference examples 3
The difference from embodiment 1 is that after introducing carbon quantum dot middle layer, then water phase is poured into, it is extra to remove ten minutes later
Water phase is added without pyromellitic trimethylsilyl chloride solution, is then placed in water and saves.The film that this reference examples is prepared is named as subsequent
2% CQDs-PEI/PES film
Characterization experiment
Water flux characterization experiment carries out at normal temperature, needs pre- logical half an hour so that the film prepared reaches before test
Performance is stablized；
Rejection test be use concentration for the magnesium chloride solution of 1000 mg/L, under the conditions of the operating pressure of 6 bar, 20 DEG C
The test of progress also needs the pre- of half an hour before test and passes to and be added stirring, prevents the generation of concentration polarization phenomenon.
Water flux result is as shown in Figure 1, the water flux maximum for the film being prepared using embodiment 1 has been increased to 9.72
L/m2·h·bar-1, 4.23 and 6.11 L/m have been respectively increased in the nanometer filtering film water flux of middle-molecular-weihydroxyethyl 1.8K and 10K2·
h·bar-1.It can be seen that with the increase of molecular weight, the increased degree of nanofiltration membrane flux is gradually decreased, this is because with dividing
The reduction of son amount, the degree of cross linking of interfacial polymerization will increase, and the influence that the middle layer of carbon quantum dot is played can reduce.Rejection number
According to as shown in Fig. 2, simultaneously for magnesium chloride rejection there is no too big reduction, 96% or so.
And using in reference examples 2 is the water flux of the nanofiltration membrane of 1.8K, 10K and 70K for respectively based on molecular weight
4.20,5.01 and 6.86 LMHbar-1, therefore, the carbon quantum dot after being activated using the chloro- 1- methylpyridinium iodide of 2- can
To effectively improve the water flux in filter process.
XPS characterization
Fig. 3 is film surface C, N, O obtained in different embodiments, elemental analysis map (the wide spectrum scanning figure of (a) difference basement membrane.
(b) 2% CQDs–PEI/PES.(c) TFC and (d) CQDs/TFC membrane.Can significantly it see in embodiment
Obtained film surface has been successfully formed polyamide structure.In addition to this prove out membrane surface carbon quantum dot successfully and PEI
Reaction, to reduce the degree of cross linking of interfacial polymerization layer.
MWCO characterization
Fig. 4 is different the phenogram of the molecular cut off of film.As we can see from the figure it can be observed that CQDs/TFC-PEI
The aperture of 70K film and MWCO are greater than the aperture of TFC-PEI 70K film, while by reducing PEI molecular weight, the aperture of CQD/TFC
It is gradually reduced.The MWCO of CQDs/TFC-PEI 1.8K and original TFC film are closely similar.
The test of biogas slurry purifying
According to the obtained examining report from biogas slurry treatment company, Jieyang City, corresponding biogas slurry simulated solution has been prepared in laboratory
It is purified.The concentration of wherein lysine, leucine and glutamic acid is not 200ppm, 200ppm and 400ppm.And Na2SO4With
The concentration of NaCl is 400ppm and 300ppm respectively.
The model mixtures filtration experiment of amino acid and inorganic ions under different ph values is tested first.Fig. 5
It is shown, optimal separation is observed when pH is adjusted to 3, the separation factor between amino acid and hybrid ionic is shown in pH=3
Peak 2.45 shows that main separation mechanism is Donnan effect.Under higher pH condition, film surface charge becomes negative electricity
Lotus, to increase SO4 2-And Cl-Repulsion, reduce separation factor.By comparing the filterability of pH=3 pair business DK and DL film
Energy.As shown in Figure 6, the separation factor of commercial membranes is far below CQD/TFC film, this is because DK and DL film is almost in pH=3
(Fig. 5) of electroneutral, this is easily detected by electronegative ion.Due to lacking electrostatic row between amino acid and film surface
Denounce, the repulsion of amino acid is relatively low in business DK and DL film.
Biogas slurry concentration test
10 times are enriched with by the biogas slurries model solution that will be simulated, i.e., by amino acid and salting liquid volume in dead-end filtration pond
It reduces from 500ml to 50ml, compares the concentration performance of CQDs/TFC film and commercial membranes.The region a of Fig. 8 shows CQDs/TFC
The high osmosis of film is maintained and reaches steady state, is clearly observed permeability decline simultaneously for commercial membranes.This is
Because salinity increases concentration polarization and increases osmotic pressure, so that effective driving force is reduced, to reduce water penetration
Property, this also demonstrate for the value-added NF film of biogas slurry should be specially design rather than realized using commercial membranes.Fig. 8
The region b show, in the final stage of concentration process, the retention to ion of DL and DK commercial membranes point compared with original state
Do not reduce 6.7% and 15.2%, and amino acid repulsion reduces 13.4% and 13% difference.Section of CQDs/TFC film simultaneously
It stays almost unchanged, it was demonstrated that the film of preparation has a good application prospect biogas slurry purifying.
Claims (10)
1. a kind of nanofiltration membrane, which is characterized in that be sequentially compounding by basement membrane, carbon quantum dot middle layer and selection separating layer.
2. nanofiltration membrane according to claim 1, which is characterized in that in one embodiment, the selection separating layer
It is by polyamide polymer；In one embodiment, the selection separating layer has lotus electropositive；In an embodiment
In, the material of the basement membrane is selected from polyether sulfone (PES), sulfonated polysulfone (SPSF), polyetherimide (PEI) etc..
3. the preparation method of nanofiltration membrane described in claim 1, which comprises the steps of:
Step 1 provides basement membrane；
Step 2 coats carbon quantum dot middle layer on the surface of basement membrane；
Step 3 prepares interfacial polymerization layer by the method for interfacial polymerization in carbon quantum dot middle layer.
4. the preparation method of nanofiltration membrane according to claim 3, which is characterized in that in one embodiment, described
The material of basement membrane is selected from polyether sulfone (PES), sulfonated polysulfone (SPSF), polyetherimide (PEI) etc.；It is to soak basement membrane in step 2
It is coated in the suspension containing carbon quantum dot；Concentration 2~6wt% of the carbon quantum dot in suspension, the table of carbon quantum dot
Face have passed through Treatment with activating agent；In one embodiment, activator is the chloro- 1- methylpyridinium iodide (CMPI) of 2-.
5. the preparation method of nanofiltration membrane according to claim 3, which is characterized in that in one embodiment, step 3 is
It is prepared with acyl chloride monomer by interfacial polymerization by amine monomers；In one embodiment, amine monomers are poly-
Aziridine, concentration 1-3% of the amine monomers in water phase；Acyl chloride monomer is trimesoyl chloride, and acyl chloride monomer is in organic phase
In concentration 0.1-3%.
6. nanofiltration membrane described in claim 1 is for the application in the separation to amino acid and inorganic salts in biogas slurry.
7. application according to claim 11, which is characterized in that in one embodiment, the amino acid, which is selected from, to be relied
Propylhomoserin, leucine or glutamic acid, the inorganic salts are selected from Na2SO4Or NaCl；In one embodiment, nanofiltration membrane is used
In raising to the separation factor of amino acid and inorganic salts；Nanofiltration membrane is used to improve the water flux in the separation process to biogas slurry.
8. carbon quantum dot is as the middle layer of basement membrane and selection separating layer for improving in the flux in biogas slurry filter process
Application.
Application of the chloro- 1- methylpyridinium iodide (CMPI) of 9.2- in preparation nanofiltration membrane.
10. application according to claim 16, which is characterized in that in one embodiment, the chloro- 1- methyl of the 2-
Iodo-pyridin (CMPI) is for activating carbon quantum dot；In one embodiment, the chloro- 1- methyl iodide of the 2- is for pyrrole
Pyridine (CMPI) is for improving nanofiltration membrane to the water flux in biogas slurry separation process.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1985000985A1 (en) * | 1983-08-26 | 1985-03-14 | Brunswick Corporation | Reverse osmosis membrane and process for making |
| WO2017085054A1 (en) * | 2015-11-16 | 2017-05-26 | Basf Se | Nanofiltration composite membranes comprising self-assembled supramolecular separation layer |
| CN108435002A (en) * | 2018-03-27 | 2018-08-24 | 东华大学 | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified |
| CN108745002A (en) * | 2018-06-08 | 2018-11-06 | 太原理工大学 | A kind of sulfonated polyether-ether-ketone mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application of doping carbon quantum dot in situ |
| CN109200823A (en) * | 2018-08-28 | 2019-01-15 | 浙江工业大学 | A kind of preparation method and application for the ecosystem positively charged nanofiltration membranes that polyethyleneimine is amine-modified |
| CN109200833A (en) * | 2018-10-17 | 2019-01-15 | 南京理工大学 | Remove the preparation method of bivalent cation and the nanofiltration membrane of lotus positive electricity PPCPs |
-
2019
- 2019-07-24 CN CN201910669678.1A patent/CN110449047B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1985000985A1 (en) * | 1983-08-26 | 1985-03-14 | Brunswick Corporation | Reverse osmosis membrane and process for making |
| WO2017085054A1 (en) * | 2015-11-16 | 2017-05-26 | Basf Se | Nanofiltration composite membranes comprising self-assembled supramolecular separation layer |
| CN108435002A (en) * | 2018-03-27 | 2018-08-24 | 东华大学 | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified |
| CN108745002A (en) * | 2018-06-08 | 2018-11-06 | 太原理工大学 | A kind of sulfonated polyether-ether-ketone mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application of doping carbon quantum dot in situ |
| CN109200823A (en) * | 2018-08-28 | 2019-01-15 | 浙江工业大学 | A kind of preparation method and application for the ecosystem positively charged nanofiltration membranes that polyethyleneimine is amine-modified |
| CN109200833A (en) * | 2018-10-17 | 2019-01-15 | 南京理工大学 | Remove the preparation method of bivalent cation and the nanofiltration membrane of lotus positive electricity PPCPs |
Non-Patent Citations (1)
| Title |
|---|
| 陆佳等: "浅谈沼液处理与纳滤膜技术", 《黑龙江科学》 * |
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