CN115090136B - High-flux high-selectivity material membrane and preparation method and application thereof - Google Patents

High-flux high-selectivity material membrane and preparation method and application thereof Download PDF

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CN115090136B
CN115090136B CN202210502589.XA CN202210502589A CN115090136B CN 115090136 B CN115090136 B CN 115090136B CN 202210502589 A CN202210502589 A CN 202210502589A CN 115090136 B CN115090136 B CN 115090136B
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membrane
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CN115090136A (en
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孔新
王柯
陈良
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Entai Environmental Technology Changzhou Co ltd
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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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/08—Apparatus therefor
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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 discloses a high-flux high-selectivity material membrane, a preparation method and application thereof, and the preparation method comprises the following steps: (1) preparing aqueous phase solution by using homopiperazine, an acid absorber and water; (2) soaking the base film in aqueous phase liquid; (3) Dissolving trimesic acid chloride in an organic solvent to prepare an oil phase solution; (4) Immersing the first immersed base film in oil phase liquid for interfacial polymerization reaction, cleaning and immersing in alkali liquid to obtain a wet film covering the polyamide separation layer; (5) preparing a pore-protecting solution by using glycerol, polyglycerol and water; (6) Immersing the wet film covered with the polyamide separating layer in a pore-protecting liquid; (7) Mixing polycarbodiimide and water to prepare a post-treatment solution; (8) And (3) dripping the post-treatment solution on the surface of the membrane subjected to the third impregnation, and drying to obtain the high-flux high-selectivity material membrane. Application: the material membrane is used in the field of wastewater treatment for selective separation of organic matters and inorganic salts or material separation or in the field of landfill leachate nanofiltration concentrated solution treatment.

Description

High-flux high-selectivity material membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of water treatment membranes, in particular to a high-flux high-selectivity material membrane and a preparation method and application thereof.
Background
The landfill leachate is high-concentration organic wastewater generated in the treatment process of household garbage, and has the characteristics of high pollutant concentration, high hardness, high alkalinity, large fluctuation of water quality and water quantity and the like. Currently, the main treatment process of landfill leachate is a combined process of pretreatment, biological treatment and double membrane method (NF+RO). The technology is mature, stable in operation and good in effluent quality, but a large amount of membrane concentrate can be produced after the biochemical effluent is concentrated and separated by nanofiltration. The concentrated solution mainly contains macromolecular humic acid and divalent salt, belongs to high-salt high-organic matter waste liquid, has high treatment difficulty, and is a heavy and difficult problem of how to effectively treat nanofiltration concentrated solution in the current household garbage leachate treatment project.
Humic acid is a complex mixture, which is classified into fulvic acid, ulmic acid and fulvic acid. Humic acid contains more functional groups, has good biological activity, and can be used as fertilizer, medical additive, adsorbent, etc. If humic acid in the nanofiltration concentrated solution can be separated and extracted, the residual concentrated solution returns to a biochemical system, so that the discharge of the nanofiltration concentrated solution can be avoided, the overall recovery rate of the membrane system is improved, and the recycling of humic acid can be realized.
The material film has a molecular weight cut-off of about 800Da (800 +/-200 Da), a removal rate of about 65 percent (65 +/-20 percent) of COD and basically no cut-off capability of divalent salt. The material film is connected with a feed pipe of the landfill leachate nanofiltration concentrated solution and is used for intercepting humic acid in the concentrated solution for recycling, the dilute phase solution obtained after passing through the material film returns to a biochemical system again for circular treatment, and no concentrated solution is discharged in the whole treatment process, so that zero discharge of the landfill leachate nanofiltration concentrated solution is realized.
Compared with the traditional nanofiltration membrane, the material membrane has high retention rate for small molecular weight, is more focused on separating substances with specific molecular weight, and enables the separation layer to react within a certain pore size range by controlling related parameters in the preparation process so as to achieve the purpose of limiting the retention molecular weight. The existing material membrane preparation method is mostly similar to the traditional nanofiltration membrane, and the separation layer is prepared by an interfacial polymerization method, a phase inversion method or a codeposition method, so that the prepared material membrane can control the molecular weight cut-off within a corresponding range to a certain extent, but the overall pore size distribution is still not uniform enough, the surface charge of the membrane can be changed, and the phenomenon that the retention rate of partial substances smaller than the molecular weight cut-off is still higher can occur. Therefore, a simple and efficient material membrane preparation method is urgently needed, membrane pore diameter uniformity is enhanced, and meanwhile, membrane surface charge is not changed, so that a high-flux high-selectivity material membrane capable of effectively treating landfill leachate nanofiltration concentrate is prepared.
Disclosure of Invention
The invention provides a preparation process of a high-flux high-selectivity material membrane based on the aperture screening effect, which solves a plurality of problems existing in the preparation of the material membrane in the prior art and has very important economic value and research significance.
The invention is realized by the following technical scheme:
the preparation method of the high-flux high-selectivity material membrane is characterized by comprising the following steps of:
(1) Preparing an aqueous phase solution: mixing homopiperazine, an acid absorbent and water to prepare aqueous phase liquid;
(2) First dipping treatment: placing a base film in the aqueous phase liquid for immersion treatment, and then separating and removing the liquid on the surface of the base film;
(3) Preparing an oil phase liquid: dissolving trimesic acid chloride in an organic solvent to prepare an oil phase solution;
(4) And (3) carrying out a second soaking treatment: immersing the base film subjected to the first immersion treatment in the oil phase liquid for interfacial polymerization reaction, separating and removing the liquid on the surface of the base film, cleaning, and immersing in alkali liquor to obtain a wet film covering the polyamide separation layer;
(5) Preparing a pore-protecting liquid: mixing glycerol, polyglycerol and water to prepare a pore-protecting solution;
(6) And (3) carrying out a third soaking treatment: immersing the wet membrane covered with the polyamide separation layer in the pore-preserving liquid, and then separating and removing the liquid on the surface of the membrane;
(7) Preparing a post-treatment solution: mixing polycarbodiimide and water to prepare a post-treatment solution;
(8) Dry film preparation: and uniformly dripping the post-treatment solution on the surface of the membrane subjected to the third soaking treatment, separating and removing the liquid on the surface of the membrane, and drying to obtain the high-flux high-selectivity material membrane.
Specifically, polyglycerol is a polyol in which two or more hydroxyl groups between glycerol molecules are dehydrated to form ether bonds, is an important fine chemical product and a synthetic intermediate, and has wide application, but no report on the use of polyglycerol in the preparation of material films exists at present. In the preparation process of the high-flux high-selectivity material membrane, the polyamide separation layer formed by interfacial polymerization is soaked in sodium hydroxide (alkali liquor), so that partial polyamide reticular cross-linking structure can be broken while residual oil is cleaned, and the cross-linking pore size can be effectively enlarged. Meanwhile, polyglycerol with larger molecular weight is introduced into the preparation of the dry film sheet in the later-stage process, the collapse of polyamide cross-linking holes in the drying process is effectively prevented by polyglycerol molecules through the occupying effect, and meanwhile, the partially broken high molecular chains are repaired by using the polycarbodiimide cross-linking agent, so that the high permeability of the material film to divalent salt is ensured, and meanwhile, the interception performance of PEG800 is not reduced.
Specifically, the preparation method of the high-flux high-selectivity material membrane comprises the following steps: introducing polyglycerol substances as pore-protecting agents into the preparation process of the dry film sheet of the material film; the preparation method provided by the invention is simple, low in cost, good in compatibility with the traditional interfacial polymerization production process and easy to produce and amplify. Under the synergistic effect of polyglycerol and polycarbodiimide crosslinking agent, the prepared material film has a molecular weight cut-off of about 800Da, a divalent salt cut-off rate of less than 5%, and shows excellent organic matter/divalent salt selectivity. The high-flux high-selectivity material membrane prepared by the invention has water flux higher than 100LMH under extremely low pressure (0.2 MPa).
Further, a preparation method of the high-flux high-selectivity material film comprises the following steps: step (1) preparing aqueous phase liquid: the concentration of the homopiperazine in the aqueous phase liquid is 0.1-2.0wt% and the concentration of the acid absorber is 0.5-3.0wt%; and the acid absorbing agent is one or more selected from sodium carbonate, trisodium phosphate, triethylamine and sodium hydroxide. Preferably, the concentration of the homopiperazine in the aqueous phase liquid is 0.2-1.0wt% and the concentration of the acid absorber is 1.0-2.5wt%; the preferred acid acceptor is trisodium phosphate.
Further, a preparation method of the high-flux high-selectivity material film comprises the following steps: step (2) first dipping treatment: wherein the base membrane is a polysulfone base membrane; the time of the dipping treatment is 0.5-5 minutes.
Further, a preparation method of the high-flux high-selectivity material film comprises the following steps: and (3) preparing an oil phase liquid: wherein the organic solvent is at least one selected from n-hexane, cyclohexane, ethylcyclohexane, n-heptane and isoparaffin solvents; the concentration of the trimesic acid chloride in the oil phase liquid is 0.05-0.5wt%.
Further, a preparation method of the high-flux high-selectivity material film comprises the following steps: and (4) carrying out a second soaking treatment: and (3) soaking the base film subjected to the first soaking treatment in the oil phase liquid for interfacial polymerization for 5-20 seconds, separating and removing liquid on the surface of the film, cleaning, and then soaking in 0.1-4.0wt% sodium hydroxide aqueous solution for 0.5-5 minutes to obtain the wet film covering the polyamide separation layer.
Further, a preparation method of the high-flux high-selectivity material film comprises the following steps: and (5) preparing a pore-protecting solution: the concentration of glycerin in the pore-protecting liquid is 1.0-15.0wt% and the concentration of polyglycerol is 0.2-3.0wt%; the polyglycerol is n polyglycerol, wherein n=6 to 10, preferably octapolyglycerol. Preferably, the concentration of glycerin in the pore-protecting liquid is 3.0-8.0wt% and the concentration of polyglycerol is 0.5-1.5wt%.
Further, a preparation method of the high-flux high-selectivity material film comprises the following steps: and (6) carrying out a third soaking treatment: the wet membrane covered with the polyamide separation layer is immersed in the pore-protecting liquid for 0.5 to 5 minutes, and then the liquid on the surface of the membrane is separated and removed.
Further, the preparation method of the high-flux high-selectivity material membrane comprises the following steps: step (7) preparing a post-treatment solution: the concentration of the polycarbodiimide in the post-treatment solution is 0.05 to 1.0wt%.
Further, the preparation method of the high-flux high-selectivity material membrane comprises the following steps: and (8) preparing a dry film sheet: the drying temperature is 30-90 ℃ and the drying time is 2-10 minutes.
The high-flux high-selectivity material membrane is characterized by being prepared by the preparation method.
The application of the high-flux high-selectivity material membrane is characterized in that the high-flux high-selectivity material membrane prepared by the preparation method is used in the field of wastewater treatment or material separation needing selective separation of organic matters and inorganic salts, and is preferably used in the field of landfill leachate nanofiltration concentrated solution treatment.
The invention has the beneficial effects that:
(1) The preparation process is simple, the molecular weight cut-off of the prepared high-flux high-selectivity material membrane is about 800Da, the cut-off rate of the magnesium sulfate serving as the bivalent salt is less than 5%, and the accurate separation of organic matters and the bivalent salt can be realized.
(2) The polyglycerol introduced in the preparation process has a swelling effect on the cross-linked structure of the polyamide layer, the pore size in the cross-linked network structure can be uniformly enlarged under the effects of alkali liquor soaking and polyglycerol, the water permeation efficiency is effectively improved, and the prepared high-flux high-selectivity material membrane has a water flux of more than 100LMH under extremely low pressure (0.2 MPa).
(3) The preparation method of the high-flux high-selectivity material membrane provided by the invention is simple, low in cost, good in compatibility with the traditional interfacial polymerization production process, easy to produce and amplify, and very important in economic benefit.
(4) The preparation method of the high-flux high-selectivity material membrane provided by the invention comprises the following steps: on the basis of traditional interfacial polymerization operation, alkaline solution (sodium hydroxide solution) is used for soaking and destroying part of polyamide reticular crosslinked structure, polyglycerol is introduced in the preparation of dry film sheets, the aperture size of a polyamide layer is enlarged by utilizing the occupying effect of the polyglycerol, and finally a part of broken high molecular chains are repaired by using a polycarbodiimide crosslinking agent, so that the interception molecular weight of the prepared material film is about 800Da, the interception rate of divalent salt magnesium sulfate is less than 5%, and higher water flux can be kept under extremely low pressure, thus the material film has good application prospect and economic value in the wastewater treatment field or material separation field of selective separation of organic matters and inorganic salts and the treatment field of landfill leachate nanofiltration concentrated solution.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A preparation method of a high-flux high-selectivity material membrane comprises the following steps:
(1) Preparing an aqueous phase solution: mixing homopiperazine, an acid absorbent and water to prepare aqueous phase liquid; the concentration of homopiperazine in the aqueous phase liquid is 0.1-2.0wt% (preferably 0.2-1.0 wt%), and the concentration of acid absorber is 0.5-3.0wt% (preferably 1.0-2.5 wt%); the acid absorbent is selected from one or more of sodium carbonate, trisodium phosphate, triethylamine and sodium hydroxide, and the preferable acid absorbent adopts trisodium phosphate;
(2) First dipping treatment: immersing a base membrane (polysulfone base membrane) in the aqueous phase solution for 0.5-5 minutes, and then separating and removing the surface liquid of the base membrane;
(3) Preparing an oil phase liquid: dissolving trimesic acid chloride in an organic solvent to prepare an oil phase liquid; the concentration of trimesic acid chloride in the oil phase liquid is 0.05-0.5wt%; wherein the organic solvent can be selected from one or more of n-hexane, cyclohexane, ethylcyclohexane, n-heptane and isoparaffin solvents;
(4) And (3) carrying out a second soaking treatment: immersing the base film subjected to the first immersion treatment in the oil phase liquid for interfacial polymerization reaction for 5-20 seconds, separating and removing liquid on the surface of the base film, cleaning, and then immersing in 0.1-4.0wt% sodium hydroxide aqueous solution for 0.5-5 minutes to obtain a wet film covering the polyamide separation layer;
(5) Preparing a pore-protecting liquid: mixing glycerol, polyglycerol and water to prepare a pore-protecting solution; the concentration of glycerin in the pore-protecting liquid is 1.0-15.0wt% (preferably 3.0-8.0 wt%), and the concentration of polyglycerol is 0.2-3.0wt% (preferably 0.5-1.5 wt%); wherein the polyglycerol is n polyglycerol, n=6 to 10, n is a positive integer, and the polyglycerol can be preferably octapolyglycerol;
(6) And (3) carrying out a third soaking treatment: immersing the wet membrane covered with the polyamide separation layer in the pore-preserving liquid for 0.5-5 minutes, and then separating and removing the liquid on the surface of the membrane;
(7) Preparing a post-treatment solution: mixing polycarbodiimide and water to prepare a post-treatment solution; the concentration of polycarbodiimide in the post-treatment solution is 0.05 to 1.0wt%;
(8) Dry film preparation: uniformly dripping the post-treatment solution on the surface of the membrane subjected to the third soaking treatment, separating and removing liquid on the surface of the membrane, and drying for 2-10 minutes at the temperature of 30-90 ℃ to obtain the high-flux high-selectivity material membrane.
Example 1
The preparation method of the high-flux high-selectivity material membrane comprises the following specific steps:
(1) Preparing an aqueous phase solution: mixing Homopiperazine (HPIP), trisodium phosphate (acid absorber) and water to prepare aqueous phase liquid; the concentration of the homopiperazine in the aqueous phase liquid is 0.6wt% and the concentration of trisodium phosphate is 2.0wt%;
(2) First dipping treatment: immersing the polysulfone base membrane in the aqueous phase solution for 1 minute, and then separating and removing the liquid on the surface of the polysulfone base membrane;
(3) Preparing an oil phase liquid: dissolving trimesic acid chloride (TMC) in ethylcyclohexane to prepare oil phase liquid; and the concentration of trimesic acid chloride in the oil phase liquid is 0.15wt%;
(4) And (3) carrying out a second soaking treatment: immersing the polysulfone base membrane subjected to the first immersion treatment in the oil phase liquid for interfacial polymerization reaction for 10 seconds, separating and removing the liquid on the surface of the membrane, cleaning, and immersing in 1.0wt% sodium hydroxide aqueous solution for 1 minute to obtain a wet membrane covering the polyamide separation layer;
(5) Preparing a pore-protecting liquid: mixing glycerol, octaglycerol and water to prepare a pore-protecting solution; the concentration of glycerin in the pore-protecting liquid is 5.0wt% and the concentration of octaglycerin is 1.0wt%;
(6) And (3) carrying out a third soaking treatment: immersing the wet film covered with the polyamide separation layer in the pore-preserving liquid for 1 minute, and then separating and removing the liquid on the surface of the film;
(7) Preparing a post-treatment solution: mixing polycarbodiimide and water to prepare a post-treatment solution; and the concentration of polycarbodiimide in the post-treatment solution was 0.2wt%;
(8) Dry film preparation: and uniformly dripping the post-treatment solution on the surface of the membrane subjected to the third soaking treatment, separating and removing liquid on the surface of the membrane, and drying in a 60 ℃ oven for 5 minutes to obtain the high-flux high-selectivity material membrane.
Example 2
Example 2 differs from example 1 above in that the concentration of glycerin in the pore-protecting liquid described in step (5) of example 2 is 1.0wt%; the remaining preparation conditions of example 2 were the same as those of example 1.
Example 3
Example 3 differs from example 1 above in that the concentration of glycerol in the pore-protecting liquid described in step (5) of example 3 is 3.0wt%; the remaining preparation conditions of example 3 were the same as those of example 1.
Example 4
Example 4 differs from example 1 above in that the concentration of glycerin in the pore-protecting liquid described in step (5) of example 4 is 12.0wt%; the remaining preparation conditions of example 4 were the same as those of example 1.
Example 5
Example 5 differs from example 1 above in that the concentration of octapolyglycerol in the pore-protecting liquid described in step (5) of example 5 is 0.2wt%; the remaining preparation conditions of example 5 were the same as those of example 1.
Example 6
Example 6 differs from example 1 above in that the concentration of octapolyglycerol in the pore-protecting liquid described in step (5) of example 6 is 1.5wt%; the remaining preparation conditions of example 6 were the same as those of example 1.
Example 7
Example 7 differs from example 1 above in that the concentration of octapolyglycerol in the pore-protecting liquid described in step (5) of example 7 is 3.0wt%; the remaining preparation conditions of example 7 were the same as those of example 1.
Example 8
Example 8 differs from example 1 above in that the interfacial polymerization reaction time described in step (4) of example 8 is 20 seconds; the remaining preparation conditions of example 8 were the same as those of example 1.
Example 9
Example 9 differs from example 1 above in that the concentration of polycarbodiimide in the aftertreatment solution described in step (7) of example 9 is 0.05 wt.%; the remaining preparation conditions of example 9 were the same as those of example 1.
Example 10
Example 10 differs from example 1 above in that the concentration of polycarbodiimide in the post-treatment solution of step (7) of example 10 is 1.0wt%; the remaining preparation conditions of example 10 were the same as those of example 1.
Example 11
Example 11 differs from example 1 above in that the pore-protecting liquid described in step (5) of example 11 is prepared by mixing glycerin, hexaglycerin and water; namely, the octapolyglycerol in example 1 was replaced with hexapolyglycerol; example 11 the concentration of glycerol in the pore-protecting solution was 5.0wt% and the concentration of hexaglycerol was 1.0wt%; the remaining preparation conditions of example 11 were the same as those of example 1.
Example 12
Example 12 differs from example 1 above in that the pore-protecting liquid described in step (5) of example 12 is prepared by mixing glycerin, decaglycerin and water; namely, the octapolyglycerol in example 1 was replaced with decapolyglycerol; example 12 the concentration of glycerol in the pore-protecting solution was 5.0wt% and the concentration of decaglycerol was 1.0wt%; the remaining preparation conditions of example 12 were the same as those of example 1.
Comparative example 1
Comparative example 1 differs from example 1 above in that no octapolyglycerol was added to the pore-protecting liquid in step (5) of comparative example 1; the remaining preparation conditions of comparative example 1 were the same as those of example 1.
Comparative example 2
Comparative example 2 differs from example 2 above in that no octapolyglycerol was added to the pore-protecting liquid in step (5) of comparative example 2; the remaining preparation conditions of comparative example 2 were the same as those of example 2.
Comparative example 3
Comparative example 3 differs from example 3 above in that no octapolyglycerol was added to the pore-protecting liquid in step (5) of comparative example 3; the remaining preparation conditions of comparative example 3 were the same as those of example 3.
Comparative example 4
Comparative example 4 differs from example 4 above in that no octapolyglycerol was added to the pore-protecting liquid in step (5) of comparative example 4; the remaining preparation conditions of comparative example 4 were the same as those of example 4.
Comparative example 5
Comparative example 5 differs from example 1 above in that the interfacial polymerization reaction time described in comparative example 5, step (4), was 40 seconds; the remaining preparation conditions of comparative example 5 were the same as in example 1.
Comparative example 6
Comparative example 6 differs from example 1 above in that the interfacial polymerization reaction described in step (4) of comparative example 6 was not followed by a soaking treatment with aqueous sodium hydroxide solution; the remaining preparation conditions of comparative example 6 were the same as in example 1.
Comparative example 7
Comparative example 7 differs from example 1 above in that the concentration of polycarbodiimide in the aftertreatment solution described in step (7) of comparative example 7 is 0; the remaining preparation conditions of comparative example 7 were the same as in example 1.
And (3) testing:
the material films obtained in examples 1 to 12 and comparative examples 1 to 7 above were tested for properties: the membrane separation performance of the prepared material is evaluated, and is mainly characterized by two characteristic parameters, namely the water flux (LMH) and the solute rejection rate of the membrane.
The water flux (LMH) is defined as: the volume of water that permeates through the active membrane area per unit time under certain operating pressure conditions.
Solute rejection rate calculation formula: r= (1-C p /C f ) X100%, wherein R represents the retention rate, C f And C p The concentration (ppm) of the solute in the permeate and feed solutions, respectively.
The test conditions of the separation performance of the material film are as follows: the feed solutions were 2000ppm of magnesium sulfate aqueous solution and 200ppm of polyethylene glycol (PEG) aqueous solution having a molecular weight of 800Da, respectively, at a feed solution temperature of 25℃and an operating pressure of 0.2MPa.
PEG concentration was determined by total organic carbon analyzer (TOC-VCHP, shimadzu, japan). It is generally believed that the corresponding relative molecular weight when the membrane has achieved 90% PEG rejection is the membrane's molecular weight cut-off.
The material films prepared in examples 1 to 7 and comparative examples 1 to 4 were subjected to performance test by the above method, and the test results are shown in Table 1 below.
Table 1 shows the results of the membrane separation performance test for the materials prepared in examples 1 to 7 and comparative examples 1 to 4
Figure BDA0003634860530000131
Figure BDA0003634860530000141
From the test results in Table 1, the addition of octaglycerol in the pore-protecting solution can obviously reduce the retention rate of the material film on divalent salt magnesium sulfate, and meanwhile, the retention rate of PEG is kept at about 90%, and the retention molecular weight is precisely controlled at about 800 Da; meanwhile, compared with glycerol, the octaglycerol has stronger pore-protecting capability, has a swelling effect on a cross-linked structure of a polyamide layer, and can improve the water flux of the membrane by adding the lower concentration of the triglycerol.
The material films prepared in examples 8 to 12 and comparative examples 5 to 7 were subjected to performance test by the above method, and the test results are shown in Table 2 below.
Table 2 shows the results of the membrane separation performance test for the materials prepared in examples 8 to 12 and comparative examples 5 to 7
Figure BDA0003634860530000142
As can be seen from the test results in Table 2, the polyglycerols with different molecular weights have different influences on the performance of the prepared material film, compared with octapolyglycerol, the decapolyglycerol with larger molecular weight has stronger swelling effect on the polyamide crosslinked layer, the prepared material film has larger water flux, but has reduced interception of PEG, and the pore diameter of the material film prepared by hexapolyglycerol with smaller molecular weight is reduced, so that interception of PEG and magnesium sulfate is obviously improved. In addition, the interfacial polymerization reaction time in the preparation process of the material film is not easy to be overlong, otherwise, the formed polyamide layer is compact, and the retention rate of magnesium sulfate cannot be effectively reduced.
The sources of the raw materials used in examples 1 to 14 and comparative examples 1 to 5 described above are shown in Table 3 below.
Raw material name Parameter index Manufacturing factories
Homopiperazine Purity is more than or equal to 98 percent Ara Ding Shiji
Trisodium phosphate Purity is more than or equal to 98 percent Xiyong reagent
Trimesic acid chloride Purity is more than or equal to 99 percent Sanli benno
Sodium hydroxide The purity is more than or equal to 97 percent Microphone forest
Glycerol Purity is more than or equal to 99 percent Kang Disi
Polyglycerol Purity is more than or equal to 99 percent Kang Disi
Polycarbodiimide UN-557 Industrial grade Shanghai You En
Magnesium sulfate Purity is more than or equal to 98 percent Beijing enokie
Polyethylene glycol 800 Purity is more than or equal to 99 percent Beijing enokie
The above-described preferred embodiments of the present invention are only for illustrating the present invention, and are not to be construed as limiting the present invention. Obvious changes and modifications of the invention, which are introduced by the technical solution of the present invention, are still within the scope of the present invention.

Claims (9)

1. The preparation method of the high-flux high-selectivity material membrane is characterized by comprising the following steps of:
(1) Preparing an aqueous phase solution: mixing homopiperazine, an acid absorbent and water to prepare aqueous phase liquid;
(2) First dipping treatment: placing a base film in the aqueous phase liquid for immersion treatment, and then separating and removing the liquid on the surface of the base film;
(3) Preparing an oil phase liquid: dissolving trimesic acid chloride in an organic solvent to prepare an oil phase solution;
(4) And (3) carrying out a second soaking treatment: immersing the base film subjected to the first immersion treatment in the oil phase liquid for interfacial polymerization reaction, separating and removing the liquid on the surface of the base film, cleaning, and immersing in alkali liquor to obtain a wet film covering the polyamide separation layer;
(5) Preparing a pore-protecting liquid: mixing glycerol, polyglycerol and water to prepare a pore-protecting solution;
(6) And (3) carrying out a third soaking treatment: immersing the wet membrane covered with the polyamide separation layer in the pore-preserving liquid, and then separating and removing the liquid on the surface of the membrane;
(7) Preparing a post-treatment solution: mixing polycarbodiimide and water to prepare a post-treatment solution;
(8) Dry film preparation: uniformly dripping the post-treatment solution on the surface of the membrane subjected to the third soaking treatment, separating and removing the liquid on the surface of the membrane, and drying to obtain a high-flux high-selectivity material membrane;
application of high flux high selectivity material film: the prepared high-flux high-selectivity material membrane is used in the field of wastewater treatment or material separation needing selective separation of organic matters and inorganic salts, and is preferably used in the field of landfill leachate nanofiltration concentrated solution treatment.
2. The method for preparing a high-flux high-selectivity material membrane according to claim 1, wherein the step (1) comprises the steps of: the concentration of homopiperazine in the aqueous phase liquid is 0.1-2.0wt% and the concentration of the acid absorbing agent is 0.5-
3.0wt%; and the acid absorbing agent is one or more selected from sodium carbonate, trisodium phosphate, triethylamine and sodium hydroxide.
3. The method for preparing a high flux high selectivity material membrane according to claim 1, wherein the step (2) comprises a first immersion treatment: the base membrane is a polysulfone base membrane; the time of the dipping treatment is 0.5-5 minutes.
4. The method for preparing the high-flux high-selectivity material membrane according to claim 1, wherein the step (3) is to prepare an oil phase liquid: wherein the organic solvent is at least one selected from n-hexane, cyclohexane, ethylcyclohexane, n-heptane and isoparaffin solvents; the concentration of the trimesic acid chloride in the oil phase liquid is 0.05-0.5wt%.
5. The method for preparing a high flux high selectivity material membrane according to claim 1, wherein the step (4) comprises a second impregnation treatment: and (3) soaking the base film subjected to the first soaking treatment in the oil phase liquid for interfacial polymerization for 5-20 seconds, separating and removing liquid on the surface of the film, cleaning, and then soaking in 0.1-4.0wt% sodium hydroxide aqueous solution for 0.5-5 minutes to obtain the wet film covering the polyamide separation layer.
6. The method for preparing a high-flux high-selectivity material membrane according to claim 1, wherein the step (5) comprises the steps of: the concentration of glycerin in the pore-protecting liquid is 1.0-15.0wt% and the concentration of polyglycerol is 0.2-3.0wt%; the polyglycerol is n polyglycerol, wherein n=6 to 10, preferably octapolyglycerol.
7. The method for preparing a high flux and high selectivity material membrane according to claim 1, wherein the step (7) comprises the steps of: the concentration of polycarbodiimide in the post-treatment solution is 0.05-1.0wt%.
8. The method for preparing a high-flux high-selectivity material film according to claim 1, wherein the dry film sheet prepared in the step (8) is as follows: the drying temperature is 30-90 ℃ and the drying time is 2-10 minutes.
9. A high flux high selectivity material membrane produced by the method of any one of claims 1 to 8.
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