CN112675716B - UIO-66-NH 2 Method for preparing high-flux defect-free polyamide membrane by using base derivative - Google Patents
UIO-66-NH 2 Method for preparing high-flux defect-free polyamide membrane by using base derivative Download PDFInfo
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Abstract
The invention relates to a high-performance polyamide composite membrane which is formed by non-woven fabrics, a porous supporting layer and a porous layer, wherein the porous supporting layer contains UIO-66-NH 2 A polyamide dense layer of a base derivative, wherein the porous support layer is a polysulfone ultrafiltration layer contained on the surface of the nonwoven fabric; containing UIO-66-NH 2 The polyamide compact layer of the base derivative is formed by placing a porous supporting layer in an aqueous phase amine solution and an oil phase acyl chloride solution in sequence and carrying out interfacial polymerization, wherein the aqueous phase amine monomer solution or the oil phase acyl chloride solution can contain UIO-66-NH 2 And (3) a base derivative. The acid chloride, anhydride and epoxy ether micromolecules used for modification have the advantages of simple structure, low cost, easy obtainment and the like, and the modification method is simple and is convenient for popularization in industrial application.
Description
Technical Field
The invention relates to a reverse osmosis composite membrane and a preparation method thereof, in particular to a reverse osmosis composite membrane adopting UIO-66-NH 2 A method for preparing a polyamide membrane with high flux, stability and uniformity in situ belongs to the technical field of membrane separation.
Background
Since the reverse osmosis membrane preparation process is changed from phase inversion to interfacial polymerization, the membrane structure is also changed from the traditional asymmetric structure to the current mature composite structure. The composite membrane prepared by interfacial polymerization consists of non-woven fabrics, ultrafiltration membranes and compact polyamide layers, has good stability, large water flux and certain pressure resistance, and can meet the diversified requirements of household use, industry, brackish water/sea water desalination and the like. With the increasing popularity of membrane technology, water depth treatment is becoming a common public place, and at the same time, diversified applications place higher demands on the performance of polyamide composite membranes. How to prepare high flux, high selectivity polyamide membranes is a new challenge.
In 2005, hoek and his colleagues proposed for the first time to incorporate nanoparticles into polyamide films to form polyamide nanocomposite films, i.e. to disperse the nanomaterial in a conventional polyamide polymer segment, the nanoparticles may interact with specific functional groups present on the polymer chain backbone, typically groups that are ionic or have lone pair electrons, which may act as chelators and may also exert a stabilizing effect on the nanoparticles. The nano composite membranes can be used in the fields of water treatment, organic solvent nanofiltration, gas separation, pervaporation, sensor application and the like. Commonly used nanomaterials are e.g. carbon-based nanofillers (carbon nanotubes, graphene oxide, carbon quantum dots, reduced graphene oxide with metals and metal oxides), metal and metal oxide based nanofillers (based on silver, copper, titanium dioxide, zinc oxide, alumina and metal organic frameworks) and other nano-sized fillers (based on silica, halloysite, zeolites and cellulose nanocrystals).
The carbon nano tube has excellent rapid water molecule conveying characteristic and good antifouling characteristic, the graphene oxide has antifouling and antimicrobial characteristics, and the nano particles can be used for preparing an anti-pollution film. Researchers prepare polyamide membranes doped with carbon quantum dots, and have certain chlorine resistance, stable flux and retention rate. Other researchers have immobilized silver nanoparticles on the membrane surface, providing polyamide membranes with effective and direct antimicrobial properties. In addition, researchers add nano particles CuO, znO and alumina into a polyamide reverse osmosis membrane, and the prepared membrane has excellent hydrophilicity, can improve the microbial scaling capability of the membrane, and does not influence the desalination efficiency. The nano silicon dioxide is added into the polyamide membrane, so that the mechanical and chemical stability and the hydrophilicity can be improved, and the water flux and the anti-scaling performance can be improved. The water flux can be improved by adopting NaY zeolite nano particles for post-treatment. MOFs-doped polyamide membranes show an increase in retention and water flux in existing nanomaterials. Generally, very little nanoparticle concentration is used in polyamide membranes. Thus, these smaller amounts of nanoparticles do not have any negative effect on the membrane material during water treatment, and as the nanoparticles are present in the polyamide membrane, they have a positive effect on the permeability and selectivity of the reverse osmosis membrane, such as improved membrane hydrophilicity, mechanical properties, and good chemical stability, thermal stability, and most importantly, increased rejection and water flux. At present, improving the interfacial interaction between nanoparticles and organic polyamide membranes is crucial for the construction of next-generation high-selectivity and high-stability polyamide reverse osmosis and nanofiltration membranes.
Efforts are now being made in all countries around the world to develop polyamide reverse osmosis and nanofiltration membranes with high selectivity and high stability, but more remain in the laboratory stage and once applied on a large scale no better results are achieved. For example, chinese patent 201410765612.X adds dopamine molecules to the aqueous phase to increase water flux; chinese patent 201410088977.3 adopts nano silicon dioxide, nano zinc oxide, nano silver and nano calcium oxide to carry out post-treatment on the prepared polyamide membrane so as to improve flux; china patent 201710587996.4 prepares a polyamide reverse osmosis membrane with high water flux and high selectivity by incorporating octaamino POSS into an aqueous phase. Although the water flux can be obviously improved by adding the nano particles into the polyamide membrane, the nano particles are easy to form defects between interfaces of the nano particles and the polyamide membrane due to poor compatibility between the nano particles and an oil phase acyl chloride solution or an amine monomer solution in a water phase, and the rejection rate of the finally formed reverse osmosis membrane is low. This is mainly due to UIO-66-NH 2 Is a MOFs material with amino group, and only UIO-66-NH is used at present 2 Blending with aqueous solutions to prepare interfacial polymeric membranes makes it difficult to form defect free polyamide membranes. Modification with amine groups to improve UIO-66-NH has also been investigated 2 The compatibility of the nanoparticles with the oil phase solution does not give good results. Thus, how to do UIO-66-NH 2 The nano particles are modified to improve the compatibility with aqueous or oil phase solutions, thereby preparing defect-free UIO-66-NH 2 The base polyamide reverse osmosis membrane is UIO-66-NH at present 2 The nano particles have technical problems in the application process of the reverse osmosis membrane field.
In order to solve the problem of poor compatibility of the existing nano particles and the aqueous phase/oil phase solution, the invention utilizes UIO-66-NH 2 The amino group is carboxylated and modified, and then the amino group is subjected to electrostatic interaction with aqueous phase amine solution, or acyl chloride molecules of ethoxy and hydrocarbyl react with amino group, and then the amino group reacts with oil phase solvent, or glycerol ether molecules react with amino group, and then the amino group reacts with solvent of aqueous phase amine solution, so that a defect-free UIO66-NH 2-based reverse osmosis membrane material can be formed with polyamide polymer chain segments.
Disclosure of Invention
The invention aims to overcome the defect of inorganic nano particles UIO-66-NH 2 The preparation of the high flux polyamide membrane has the defect of providing a method adopting UIO-66-NH 2 Method for preparing high-flux and stable polyamide nanofiltration and reverse osmosis membrane by derivative in situ, UIO-66-NH 2 Can stably carry out industrialized preparation, has simple modification process and is easy to be popularized in industry.
The invention uses UIO-66-NH 2 The modified polyurethane resin can be stably present in aqueous phase amine solution or oil phase acyl chloride solution by modifying to different degrees, and further can be well compatible with a polyamide chain segment or a crosslinking part formed by interfacial polymerization, thereby improving UIO-66-NH 2 The stability of the nano particles in the polyamide membrane, and the prepared polyamide membrane has higher water flux, stable retention rate and stability.
In order to achieve the technical effects, the invention is realized by the following technical scheme:
a high-performance polyamide composite membrane is prepared from non-woven fabric, porous supporting layer and UIO-66-NH 2 A polyamide dense layer of a base derivative, wherein the porous support layer is a polysulfone ultrafiltration layer contained on the surface of the nonwoven fabric; containing UIO-66-NH 2 The polyamide compact layer of the base derivative is formed by placing a porous supporting layer in an aqueous phase amine solution and an oil phase acyl chloride solution in sequence and carrying out interfacial polymerization, wherein the aqueous phase amine monomer solution or the oil phase acyl chloride solution can contain UIO-66-NH 2 And (3) a base derivative.
The structural formula of the amine is as follows:
wherein R1 and R2 are- (CH) 2 ) n-or-NH-, n is 1-3; r3, R4, R5 and R6 are-NH 2 Or CH (CH) 3 ；-NH-、-NH 2 The number of (2) is 1-4; and-NH 2 On the same side of the ring, both cis and trans conformations are included;
the amine is two or more of "-NH-, -NH 2 "attached to a saturated alicyclic hydrocarbon or substituted for the original aliphatic or aromatic C, wherein the amine monomer may be one or more of m-phenylenediamine, piperazine, p-phenylenediamine, 2, 5-dimethylpiperazine, (1R, 2R) - (-) -1, 2-cyclohexanediamine, N-bis (2-aminoethyl) ethylenediamine, 2, 6-dimethylpiperazine, ethylenediamine, 1, 4-cyclohexanediamine.
The structural formula of the acyl chloride is as follows:
wherein A is aromatic or aliphatic, and is a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring or an eight-membered ring; r1, R2, R3 and R4 are-C (O) Cl-or H, the number of-C (O) Cl-is 3-6, and ortho-position or meta-position is between two-C (O) Cl-groups;
the acyl chloride is three or more "-COCl" which is connected to saturated hydrocarbon or aromatic hydrocarbon, and the alicyclic acyl chloride can be selected as one or more of trimesoyl chloride, 1,2,4, 5-pyromellitic chloride, terephthaloyl chloride, isophthaloyl chloride, 1,2,3, 4-cyclobutanetetracarboxylic acid chloride, 1,2,4, 5-cyclohexanetetraformyl chloride, 1, 3, 5-cyclohexanetetraacyl chloride, 1,2, 4-cyclopentanetriacyl chloride, 1,2,3, 4-cyclopentanetetraacyl chloride and 1,2,3,4,5, 6-cyclohexanetetraacyl chloride which belong to an oil phase monomer.
The UIO-66-NH 2 The preparation method of the base derivative comprises the following steps: in organic solventAdding a proper amount of UIO-66-NH into the agent 2 Stirring, ultrasonic treating, adding anhydride, epoxy and acyl chloride micromolecules or chain micromolecules, reacting for 2-4 hr, precipitating with methanol, washing, filtering, freeze drying to obtain UIO-66-NH 2 And (3) a base derivative.
The UIO-66-NH 2 The method comprises the following steps:
the preparation method comprises the following steps: adding proper amount of UIO-66-NH into organic solvent 2 Stirring, ultrasonic treating, adding anhydride, epoxy ether, acyl chloride or chain micromolecule, reacting for 2-4 hr, precipitating with methanol, washing, filtering, freeze drying to obtain UIO-66-NH 2 And (3) a base derivative.
Preferably, after 2-4 hours of reaction, 0-1mL of water or another anhydride, epoxy ether, acid chloride micromolecule or chain micromolecule is added, and stirring is carried out at 0-60 ℃ to continue the reaction for 2-4 h.
Wherein, UIO-66-NH 2 The mass ratio of the acid anhydride, the epoxy ether and the acyl chloride micromolecules or chain micromolecules is as follows: 1:1.5-1:2.
The reaction temperature range is as follows: 0-60 DEG C
The organic solvent is selected from the group consisting of: n-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and the like.
The acid anhydrides are: one of diethanol anhydride, glutaric anhydride, succinic anhydride, 3-methyl glutaric anhydride, phthalic anhydride, 4, 5-dichlorophthalic anhydride, 1,2, 4-trimellitic anhydride, chlorinated trimellitic anhydride, ethane tetracarboxylic dianhydride, and ethylenediamine tetraacetic anhydride.
The acyl chloride is as follows: 2- (2-methoxyethoxy) acetyl chloride, acetoxyacetyl chloride, 2- (2- (2-methoxyethoxy) ethoxy) acetyl chloride, methoxyacetyl chloride, hexanoyl chloride, octanoyl chloride, n-pentanoyl chloride.
The epoxy ethers are as follows: 1, 4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
UIO-66-NH 2 After reacting with the acyl chloride, anhydride and epoxy ether molecules, the modified epoxy resin can form certain interaction with aqueous phase amine solution and organic phase acyl chloride solution to improve the compatibility, thereby forming defect-free UIO-66-NH 2 A base polyamide membrane material.
Further, the invention provides a preparation method of the high-performance reverse osmosis composite membrane, which comprises the following steps:
(1) Preparing aqueous amine solution: UIO-66-NH 2 Dissolving the base derivative and polyamine in pure water, and then adding triethylamine, camphorsulfonic acid and sodium lauryl sulfate as additives; generally, UIO-66-NH 2 The mass concentration of the base derivative and the polyamine is 0.1-1wt%, the mass concentration of the triethylamine and the camphorsulfonic acid is 0-2.3wt%, the mass concentration of the sodium laurylsulfate is 0.05-0.2wt%;
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: UIO-66-NH 2 The base derivative and the polybasic acyl chloride are dissolved in an organic solvent, and then ethyl acetate and acetone are added as additives, generally, UIO-66-NH 2 The mass concentration of the base derivative and the polybasic acyl chloride is 0.005-0.1wt%, 0.05-0.25wt%, and the mass concentration of the ethyl acetate and the acetone is 0-2wt%, 0-2wt%; the oil phase monomer solvent is one or more of cyclohexane, n-hexane, cycloheptane and ISOPAR-G, ISOPAR-E, ISOPAR-H.
(3) Preparation of high-performance polyamide film: the ultrafiltration porous supporting layer adopts 1% sodium hydroxide or 1.5% NaHCO 3 Soaking in aqueous solution for 30min, washing with ultrapure water, air drying, soaking ultrafiltration porous support layer in the aqueous amine solution for 1-10min, removing surface water drop, soaking in polyacyl chloride solution for 30-300s to form polyamide compact layer; taking out, and heat treating at 60-100deg.C for 1-10 min; preferably, the pore size of the porous support layer is in the range of 10-40nm.
Compared with the prior art, the preparation method of the high-performance polyamide membrane has the following advantages:
1. the prepared polyamide reverse osmosis membrane sheet (0.2% NaCl is added under 225 psi) is tested under the simulated brackish water condition, and the water flux is 36.41-72.72L/m 2 h, the retention rate is 99.0-99.5%; the prepared polyamide nanofiltration membrane sheet (in 0.2% NaCl/MgSO) was tested under simulated drinking water conditions 4 145 psi) at a water flux of 62.76-82.93/m 2 h，MgSO 4 The retention rate is above 99%, the NaCl retention rate is 25-45%, and the water flux and the retention rate are excellent; and the retention rate and the water flux are kept basically unchanged in the operation time of one week.
2. In addition, the acid chloride, anhydride and epoxy ether micromolecules used for modification have the advantages of simple structure, low cost, easy obtainment and the like, and the modification method is simple and is convenient to popularize in industrial application.
3.UIO-66-NH 2 The derivative is octahedral, can stably exist in a polyamide high molecular chain segment through interfacial polymerization, overcomes the defects, improves the retention rate, is a porous material, and can remarkably improve the water flux.
Drawings
FIG. 1 UIO-66-NH 2 SEM electron microscope image of (c)
FIG. 2 UIO-66-NH modified with diethanol anhydride/1, 4-butanediol diglycidyl ether 2 SEM electron microscope image of (c)
FIG. 3 UIO-66-NH 2 SEM (scanning electron microscope) image for doping preparation of polyamide film
FIG. 4 UIO-66-NH modified with diethanol anhydride/1, 4-butanediol diglycidyl ether 2 SEM electron microscopy of doped to produce polyamide films.
Detailed Description
The technical scheme of the invention is further explained and illustrated below by combining specific examples and test examples so that the technical scheme of the invention can be fully understood by those skilled in the art, but the explanation and the illustration are not further limiting of the technical scheme of the invention, and the technical scheme obtained by simple numerical replacement and conventional adjustment based on the invention belongs to the protection scope of the invention.
Example 1
Preparation of UIO-66-NH 2 (mw= 2828.95) derivative: to 20mL of NMP, 1.414g of UIO-66-NH was added 2 2.04g of ethane tetracarboxylic dianhydride, stirring at room temperature under the protection of nitrogen, reacting for 2.5 hours, adding 0.4mL of water, reacting for 2 hours at 40 ℃, and obtaining the ethane tetracarboxylic dianhydride modified UIO-66-NH after methanol precipitation, washing, filtering and freeze drying of the product 2 The derivative has 88 percent (2.14 g) yield and the structure is shown as a structural formula (I):
(1) Preparing aqueous amine solution: preparing ethane tetracarboxylic dianhydride derivative with mass concentration of 0.2%, 1.9% m-phenylenediamine solution, 2.02% triethylamine, 4.646% camphorsulfonic acid and 0.2% sodium lauryl sulfate aqueous solution;
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: preparing ISOPAR-G solution with mass concentration of 0.15% of trimesoyl chloride and 0.03% of tetrabutyl orthotitanate;
(3) Preparation of high-performance polyamide film: soaking the polysulfone ultrafiltration membrane in ultrapure water for 120min, washing, airing, immersing in the aqueous phase amine solution in the step (1) for 5min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 60s to form a polyamide compact layer, immersing in water for 5min, taking out, placing at 80 ℃ and carrying out heat treatment for 4 min.
The prepared reverse osmosis composite membranes were each continuously filtered for 1 hour at 225psi operating pressure using 0.2% aqueous NaCl as a test solution, and tested for performance. After 1h, the water flux was 48. L.m-2.h-1 and the salt rejection was 99.3%.
Example 2
Preparation of UIO-66-NH 2 (mw= 2828.95) derivative: 1.414g of UIO-66-NH was added to 20mL of DMSO 2 2.36g of 2- (2- (2-methoxyethoxy) ethoxy) acetyl chloride (MW= 196.33) were reacted for 2.5 hours under nitrogen with stirring and dissolution at room temperature, 0.6mL of water was added and reacted for 2 hours at 40 ℃The product is subjected to methanol precipitation, washing, filtering and freeze drying to obtain the 2- (2- (2-methoxyethoxy) ethoxy) acetyl chloride modified UIO-66-NH2 derivative with the yield of 72 percent (1.97 g), and the structure is shown as the structural formula (II):
(1) Preparing aqueous amine solution: preparing piperazine with the mass concentration of 1.5% and sodium lauryl sulfate aqueous solution with the mass concentration of 0.2%;
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: preparing an ISOPAR-G solution of 0.15% of cyclobutanetetra formyl chloride, 0.01% of 2- (2- (2-methoxyethoxy) ethoxy) acetyl chloride modified UIO-66-NH2 derivative and 2% of acetone;
(3) Preparation of high-performance polyamide film: soaking the porous support layer in 1% NaOH aqueous solution for 10min, washing with ultrapure water, airing, immersing in the aqueous amine solution in the step (1) for 2min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 40s to form a polyamide compact layer, and then placing at 60 ℃ for heat treatment for 2 min.
With 0.2% MgSO 4 The prepared polyamide nanofiltration composite membrane was continuously filtered for 1 hour under 145psi operating pressure as a test solution to test the performance of the reverse osmosis composite membrane. After 1h, mgSO 4 The retention rate was 99.3% and the salt/water flux was 76.5 L.m -2 · h -1 The NaCl rejection was 82.4% and the salt/water flux was 74.1 L.m -2 · h -1 。
Example 3
Preparation of UIO-66-NH 2 (mw= 2828.95) derivative: in 25mL of DMSO, 2.26 of UIO-66-NH was added 2 2.23g of diethanol anhydride is stirred and dissolved for 3.5 hours at room temperature under the protection of nitrogen, and the product is subjected to methanol precipitation, washing, filtering and freeze drying to obtain the diethanol anhydride modified UIO-66-NH 2 The derivative has a yield of 71% (2.4 g) and a structure shown in a structural formula (III):
(1) Preparing aqueous amine solution: preparing the diethanol anhydride modified UIO-66-NH with the mass concentration of 0.03 percent 2 A base derivative, 2.5% m-phenylenediamine solution, 2.02% triethylamine, 6.6% camphorsulfonic acid and 0.1% sodium lauryl sulfate aqueous solution;
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: preparing ISOPAR-G solution of trimesoyl chloride with mass concentration of 0.12% and acetone with mass concentration of 2%;
(3) Preparation of high-performance polyamide film: the porous support layer was treated with 1.5% NaHCO 3 Soaking in aqueous solution for 10min, washing with ultrapure water, airing, immersing in aqueous amine solution in the step (1) for 5min, removing surface water drops, immersing in acyl chloride solution in the step (2) for 90s to form a polyamide compact layer, then placing in a 65 ℃ oven, heat-treating for 5min, washing with pure water for 10min, then placing in 80 ℃ and heat-treating for 6 min.
The prepared polyamide reverse osmosis composite membrane was continuously filtered for 1 hour at 225psi operating pressure using 0.2% aqueous NaCl as a test solution, and the performance of the reverse osmosis composite membrane was tested. After 1h, the NaCl rejection was 99.4% and the salt/water flux was 66. L.m -2 · h -1 。
Example 4
Preparation of UIO-66-NH 2 (mw= 2828.95) derivative: 1.981g of UIO-66-NH was added to 30mL of NMP 2 1.95g of diethanol anhydride is stirred and dissolved for 3.5 hours at room temperature under the protection of nitrogen, then 2.04g of 1, 4-butanediol diglycidyl ether is added, and is stirred and reacted for 2 hours at 40 ℃, and the product is subjected to methanol precipitation, washing, filtration and freeze drying to obtain the diethanol anhydride/1, 4-butanediol diglycidyl ether modified UIO-66-NH 2 The derivative has a yield of 70% (3.24 g) and a structure shown in a structural formula (IV):
(1) Preparing aqueous amine solution: preparing 0.1% mass concentration of diethanol anhydride/1, 4-butanediol diglycidyl ether modified UIO-66-NH 2 Derivative, 2.5% m-phenylenediamine solution, 2.02% triethylamine and 4.06% camphorsulfonic acid aqueous solution;
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: preparing ISOPAR-G solution of trimesoyl chloride with mass concentration of 0.18% and ethyl acetate with mass concentration of 2%;
(3) Preparation of high-performance polyamide film: soaking the porous support layer in 1.5% NaHCO3 aqueous solution for 10min, washing with ultrapure water, airing, immersing in the aqueous amine solution in the step (1) for 10min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 90s to form a polyamide compact layer, then placing at 60 ℃, heat-treating for 6min, washing with 8% glycerol aqueous solution for 10min, then placing at 80 ℃ and heat-treating for 6 min.
The prepared polyamide nanofiltration composite membrane was continuously filtered for 1 hour at 225psi operating pressure using 0.2% aqueous NaCl solution as a test solution, and the performance of the reverse osmosis composite membrane was tested. After 1h, the NaCl rejection was 99.3% and the salt/water flux was 72.72 L.m -2 · h -1 。
Example 5
(1) Preparing aqueous amine solution: preparing piperazine (PIP) solution with a mass concentration of 1.5% and 0.05% Sodium Lauryl Sulfate (SLS) water solution;
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: preparing trimesoyl chloride with mass concentration of 0.13% and UIO-66-NH modified by 2- (2- (2-methoxyethoxy) ethoxy) acetyl chloride with mass concentration of 0.03% 2 Derivatives (from example 2), 2% ethyl acetate in ISOPAR-G;
(3) Preparation of high-performance polyamide film: the porous support layer was treated with 1.5% NaHCO 3 Soaking in aqueous solution for 10min, washing with ultrapure water, air drying, immersing in aqueous amine solution in the step (1) for 4min, removing surface water drops, immersing in acyl chloride solution in the step (2) for 90s to form a polyamide compact layer, and then placing at 60 ℃ for heat treatment for 6 min.
With 0.2% MgSO 4 Aqueous NaCl solution as test solution, operated at 145psiAnd continuously filtering the prepared polyamide nanofiltration composite membrane for 1h under pressure, and testing the performance of the reverse osmosis composite membrane. After 1h, the MgSO4 retention was 99.0%, the salt/water flux was 74.87 L.m-2.h-1, the NaCl retention was 32.4%, and the salt/water flux was 79.3L.m -2 · h -1 。
Example 6
Preparation of UIO-66-NH 2 (mw= 2828.95) derivative: 1.132g of UIO-66-NH was added to 20mL of DMSO 2 (Mw= 2828.95) and 1.845g of ethylenediamine tetraacetic acid dianhydride, stirring and dissolving the mixture at room temperature under the protection of nitrogen for 1.5h, and obtaining the ethylenediamine tetraacetic acid dianhydride modified UIO-66-NH after methanol precipitation, washing, filtering and freeze drying of the product 2 (mw= 2828.95) derivative (yield 81% (1.912 g), structure as shown in structural formula (V):
(1) Preparing aqueous amine solution: preparing 0.2% ethylenediamine tetraacetic anhydride modified UIO-66-NH2 derivative-1, 2.0% m-phenylenediamine solution, 2.02% triethylamine, 3.3% camphorsulfonic acid and 0.1% sodium lauryl sulfate aqueous solution;
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: preparing trimesoyl chloride with mass concentration of 0.15% and 2- (2- (2-methoxyethoxy) ethoxy) acetyl chloride modified UIO-66-NH with mass concentration of 0.02% 2 Derivatives (from example 2), 4% acetone in ISOPAR-G;
(3) Preparation of high-performance polyamide film: soaking the porous support layer in 1% NaOH aqueous solution for 10min, washing with ultrapure water, airing, immersing in the aqueous amine solution in the step (1) for 6min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 90s to form a polyamide compact layer, then placing in a 60 ℃ for heat treatment for 6min, washing in 8% glycerol aqueous solution for 10min, then placing in a 80 ℃ for heat treatment for 6min, and finally obtaining the porous support layer.
The prepared polyamide reverse osmosis composite membrane was connected using 0.2% aqueous NaCl solution as a test solution at an operating pressure of 225psiAnd filtering for 1h, and testing the performance of the reverse osmosis composite membrane. After 1h, the NaCl rejection was 99.0% and the salt/water flux was 72.5L. Mu.m -2 · h -1 。
Example 7
(1) Preparing aqueous amine solution: the configuration mass concentration is as follows: preparing ethylenediamine tetraacetic dianhydride modified UIO-66-NH with mass concentration of 0.2% 2 The derivative (prepared from example 6), a 2.0% solution of m-phenylenediamine, 2.02% Triethylamine (TEA), 3.3% camphorsulfonic acid (CSA), 0.1% aqueous Sodium Lauryl Sulfate (SLS);
(2) The preparation of the oil phase acyl chloride solution comprises the following steps: preparing an ISOPAR-H solution with the mass concentration of 0.18% and containing 1,2,4, 5-pyromellitic chloride (BTC) and 2% of acetone;
(3) Preparation of high-performance polyamide film: soaking the porous support layer in 1.5% NaHCO3 aqueous solution for 10min, washing with ultrapure water, airing, immersing in the aqueous amine solution in the step (1) for 4min, removing surface water drops, immersing in the acyl chloride solution in the step (2) for 90s to form a polyamide nanofiltration membrane compact layer, then placing at 60 ℃, heat-treating for 6min, washing with 8% glycerol aqueous solution for 10min, then placing at 80 ℃ and heat-treating for 6 min.
Example 8 comparative experiments
In the comparative experiment, the conditions of the oil phase acyl chloride solution and the post-treatment are the same as those of the example 4, except that UIO-66-NH is used in the aqueous amine solution in the comparative experiment 2 Unmodified, directly incorporated into the aqueous amine solution.
The prepared polyamide reverse osmosis composite membrane was continuously filtered for 1 hour at 225psi operating pressure using 0.2% aqueous NaCl as a test solution, and the performance of the reverse osmosis composite membrane was tested. After 1h, the NaCl rejection was 99.3% and the salt/water flux was 63.3L. Mu.m -2 · h -1 。
The flux and the retention rate of the high-flux polyamide membrane prepared by the invention are shown in table 1:
TABLE 1
As can be seen from Table 1, UIO-66-NH modified with diethanol anhydride/1, 4-butanediol diglycidyl ether 2 The derivative has good compatibility with aqueous amine solution, so the prepared polyamide membrane has excellent water flux and selectivity, and the water flux reaches 72.72L m –2 · h –1 The retention rate of NaCl is 99.3 percent, and the UIO-66-NH modified by diethanol anhydride/1, 4-butanediol diglycidyl ether 2 And electron microscope images of the prepared high-flux polyamide membrane are shown in fig. 2 and 4; in contrast, unmodified UIO-66-NH 2 The electron microscope image of the polyamide film prepared by the method is shown as figure 1, and the electron microscope image of the polyamide film prepared by the method is shown as figure 3, which shows that UIO-66-NH 2 The compatibility with the polyamide membrane is poor, and defects exist on the surface of the membrane, so that the prepared polyamide membrane has low interception rate and high water flux.
The reverse osmosis composite membrane and the preparation method thereof provided by the invention are described in detail, specific examples are used for describing the principle and the implementation mode of the invention, the description of the examples is only used for helping to understand the method and the core idea of the invention, and it should be pointed out that, for those skilled in the art, several improvements and modifications can be made to the invention without departing from the principle of the invention, and the improvements and modifications also fall within the protection scope of the claims of the invention.
Claims (2)
1. A preparation method of a high-flux and defect-free reverse osmosis composite membrane comprises the following steps:
(1) Preparing aqueous amine solution: carboxylated UIO-66-NH 2 Dissolving the base derivative and polyamine in pure water, and then adding triethylamine, camphorsulfonic acid and sodium lauryl sulfate as additives;
(2) Preparation of oil phase acyl chloride solution: UIO-66-NH 2 The base derivative and the polybasic acyl chloride are dissolved in an organic solvent, then ethyl acetate and acetone are added as additives,
(3) Preparation of high-performance polyamide film: soaking the ultrafiltration porous support layer in alkaline solution, washing with ultrapure water, air drying, soaking the ultrafiltration porous support layer in the aqueous amine solution for 1-10min, removing surface water drops, and soaking in the polyacyl chloride solution for 30-300s to form a polyamide compact layer; taking out, placing at 60-100deg.C, and heat treating for 1-10min, wherein the porous support layer is formed by coating polysulfone solution on non-woven fabric to form polysulfone ultrafiltration layer;
wherein carboxylated UIO-66-NH in step (1) 2 The mass concentration of the base derivative and the polyamine is 0.1-1wt%, the mass concentration of the triethylamine and the camphorsulfonic acid is 0-2.3wt%, the mass concentration of the sodium laurylsulfate is 0.05-0.2wt%;
wherein the carboxylated UIO-66-NH 2 The preparation method of the base derivative comprises the following steps: adding proper amount of UIO-66-NH into organic solvent 2 Stirring, ultrasonic treating, adding acid anhydride micromolecule, reacting for 2-4 hr, precipitating with methanol, washing, filtering, freeze drying to obtain carboxylated UIO-66-NH 2 A base derivative;
the acid anhydrides are: one of diethanol anhydride, glutaric anhydride, succinic anhydride, 3-methyl glutaric anhydride, phthalic anhydride, 4, 5-dichlorophthalic anhydride, 1,2, 4-trimellitic anhydride, chlorinated trimellitic anhydride, ethane tetracarboxylic dianhydride, and ethylenediamine tetraacetic anhydride.
2. A high-throughput, defect-free polyamide membrane prepared by the process of claim 1, characterized in that the membrane is composed of a nonwoven fabric, a porous support layer, and a layer containing UIO-66-NH 2 A polyamide dense layer of a base derivative, wherein the porous support layer is a polysulfone ultrafiltration layer contained on the surface of the nonwoven fabric; containing UIO-66-NH 2 The polyamide compact layer of the base derivative is formed by placing a porous supporting layer in an aqueous phase amine solution and an oil phase acyl chloride solution in sequence and carrying out interfacial polymerization, wherein the carboxylated UIO-66-NH2 base derivative can generate electrostatic interaction with the aqueous phase amine solution to form a stable UIO-66-NH 2/aqueous phase amine solution, and then the interfacial polymerization is carried out to obtain the defect-free polyamide compact layer.
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