CN115414795A - Preparation method of novel polyamide composite separation membrane - Google Patents
Preparation method of novel polyamide composite separation membrane Download PDFInfo
- Publication number
- CN115414795A CN115414795A CN202211198695.XA CN202211198695A CN115414795A CN 115414795 A CN115414795 A CN 115414795A CN 202211198695 A CN202211198695 A CN 202211198695A CN 115414795 A CN115414795 A CN 115414795A
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- separation membrane
- composite separation
- mof
- preparing
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 147
- 238000000926 separation method Methods 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000004952 Polyamide Substances 0.000 title claims abstract description 23
- 229920002647 polyamide Polymers 0.000 title claims abstract description 23
- 239000013119 CD-MOF Substances 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- OVYMWJFNQQOJBU-UHFFFAOYSA-N 1-octanoyloxypropan-2-yl octanoate Chemical compound CCCCCCCC(=O)OCC(C)OC(=O)CCCCCCC OVYMWJFNQQOJBU-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 63
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 63
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 50
- 229920000570 polyether Polymers 0.000 claims abstract description 50
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 36
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims abstract description 36
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims abstract description 36
- 229920002472 Starch Polymers 0.000 claims abstract description 33
- 235000019698 starch Nutrition 0.000 claims abstract description 33
- 239000008107 starch Substances 0.000 claims abstract description 33
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 26
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920002261 Corn starch Polymers 0.000 claims abstract description 22
- 239000008120 corn starch Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 108090000637 alpha-Amylases Proteins 0.000 claims abstract description 17
- 150000001263 acyl chlorides Chemical group 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- -1 2-acetoxyl-9-octadecenoic acid methyl ester Chemical compound 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 230000004907 flux Effects 0.000 abstract description 28
- 239000000243 solution Substances 0.000 description 110
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000008055 phosphate buffer solution Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000004108 freeze drying Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 239000002569 water oil cream Substances 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001805 chlorine compounds Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- LTIPUQSMGRSZOQ-UHFFFAOYSA-N [C].[C].[O] Chemical compound [C].[C].[O] LTIPUQSMGRSZOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of a novel polyamide composite separation membrane, belongs to the technical field of separation membranes, and particularly relates to a method for preparing bi-terminal acyl chloride polyethylene glycol from polyethylene glycol and isophthaloyl dichloride, and then preparing polyether copolyamide from the bi-terminal acyl chloride polyethylene glycol and 1,4 bis (3-aminopropyl) piperazine; preparing gamma-cyclodextrin and starch short chain seed crystals to obtain cyclodextrin-MOF, wherein the starch short chain seed crystals are obtained by carrying out enzymolysis treatment on waxy corn starch by pullulanase, and the cyclodextrin-MOF contains propylene glycol dicaprylate; mixing polyether copolyamide and cyclodextrin-MOF in a solvent to prepare a membrane casting solution, and drying in a mold to obtain the composite separation membrane. Mechanics of the composite separation membrane prepared by the inventionThe performance is good; high water flux (145-170 L.m) ‑2 h ‑1 (ii) a The oil-water separation performance is good.
Description
Technical Field
The invention belongs to the technical field of separation membranes, and particularly relates to a preparation method of a novel polyamide composite separation membrane.
Background
If these oily wastewaters are not properly treated, their effects on human health and the ecosystem are often long-term and fatal. Furthermore, with the rapid growth of the population, the scarcity of fresh water has become a serious problem, especially in certain underdeveloped water areas. The use efficiency of the fresh water can be improved by recovering the oily wastewater, and the method has important significance for effectively recovering the oily wastewater.
The separation membrane technology is considered to be an advanced separation technology, can be used for separating various oil-water emulsions, particularly surfactant-stabilized emulsified oil, and has considerable separation efficiency and a relatively simple operation process. The ceramic separation membrane and the polymer separation membrane are two filtering membranes mainly used for oil-water separation at present, and the membrane technology has the advantages that no chemical substance is required to be added during working operation, low energy is required, the treatment is easy, and the process preparation conditions are simple. Despite these advantages, the widespread use of separation membranes in various industrial fields for treating oily sewage is still limited. The main problem is membrane fouling by adsorption on the membrane surface or clogging of the membrane pores by oil droplets, which leads to severe flux and rejection losses.
Disclosure of Invention
The invention aims to provide a preparation method of a novel polyamide composite separation membrane with good mechanical property, high water flux and good oil-water separation performance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of a novel polyamide composite separation membrane comprises the following steps:
preparing double-end acyl chloride polyethylene glycol from polyethylene glycol and isophthaloyl dichloride, and then preparing polyether copolyamide from the double-end acyl chloride polyethylene glycol and 1,4 bis (3-aminopropyl) piperazine;
preparing gamma-cyclodextrin and starch short chain seed crystals to obtain cyclodextrin-MOF, wherein the starch short chain seed crystals are obtained by carrying out enzymolysis treatment on waxy corn starch by pullulanase, and the cyclodextrin-MOF contains propylene glycol dicaprylate;
mixing polyether copolyamide and cyclodextrin-MOF in a solvent to prepare a membrane casting solution, and drying in a mold to obtain the composite separation membrane. According to the invention, cyclodextrin-MOF is introduced into polyether copolyamide to prepare a membrane casting solution, and then the membrane casting solution is used for preparing a composite separation membrane, wherein the cyclodextrin-MOF can provide pores different from the polyether copolyamide to improve the performance of the composite separation membrane, but when the cyclodextrin-MOF is used, the entrapment rate of the cyclodextrin-MOF to oil-water emulsion is below 95%.
Preferably, propylene glycol dicaprylate is used in an amount of 0.4-3.6wt% of the gamma-cyclodextrin.
Preferably, the starch short chain seed crystals are used in an amount of 1.5-6.0wt% of the gamma-cyclodextrin.
Preferably, the cyclodextrin-MOF is used in an amount of 10 to 30wt% of the polyether copolyamide.
Preferably, in the preparation of the cyclodextrin-MOF, gamma-cyclodextrin, starch short chain seed crystals and an alkaline reagent are treated and dried in deionized water, then propylene glycol dicaprylate solution is added, and standing treatment is carried out at the temperature of 40-60 ℃.
Preferably, the solvent is DMF.
Preferably, the composite separation membrane contains 2-acetoxy-9-octadecenoic acid methyl ester.
Preferably, in the preparation of the starch short chain seed crystal, waxy corn starch is added into a phosphate buffer solution, the mixture is stirred for 20-60min at the temperature of 80-100 ℃, then the temperature is cooled to 40-60 ℃, pullulanase is added, enzymolysis is carried out for 4-16h, after the enzymolysis is finished, the mixture is centrifuged for 5-10min at the speed of 3000-5000r/min, supernatant liquid is taken for enzyme deactivation treatment, ethanol is added to precipitate, the precipitate is centrifuged at the speed of 9000-12000r/min, the precipitate is collected, and freeze drying is carried out to obtain the starch short chain seed crystal.
More preferably, the phosphate buffer is prepared at a pH of 4-5 in the preparation of the starch short chain seeds.
More preferably, the waxy corn starch is used in an amount of 4-12wt% of the phosphate buffer in the preparation of the starch short chain seeds.
More preferably, in the preparation of the starch short chain seed crystal, the pullulanase is used in an amount of 30-60U/g dry weight of waxy corn starch.
Preferably, in the preparation of the cyclodextrin-MOF, the gamma-cyclodextrin and an alkaline reagent are added into deionized water, then starch short-chain seed crystals are added, ultrasonic dispersion is carried out, a water system membrane is passed through, standing treatment is carried out for 3-9h at the temperature of 40-60 ℃, then methanol is added to separate out precipitates, centrifugation is carried out under the condition of 3000-5000r/min, the precipitates are collected, methanol is washed, dried, propylene glycol dicaprylate solution is added to treat for 3-6h, and freeze drying is carried out to obtain the cyclodextrin-MOF.
More preferably, in the preparation of cyclodextrin-MOF, gamma-cyclodextrin is used in an amount of 1-5wt% of deionized water.
More preferably, in the preparation of the cyclodextrin-MOF, the alkaline agent is potassium hydroxide and the amount of alkaline agent used is 20-40wt% of the gamma-cyclodextrin.
More preferably, in the preparation of cyclodextrin-MOF, the amount of starch short chain seeds used is 1.5-6.0wt% of γ -cyclodextrin.
More preferably, in the preparation of cyclodextrin-MOF, the solvent of the propylene glycol dicaprylate solution is an absolute ethanol solution with the mass fraction of 30-70 wt%.
More preferably, in the preparation of cyclodextrin-MOF, the propylene glycol dicaprylate solution contains 2-6wt% of propylene glycol dicaprylate.
More preferably, in the preparation of cyclodextrin-MOF, the propylene glycol dicaprylate solution is used in an amount such that the propylene glycol dicaprylate is 0.4-3.6wt% of the gamma-cyclodextrin.
Preferably, in the preparation of the double-end acyl chloride polyethylene glycol, the polyethylene glycol is added into dichloromethane in the nitrogen atmosphere, stirred, mixed and dissolved to obtain a polyethylene glycol solution, triethylamine is added, stirred and mixed uniformly, the isophthaloyl dichloride solution is added at the temperature of 0-5 ℃, and after the addition is finished, the reaction is carried out for 4-12 hours at the temperature of 20-50 ℃ to obtain the double-end acyl chloride polyethylene glycol solution.
More preferably, the bi-terminal acid chloride polyethylene glycol is prepared such that the polyethylene glycol solution contains 5-15wt% polyethylene glycol.
More preferably, in the preparation of the bis-end acid chloride polyethylene glycol, triethylamine is used in an amount of 40-80wt% of the polyethylene glycol.
More preferably, in the preparation of the bis-end acid chloride polyethylene glycol, the solvent of the isophthaloyl chloride solution is dichloromethane, and the isophthaloyl chloride solution contains 2-6wt% of isophthaloyl chloride.
More preferably, in the preparation of the bis-end acid chloride polyethylene glycol, the isophthaloyl chloride solution is used in an amount such that the isophthaloyl chloride is 100-130% of the molar amount of polyethylene glycol used.
Preferably, in the preparation of the polyether copolyamide, 1,4 bis (3-aminopropyl) piperazine solution is added into a bis (3-aminopropyl) polyethylene glycol bi-end chloride solution at the temperature of 0-5 ℃, after the addition is finished, the reaction is carried out for 4-12h at the temperature of 20-50 ℃, after the reaction is finished, deionized water is used for extraction, the mixture is kept stand for 18-36h, liquid separation is carried out to remove a water phase, ice ether is added to precipitate, and the polyether copolyamide is obtained by washing and drying.
More preferably, in the preparation of the polyether copolyamide, the solvent of the 1,4 bis (3-aminopropyl) piperazine solution is dichloromethane, and the 1,4 bis (3-aminopropyl) piperazine solution is used in an amount such that 1,4 bis (3-aminopropyl) piperazine is 100 to 130% of the molar amount of the initial polyethylene glycol used.
Preferably, in the preparation of the composite separation membrane, the polyether copolyamide is added into DMF, stirred, mixed and dissolved to obtain a polyether copolyamide solution, the cyclodextrin-MOF dispersion solution is added, stirred and mixed uniformly to obtain a membrane casting solution, then the membrane casting solution is transferred into a mold, dried for 6-12h at the temperature of 40-60 ℃ to obtain a composite membrane, and then dried for 6-24h in vacuum at the temperature of 40-60 ℃ to obtain the composite separation membrane.
More preferably, in the preparation of the composite separation membrane, the polyether copolyamide solution contains 3-9wt% of polyether copolyamide.
More preferably, in the preparation of the composite separation membrane, the solvent of the cyclodextrin-MOF dispersion liquid is DMF, and the cyclodextrin-MOF dispersion liquid contains 2-6wt% of cyclodextrin-MOF.
More preferably, in the preparation of the composite separation membrane, the cyclodextrin-MOF dispersion is used in an amount such that the cyclodextrin-MOF is 10-30wt% of the polyether copolyamide.
Preferably, the preparation of the composite separation membrane can be added with 2-acetoxy-9-octadecenoic acid methyl ester, and the usage amount of the 2-acetoxy-9-octadecenoic acid methyl ester is 0.3-1.2wt% of the polyether copolyamide. When the composite separation membrane is prepared, the 2-acetoxyl-9-octadecenoic acid methyl ester and cyclodextrin-MOF containing propylene glycol dicaprylate act together, so that the mechanical property, water flux and oil-water emulsion separation performance of the prepared composite separation membrane are improved, and the effect of improving the water flux is very obvious.
The invention discloses a novel polyamide composite separation membrane prepared by the method.
The invention discloses the cyclodextrin-MOF containing the propylene glycol dicaprylate.
The invention discloses application of the cyclodextrin-MOF in preparation of a composite separation membrane.
The invention adopts cyclodextrin-MOF containing propylene glycol dicaprylate and polyether copolyamide for preparing the composite separation membrane, and the use of a proper amount of propylene glycol dicaprylate improves the performance of the composite separation membrane, so the invention has the following beneficial effects: the composite separation membrane prepared by the invention has good mechanical property, the tensile strength is 3.3-3.7MPa, and the elongation at break is 275-300%; high water flux (145-170 L.m) -2 h -1 (ii) a The oil-water separation performance is good, and the retention rate is more than 95%. Therefore, the invention is a preparation method of the novel polyamide composite separation membrane with good mechanical property, high water flux and good oil-water separation performance.
Drawings
FIG. 1 is a cyclodextrin-MOF infrared spectrum;
FIG. 2 is a graph of tensile strength of a composite separation membrane;
FIG. 3 is a graph of elongation at break of a composite separation membrane;
FIG. 4 is a water flux diagram of a composite separation membrane;
FIG. 5 is a diagram showing oil-water emulsion separation by a composite separation membrane.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a preparation method of a novel polyamide composite separation membrane,
preparing the bi-terminal acyl chloride polyethylene glycol: adding polyethylene glycol into dichloromethane in a nitrogen atmosphere, stirring, mixing and dissolving to obtain a polyethylene glycol solution, adding triethylamine, stirring and mixing uniformly, adding an isophthaloyl dichloride solution at the temperature of 0 ℃, and after the addition is finished, reacting for 8 hours at the temperature of 40 ℃ to obtain a bi-terminal acyl chloride polyethylene glycol solution. The polyethylene glycol solution contains 10wt% of polyethylene glycol, the triethylamine is used in an amount of 60wt% of the polyethylene glycol, the isophthaloyl chloride solution is dichloromethane in a solvent, the isophthaloyl chloride solution contains 4wt% of isophthaloyl chloride, and the isophthaloyl chloride solution is used in an amount of 110% of the molar amount of the polyethylene glycol.
Preparation of polyether copolyamide: adding 1,4 bis (3-aminopropyl) piperazine solution into bis (3-aminopropyl) polyethylene glycol bi-terminal chloride solution at the temperature of 0 ℃, reacting for 8 hours at the temperature of 40 ℃ after the addition is finished, extracting with deionized water, standing for 24 hours, separating liquid to remove a water phase, adding glacial ethyl ether to precipitate, washing and drying to obtain the polyether copolyamide. The solvent of the 1,4 bis (3-aminopropyl) piperazine solution was dichloromethane, and the 1,4 bis (3-aminopropyl) piperazine solution was used in such an amount that 1,4 bis (3-aminopropyl) piperazine was 110% of the molar amount of the initial polyethylene glycol used.
Preparation of starch short chain seed crystal: adding waxy corn starch into a phosphate buffer solution, stirring for 40min at the temperature of 90 ℃, then cooling to 50 ℃, adding pullulanase, carrying out enzymolysis for 8h, centrifuging for 5min at the speed of 4000r/min after the enzymolysis is finished, taking supernatant liquid, carrying out enzyme deactivation treatment, adding ethanol to precipitate, centrifuging at the speed of 11000r/min, collecting precipitate, and carrying out freeze drying to obtain the starch short-chain seed crystal. The pH of the phosphate buffer solution is 5, the using amount of the waxy corn starch is 9wt% of the phosphate buffer solution, the using amount of the pullulanase is based on the dry weight of the waxy corn starch, and the using amount of the pullulanase is 40U/g of the dry weight of the waxy corn starch.
Preparation of cyclodextrin-MOF: adding gamma-cyclodextrin and an alkaline reagent into deionized water, then adding starch short chain seed crystals, performing ultrasonic dispersion, passing through a 0.45-micron water system film, standing at the temperature of 50 ℃ for 6 hours, then adding methanol to separate out a precipitate, centrifuging at 5000r/min, collecting the precipitate, washing with methanol, drying, adding a propylene glycol dicaprylate solution to treat for 5 hours, and performing freeze drying to obtain the cyclodextrin-MOF. The usage amount of the gamma-cyclodextrin is 3wt% of deionized water, the alkaline reagent is potassium hydroxide, the usage amount of the alkaline reagent is 30wt% of the gamma-cyclodextrin, the usage amount of the starch short chain seed crystal is 3wt% of the gamma-cyclodextrin, the solvent of the propylene glycol dicaprylate solution is an absolute ethyl alcohol solution with the mass fraction of 50wt%, the propylene glycol dicaprylate solution contains 4wt% of propylene glycol dicaprylate, and the usage amount of the propylene glycol dicaprylate solution enables the propylene glycol dicaprylate to be 2wt% of the gamma-cyclodextrin.
Preparing a composite separation membrane: adding polyether copolyamide into DMF, stirring, mixing and dissolving to obtain a polyether copolyamide solution, adding cyclodextrin-MOF dispersion liquid, stirring and mixing uniformly to obtain a membrane casting solution, transferring the membrane casting solution into a mold, drying for 9h at the temperature of 50 ℃ to obtain a composite membrane, and then drying for 12h in vacuum at the temperature of 50 ℃ to obtain the composite separation membrane. The polyether copolyamide solution contains 6wt% of polyether copolyamide, the solvent of the cyclodextrin-MOF dispersion liquid is DMF, the cyclodextrin-MOF dispersion liquid contains 4wt% of cyclodextrin-MOF, and the usage amount of the cyclodextrin-MOF dispersion liquid is 15wt% of the polyether copolyamide.
Example 2:
a preparation method of a novel polyamide composite separation membrane,
preparing the bi-terminal acyl chloride polyethylene glycol: adding polyethylene glycol into dichloromethane in a nitrogen atmosphere, stirring, mixing and dissolving to obtain a polyethylene glycol solution, adding triethylamine, stirring and mixing uniformly, adding an isophthaloyl dichloride solution at the temperature of 0 ℃, and after the addition is finished, reacting for 8 hours at the temperature of 40 ℃ to obtain a bi-terminal acyl chloride polyethylene glycol solution. The polyethylene glycol solution contains 10wt% of polyethylene glycol, the triethylamine is used in an amount of 60wt% of the polyethylene glycol, the isophthaloyl chloride solution is dichloromethane in a solvent, the isophthaloyl chloride solution contains 4wt% of isophthaloyl chloride, and the isophthaloyl chloride solution is used in an amount of 110% of the molar amount of the polyethylene glycol.
Preparation of polyether copolyamide: adding 1,4 bis (3-aminopropyl) piperazine solution into bis (3-aminopropyl) polyethylene glycol bi-terminal chloride solution at the temperature of 0 ℃, reacting for 8 hours at the temperature of 40 ℃ after the addition is finished, extracting with deionized water, standing for 24 hours, separating liquid to remove a water phase, adding glacial ethyl ether to precipitate, washing and drying to obtain the polyether copolyamide. The solvent of the 1,4 bis (3-aminopropyl) piperazine solution was dichloromethane, and the 1,4 bis (3-aminopropyl) piperazine solution was used in such an amount that 1,4 bis (3-aminopropyl) piperazine was 110% of the molar amount of the initial polyethylene glycol used.
Preparation of starch short chain seed crystal: adding waxy corn starch into a phosphate buffer solution, stirring for 40min at the temperature of 90 ℃, then cooling to 50 ℃, adding pullulanase, carrying out enzymolysis for 8h, centrifuging for 5min at the speed of 4000r/min after the enzymolysis is finished, taking supernatant liquid, carrying out enzyme deactivation treatment, adding ethanol to precipitate, centrifuging at the speed of 11000r/min, collecting precipitate, and carrying out freeze drying to obtain the starch short-chain seed crystal. The pH of the phosphate buffer solution is 5, the using amount of the waxy corn starch is 9wt% of the phosphate buffer solution, the using amount of the pullulanase is based on the dry weight of the waxy corn starch, and the using amount of the pullulanase is 40U/g of the dry weight of the waxy corn starch.
Preparation of cyclodextrin-MOF: adding gamma-cyclodextrin and an alkaline reagent into deionized water, then adding starch short chain seed crystals, performing ultrasonic dispersion, passing through a 0.45-micron water system film, standing at the temperature of 50 ℃ for 6 hours, then adding methanol to separate out a precipitate, centrifuging at 5000r/min, collecting the precipitate, washing with methanol, drying, adding a propylene glycol dicaprylate solution to treat for 5 hours, and performing freeze drying to obtain the cyclodextrin-MOF. The usage amount of the gamma-cyclodextrin is 3wt% of deionized water, the alkaline reagent is potassium hydroxide, the usage amount of the alkaline reagent is 30wt% of the gamma-cyclodextrin, the usage amount of the starch short chain seed crystal is 3wt% of the gamma-cyclodextrin, the solvent of the propylene glycol dicaprylate solution is an absolute ethyl alcohol solution with the mass fraction of 50wt%, the propylene glycol dicaprylate solution contains 4wt% of propylene glycol dicaprylate, and the usage amount of the propylene glycol dicaprylate solution enables the propylene glycol dicaprylate to be 2wt% of the gamma-cyclodextrin.
Preparing a composite separation membrane: adding polyether copolyamide into DMF, stirring, mixing and dissolving to obtain a polyether copolyamide solution, adding cyclodextrin-MOF dispersion liquid, stirring and mixing uniformly to obtain a membrane casting solution, transferring the membrane casting solution into a mold, drying for 9h at the temperature of 50 ℃ to obtain a composite membrane, and then drying for 12h in vacuum at the temperature of 50 ℃ to obtain the composite separation membrane. The polyether copolyamide solution contains 6wt% of polyether copolyamide, the solvent of the cyclodextrin-MOF dispersion liquid is DMF, the cyclodextrin-MOF dispersion liquid contains 4wt% of cyclodextrin-MOF, and the usage amount of the cyclodextrin-MOF dispersion liquid is 25wt% of the polyether copolyamide.
Example 3:
a preparation method of a novel polyamide composite separation membrane,
preparing the bi-terminal acyl chloride polyethylene glycol: adding polyethylene glycol into dichloromethane in the nitrogen atmosphere, stirring, mixing and dissolving to obtain a polyethylene glycol solution, adding triethylamine, stirring and mixing uniformly, adding an isophthaloyl dichloride solution at the temperature of 0 ℃, and reacting at the temperature of 40 ℃ for 8 hours after the addition is finished to obtain a bi-terminal acyl chloride polyethylene glycol solution. The polyethylene glycol solution contains 10wt% of polyethylene glycol, the use amount of triethylamine is 60wt% of polyethylene glycol, the solvent of the isophthaloyl chloride solution is dichloromethane, the isophthaloyl chloride solution contains 4wt% of isophthaloyl chloride, and the use amount of the isophthaloyl chloride solution enables the isophthaloyl chloride to be 110% of the use molar amount of the polyethylene glycol.
Preparation of polyether copolyamide: adding 1,4 bis (3-aminopropyl) piperazine solution into bis (3-aminopropyl) polyethylene glycol bi-terminal chloride solution at the temperature of 0 ℃, reacting for 8 hours at the temperature of 40 ℃ after the addition is finished, extracting with deionized water, standing for 24 hours, separating liquid to remove a water phase, adding glacial ethyl ether to precipitate, washing and drying to obtain the polyether copolyamide. The solvent of the 1,4 bis (3-aminopropyl) piperazine solution was dichloromethane, and the 1,4 bis (3-aminopropyl) piperazine solution was used in such an amount that 1,4 bis (3-aminopropyl) piperazine was 110% of the molar amount of the initial polyethylene glycol used.
Preparation of starch short chain seed crystal: adding waxy corn starch into a phosphate buffer solution, stirring for 40min at the temperature of 90 ℃, then cooling to 50 ℃, adding pullulanase, carrying out enzymolysis for 8h, centrifuging for 5min at the speed of 4000r/min after the enzymolysis is finished, taking supernatant liquid, carrying out enzyme deactivation treatment, adding ethanol to precipitate, centrifuging at the speed of 11000r/min, collecting precipitate, and carrying out freeze drying to obtain the starch short-chain seed crystal. The pH of the phosphate buffer solution is 5, the using amount of the waxy corn starch is 9wt% of the phosphate buffer solution, the using amount of the pullulanase is based on the dry weight of the waxy corn starch, and the using amount of the pullulanase is 40U/g of the dry weight of the waxy corn starch.
Preparation of cyclodextrin-MOF: adding gamma-cyclodextrin and an alkaline reagent into deionized water, then adding starch short chain seed crystals, performing ultrasonic dispersion, passing through a 0.45-micron water system film, standing at the temperature of 50 ℃ for 6 hours, then adding methanol to separate out a precipitate, centrifuging at 5000r/min, collecting the precipitate, washing with methanol, drying, adding a propylene glycol dicaprylate solution to treat for 5 hours, and performing freeze drying to obtain the cyclodextrin-MOF. The usage amount of the gamma-cyclodextrin is 3wt% of deionized water, the alkaline reagent is potassium hydroxide, the usage amount of the alkaline reagent is 30wt% of the gamma-cyclodextrin, the usage amount of the starch short chain seed crystal is 3wt% of the gamma-cyclodextrin, the solvent of the propylene glycol dicaprylate solution is an absolute ethyl alcohol solution with the mass fraction of 50wt%, the propylene glycol dicaprylate solution contains 4wt% of propylene glycol dicaprylate, and the usage amount of the propylene glycol dicaprylate solution enables the propylene glycol dicaprylate to be 2wt% of the gamma-cyclodextrin.
Preparing a composite separation membrane: adding polyether copolyamide into DMF, stirring, mixing and dissolving to obtain a polyether copolyamide solution, adding cyclodextrin-MOF dispersion, adding 2-acetoxyl-9-octadecenoic acid methyl ester, stirring and mixing uniformly to obtain a membrane casting solution, transferring the membrane casting solution into a mold, drying for 9h at the temperature of 50 ℃ to obtain a composite membrane, and then drying for 12h in vacuum at the temperature of 50 ℃ to obtain the composite separation membrane. The polyether copolyamide solution contains 6wt% of polyether copolyamide, the solvent of the cyclodextrin-MOF dispersion liquid is DMF, the cyclodextrin-MOF dispersion liquid contains 4wt% of cyclodextrin-MOF, the usage amount of the cyclodextrin-MOF dispersion liquid is 25wt% of the polyether copolyamide, and the usage amount of the 2-acetoxy-9-octadecenoic acid methyl ester is 0.5wt% of the polyether copolyamide.
Example 4:
a preparation method of a novel polyamide composite separation membrane,
preparing the bi-terminal acyl chloride polyethylene glycol: adding polyethylene glycol into dichloromethane in a nitrogen atmosphere, stirring, mixing and dissolving to obtain a polyethylene glycol solution, adding triethylamine, stirring and mixing uniformly, adding an isophthaloyl dichloride solution at the temperature of 0 ℃, and after the addition is finished, reacting for 8 hours at the temperature of 40 ℃ to obtain a bi-terminal acyl chloride polyethylene glycol solution. The polyethylene glycol solution contains 10wt% of polyethylene glycol, the triethylamine is used in an amount of 60wt% of the polyethylene glycol, the isophthaloyl chloride solution is dichloromethane in a solvent, the isophthaloyl chloride solution contains 4wt% of isophthaloyl chloride, and the isophthaloyl chloride solution is used in an amount of 110% of the molar amount of the polyethylene glycol.
Preparation of polyether copolyamide: adding 1,4 bis (3-aminopropyl) piperazine solution into bis (3-aminopropyl) polyethylene glycol bi-terminal chloride solution at the temperature of 0 ℃, reacting for 8 hours at the temperature of 40 ℃ after the addition is finished, extracting with deionized water, standing for 24 hours, separating liquid to remove a water phase, adding glacial ethyl ether to precipitate, washing and drying to obtain the polyether copolyamide. The solvent of the 1,4 bis (3-aminopropyl) piperazine solution was dichloromethane, and the 1,4 bis (3-aminopropyl) piperazine solution was used in such an amount that 1,4 bis (3-aminopropyl) piperazine was 110% of the molar amount of the initial polyethylene glycol used.
Preparation of starch short chain seed crystal: adding waxy corn starch into a phosphate buffer solution, stirring for 40min at the temperature of 90 ℃, then cooling to 50 ℃, adding pullulanase, carrying out enzymolysis for 8h, centrifuging for 5min at the speed of 4000r/min after the enzymolysis is finished, taking supernatant liquid, carrying out enzyme deactivation treatment, adding ethanol to precipitate, centrifuging at the speed of 11000r/min, collecting precipitate, and carrying out freeze drying to obtain the starch short-chain seed crystal. The pH of the phosphate buffer solution is 5, the using amount of the waxy corn starch is 9wt% of the phosphate buffer solution, the using amount of the pullulanase is based on the dry weight of the waxy corn starch, and the using amount of the pullulanase is 40U/g of the dry weight of the waxy corn starch.
Preparation of cyclodextrin-MOF: adding gamma-cyclodextrin and an alkaline reagent into deionized water, then adding starch short chain seed crystals, performing ultrasonic dispersion, passing through a 0.45-micron water system film, standing at the temperature of 50 ℃ for 6 hours, then adding methanol to separate out a precipitate, centrifuging at 5000r/min, collecting the precipitate, washing with methanol, drying, adding a propylene glycol dicaprylate solution to treat for 5 hours, and performing freeze drying to obtain the cyclodextrin-MOF. The usage amount of the gamma-cyclodextrin is 3wt% of deionized water, the alkaline reagent is potassium hydroxide, the usage amount of the alkaline reagent is 30wt% of the gamma-cyclodextrin, the usage amount of the starch short chain seed crystal is 3wt% of the gamma-cyclodextrin, the solvent of the propylene glycol dicaprylate solution is an absolute ethyl alcohol solution with the mass fraction of 50wt%, the propylene glycol dicaprylate solution contains 4wt% of propylene glycol dicaprylate, and the usage amount of the propylene glycol dicaprylate solution enables the propylene glycol dicaprylate to be 2wt% of the gamma-cyclodextrin.
Preparing a composite separation membrane: adding polyether copolyamide into DMF, stirring, mixing and dissolving to obtain a polyether copolyamide solution, adding cyclodextrin-MOF dispersion, adding 2-acetoxy-9-octadecenoic acid methyl ester, stirring and mixing uniformly to obtain a membrane casting solution, transferring the membrane casting solution into a mold, drying for 9 hours at the temperature of 50 ℃ to obtain a composite membrane, and then drying for 12 hours at the temperature of 50 ℃ in vacuum to obtain the composite separation membrane. The polyether copolyamide solution contains 6wt% of polyether copolyamide, the solvent of the cyclodextrin-MOF dispersion liquid is DMF, the cyclodextrin-MOF dispersion liquid contains 4wt% of cyclodextrin-MOF, the usage amount of the cyclodextrin-MOF dispersion liquid is that the cyclodextrin-MOF is 25wt% of the polyether copolyamide, and the usage amount of the 2-acetoxy-9-octadecenoic acid methyl ester is 0.9wt% of the polyether copolyamide.
Comparative example 1:
a preparation method of a novel polyamide composite separation membrane,
this comparative example differs from example 2 only in that the amount of propylene glycol dicaprylate solution used in the preparation of the cyclodextrin-MOF was such that the propylene glycol dicaprylate was 0.2wt% of the gamma-cyclodextrin.
Comparative example 2:
a preparation method of a novel polyamide composite separation membrane,
this comparative example differs from example 2 only in that the amount of propylene glycol dicaprylate solution used in the preparation of the cyclodextrin-MOF was such that the propylene glycol dicaprylate was 4wt% of the gamma-cyclodextrin.
Comparative example 3:
a preparation method of a novel polyamide composite separation membrane,
this comparative example is compared to example 2, only with the difference that in the preparation of cyclodextrin-MOF, the propylene glycol dicaprylate solution was replaced with the same weight of solvent.
Test example:
1. infrared spectroscopic analysis
Test samples: example 2 the resulting cyclodextrin-MOF was prepared.
The infrared spectrogram of the cyclodextrin-MOF prepared in example 2 of the invention is shown in figure 1, wherein the infrared spectrogram is 3000-3700cm -1 The infrared absorption peak of hydroxyl is 2800-3000cm -1 The infrared absorption peak of methyl and methylene is between 1685 cm -1 The infrared absorption peak of the carbon-oxygen double bond is located at 1035 cm -1 The infrared absorption peak of carbon-oxygen carbon shows that the cyclodextrin-MOF containing propylene glycol dicaprylate is obtained.
2. Mechanical Property test
Test samples: the composite separation membranes prepared in the respective examples and comparative examples were manufactured to a size specification of 5X 0.5 cm.
The mechanical properties of the above test samples were measured using an electronic universal tester.
The tensile strength test results of the composite separation membrane prepared by the present invention are shown in fig. 2, wherein a is example 1, b is example 2, c is example 3, d is example 4, e is comparative example 1, f is comparative example 2, g is comparative example 3, the tensile strength of the composite separation membrane prepared by example 1 is 3.36MPa, the tensile strength of the composite separation membrane prepared by example 2 is 3.39MPa, the tensile strength of the composite separation membrane prepared by comparative example 1 is 3.28MPa, the tensile strength of the composite separation membrane prepared by comparative example 2 is 3.22MPa, the tensile strength of the composite separation membrane prepared by comparative example 3 is 3.19MPa, and the tensile strength of the composite separation membrane prepared by the method of example 2 is the best as compared with comparative examples 1-3, compared with the comparative example 3, the tensile strength of the composite separation membrane prepared in the example 2 is improved by 6.27%, which shows that when a proper amount of propylene glycol dicaprylate is added in the preparation of the cyclodextrin-MOF, and then the cyclodextrin-MOF containing the propylene glycol dicaprylate is used for preparing the composite separation membrane, the tensile strength of the composite separation membrane is improved, while the propylene glycol dicaprylate is used in an excessively high or excessively low amount, and after the cyclodextrin-MOF containing the propylene glycol dicaprylate is used for preparing the composite separation membrane, the tensile property of the composite separation membrane is slightly improved compared with that of the cyclodextrin-MOF not containing the propylene glycol dicaprylate; the tensile strength of the composite separation membrane prepared in example 3 was 3.51MPa, the tensile strength of the composite separation membrane prepared in example 4 was 3.57MPa, and the tensile strength of the composite separation membrane prepared in example 3-4 was 5.31% higher than that of example 2 due to the use of methyl 2-acetoxy-9-octadecenoate, and the tensile strength of the composite separation membrane prepared in example 4 was greatly increased compared to that of comparative example 3 due to the further addition of methyl 2-acetoxy-9-octadecenoate after the appropriate amount of cyclodextrin-MOF of propylene glycol dicaprylate was used.
The elongation at break test results of the composite separation membrane prepared by the present invention are shown in fig. 3, wherein a is example 1, b is example 2, c is example 3, d is example 4, e is comparative example 1, f is comparative example 2, g is comparative example 3, the elongation at break of the composite separation membrane prepared by example 1 is 281%, the elongation at break of the composite separation membrane prepared by example 2 is 286%, the elongation at break of the composite separation membrane prepared by comparative example 1 is 270%, the elongation at break of the composite separation membrane prepared by comparative example 2 is 268%, the elongation at break of the composite separation membrane prepared by comparative example 3 is 265%, and the elongation at break of the composite separation membrane prepared by example 2 is the best as compared with comparative examples 1-3, and the elongation at break of the composite separation membrane prepared by example 2 is increased by 7.92% as compared with comparative example 3, indicating that when cyclodextrin-MOF is prepared, a suitable amount of propylene glycol dicaprylate is added, and then the cyclodextrin-MOF containing propylene glycol dicaprylate is used for preparing the composite separation membrane, the MOF containing only a slightly increased amount of propylene glycol dicaprylate after the composite separation membrane is prepared, and the MOF containing high or the MOF containing propylene glycol dicaprylate is used for preparing the composite separation membrane containing a composite separation membrane containing high elongation at which is slightly increased after the elongation at break of propylene glycol-MOF containing propylene glycol dicaprylate; the elongation at break of the composite separation membrane prepared in example 3 was 296%, the elongation at break of the composite separation membrane prepared in example 4 was 301%, and the use of methyl 2-acetoxy-9-octadecenoate in examples 3-4 showed that the elongation at break of the composite separation membrane was increased as compared with example 2, the elongation at break of the composite separation membrane prepared in example 4 was 5.24% higher than that of example 2, and the elongation at break of the composite separation membrane prepared in example 3 was greatly increased as compared with comparative example 3 by further adding methyl 2-acetoxy-9-octadecenoate after using a suitable amount of cyclodextrin-MOF of propylene glycol dicaprylate.
The composite separation membrane prepared by the invention has good mechanical property, the tensile strength is 3.3-3.7MPa, and the elongation at break is 275-300%.
3. Water flux test
Test samples: the composite separation membranes obtained in the respective examples and comparative examples were prepared.
The test sample is made into a round shape according to the diameter of the mouth of the ultrafiltration cup, the round test sample is filled into the ultrafiltration cup, deionized water is filled into the ultrafiltration cup, nitrogen is used as driving pressure, the pressure is adjusted to be 0.15MPa, the deionized water is pre-pressed for 20min, then the pressure is adjusted to be 0.1MPa, and the volume of the passing deionized water within 3h is tested.
The water flux is calculated as follows:
water flux = permeate water volume/(membrane effective area x time).
The results of the water flux test of the composite separation membrane prepared according to the present invention are shown in FIG. 4, wherein A is example 1, B is example 2, C is example 3, D is example 4, E is comparative example 1, F is comparative example 2, G is comparative example 3, and the water flux of the composite separation membrane prepared according to example 1 is 149 L.m -2 h -1 The water flux of the composite separation membrane prepared in example 2 was 154L · m -2 h -1 The composite separation membrane prepared in comparative example 1 had a water flux of 134 L.m -2 h -1 In comparative example 2, the water flux of the composite separation membrane was 133L · m -2 h -1 Comparative example 3 the composite separation membrane prepared in comparative example 3 had a water flux of 130 L.m -2 h -1 Compared with the comparative examples 1 to 3, the water flux of the composite separation membrane prepared by the method in example 2 is optimal, and compared with the comparative example 3, the water flux of the composite separation membrane prepared by example 2 is improved by 18.46%, which shows that after the cyclodextrin-MOF containing the propylene glycol dicaprylate is used for preparing the composite separation membrane, the water flux of the composite separation membrane is improved, the propylene glycol dicaprylate is used in an excessively high or excessively low amount, and the water flux of the composite separation membrane is slightly improved after the cyclodextrin-MOF containing the propylene glycol dicaprylate is used for preparing the composite separation membrane; the water flux of the composite separation membrane prepared in example 3 was 161L · m -2 h -1 The composite separation membrane prepared in example 4 had a water flux of 166L · m -2 h -1 In comparison with example 2, examples 3 to 4 show that the use of 2-acetoxy-9-octadecenoic acid methyl ester improves the water flux of the composite separation membrane, compared with example 2, the water flux of the composite separation membrane prepared in example 4 is improved by 7.79%, compared with comparative example 3, the water flux of the composite separation membrane obtained after adding 2-acetoxy-9-octadecenoic acid methyl ester after using a proper amount of cyclodextrin-MOF of propylene glycol dicaprylate is greatly enhanced.
The composite separation membrane prepared by the invention has high water flux which is 145-170 L.m -2 h -1 。
4. Oil-water emulsion separation Performance test
Test samples: the composite separation membranes obtained in the respective examples and comparative examples were prepared.
Adding soybean oil and lauryl sodium sulfate into deionized water, and stirring and mixing to obtain an oil-water emulsion. The oil-water emulsion was tested according to the water flux test method. The absorbance at 200nm was measured using an ultraviolet spectrophotometer. The oil-water emulsion contains 1wt% of soybean oil, and the usage amount of the sodium dodecyl sulfate is 20wt% of the soybean oil.
The rejection of the membrane is calculated as follows:
retention = (1-percolate absorbance/initial emulsion absorbance) × 100%.
The oil-water separation performance of the composite separation membrane prepared by the invention is shown in fig. 5, wherein A is example 1, B is example 2, C is example 3, D is example 4, E is comparative example 1, F is comparative example 2, G is comparative example 3, the oil-water separation performance of the composite separation membrane obtained in each example is more than 95%, and the composite separation membrane has good oil-water separation performance.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A preparation method of a novel polyamide composite separation membrane comprises the following steps:
preparing double-end acyl chloride polyethylene glycol from polyethylene glycol and isophthaloyl dichloride, and then preparing polyether copolyamide from the double-end acyl chloride polyethylene glycol and 1,4 bis (3-aminopropyl) piperazine;
preparing gamma-cyclodextrin and starch short chain seed crystals to obtain cyclodextrin-MOF, wherein the starch short chain seed crystals are obtained by performing enzymolysis treatment on waxy corn starch by pullulanase, and the cyclodextrin-MOF contains propylene glycol dicaprylate;
mixing polyether copolyamide and cyclodextrin-MOF in a solvent to prepare a membrane casting solution, and drying in a mold to obtain the composite separation membrane.
2. The method for preparing a novel polyamide composite separation membrane according to claim 1, characterized in that: the using amount of the propylene glycol dicaprylate is 0.4-3.6wt% of the gamma-cyclodextrin.
3. The method for preparing a novel polyamide composite separation membrane according to claim 1, characterized in that: the using amount of the starch short chain seed crystal is 1.5-6.0wt% of the gamma-cyclodextrin.
4. The method for preparing a novel polyamide composite separation membrane according to claim 1, wherein the method comprises the following steps: the usage amount of the cyclodextrin-MOF is 10-30wt% of the polyether copolyamide.
5. The method for preparing a novel polyamide composite separation membrane according to claim 1, wherein the method comprises the following steps: in the preparation of the cyclodextrin-MOF, gamma-cyclodextrin, starch short chain seed crystal and alkaline reagent are treated and dried in deionized water, then propylene glycol dicaprylate solution is added, and standing treatment is carried out at the temperature of 40-60 ℃.
6. The method for preparing a novel polyamide composite separation membrane according to claim 1, characterized in that: the solvent is DMF.
7. The method for preparing a novel polyamide composite separation membrane according to claim 1, characterized in that: the composite separation membrane contains 2-acetoxyl-9-octadecenoic acid methyl ester.
8. A novel polyamide composite separation membrane produced by the method according to any one of claims 1 to 6.
9. The cyclodextrin-MOF of claim 1.
10. Use of a cyclodextrin-MOF of claim 1 in the preparation of a composite separation membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211198695.XA CN115414795B (en) | 2022-09-29 | 2022-09-29 | Preparation method of novel polyamide composite separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211198695.XA CN115414795B (en) | 2022-09-29 | 2022-09-29 | Preparation method of novel polyamide composite separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115414795A true CN115414795A (en) | 2022-12-02 |
| CN115414795B CN115414795B (en) | 2024-02-20 |
Family
ID=84205403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211198695.XA Active CN115414795B (en) | 2022-09-29 | 2022-09-29 | Preparation method of novel polyamide composite separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115414795B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070209506A1 (en) * | 2006-03-10 | 2007-09-13 | Chunqing Liu | Flexible Template-Directed Microporous Partially Pyrolyzed Polymeric Membranes |
| CN107151329A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院上海药物研究所 | The fast synthesis method of cyclodextrin-metal-organic framework materials |
| WO2021001727A1 (en) * | 2019-07-03 | 2021-01-07 | King Abdullah University Of Science And Technology | Solution processable metal-organic frameworks via surface functionalization |
| CN113546522A (en) * | 2021-08-10 | 2021-10-26 | 大连理工大学盘锦产业技术研究院 | Preparation method of reinforced Pebax mixed matrix membrane |
| CN113893691A (en) * | 2021-11-09 | 2022-01-07 | 白银图微新材料科技有限公司 | Method for preparing nanofiltration membrane by interfacial polymerization modified poly (amino) sulfate |
| CN115109322A (en) * | 2022-06-20 | 2022-09-27 | 宁波大学 | Preparation method and application of gamma-cyclodextrin metal-organic framework film loaded with terpinene-4-alcohol |
-
2022
- 2022-09-29 CN CN202211198695.XA patent/CN115414795B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070209506A1 (en) * | 2006-03-10 | 2007-09-13 | Chunqing Liu | Flexible Template-Directed Microporous Partially Pyrolyzed Polymeric Membranes |
| CN107151329A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院上海药物研究所 | The fast synthesis method of cyclodextrin-metal-organic framework materials |
| WO2021001727A1 (en) * | 2019-07-03 | 2021-01-07 | King Abdullah University Of Science And Technology | Solution processable metal-organic frameworks via surface functionalization |
| CN113546522A (en) * | 2021-08-10 | 2021-10-26 | 大连理工大学盘锦产业技术研究院 | Preparation method of reinforced Pebax mixed matrix membrane |
| CN113893691A (en) * | 2021-11-09 | 2022-01-07 | 白银图微新材料科技有限公司 | Method for preparing nanofiltration membrane by interfacial polymerization modified poly (amino) sulfate |
| CN115109322A (en) * | 2022-06-20 | 2022-09-27 | 宁波大学 | Preparation method and application of gamma-cyclodextrin metal-organic framework film loaded with terpinene-4-alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115414795B (en) | 2024-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6574061B2 (en) | Filtration membrane production method using naphthoquinone mixture | |
| CN111004411B (en) | Preparation method of biomass-based molecularly imprinted composite membrane for selectively separating tetracycline | |
| CN102229681A (en) | Preparation method for producing heparin sodium by using porcine small intestines | |
| CN109174023A (en) | A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application | |
| CN106749689B (en) | The whisker modified difunctional photoinitiator and preparation method thereof of nano-cellulose | |
| CN108744974A (en) | A kind of nano-material modified organic solvent nanofiltration film of cyclodextrin grafting fiber and preparation method thereof | |
| CA3127968A1 (en) | Amphoteric biomass-based hyperbranched adsorption material to multiple heavy metal ions and preparation method and use thereof | |
| CN114669196B (en) | Method for hydrophilically modifying microporous membrane surface based on bionic adhesive and amine oxide | |
| CN108636360A (en) | A kind of preparation method and application of functionalized nano iron sulfide | |
| CN115414795A (en) | Preparation method of novel polyamide composite separation membrane | |
| CN112915808A (en) | Clustering rotaxane membrane, preparation method and application in separation of biodiesel wastewater | |
| CN112058100A (en) | Preparation method of filtering membrane applied to sewage treatment | |
| CN111646660A (en) | Method for extracting microbial extracellular polymer from nitrified sludge | |
| CN115475525B (en) | Method for purifying biological dust suppressant by double-stage ultrafiltration | |
| CN113582283B (en) | Micro-nano bubble surface function modifier and air-flotation-enhanced water purification method thereof | |
| Guan et al. | Construction of dual-functional membrane with novel structured β-cyclodextrin hybridization for simultaneous oily wastewater separation and hazardous aromatics removal | |
| CN109456422A (en) | A kind of hyperbranched hemicellulose polymer and its preparation method and application | |
| CN109331784B (en) | Monosubstituted beta-cyclodextrin derivative for removing organic pollutants in water and preparation and use method thereof | |
| CN102815809B (en) | A kind of method and system thereof processing high chlorine mercury containing waste water in chlor-alkali industry | |
| CN110105467A (en) | A kind of polymer material and preparation method thereof for formaldehyde adsorption | |
| CN108421535A (en) | A kind of method of cellulose/hectorite hybrid composite material purification organic wastewater containing phenol | |
| CN114904400B (en) | Preparation method and application of TCPP@HPAMM@PA/PVDF dual-function composite membrane | |
| CN114130226B (en) | Modified polyvinylidene fluoride oil-water separation membrane and application thereof in sewage treatment | |
| CA1097833A (en) | Polyvinyl butyraldehyde binder used in paint and varnish | |
| CN111087603B (en) | Preparation method of pentaerythritol block polyether with high defoaming capability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240126 Address after: No. 18 Weiting Tonghe Road, Suzhou Industrial Park, Suzhou City, Jiangsu Province, 215000 Applicant after: Suzhou Xingrui packaging material Co.,Ltd. Country or region after: China Address before: No. 2, Shanjiao Group, Shuitang Village, Changshi Town, Dafang County, Bijie City, Guizhou Province, 551700 Applicant before: Wang Caiguang Country or region before: China |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |