CN114797505A - Preparation method of loose polyamine aqueous phase solution and hollow fiber composite nanofiltration membrane - Google Patents
Preparation method of loose polyamine aqueous phase solution and hollow fiber composite nanofiltration membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 144
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 69
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 69
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 65
- 229920000768 polyamine Polymers 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000012074 organic phase Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 115
- 210000004379 membrane Anatomy 0.000 claims description 76
- 210000002469 basement membrane Anatomy 0.000 claims description 48
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 26
- 239000001099 ammonium carbonate Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 238000002791 soaking Methods 0.000 claims description 21
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 20
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 14
- 229920002873 Polyethylenimine Polymers 0.000 claims description 12
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 9
- 239000004067 bulking agent Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims 2
- 230000004907 flux Effects 0.000 abstract description 21
- 238000010612 desalination reaction Methods 0.000 abstract description 14
- 230000035699 permeability Effects 0.000 abstract description 8
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000002585 base Substances 0.000 description 29
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- 238000007664 blowing Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 238000000108 ultra-filtration Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- 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
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a loose polyamine aqueous phase solution, a hollow fiber composite nanofiltration membrane and a preparation method thereof, aiming at improving the permeability of the hollow fiber nanofiltration membrane. A loose polyamine aqueous phase solution is prepared by dissolving a loosening agent and a polyamine monomer in water. The hydrophobic polyamine aqueous phase solution and the polybasic acyl chloride organic phase solution are subjected to interfacial polymerization reaction on a base membrane, and then the hollow fiber composite nanofiltration membrane is prepared by two times of heat treatment. The loose aqueous phase solution and the preparation method of the hollow fiber composite nanofiltration provided by the invention can prevent the permeability of the hollow fiber composite nanofiltration membrane from being reduced due to excessive shrinkage, and can enlarge the aperture of the hollow fiber composite nanofiltration membrane so as to improve the permeability of the hollow fiber composite nanofiltration membrane. Finally, the water flux of the hollow fiber composite nanofiltration membrane can be improved under the condition of not influencing the desalination rate.
Description
Technical Field
The invention relates to the field of filter membrane materials, in particular to a loose polyamine aqueous phase solution, a preparation method of a hollow fiber composite nanofiltration membrane and the hollow fiber composite nanofiltration membrane.
Background
The water flux is an important performance index of the current nanofiltration membrane technology, the current mainstream hollow fiber nanofiltration membrane has limitations in internal space design and flow channel distribution, the water flux is difficult to improve, the pressure compensation water flux can be improved only through external force, and the operation energy consumption can be increased. The problem of irreversible membrane performance attenuation caused by membrane pollution is also faced in long-term operation, and the element replacement cost is increased. In view of the fact that the performance of the current hollow fiber nanofiltration membrane is close to the limit, the hollow fiber nanofiltration membrane with higher treatment efficiency can be developed by breakthrough innovation from the aspect of membrane materials.
Disclosure of Invention
The first purpose of the invention is to provide a loose polyamine aqueous phase solution, and the preparation method of the loose polyamine aqueous phase solution comprises the steps of dissolving a loosening agent and a polyamine monomer in water to prepare the loose polyamine aqueous phase solution.
In one embodiment, the bulking agent is one or more of ammonium bicarbonate, ammonium carbonate, and ammonium chloride.
As an embodiment, the mass concentration fraction of the bulking agent in the loose polyamine aqueous phase solution is 1.00% -5.00% or 2.00% -3.00%.
In one embodiment, the polyamine monomer has a mass fraction in the aqueous solution of 0.20% to 2.00% or 0.50% to 2.00%.
In one embodiment, the polyamine monomer may be selected from one or more of piperazine, polyethyleneimine, m-phenylenediamine and p-phenylenediamine.
The second purpose of the invention is to provide a preparation method of the hollow fiber composite nanofiltration membrane, which comprises the following steps: firstly, placing a base membrane in the loose polyamine aqueous phase solution for soaking for one time to form the base membrane with the loose polyamine aqueous phase solution on the surface; secondly, placing the base membrane with the loose polyamine aqueous phase solution on the surface into a polybasic acyl chloride organic phase solution for secondary soaking, taking out after secondary soaking, and then sequentially carrying out two times of heat treatment at the temperature lower than the decomposition temperature of a loosening agent and the temperature higher than the decomposition temperature of the loosening agent to finally obtain the hollow fiber nanofiltration composite membrane; wherein, the polybasic acyl chloride organic phase solution is prepared by dissolving polybasic acyl chloride monomer in organic solvent.
In one embodiment, the polyamine monomer may be selected from one or more of piperazine, polyethyleneimine, m-phenylenediamine and p-phenylenediamine.
As an embodiment, the poly-acid chloride monomer may be selected from one or more of terephthaloyl chloride, isophthaloyl chloride, trimesoyl chloride.
In one embodiment, the polyamine monomer is Polyethyleneimine (PEI), the polyacyl chloride monomer is trimesoyl chloride (TMC), and the reactants of the second soaking (interfacial polymerization) are as follows,
the product of the second soaking (interfacial polymerization) is as follows,
according to the method, ammonium carbonate (hydrogen) salts or ammonium chloride with decomposition temperature are taken as bulking agents and introduced into the process of preparing the nanofiltration membrane through interfacial polymerization reaction. The loosening agent is not decomposed or is slightly decomposed at the temperature lower than the decomposition temperature, the solvent in the aqueous phase solution and the organic phase solution on the interface of the hollow fiber composite nanofiltration membrane is dried, the residual loosening agent (which can account for 50-100% of the total mass of the initially added loosening agent in some embodiments) is crystallized out and filled or attached to the pores of the hollow fiber composite nanofiltration membrane, and the hollow fiber composite nanofiltration membrane is prevented from shrinking during solvent removal (water in the aqueous phase solution and alkane solvent in the organic phase solution) so that the pore diameter is reduced, thereby reducing the permeability (water flux). When the loosening agent is higher than the decomposition temperature and lower than the membrane component failure temperature (higher than the membrane component failure temperature, the loosening agent can damage the hollow fiber composite nanofiltration membrane), the residual loosening agent can be quickly decomposed to form a large amount of gas (ammonia gas, carbon dioxide or hydrochloric acid gas), and the large amount of gas can increase the aperture of the hollow fiber composite nanofiltration membrane, so that the density of the hollow fiber composite nanofiltration membrane layer is reduced (the aperture is smaller when the density is higher, and the aperture is larger when the density is lower), and the permeability (water flux) of the hollow fiber composite nanofiltration membrane is further improved. The salt rejection rate of the nanofiltration membrane is related to the composition and structure of the membrane, and in some embodiments, changing the membrane density slightly affects the salt rejection rate of the membrane, but significantly increases the permeability (water flux) of the membrane. In conclusion, the preparation method of the loose aqueous phase solution and the hollow fiber composite nanofiltration membrane can improve the water flux of the hollow fiber composite nanofiltration membrane without influencing the desalination rate.
As an embodiment, the basement membrane in the first step is washed by alkali liquor with the pH value of 8-12 before being soaked for one time.
Thus, the base film is soaked in a sodium hydroxide solution having a pH of 8 to 12, whereby oil-soluble impurities in the base film can be washed out.
As an implementation mode, the primary soaking time in the step one is 1-30 minutes; or 3-5 minutes.
As an embodiment, after the first soaking step, the basement membrane with the loose type polyamine aqueous phase solution is dried in the air for 1-30 minutes or 5-10 minutes, and the excessive loose type polyamine aqueous phase solution on the basement membrane is wiped dry.
In one embodiment, the base film material in the first step is one or more of polyamide, polyacrylonitrile, polysulfone, and polyvinylidene fluoride.
In one embodiment, in the second step, the mass fraction of the polybasic acyl chloride monomer in the organic phase solution of polybasic acyl chloride is 0.10% -0.50%, or 0.15% -0.40%.
In one embodiment, the solvent of the organic phase solution of the polybasic acyl chloride is one or more of pentane, hexane, cyclohexane and heptane.
As an implementation mode, the secondary soaking time in the step two is 1-20 minutes; or 2-5 minutes.
In the second step, after the second soaking, the mixture is taken out and kept for 10 to 60 minutes or 15 to 18 minutes at the temperature lower than the decomposition temperature of the bulking agent; and then keeping for 5-20 minutes or 6-8 minutes at the temperature higher than the decomposition temperature of the bulking agent and lower than the failure temperature of the membrane component. And finally, washing with water to obtain the hollow fiber composite nanofiltration membrane.
In some embodiments, the temperature of decomposition of the bulking agent is 80-120 ℃ and the membrane component failure temperature is 140-.
In the second step, the first air drying oven with the temperature of 50-90 ℃ is kept for 10-20 minutes or the second air drying oven with the temperature of 60-80 ℃ is kept for 15-18 minutes; then keeping the temperature in a second air-blast drying oven with the temperature of 100-140 ℃ for 5-10 minutes or keeping the temperature in a second air-blast drying oven with the temperature of 120-130 ℃ for 6-8 minutes. And finally, washing with water to obtain the hollow fiber composite nanofiltration membrane.
The fourth purpose of the invention is to provide the hollow fiber composite nanofiltration membrane, which is prepared by adopting the preparation method of the hollow fiber composite nanofiltration membrane.
The invention has the beneficial effects that:
after the hollow fiber composite nanofiltration membrane is formed into a membrane through interfacial polymerization reaction, the loosening agent is an inert substance and is remained on the membrane. Then, through two times of heat treatment, when the temperature of the loosening agent is lower than the decomposition temperature of the loosening agent, part of the loosening agent remains in the membrane and the membrane pores, and the phenomenon that the membrane permeability is reduced due to membrane formation and membrane pore shrinkage caused by solvent removal of the hollow fiber composite nanofiltration membrane is prevented; when the temperature is higher than the decomposition temperature of the loosening agent and lower than the failure temperature of membrane components, the residual loosening agent is accelerated to decompose to generate a large amount of gas (ammonia gas, carbon dioxide or hydrochloric acid gas), and the aperture of the hollow fiber composite nanofiltration membrane is enlarged, so that the permeability of the hollow fiber composite nanofiltration membrane is improved. In conclusion, the preparation method of the loose aqueous phase solution and the hollow fiber composite nanofiltration membrane can improve the water flux of the hollow fiber composite nanofiltration membrane without influencing the desalination rate.
Detailed Description
The method for testing the flux and the desalination rate of the hollow fiber nanofiltration membrane is as follows:
the prepared hollow fiber nanofiltration membrane is treated with 0.20 percent of magnesium sulfate (MgSO) with mass fraction of 0.31MPa 4 ) Prepressing the aqueous solution for half an hour, testing the hollow fiberThe water flux and the desalting performance of the composite nanofiltration membrane.
The calculation formula of the water flux is as follows:
wherein A ═ π DL (A-effective membrane area, unit is m) 2 (ii) a D-the average diameter (outer diameter) of the membrane filaments in m; the effective length of the L-membrane filaments, in m); t-the time required for collecting the Q volume of produced fluid, with the unit being h; q-volume of product fluid collected over time t in L.
The method for calculating the desalination rate of the membrane is as follows:
wherein, the salt rejection of the R-membrane, C f -the conductivity of the stock solution in μ S/cm; c p Conductivity of the produced water in μ S/cm.
The following specific examples describe the present invention in detail, however, the present invention is not limited to the following examples.
Example 1
Dissolving ammonium bicarbonate in water to prepare an ammonium bicarbonate aqueous phase solution with the mass fraction of 1.00%, adding piperazine monomer into the ammonium bicarbonate aqueous phase solution to ensure that the mass fraction of the piperazine monomer in the aqueous phase solution is 0.20%, and finally stirring to form the loose polyamine aqueous phase solution.
Example 2
Dissolving ammonium carbonate in water to prepare an ammonium carbonate aqueous phase solution with the mass fraction of 5.00%, adding a polyethyleneimine monomer into the ammonium carbonate aqueous phase solution to ensure that the mass fraction of the polyethyleneimine monomer in the aqueous phase solution is 2.00%, and finally stirring to form the loose polyamine aqueous phase solution.
Example 3
Dissolving ammonium bicarbonate in water to prepare an ammonium bicarbonate aqueous phase solution with the mass fraction of 2.00%, adding m-phenylenediamine monomer into the ammonium bicarbonate aqueous phase solution to ensure that the mass fraction of the m-phenylenediamine monomer in the aqueous phase solution is 1.00%, and finally stirring to form the loose polyamine aqueous phase solution.
Example 4
Dissolving ammonium carbonate in water to prepare an ammonium carbonate aqueous phase solution with the mass fraction of 4.00%, adding a p-phenylenediamine monomer into the ammonium carbonate aqueous phase solution to ensure that the mass fraction of the p-phenylenediamine monomer in the aqueous phase solution is 1.50%, and finally stirring to form the loose polyamine aqueous phase solution.
Example 5
Dissolving ammonium bicarbonate in water to prepare an ammonium bicarbonate aqueous phase solution with the mass fraction of 1.00%, adding piperazine monomer into the ammonium bicarbonate aqueous phase solution to ensure that the mass fraction of the piperazine monomer in the aqueous phase solution is 2.00%, and finally stirring to form the loose polyamine aqueous phase solution.
Example 6
Dissolving ammonium carbonate in water to prepare an ammonium carbonate aqueous phase solution with the mass fraction of 1.00%, adding a polyethyleneimine monomer into the ammonium carbonate aqueous phase solution to ensure that the mass fraction of the polyethyleneimine monomer in the aqueous phase solution is 0.80%, and finally stirring to form the loose polyamine aqueous phase solution.
Example 7
Dissolving ammonium bicarbonate in water to prepare an ammonium bicarbonate aqueous phase solution with the mass fraction of 3.00%, adding a p-phenylenediamine monomer into the ammonium bicarbonate aqueous phase solution to ensure that the mass fraction of the p-phenylenediamine monomer in the aqueous phase solution is 0.20%, and finally stirring to form the loose polyamine aqueous phase solution.
Example 8 (comparative example 1)
The preparation method comprises the steps of adopting a polyamide hollow fiber ultrafiltration basal membrane (the molecular weight cut-off is approximately equal to 30000-50000), and soaking the basal membrane in a sodium hydroxide solution (the pH value is 8-12). Preparing a piperazine monomer aqueous phase solution with the mass fraction of 0.20%. Then preparing a terephthaloyl chloride organic phase solution with the mass fraction of 0.10%, wherein the solvent is pentane. The base membrane cleaned by alkali liquor is firstly put into piperazine monomer aqueous phase solution and kept for 1 minute. The base film was then removed from the aqueous solution of piperazine monomer and hung vertically for 1 minute. Then immersing the basement membrane into the terephthaloyl chloride organic phase solution for 1 minute, then extracting the basement membrane from the terephthaloyl chloride organic phase solution, firstly placing the basement membrane into a first air-blowing drying oven at 50 ℃ for 10 minutes, then transferring the basement membrane into a second air-blowing drying oven at 100 ℃ for 5 minutes, and finally washing the basement membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane filaments is 98.7 percent, and the water flux is 13.1L/m 2 h。
Example 9 (comparative example 2)
Adopting polyacrylonitrile polyamide hollow fiber ultrafiltration basal membrane (the cut-off molecular weight is approximately equal to 30000-50000), and adding the basal membrane into sodium hydroxide solution (pH is 8-12) for soaking. Preparing a polyethyleneimine water-phase solution with the mass fraction of 2.00%. And preparing an isophthaloyl dichloride organic phase solution with the mass fraction of 0.50%, wherein the solvent is hexane. The basement membrane cleaned by alkali liquor is firstly put into the polyethyleneimine aqueous phase solution and kept for 10 minutes. The base film was then removed from the aqueous polyethyleneimine solution and hung vertically for 10 minutes. And then immersing the base membrane into the isophthaloyl dichloride organic phase solution for 8 minutes, then extracting the base membrane from the isophthaloyl dichloride organic phase solution, firstly placing the base membrane into a No. one air-blast drying oven at 90 ℃ for keeping for 20 minutes, then transferring the base membrane into a No. two air-blast drying oven at 140 ℃ for keeping for 10 minutes, and finally washing the base membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane filaments is 96.6 percent, and the water flux is 18.3L/m 2 h。
Example 10
The preparation method comprises the steps of adopting a polyamide hollow fiber ultrafiltration basal membrane (the molecular weight cut-off is approximately equal to 30000-50000), and soaking the basal membrane in a sodium hydroxide solution (the pH value is 8-12). An aqueous solution of the loose polyamine as in example 1 was prepared. Then preparing a terephthaloyl chloride organic phase solution with the mass fraction of 0.10%, wherein the solvent is pentane. The basement membrane cleaned by alkali liquor is firstly put into the loose polyamine aqueous phase solution and kept for 1 minute. The base film was then taken out of the loose polyamine aqueous solution and hung vertically for 1 minute. Then immersing the basement membrane into the terephthaloyl chloride organic phase solution for 1 minute, then extracting the basement membrane from the terephthaloyl chloride organic phase solution, firstly placing the basement membrane into a first air-blowing drying oven at 50 ℃ for 10 minutes, then transferring the basement membrane into a second air-blowing drying oven at 100 ℃ for 5 minutes, and finally washing the basement membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane filaments is 95.8 percent, and the water flux is 29.3L/m 2 h。
Example 11
Adopting polyacrylonitrile polyamide hollow fiber ultrafiltration basal membrane (the cut-off molecular weight is approximately equal to 30000-50000), and adding the basal membrane into sodium hydroxide solution (pH is 8-12) for soaking. An aqueous solution of the loose polyamine as in example 2 was prepared. And preparing an isophthaloyl dichloride organic phase solution with the mass fraction of 0.50%, wherein the solvent is hexane. The basement membrane cleaned by alkali liquor is firstly put into the loose polyamine aqueous phase solution and kept for 10 minutes. Then taking out the basement membrane from the loose polyamine aqueous phase solution, and vertically hanging for 10 minutes. And then immersing the base membrane into the isophthaloyl dichloride organic phase solution for 8 minutes, then extracting the base membrane from the isophthaloyl dichloride organic phase solution, firstly placing the base membrane into a No. one air-blast drying oven at 90 ℃ for keeping for 20 minutes, then transferring the base membrane into a No. two air-blast drying oven at 140 ℃ for keeping for 10 minutes, and finally washing the base membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the nano-filtration membrane wire has a desalination rate of 94.9% and a water flux of 38.6L/m 2 h。
Example 12
Polysulfone hollow fiber ultrafiltration basal membrane (the molecular weight cut-off is approximately equal to 30000-50000) is adopted, and the basal membrane is added into sodium hydroxide solution (pH is 8-12) for soaking. An aqueous solution of the loose polyamine as in example 3 was prepared. And preparing 0.20 mass percent trimesoyl chloride organic phase solution, wherein the solvent is cyclohexane. The basement membrane cleaned by alkali liquor is firstly put into the loose polyamine aqueous phase solution and kept for 5 minutes. Then taking out the basement membrane from the loose polyamine aqueous phase solution, and vertically hanging for 5 minutes. And then immersing the base membrane into the trimesoyl chloride organic phase solution for 4 minutes, then extracting the base membrane from the trimesoyl chloride organic phase solution, firstly placing the base membrane into a first air-blowing drying box at 60 ℃ for keeping for 15 minutes, then transferring the base membrane into a second air-blowing drying box at 120 ℃ for keeping for 7 minutes, and finally washing the base membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane filaments is 98.1 percent, and the water flux is 27.8L/m 2 h。
Example 13
The method comprises the steps of adopting a polyvinylidene fluoride hollow fiber ultrafiltration basal membrane (the cut-off molecular weight is approximately equal to 30000-50000), and adding the basal membrane into a sodium hydroxide solution (the pH value is 8-12) for soaking. An aqueous solution of the loose polyamine as in example 4 was prepared. And then preparing a terephthaloyl chloride organic phase solution with the mass fraction of 0.40%, wherein the solvent is heptane. The basement membrane cleaned by alkali liquor is firstly put into the loose polyamine aqueous phase solution and kept for 8 minutes. Then taking out the basement membrane from the loose polyamine aqueous phase solution, and vertically hanging for 7 minutes. Then immersing the basement membrane into the terephthaloyl chloride organic phase solution for 6 minutes, then extracting the basement membrane from the terephthaloyl chloride organic phase solution, firstly placing the basement membrane into a first air-blowing drying oven at 80 ℃ for keeping for 15 minutes, then transferring the basement membrane into a second air-blowing drying oven at 130 ℃ for keeping for 8 minutes, and finally washing the basement membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane filaments is 98.1 percent, and the water flux is 26.4L/m 2 h。
Example 14
The method comprises the steps of adopting a polyvinylidene fluoride hollow fiber ultrafiltration basal membrane (the cut-off molecular weight is approximately equal to 30000-50000), and adding the basal membrane into a sodium hydroxide solution (the pH value is 8-12) for soaking. An aqueous solution of the loose polyamine as in example 5 was prepared. And then preparing a terephthaloyl chloride organic phase solution with the mass fraction of 0.50%, wherein the solvent is pentane. The basement membrane cleaned by alkali liquor is firstly put into the loose polyamine aqueous phase solution and kept for 10 minutes. The base film was then taken out of the loose polyamine aqueous solution and hung vertically for 1 minute. Then immersing the basement membrane into the terephthaloyl chloride organic phase solution for 1 minute, then extracting the basement membrane from the terephthaloyl chloride organic phase solution, firstly placing the basement membrane into a first air-blowing drying oven at 90 ℃ for keeping for 20 minutes, then transferring the basement membrane into a second air-blowing drying oven at 100 ℃ for keeping for 5 minutes, and finally washing the basement membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane filaments is 95.8 percent, and the water flux is 33.2L/m 2 h。
Example 15
The method comprises the steps of adopting a polyvinylidene fluoride hollow fiber ultrafiltration base membrane (the molecular weight cut-off is approximately equal to 30000-50000), adding the base membrane into a sodium hydroxide solution (the pH value is 8-12), soaking, and washing out oil-soluble impurities in the base membrane for later use. An aqueous solution of the loose polyamine as in example 6 was prepared. And preparing an isophthaloyl dichloride organic phase solution with the mass fraction of 0.30%, wherein the solvent is cyclohexane. The basement membrane cleaned by alkali liquor is firstly put into the loose polyamine aqueous phase solution and kept for 1 minute. Then taking out the basement membrane from the loose polyamine aqueous phase solution, and vertically hanging for 5 minutes. Then immersing the basement membrane into the terephthaloyl chloride organic phase solution for 6 minutes, then extracting the basement membrane from the terephthaloyl chloride organic phase solution, firstly placing the basement membrane into a first air-blowing drying oven at 50 ℃ for keeping for 18 minutes, then transferring the basement membrane into a second air-blowing drying oven at 100 ℃ for keeping for 5 minutes, and finally washing the basement membrane with water to obtain the hollow fiber composite nanofiltration membrane.
At 25 deg.C and 0.31MPa pressure, in an amount of 0.20% by massFractional magnesium sulfate (MgSO) 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane filaments is 94.6 percent, and the water flux is 40.3L/m 2 h。
Example 16
Adopting polyacrylonitrile hollow fiber ultrafiltration basal membrane (the cut-off molecular weight is approximately equal to 30000-50000), adding the basal membrane into sodium hydroxide solution (pH is 8-12) for soaking, and washing out oil-soluble impurities in the basal membrane for later use. An aqueous solution of the loose polyamine as in example 7 was prepared. And preparing 0.10 mass percent trimesoyl chloride organic phase solution, wherein the solvent is heptane. The basement membrane cleaned by alkali liquor is firstly put into the loose polyamine aqueous phase solution and kept for 4 minutes. Then taking out the basement membrane from the loose polyamine aqueous phase solution, and vertically hanging for 7 minutes. Then immersing the basement membrane into the terephthaloyl chloride organic phase solution for 6 minutes, then extracting the basement membrane from the terephthaloyl chloride organic phase solution, firstly placing the basement membrane into a first air-blowing drying oven at 80 ℃ for keeping for 20 minutes, then transferring the basement membrane into a second air-blowing drying oven at 140 ℃ for keeping for 4 minutes, and finally washing the basement membrane with water to obtain the hollow fiber composite nanofiltration membrane.
Magnesium sulfate (MgSO) at 25 deg.C and 0.31MPa in 0.20% mass fraction 4 ) The aqueous solution is a test water sample, the separation performance of the membrane filaments is tested, and the obtained results are as follows: the desalination rate of the nanofiltration membrane yarn is 97.1 percent, and the water flux is 27.3L/m 2 h。
Examples 1 to 7 are the preparation process and method of the loose polyamine aqueous phase solution; examples 8-16 are hollow fiber composite nanofiltration membrane preparation and test results, as shown in table 1.
TABLE 1 influence of bulking agent on the Performance of hollow fiber composite nanofiltration membranes
The foregoing is only a few specific embodiments of the invention. The protection scope of the present invention is subject to the protection scope of the claims.
Claims (11)
1. The preparation method of the loose polyamine aqueous phase solution is characterized in that a loose polyamine aqueous phase solution is prepared by dissolving a loosening agent and a polyamine monomer in water.
2. A loose aqueous solution of a polyamine according to claim 1 wherein the bulking agent is one or more of ammonium bicarbonate, ammonium carbonate and ammonium chloride.
3. A loose aqueous solution of a polyamine according to claim 1 wherein the weight fraction of the bulking agent in the loose aqueous solution of a polyamine is 1.00% to 5.00%.
4. A loose aqueous polyamine solution according to claim 1 wherein the mass fraction of polyamine monomer in the loose aqueous polyamine solution is 0.20% to 2.00%.
5. The aqueous solution of a loose polyamine of claim 1 wherein the polyamine monomer is one or more of piperazine, polyethyleneimine, m-phenylenediamine and p-phenylenediamine.
6. The preparation method of the hollow fiber nanofiltration composite membrane is characterized by comprising the following steps:
firstly, placing a basement membrane into the loose polyamine aqueous phase solution as defined in any one of claims 1 to 5 for primary soaking to form the basement membrane with the loose polyamine aqueous phase solution on the surface;
secondly, placing the base membrane with the loose polyamine aqueous phase solution on the surface into a polybasic acyl chloride organic phase solution for secondary soaking, taking out after secondary soaking, and then sequentially carrying out two times of heat treatment at the temperature lower than the decomposition temperature of a loosening agent and the temperature higher than the decomposition temperature of the loosening agent to finally obtain the hollow fiber composite nanofiltration membrane; the polybasic acyl chloride organic phase solution is prepared by dissolving polybasic acyl chloride monomer in organic solvent.
7. The method for preparing a hollow fiber composite nanofiltration membrane according to claim 6, wherein the material of the base membrane in the first step is one or more of polyamide, polyacrylonitrile, polysulfone and polyvinylidene fluoride.
8. The method for preparing a hollow fiber composite nanofiltration membrane according to claim 6, wherein in the second step, the mass fraction of the polybasic acid chloride monomer in the polybasic acid chloride organic phase solution is 0.10% -0.50%.
9. The method for preparing the hollow fiber composite nanofiltration membrane according to claim 6, wherein the solvent of the polyacyl chloride organic phase solution is one or more of pentane, hexane, cyclohexane and heptane.
10. The method for preparing the hollow fiber composite nanofiltration membrane according to claim 6, wherein the poly-acyl chloride monomer is one or more of terephthaloyl chloride, isophthaloyl chloride and trimesoyl chloride.
11. The hollow fiber composite nanofiltration membrane is prepared by the preparation method of any one of claims 6 to 10.
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| CN105617875A (en) * | 2014-11-03 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof |
| CN106422811A (en) * | 2015-08-11 | 2017-02-22 | 贵阳时代沃顿科技有限公司 | Novel polyelectrolyte nanofiltration membrane and preparation method thereof |
| CN109603586A (en) * | 2018-11-16 | 2019-04-12 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system |
| CN110449045A (en) * | 2019-08-01 | 2019-11-15 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105617875A (en) * | 2014-11-03 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof |
| CN106422811A (en) * | 2015-08-11 | 2017-02-22 | 贵阳时代沃顿科技有限公司 | Novel polyelectrolyte nanofiltration membrane and preparation method thereof |
| CN109603586A (en) * | 2018-11-16 | 2019-04-12 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system |
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