CN110975622A - Novel charged nanofiltration membrane and preparation method thereof - Google Patents
Novel charged nanofiltration membrane and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention belongs to the technical field of nanofiltration membrane separation, and particularly relates to a novel charged nanofiltration membrane and a preparation method thereof. The method comprises the following steps: (1) dissolving piperazine, a charged modifier and an anti-pollution additive in water, then adding an alkaline catalyst, and adjusting the pH value of the solution to 10-12 to form a piperazine water phase solution; (2) dissolving trimesoyl chloride in an organic solvent to obtain a trimesoyl chloride oil phase solution; (3) soaking the porous base membrane in a piperazine water phase solution for 1-3min, then reacting in a trimesoyl chloride oil phase solution for 0.5-2min, and drying to obtain an initial nanofiltration membrane; (4) and soaking the initial nanofiltration membrane in the charged neutralizer water solution for 2-3min, and soaking in pure water for 1-2min to obtain the novel charged nanofiltration membrane. The novel charged nanofiltration membrane prepared by the invention has excellent water flux and pollution resistance under the low-pressure condition, and has great advantages in the separation of low-valence metal salt and high-valence metal salt.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membrane separation, and particularly relates to a novel charged nanofiltration membrane and a preparation method thereof.
Background
Along with the intensification of industrialization degree and the increase of world population in recent years, the problem of water resource shortage is increasing day by day, and in addition, the intensification of the treatment degree of water pollution by countries in the world in recent years promotes the rapid development of the fields of water resource recovery, seawater desalination and the like. The membrane method technology gradually becomes a mainstream technology in the field of water treatment due to the advantages of energy conservation, environmental protection, small occupied area, high recovery rate and the like. The nanofiltration membrane is a pressure driving membrane with the aperture between that of ultrafiltration and that of reverse osmosis membrane, mainly separates substances by means of aperture screening and surface charge rejection, has low rejection rate on monovalent salt and low molecular weight organic substances, and has the rejection rate on multiple salt and high molecular weight substances up to over 96 percent. At present, the method is widely applied to a plurality of fields of organic matter extraction, wastewater treatment, water quality desalination and the like.
The current commercialized nanofiltration membrane is mainly compounded by a non-woven fabric layer, a porous polyether sulfone layer, a surface polyamide layer, an anti-pollution layer and other multilayer structures. The surface polyamide layer is mainly formed by polymerizing piperazine and trimesoyl chloride on the surface of porous polyether sulfone, and the membrane surface has a large number of hydrophilic functional groups, so that the membrane surface presents electronegativity, and the electronegativity membrane has the characteristics of large water flux and poor pollution resistance. In many application fields, such as metal wastewater treatment, electroplating wastewater recovery in the electronics industry, hard water desalination, etc., a neutral-charged membrane or a positive-charged membrane is often required. At present, the production of positively charged or neutral charged membranes is less, the common preparation means mainly adopts macromolecular amine monomer synthesis combined with surface grafting charged materials and light radiation modification, and has the defects of complex preparation process, low membrane water yield and poor pollution resistance, and large-scale production cannot be realized. Along with the aging of membrane separation technology, the demand of charged membranes is increasing, so that the development of a novel charged membrane preparation method with simple preparation process and excellent membrane performance is urgently needed.
The present invention has been made in view of the above problems.
Disclosure of Invention
The invention provides a novel charged nanofiltration membrane and a preparation method thereof, aiming at solving the defects of complex preparation process, low water yield and poor pollution resistance of the charged nanofiltration membrane in the prior art.
The invention is realized by the following technical scheme:
a preparation method of a novel charged nanofiltration membrane comprises the following steps:
(1) dissolving piperazine, a charged modifier and an anti-pollution additive in water, uniformly mixing, adding an alkaline catalyst, and adjusting the pH value of the solution to 10-12 to form a piperazine water phase solution;
(2) dissolving trimesoyl chloride in an organic solvent, and uniformly mixing to obtain a trimesoyl chloride oil phase solution;
(3) soaking the porous base membrane in the piperazine water phase solution obtained in the step (1) for 1-3min, then soaking in the trimesoyl chloride oil phase solution obtained in the step (2) for reaction for 0.5-2min, and drying to obtain an initial nanofiltration membrane;
(4) and (4) soaking the initial nanofiltration membrane obtained in the step (3) in a charged neutralizer water solution for 2-3min, then soaking in pure water for 1-2min, and drying to obtain the novel charged nanofiltration membrane.
Preferably, the charged modifier in the step (1) is prepared by mixing chitosan and polyethyleneimine according to a mass ratio of 5: 5.
Preferably, the anti-pollution additive in the step (1) is polyvinyl alcohol with the molecular weight of 50000-.
Preferably, the basic catalyst in step (1) is one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, trisodium phosphate, triethylamine, ethylenediamine, tetraethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride and ethanolamine, and the basic catalyst is added in an amount such that the aqueous piperazine solution has a pH of 10 to 12.
Preferably, the mass concentration of the piperazine in the aqueous phase solution is 0.2%, the mass concentration of the charged modifier is 0.02-0.1%, and the mass concentration of the anti-pollution additive is 0.1-0.3%.
Preferably, the organic solvent in step (2) is one or more of isopar G, isopar E, isopar L, n-hexane, ethylcyclohexane, methylcyclohexane, cyclohexane and decane.
Preferably, the mass concentration of the trimesoyl chloride in the oil-phase solution of the trimesoyl chloride in the step (2) is 0.08-0.2%.
Preferably, the mass concentration of the charged neutralizer in the aqueous solution of the charged neutralizer in the step (4) is 0.5-2%, and the charged neutralizer is one or more of triethanolamine, triethylamine, diethanolamine, ethanolamine, monoethanolamine, ethylenediamine and hydrazine hydrate.
The invention also provides a novel charged nanofiltration membrane prepared by the method, which comprises a porous base membrane and a polyamide desalting layer, wherein the porous base membrane comprises a non-woven fabric layer and a porous polysulfone layer.
Preferably, the surface of the polyamide desalting layer is positively or neutrally charged.
The invention has the beneficial effects that:
(1) according to the invention, polyethyleneimine and chitosan components are simultaneously introduced into a piperazine aqueous phase solution, wherein the polyethyleneimine is a water-soluble high-molecular polymer and has a polar group (amino) and a hydrophobic group (vinyl) structure, so that one end of the polyethyleneimine can be combined with the surface of a porous polysulfone layer, and the polar group (amino) at the other end of the polyethyleneimine can be polymerized with trimesoyl chloride, so that a desalting layer generated by polymerization is combined with the porous polysulfone layer more firmly, and the surface desalting layer is prevented from falling off due to long-time washing of a nanofiltration membrane; meanwhile, polyethyleneimine exists in water as a polymeric cation and can neutralize and adsorb anionic substances, so that partial negative charges on the surface of the desalting layer can be neutralized, and the charge property of the membrane surface is improved. The chitosan is a macromolecular glucosamine, the molecule contains amino and hydroxyl functional groups, and can actively participate in polymerization reaction, and the molecular chain of the chitosan is longer, so that the crosslinking degree of a desalting layer of the composite membrane can be reduced in the polymerization reaction process, and the water flux of the charged nanofiltration membrane is improved.
(2) The anti-pollution additive (polyvinyl alcohol) is added into the piperazine aqueous phase solution, and a hydrophilic, ultrathin and strong-adhesion anti-pollution layer can be formed in the desalting layer in the interfacial polymerization process, so that the water flux of the nanofiltration composite membrane is increased, and the polyvinyl alcohol membrane has a smooth surface, so that the adsorption of pollutants on the membrane surface can be effectively inhibited, and the anti-pollution capacity of the nanofiltration composite membrane is increased.
(3) Because the desalting layer on the surface of the nanofiltration membrane is mainly formed by polymerizing piperazine and trimesoyl chloride on the surface of a porous base membrane, the surface of the formed polyamide desalting layer contains a large amount of carboxylic acid (-COOH) functional groups hydrolyzed from unreacted acyl chloride, and the carboxylic acid (-COOH) functional groups are easily hydrolyzed to be carboxylate radicals, so that the desalting layer has a large amount of negative charges; meanwhile, residual amine substances can be cleaned in the rinsing process, and the water yield and the storage period of the nanofiltration membrane are increased.
Drawings
Figure 1 is an SEM image of the novel charged nanofiltration membrane prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific embodiments, but the invention is not limited thereto, and any modification or replacement within the basic spirit of the embodiments of the present invention will still fall within the scope of the present invention.
Preparation of novel charged nanofiltration membrane
Example 1
The preparation method of the novel charged nanofiltration membrane comprises the following steps:
(1) dissolving 2g of piperazine, 0.2g of charge modifier (0.1g of chitosan and 0.1g of polyethyleneimine) and 2g of anti-pollution additive (polyvinyl alcohol with the molecular weight of 60000) in water, uniformly mixing, diluting to 1000g, and then adding sodium carbonate to adjust the pH value of the solution to 10-12 to form a piperazine aqueous phase solution for later use;
(2) dissolving 2G of trimesoyl chloride in 998G of Isopar G organic solvent, and uniformly mixing to obtain a trimesoyl chloride oil phase solution;
(3) soaking a porous polysulfone base membrane (comprising a non-woven fabric layer and a porous polysulfone layer) in a piperazine water phase solution for 2min, taking out, draining, soaking in a trimesoyl chloride oil phase solution for 1min, drying in the air, and drying at 90 ℃ for later use to obtain an initial nanofiltration membrane;
(4) soaking the initial nanofiltration membrane obtained in the step (3) in triethanolamine (charged neutralizer) water solution for 2min, then soaking in pure water for 2min, taking out and drying at 80 ℃ to obtain a novel charged nanofiltration membrane; wherein the mass concentration of the triethanolamine in the triethanolamine aqueous solution is 1.5 percent.
Fig. 1 is an SEM image of the novel charged nanofiltration membrane prepared in this embodiment at a magnification of 10K, and it can be seen from the figure that the surface of the nanofiltration membrane is smooth, and this regular morphology can reduce the adsorption of microbial contamination sources on the surface of the nanofiltration membrane, and improve the anti-contamination capability of the nanofiltration membrane, and it can be seen from fig. 1 that, due to the addition of hydrophilic substances, a convex morphology appears on the surface of the nanofiltration membrane prepared in this embodiment, which is more favorable for the aggregation and diffusion of water molecules on the membrane surface in the use process, reduces the diffusion resistance of water molecules, and increases the water yield of the membrane.
Examples 2 to 9
The preparation method of the novel charged nanofiltration membrane in the embodiments 2 to 10 is basically the same as that in the embodiment 1, and the difference is only that: the charged modifier and the anti-pollution additive added in the step (1) and the charged neutralizer added in the step (4) are different in type and mass concentration, and are specifically shown in table 1:
TABLE 1
Comparative example 1
The preparation method of the novel charged nanofiltration membrane in the comparative example is different from that in the example 1 in that: the charge modifier in step (1) of example 1 is omitted, and the specific implementation method is as follows:
(1) dissolving 2g of piperazine and 2g of an anti-pollution additive (polyvinyl alcohol with the molecular weight of 60000) in water, uniformly mixing, diluting to 1000g, and then adding sodium carbonate to adjust the pH value of the solution to 10-12 to form a piperazine water phase solution for later use;
steps (2) to (4) were the same as in example 1.
Comparative example 2
The preparation method of the novel charged nanofiltration membrane in the comparative example is different from that in the example 1 in that: the anti-contamination additive in step (1) of example 1 was omitted, and the specific implementation method was as follows:
(1) dissolving 2g of piperazine and 0.2g of charged modifier (0.1g of chitosan and 0.1g of polyethyleneimine) in water, uniformly mixing, diluting to 1000g, and then adding sodium carbonate to adjust the pH value of the solution to 10-12 to form a piperazine aqueous phase solution for later use;
steps (2) to (4) were the same as in example 1.
Comparative example 3
The preparation method of the novel charged nanofiltration membrane in the comparative example is different from that in the example 1 in that: the charge neutralizer in the step (4) of the embodiment 1 is omitted, and the specific implementation method is as follows:
steps (1) to (3) were the same as in example 1;
(4) and (4) soaking the initial nanofiltration membrane obtained in the step (3) in pure water for 2min, taking out and drying at 80 ℃ to obtain the novel charged nanofiltration membrane.
Second, performance test of nanofiltration membrane
1. Water flux and salt rejection test
Carrying out membrane water on the nanofiltration membranes prepared in the embodiments 1-10 and the comparative examples 1-3 on a membrane detection tableFlux and salt rejection tests, test solutions of 2000ppm CaCl, respectively2The pH value of a test solution is adjusted to 7.5 +/-0.5 by hydrochloric acid or sodium hydroxide, a nanofiltration membrane diaphragm is firstly placed into deionized water for soaking for about 30min before testing, then the nanofiltration membrane diaphragm is cut to a corresponding size and placed into a test membrane pool, the test pressure is adjusted to be 0.5MPa, the test temperature is adjusted to be 25 ℃, the nanofiltration membrane diaphragm stably operates for 30min at constant temperature and constant pressure, a permeate water sample in a certain time after stable operation, the conductivity and the volume of the test solution are collected, the water flux and the desalination rate of the nanofiltration membrane diaphragm are calculated according to the following formulas, and the test results are shown in table 2.
The nanofiltration membrane desalination rate calculation formula is as follows:
in the formula:
r-salt rejection rate;
kp-permeant conductivity in microsiemens per centimeter (μ S/cm);
kf-measuring the conductivity of the fluid in microsiemens per centimeter (. mu.S/cm).
The water flux calculation formula of the nanofiltration membrane is as follows:
in the formula:
f-water flux in liters per square meter hour [ L/(m)2.h)]；
The volume of permeate collected over time V-t, in liters (L);
a-effective membrane area in square meters (m)2)；
t-the time taken to collect V volumes of permeate in hours (h).
TABLE 2
As can be seen from Table 2, the anti-pollution additive and the charged modifier are synchronously introduced into the piperazine aqueous phase solution, and the charged neutralizer is rinsed to obtain the novel charged nanofiltration membrane, wherein the CaCl content of the nanofiltration membrane prepared by the method can reach 98.79% by optimizing the process and the ratio2The removal rate of the monovalent positive ion salt NaCl is only 27 percent, the monovalent positive ion salt NaCl can well separate monovalent metal salt and divalent metal salt, and Mg in a water body is reduced2+、Ca2+And other high valence metal cations, and can be widely used in the field of water softening.
As can be seen from the data of example 1 and comparative example 2, the nanofiltration membrane obtained in comparative example 2 has CaCl-containing property because the test solution does not contain contaminants such as microorganisms2And NaCl removal rate, but flux was slightly reduced.
2. Anti-biocontamination assay
Taking the novel charged nanofiltration membranes prepared in the embodiments 1 to 10 and the comparative examples 1 to 3 as test membranes, adding 50ppm bovine serum albumin into 2000ppm NaCl aqueous solution, mixing completely, adjusting the pH of the test solution to 7.5 +/-0.5 with hydrochloric acid or sodium hydroxide, adjusting the test pressure to 0.5MPa, testing the temperature to 25 ℃, cutting the nanofiltration membranes to corresponding sizes, placing the nanofiltration membranes into a test membrane pool, continuously operating the membranes for 5 hours at constant temperature and constant pressure, collecting permeate water samples after stable operation, and calculating the water yield and the desalination rate of the test membranes, wherein the results are shown in Table 3:
TABLE 3
As can be seen from Table 3, the nanofiltration membrane added with the anti-pollution additive has relatively more excellent performance, the water flux is only reduced by about 5-6% in the 5h test process, the NaCl component removal rate is small in increase, and the addition of the anti-pollution additive is proved to reduce the adsorption of bovine serum albumin on the surface of the nanofiltration membrane, so that the nanofiltration membrane is ensured to maintain excellent water flux and separation performance in long-term use.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the novel charged nanofiltration membrane is characterized by comprising the following steps of:
(1) dissolving piperazine, a charged modifier and an anti-pollution additive in water, uniformly mixing, adding an alkaline catalyst, and adjusting the pH value of the solution to 10-12 to form a piperazine water phase solution;
(2) dissolving trimesoyl chloride in an organic solvent, and uniformly mixing to obtain a trimesoyl chloride oil phase solution;
(3) soaking the porous base membrane in the piperazine water phase solution obtained in the step (1) for 1-3min, then soaking in the trimesoyl chloride oil phase solution obtained in the step (2) for reaction for 0.5-2min, and drying to obtain an initial nanofiltration membrane;
(4) and (4) soaking the initial nanofiltration membrane obtained in the step (3) in a charged neutralizer water solution for 2-3min, then soaking in pure water for 1-2min, and drying to obtain the novel charged nanofiltration membrane.
2. The preparation method of the novel charged nanofiltration membrane according to claim 1, wherein the charged modifier in the step (1) is prepared by mixing chitosan and polyethyleneimine according to a mass ratio of 5: 5.
3. The method for preparing the novel charged nanofiltration membrane according to claim 1, wherein the anti-pollution additive in the step (1) is polyvinyl alcohol with a molecular weight of 50000-80000.
4. The method of claim 1, wherein the basic catalyst in step (1) is one or more selected from sodium hydroxide, sodium carbonate, potassium hydroxide, trisodium phosphate, triethylamine, ethylenediamine, tetraethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride and ethanolamine, and the basic catalyst is added in an amount such that the aqueous piperazine solution has a pH of 10-12.
5. The method for preparing a novel charged nanofiltration membrane according to any one of claims 1 to 3, wherein the mass concentration of piperazine in the piperazine aqueous phase solution is 0.2%, the mass concentration of the charged modifier is 0.02% to 0.1%, and the mass concentration of the anti-pollution additive is 0.1% to 0.3%.
6. The method for preparing a novel charged nanofiltration membrane according to claim 1, wherein the organic solvent in the step (2) is one or more of isopar G, isopar E, isopar L, n-hexane, ethylcyclohexane, methylcyclohexane, cyclohexane and decane.
7. The method for preparing the novel charged nanofiltration membrane according to claim 1, wherein the mass concentration of trimesoyl chloride in the oil phase solution of trimesoyl chloride in the step (2) is 0.08-0.2%.
8. The method for preparing a novel charged nanofiltration membrane according to claim 1, wherein the mass concentration of the charged neutralizer in the aqueous solution of the charged neutralizer in the step (4) is 0.5-2%, and the charged neutralizer is one or more of triethanolamine, triethylamine, diethanolamine, ethanolamine, monoethanolamine, ethylenediamine and hydrazine hydrate.
9. A novel charged nanofiltration membrane prepared by the method of any one of claims 1 to 8, comprising a porous base membrane and a polyamide desalination layer, wherein the porous base membrane comprises a nonwoven fabric layer and a porous polysulfone layer.
10. The novel charged nanofiltration membrane according to claim 9, wherein the surface of the polyamide desalination layer is positively or neutrally charged.
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