AU2020104003A4 - Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof - Google Patents
Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof Download PDFInfo
- Publication number
- AU2020104003A4 AU2020104003A4 AU2020104003A AU2020104003A AU2020104003A4 AU 2020104003 A4 AU2020104003 A4 AU 2020104003A4 AU 2020104003 A AU2020104003 A AU 2020104003A AU 2020104003 A AU2020104003 A AU 2020104003A AU 2020104003 A4 AU2020104003 A4 AU 2020104003A4
- Authority
- AU
- Australia
- Prior art keywords
- membrane
- zif
- aqueous phase
- monomer
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 24
- 239000012621 metal-organic framework Substances 0.000 title abstract description 10
- 239000004952 Polyamide Substances 0.000 title abstract description 8
- 229920002647 polyamide Polymers 0.000 title abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 90
- 239000008346 aqueous phase Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 210000004379 membrane Anatomy 0.000 claims description 85
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000877 multi-layer micromoulding Methods 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 16
- 238000012695 Interfacial polymerization Methods 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 210000002469 basement membrane Anatomy 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- -1 aromatic diamine compound Chemical class 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 45
- 230000004907 flux Effects 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 238000010612 desalination reaction Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 28
- 239000003921 oil Substances 0.000 description 19
- 230000014759 maintenance of location Effects 0.000 description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 208000029422 Hypernatremia Diseases 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000010494 opalescence Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides metal-organic frameworks (MOFs) ZIF-Based polyamide (PA) mixed
matrix membranes (MMMs). In the invention, the specific preparation method does not need
to prepare the metal-organic framework ZIF in advance, nor does it need to disperse the ZIF
into the casting solution. Instead, in the process of membrane preparation, Zn2+ is anchored to
the aqueous phase monomer by the interaction between them, so that the ZIF synthesizes in
situ in the aqueous solution, which effectively avoids the dispersion problem. Due to the
interaction between the in-situ synthesis ZIF and the aqueous phase monomer, the ZIF is firmly
fixed in the PA skin layer, that is, the ZIF is closely combined with the PA skin layer. Besides,
the ZIF-based PA MMMs have excellent water flux and desalination efficiency.
Description
Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and
Preparation Method Thereof
The invention belongs to the technical field of preparing separation membrane composite
materials, and particularly relates to a metal-organic framework based polyamide mixed
matrix membrane and preparation method thereof.
As a new type of high-efficiency separation membrane, MMMs disperse
organic/inorganic nanomaterials in polymer matrix. In recent years, they have shown
great potential in seawater desalination, sewage/wastewater treatment and other fields,
with expectation of becoming the new generation of commercial high-performance
separation membrane. At present, most of the organic/inorganic nanomaterials used to
prepare MMMs are zeolite, silicon dioxide, titanium dioxide, graphene, graphene oxide,
carbon nanotubes, MOFs, covalent organic frameworks (COFs), etc. The conventional
preparation method of MMMs is to disperse the above nanoparticles into polymer casting
solution or monomer, thereby obtaining desalted membrane mixed with nanoparticles.
However, the prepared mixed matrix desalination membrane is limited by the poor
dispersion of nanoparticles in polymer matrix and the poor interfacial compatibility
between nanoparticles and polymer, causing variable degrees of desalination rate
decrease, thus reducing the separation efficiency of the mixed matrix desalination
membrane.
Compared with traditional porous nanomaterials (such as zeolite molecular sieve, etc.),
MOFs have the advantages of large specific surface area, high porosity, adjustable pore size and surface modification, plus good chemical stability, thermal stability and hydrothermal stability. Zeolitic imidazolate framework (ZIF) is a kind of MOFs which has been widely studied at present. It is composed of ZnN 4 tetrahedral structural unit which is formed by coordination bond between metal zinc ions and nitrogen atoms in 2 methylimidazole. At present, the research on the application of ZIF to PA membrane is usually to prepare ZIF particles in advance, blend them into oil phase solution or aqueous phase solution, and then prepare thin layer composite PA membrane by interfacial polymerization. However, this method still cannot guarantee the uniformity of ZIF in PA skin layer and the compatibility between ZIF and PA skin layer, which increases the risk of membrane pore defects and reduces the desalination rate. Especially in the production of amplification membrane based on this method, the membrane stability cannot be guaranteed.
Aiming at overcoming the problems existing in the prior art, the invention provides ZIF
based PA MMMs and a preparation method thereof. Through the invention, ZIF can grow
in-situ in the PA skin layer, with uniform distribution and close combination with the PA
skin layer, so that the water flux is remarkably improved, and the high desalination rate
and membrane stability are maintained.
The preparation method of ZIF-based PA MMMs comprises the following steps:
1) Preparation of aqueous phase solution. Dissolving aqueous phase monomer and
soluble zinc salt in ultrapure water at room temperature to obtain a homogeneous
solution. Then imidazole monomer is added and dissolved to gat aqueous phase solution.
It should be noted that the aqueous phase monomer concentration is 0.01-4.wt%, the
soluble zinc salt concentration is 0.01-4.Owt%, and the imidazole monomer concentration
is 0.01-20.Owt%.
Besides, the aqueous phase monomer is aromatic diamine compound, aliphatic polyamine
compound, dihydroxy phenol compound or piperazine compound; the soluble zinc salt is
zinc nitrate or zinc chloride; the imidazole monomer is preferably 2-methylimidazole.
2) Preparation of oil phase solution. Adding polyacyl chloride monomer into n-hexane,
and completely dissolving to obtain colorless and transparent solution. Wherein, the
concentration of the polyacyl chloride monomer in n-hexane is 0.01%-4.wt%; the
polyacyl chloride monomers are trimesoyl chloride (TMC) and terephthaloyl chloride.
3) Process of interfacial polymerization. Immersing the porous basement membrane in
the aqueous phase solution obtained in step 1), then removing the excessive aqueous
phase solution on the membrane surface and immersing the basement membrane in the
oil solution obtained in step 2) for interfacial polymerization.
The porous basement membrane is ultrafiltration membrane or microfiltration membrane
such as mixed cellulose membrane, polysulfone membrane, polyethersulfone membrane,
polyacrylonitrile membrane, polyethylene (propylene) membrane, etc.
Further, the immersion time in aqueous phase is1-10min and in oil phase is 3Os-2min;
4) Post-treatment. The membrane after step 3) is subjected to heat treatment. And then
cleaning the membrane surface with organic solvent to remove unreacted monomer.
Drying in the air to obtain ZIF-based PA MMMs and immersing them in deionized water
for later use.
Wherein, the heat treatment temperature is 70-90°C and the heat treatment time is 30s
min; the organic solvent is n-hexane, acetone or methanol.
The preparation method of ZIF-based PA MMMs in the invention does not need to
prepare the metal-organic framework ZIF in advance, nor does it need to disperse the ZIF
into the casting solution. Instead, in the process of membrane preparation, Zn2+ is
anchored to the aqueous phase monomer by the interaction between them, so that the ZIF
synthesizes in situ in the aqueous solution, which effectively avoids the dispersion
problem. Due to the interaction between the in-situ synthesis ZIF and the aqueous phase
monomer, the ZIF is firmly fixed in the PA skin layer, that is, the ZIF is tightly combined
with the PA skin layer. The membrane preparation method of the invention has great
development prospects in the fields of high efficiency nanofiltration and reverse osmosis
membrane preparation, because it can be perfectly matched with the existing commercial
membrane preparation process without additional preparation process of ZIF.
Figure 1 is the structural diagram of the membrane of the present invention.
The performance test conditions of ZIF-based PA MMMs prepared in the following
embodiments are that the feed liquid is 2000ppm NaCl aqueous solution, the operating
temperature is 25C, and the operating pressure is 0.6 MPa.
The ZIF-based PA MMMs of the present invention will be further explained with
following specific embodiments.
Embodiment 1
1) Preparation of aqueous phase solution. Preparing aqueous phase monomer, m
phenylenediamine (MDP), zinc nitrate hexahydrate and 2-methylimidazole at the mass
ratio of 99.5:0.2:0.1:0.2. At first, dissolving MPD and zinc nitrate hexahydrate in
ultrapure water at room temperature to obtain homogeneous solution with weak
opalescence. Then 2-methylimidazole was added and dissolved by ultrasonic wave to
obtain homogeneous milky aqueous solution.
2) Preparation of oil phase solution. Adding TMC into n-hexane at the ratio of 0.1wt%,
and completely dissolving to obtain colourless and transparent solution.
3) Process of interfacial polymerization. Immersing the mixed cellulose basement
membrane in the aqueous phase solution obtained in step 1) for 2min, then removing the
excessive aqueous phase solution on the membrane surface and immersing the basement
membrane in the oil solution obtained in step 2) for interfacial polymerization. The oil
phase solution was removed after 30s.
4) Post-treatment. The membrane obtained from step 3) was subjected to heat treatment
at 80°C for 1min. And then cleaning the membrane surface with n-hexane to remove
unreacted monomer. Drying in the air to obtain ZIF-based PA MMMs, immersed in
deionized water for later use.
The prepared membrane was labelled as TFN-1 membrane, and the membrane
performance was determined as follows: the water flux was 3.5-5L/m 2 h bar, and the salt
retention rate was 96%. The membrane stability test results show that the water flux is
improved while the salt retention rate is guaranteed.
Embodiment 2
1) Preparation of aqueous phase solution. Preparing aqueous phase monomer, MDP, zinc
nitrate hexahydrate and 2-methylimidazole at the mass ratio of 98.3:0.2:0.5:1. At first,
dissolving MPD and zinc nitrate hexahydrate in ultrapure water at room temperature to
obtain homogeneous solution with weak opalescence. Then 2-methylimidazole was
added and dissolved by ultrasonic wave to obtain homogeneous milky aqueous solution.
2) Preparation of oil phase solution. Adding TMC into n-hexane at the ratio of 0.1wt%,
and completely dissolving to obtain colourless and transparent solution.
3) Process of interfacial polymerization. Immersing the mixed cellulose basement
membrane in the aqueous phase solution obtained in step 1) for 2min, then removing the
excessive aqueous phase solution on the membrane surface and immersing the basement
membrane in the oil solution obtained in step 2) for interfacial polymerization. The oil
phase solution was removed after 30s.
4) Post-treatment. The membrane obtained from step 3) was subjected to heat treatment
at 80°C for 1min. And then cleaning the membrane surface with n-hexane to remove
unreacted monomer. Drying in the air to obtain ZIF-based PA MMMs, immersed in
deionized water for later use.
The prepared membrane was labelled as TFN-2 membrane, and the membrane
performance was determined as follows: the water flux was 8-9L/m 2 h bar, and the salt
retention rate was 97%. The membrane stability test results show that the water flux is
improved while the salt retention rate is guaranteed.
Embodiment 3
1) Preparation of aqueous phase solution. Preparing aqueous phase monomer, MDP, zinc
nitrate hexahydrate and 2-methylimidazole at the mass ratio of 94.8:0.2:1.67:3.33. At first, dissolving MPD and zinc nitrate hexahydrate in ultrapure water at room temperature to obtain homogeneous solution with weak opalescence. Then 2-methylimidazole was added and dissolved by ultrasonic wave to obtain homogeneous milky aqueous solution.
2) Preparation of oil phase solution. Adding TMC into n-hexane at the ratio of 0.1wt%,
and completely dissolving to obtain colourless and transparent solution.
3) Process of interfacial polymerization. Immersing the mixed cellulose basement
membrane in the aqueous phase solution obtained in step 1) for 2min, then removing the
excessive aqueous phase solution on the membrane surface and immersing the basement
membrane in the oil solution obtained in step 2) for interfacial polymerization. The oil
phase solution was removed after 30s.
4) Post-treatment. The membrane obtained from step 3) was subjected to heat treatment
at 80°C for 1min. And then cleaning the membrane surface with n-hexane to remove
unreacted monomer. Drying in the air to obtain ZIF-based PA MMMs, immersed in
deionized water for later use.
The prepared membrane was labelled as TFN-3 membrane, and the membrane
performance was determined as follows: the water flux was 15-17L/m2 h bar, and the salt
retention rate was 97%. The membrane stability test results show that the water flux is
improved while the salt retention rate is guaranteed.
Comparative example 1
At room temperature, dissolving MPD in ultrapure water at the mass ratio of 99.8:0.2 to
obtain aqueous phase solution. Then adding TMC into n-hexane at the ratio of 0.1wt%,
and completely dissolving to obtain colourless and transparent oil phase solution.
Immersing the mixed cellulose basement membrane in the aqueous phase solution for
2min, then removing the excessive aqueous phase solution on the membrane surface and
immersing the basement membrane in the oil solution for interfacial polymerization. The
oil phase solution was removed after 30s. The obtained membrane f was subjected to heat
treatment at 80°Cfor 1min. And then cleaning the membrane surface with n-hexane to
remove unreacted monomer. Drying in the air to obtain PA MMMs, which were then
immersed in deionized water for later use.
The prepared membrane was labelled as TFN/MCE membrane, and the membrane
performance was determined as follows: the water flux was 1-1.5L/m2 h bar, and the salt
retention rate was 96%.
Comparative example 2
Preparing aqueous phase monomer, zinc nitrate hexahydrate and 2-methylimidazole at
the mass ratio of 95:1.67:3.33. Firstly, dissolving zinc nitrate hexahydrate and 2
methylimidazole in ultrapure water at room temperature to synthesize ZIF-8 particles.
Then the synthesized ZIF-8 particles were doped into the aqueous solution of 2wt% MPD
and were dispersed uniformly by ultrasonic. Adding TMC into n-hexane at the ratio of
0.1wt%, and completely dissolving to obtain colourless and transparent oil phase
solution. Immersing the mixed cellulose basement membrane in the aqueous phase
solution for 2min, then removing the excessive aqueous phase solution on the membrane
surface and immersing the basement membrane in the oil solution for interfacial
polymerization. The oil phase solution was removed after 30s. The obtained membrane
was subjected to heat treatment at 80 °C for 1min. And then cleaning the membrane
surface with n-hexane to remove unreacted monomer. Drying in the air to obtain PA
MMMs, which were immersed in deionized water for later use.
The prepared membrane was labelled as TFN-Z membrane, and the membrane
performance was determined as follows: the water flux was 5-6L/m2 h bar, and the salt
retention rate was 90%. The results of membrane stability test indicate that the retention
rate reduces to about 70% when the test lasts for 18h.
It can be seen from the data of above embodiments and comparative examples that the
performance of the ZIF-based PA MMMs obtained by the invention is much higher than
that of the traditional PA membrane. Moreover, the stability is much higher than that of
the PA MMMs prepared by directly doping ZIF. For example, under the same test
conditions, the water flux of the ZIF-based PA MMMs obtained by the present invention
is 15 times higher than that of the traditional PA membrane on the premise of ensuring
high salt retention rate (more than 97%); moreover, when the retention rate of the PA
MMMs prepared by directly doping ZIF decreases significantly, ZIF-based PA MMMs
obtained by the present invention still maintain stable retention rate and water flux.
Claims (10)
1. The ZIF-based PA MMMs are characterized by their preparation method comprising
the following steps.
1) Preparation of aqueous phase solution. Dissolving aqueous phase monomer and
soluble zinc salt in ultrapure water at room temperature to obtain a homogeneous
solution. Then imidazole monomer is added and dissolved to gat aqueous phase solution.
It should be noted that the aqueous phase monomer concentration is 0.01-4.wt%, the
soluble zinc salt concentration is 0.01-4.Owt%, and the imidazole monomer concentration
is 0.01-20.Owt%.
2) Preparation of oil phase solution. Adding polyacyl chloride monomer into n-hexane,
and completely dissolving to obtain colourless and transparent solution. Wherein, the
concentration of the polyacyl chloride monomer in n-hexane is 0.01%-4.wt%.
3) Process of interfacial polymerization. Immersing the porous basement membrane in
the aqueous phase solution obtained in step 1), then removing the excessive aqueous
phase solution on the membrane surface and immersing the basement membrane in the
oil solution obtained in step 2) for interfacial polymerization.
4) Post-treatment. The membrane after step 3) is subjected to heat treatment. And then
cleaning the membrane surface with organic solvent to remove unreacted monomer.
Drying in the air to obtain ZIF-based PA MMMs and immersing them in deionized water
for later use.
2. The PA membrane as described in claim 1, is characterized in that the aqueous phase
monomer in step 1) is aromatic diamine compound, aliphatic polyamine compound,
dihydroxy phenol compound or piperazine compound.
3. The PA membrane as described in claim 1, is characterized in that the soluble zinc salt
in step 1) is zinc nitrate or zinc chloride.
4. The PA membrane as described in claim 1, is characterized in that the imidazole
monomer in step 1) is preferably 2-methylimidazole.
5. The PA membrane as described in claim 1, is characterized in that in step 2) the
polyacyl chloride monomers is TMC or terephthaloyl chloride.
6. The PA membrane as described in claim 1, is characterized in that in step 3) the porous
basement membrane is ultrafiltration membrane or microfiltration membrane such as
mixed cellulose membrane, polysulfone membrane, polyethersulfone membrane,
polyacrylonitrile membrane, polyethylene (propylene) membrane, etc.
7. The PA membrane as described in claim 1, is characterized in that in step 3) the
immersion time in aqueous phase is1-10min and in oil phase is 3Os-2min;
8. The PA membrane as described in claim 1, is characterized in that in step 4) the heat
treatment temperature is 70-90°C and the heat treatment time is 30s-5min;
9. The PA membrane as described in claim 1, is characterized in that in step 4) the
organic solvent is n-hexane, acetone or methanol.
10. The application of PA membrane descrided in claim 1 in water treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2020104003A AU2020104003A4 (en) | 2020-12-10 | 2020-12-10 | Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2020104003A AU2020104003A4 (en) | 2020-12-10 | 2020-12-10 | Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2020104003A4 true AU2020104003A4 (en) | 2021-02-18 |
Family
ID=74591576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2020104003A Ceased AU2020104003A4 (en) | 2020-12-10 | 2020-12-10 | Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU2020104003A4 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113041864A (en) * | 2021-04-08 | 2021-06-29 | 大连理工大学 | Method for modifying ceramic-based TFN forward osmosis membrane by titanium dioxide intermediate layer and application of method |
| CN113694741A (en) * | 2021-09-13 | 2021-11-26 | 浙江工业大学 | Preparation method of full heat exchange membrane based on interfacial polymerization and reverse diffusion growth ZIF |
| CN113813797A (en) * | 2021-10-20 | 2021-12-21 | 西南石油大学 | Preparation method of emulsion separation membrane with high flux and self-cleaning function |
| CN114011255A (en) * | 2021-11-19 | 2022-02-08 | 天津天元新材料科技有限公司 | Base membrane of reverse osmosis membrane and preparation method thereof |
| CN114177788A (en) * | 2021-12-01 | 2022-03-15 | 河北大学 | ZIF-8 tube modified ultrathin nano composite membrane, and preparation method and application thereof |
| CN114225699A (en) * | 2021-12-14 | 2022-03-25 | 浙江工业大学 | Method for preparing nanofiltration membrane based on ZIF (zero-valent iron) in-situ growth of polyolefin composite polyamide membrane |
| CN114715977A (en) * | 2022-04-29 | 2022-07-08 | 南通大学 | POMs (polyoxymethylene) modified membrane for water treatment and preparation method and application thereof |
| CN114832641A (en) * | 2022-05-30 | 2022-08-02 | 浙江工业大学 | Method for preparing polyamide mixed matrix total heat exchange membrane by using interfacial polymerization technology and introducing ZIFs |
| CN114870656A (en) * | 2022-05-17 | 2022-08-09 | 北京碧水源膜科技有限公司 | Preparation method of zwitterionic polymer mixed matrix composite membrane |
| CN115184504A (en) * | 2022-07-22 | 2022-10-14 | 陕西中烟工业有限责任公司 | Preparation method of ZIF-8 modified monolithic column and extraction of polycyclic aromatic hydrocarbon in tobacco leaves |
| CN115193271A (en) * | 2021-04-14 | 2022-10-18 | 西陇科学股份有限公司 | Pervaporation composite membrane with ultrathin separation active layer and preparation method thereof |
| CN116023739A (en) * | 2022-12-08 | 2023-04-28 | 江阴市申美包装材料有限公司 | Composite packaging bag for oral liquid medicine and preparation method thereof |
| CN116531968A (en) * | 2023-03-26 | 2023-08-04 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
-
2020
- 2020-12-10 AU AU2020104003A patent/AU2020104003A4/en not_active Ceased
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113041864A (en) * | 2021-04-08 | 2021-06-29 | 大连理工大学 | Method for modifying ceramic-based TFN forward osmosis membrane by titanium dioxide intermediate layer and application of method |
| CN115193271A (en) * | 2021-04-14 | 2022-10-18 | 西陇科学股份有限公司 | Pervaporation composite membrane with ultrathin separation active layer and preparation method thereof |
| CN113694741A (en) * | 2021-09-13 | 2021-11-26 | 浙江工业大学 | Preparation method of full heat exchange membrane based on interfacial polymerization and reverse diffusion growth ZIF |
| CN113813797A (en) * | 2021-10-20 | 2021-12-21 | 西南石油大学 | Preparation method of emulsion separation membrane with high flux and self-cleaning function |
| CN114011255A (en) * | 2021-11-19 | 2022-02-08 | 天津天元新材料科技有限公司 | Base membrane of reverse osmosis membrane and preparation method thereof |
| CN114177788A (en) * | 2021-12-01 | 2022-03-15 | 河北大学 | ZIF-8 tube modified ultrathin nano composite membrane, and preparation method and application thereof |
| CN114225699A (en) * | 2021-12-14 | 2022-03-25 | 浙江工业大学 | Method for preparing nanofiltration membrane based on ZIF (zero-valent iron) in-situ growth of polyolefin composite polyamide membrane |
| CN114225699B (en) * | 2021-12-14 | 2023-11-17 | 浙江工业大学 | Method for preparing nanofiltration membrane based on polyolefin composite polyamide membrane in-situ growth ZIF |
| CN114715977A (en) * | 2022-04-29 | 2022-07-08 | 南通大学 | POMs (polyoxymethylene) modified membrane for water treatment and preparation method and application thereof |
| CN114715977B (en) * | 2022-04-29 | 2023-02-24 | 南通大学 | POMs (polyoxymethylene) modified membrane for water treatment and preparation method and application thereof |
| CN114870656A (en) * | 2022-05-17 | 2022-08-09 | 北京碧水源膜科技有限公司 | Preparation method of zwitterionic polymer mixed matrix composite membrane |
| CN114832641A (en) * | 2022-05-30 | 2022-08-02 | 浙江工业大学 | Method for preparing polyamide mixed matrix total heat exchange membrane by using interfacial polymerization technology and introducing ZIFs |
| CN115184504A (en) * | 2022-07-22 | 2022-10-14 | 陕西中烟工业有限责任公司 | Preparation method of ZIF-8 modified monolithic column and extraction of polycyclic aromatic hydrocarbon in tobacco leaves |
| CN116023739A (en) * | 2022-12-08 | 2023-04-28 | 江阴市申美包装材料有限公司 | Composite packaging bag for oral liquid medicine and preparation method thereof |
| CN116023739B (en) * | 2022-12-08 | 2023-09-12 | 江阴市申美包装材料有限公司 | Composite packaging bag for oral liquid medicine and preparation method thereof |
| CN116531968A (en) * | 2023-03-26 | 2023-08-04 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
| CN116531968B (en) * | 2023-03-26 | 2024-03-22 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020104003A4 (en) | Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof | |
| Ma et al. | A facile preparation of novel positively charged MOF/chitosan nanofiltration membranes | |
| CN110694492A (en) | Mixed matrix polyamide membrane of ZIF type metal organic framework and preparation method thereof | |
| US20210260535A1 (en) | Uio-66-nh2 doped organosilicon high salinity wastewater treatment membrane and a preparation method thereof | |
| CN104209022A (en) | High-flux polyamide/ZIF-8 nanofiltration composite film and preparation method thereof | |
| CN105148752A (en) | Polyamide reverse-osmosis composite membrane containing MIL type metal-organic framework material and preparation method thereof | |
| CN107551824B (en) | Preparation method of seawater boron-removing reverse osmosis membrane | |
| AU2011326483A1 (en) | Improved hybrid TFC RO membranes with non-metallic additives | |
| CN111214967A (en) | Preparation method of high-performance ZIF-8-containing nanofiltration membrane based on two-step addition of sodium polystyrene sulfonate | |
| CN113117524A (en) | Two-dimensional material MXene modified polypiperazine amide nanofiltration membrane and preparation method thereof | |
| CN114797490B (en) | Preparation method of high-selectivity separation membrane for separating anionic salt | |
| CN111420563A (en) | Hybrid composite reverse osmosis/nanofiltration membrane, preparation method and application thereof | |
| Qin et al. | The membrane-based desalination: focus on MOFs and COFs | |
| CN112426894A (en) | Preparation method of polyamide composite reverse osmosis membrane and obtained reverse osmosis membrane | |
| CN112354379A (en) | Preparation method of polytetrafluoroethylene reverse osmosis membrane with lasting and stable filtration and separation performance | |
| Shadravan et al. | Fouling in thin film nanocomposite membranes for power generation through pressure retarded osmosis | |
| CN112657348A (en) | Composite membrane containing COFs intermediate layer, preparation method and application thereof | |
| CN106139922B (en) | Ultrahigh flux nanofiltration membrane and preparation method thereof | |
| US20220062831A1 (en) | Metal-organic framework material/membrane composite material, preparation method and use thereof | |
| CN111804162A (en) | Preparation method of high-flux polytetrafluoroethylene composite nanofiltration membrane | |
| CN116159436A (en) | Nano composite reverse osmosis membrane containing ultrathin hydrophilic covalent organic framework nano material intermediate layer | |
| Lei et al. | The metal organic framework of UiO-66-NH2 reinforced nanofiltration membrane for highly efficient ion sieving | |
| CN111085117B (en) | High-water-permeability reverse osmosis membrane and preparation method thereof | |
| CN113244777A (en) | Preparation method of silver modified graphite phase carbon nitride photocatalytic composite forward osmosis membrane | |
| KR20220083902A (en) | Method of fabricating thin-film composite membrane with interlayer structure and its applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGI | Letters patent sealed or granted (innovation patent) | ||
| MK22 | Patent ceased section 143a(d), or expired - non payment of renewal fee or expiry |