WO2019179082A1 - Membrane d'osmose inverse à structure organométallique et son procédé de préparation - Google Patents

Membrane d'osmose inverse à structure organométallique et son procédé de préparation Download PDF

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WO2019179082A1
WO2019179082A1 PCT/CN2018/110429 CN2018110429W WO2019179082A1 WO 2019179082 A1 WO2019179082 A1 WO 2019179082A1 CN 2018110429 W CN2018110429 W CN 2018110429W WO 2019179082 A1 WO2019179082 A1 WO 2019179082A1
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metal organic
reverse osmosis
osmosis membrane
support layer
organic framework
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PCT/CN2018/110429
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Chinese (zh)
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章冰洁
康燕
梁松苗
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时代沃顿科技有限公司
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Publication of WO2019179082A1 publication Critical patent/WO2019179082A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • 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
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • 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
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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

Definitions

  • the present disclosure relates to the field of reverse osmosis membrane modification technology, in particular to a metal organic framework reverse osmosis membrane and a preparation method thereof.
  • the thermal method mainly includes multi-stage flash (MSF), multi-effect distillation (MED) and gas-phase compression distillation (VCD); membrane method mainly has reverse osmosis ( RO) and nanofiltration (NF).
  • MSF multi-stage flash
  • MED multi-effect distillation
  • VCD gas-phase compression distillation
  • RO reverse osmosis
  • NF nanofiltration
  • the seawater reverse osmosis membrane method has reduced the cost of seawater desalination to one-fifth, but energy conservation is an eternal topic that has been followed up all over the world. How to reduce the cost of membrane method has been the direction of many scientific and technological personnel, due to energy consumption in membrane method. The cost of consumption is 50-60% of the total cost. Therefore, how to reduce the energy consumption of the seawater membrane method becomes the most important breakthrough in cost saving (Zarzo et al., Desalination, 2018, 427, 1-9).
  • the reverse osmosis membrane will greatly reduce the energy consumption. It has been reported that if the flux of the reverse osmosis membrane is increased to more than three times that of the existing polyamide membrane, the pressure vessel can be reduced by 44% to reduce the depletion energy consumption of the 15% seawater reverse osmosis membrane (David et al., Energy). Environ. Sci., 2014, 7, 1134-1141). Therefore, how to improve the flux of the membrane under the condition of ensuring the quality of the effluent and combine the high water yield with the low energy consumption has always been the goal pursued by the global polyamide composite reverse osmosis membrane workers. Many companies have also developed many low pressure and low energy.
  • the present disclosure aims to provide a high-throughput low-energy seawater desalination reverse osmosis membrane and a preparation method thereof.
  • the blending of crosslinked metal organic framework materials in the functional layer of reverse osmosis membrane can obtain advanced mixed matrix membranes (MMMs).
  • MMMs advanced mixed matrix membranes
  • the introduction of this material improves the thermal stability and mechanical properties of the membrane on the one hand, and the metal organic of the size can be regulated on the other hand.
  • the framework nanochannel provides a selective water inlet channel, and the metal organic framework nano material can form a large number of hydrogen bonds on the one hand to increase the hydrophilicity of the surface of the membrane, and on the other hand, the inherent carboxylate can be condensed and polymerized with the acid chloride to form a total
  • the valence bond increases the degree of crosslinking of the functional layer of the membrane, so the introduction of the material can greatly increase the flux of the membrane without losing the salt rejection rate of the membrane.
  • the present application produces a thinner seawater membrane by controlling the process conditions, which on the one hand saves costs and on the other hand increases the water flux of the membrane. It has the feature of solving the technical problem that the reverse osmosis membrane of the prior art has high system energy consumption due to low flux.
  • a metal organic framework reverse osmosis membrane characterized in that the support layer is synthesized by a polymer and an active hydrophilic stabilizer, the aqueous phase solution comprises a catalyst and an aqueous phase monomer, and the oil phase solution comprises a metal organic framework nano material and an oil phase single
  • the desalting layer on the support layer is a functional layer of the support layer formed by the interfacial polymerization of the aqueous phase solution and the oil phase solution to form a crosslinked nanocrystal network structure.
  • the polymer is one of polysulfone or polyethersulfone, and has a concentration of 16 wt% to 20 wt% in the solution for preparing the support layer.
  • the active hydrophilic stabilizer is polyvinylpyrrolidone, and the concentration in the solution for preparing the support layer is 0.15 wt% to 5 wt%.
  • the solution for preparing the support layer is N,N-dimethylformamide (DMF), and the part other than the polymer and the active hydrophilic stabilizer is N,N-dimethylformamide (DMF). Added to 100% by weight.
  • the catalyst is a mixture of a phase transfer catalyst and an acid binding agent; wherein the phase transfer catalyst is tetrabutylammonium chloride, triethylamine hydrochloride, benzyltriethylammonium chloride, dodecyltrimethyl
  • concentration of one of the ammonium chlorides in the aqueous phase solution is from 0.5% by weight to 5.0% by weight; the acid binding agent is triethylamine, and the concentration in the aqueous phase solution is from 0.5% by weight to 5.0% by weight.
  • the aqueous phase monomer is m-phenylenediamine, and the concentration in the aqueous phase solution is from 0.5 wt% to 5.0 wt%.
  • the metal organic framework nano material is composed of silver ions and trimesic acid, the mass ratio of which is 1:1, the active functional group is a carboxyl group, and the concentration in the oil phase solution is 0.02 wt% to 0.1 wt%.
  • the oil phase monomer is one of phthaloyl chloride, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldichloride, and trimesoyl chloride in an oil phase solution.
  • concentration in the range is 0.005 wt% to 3 wt%.
  • the oil phase solution has a solvent of one or more of n-hexane, cyclohexane, n-heptane and Isopar G.
  • a method for preparing a metal organic framework reverse osmosis membrane comprises the following steps:
  • support layer 0.15 wt% to 5 wt% of polyvinylpyrrolidone and N,N-dimethylformamide (DMF) are mixed and dispersed, and stirred at a stirring speed of 60-90 r/min.
  • the polyvinylpyrrolidone is uniformly dispersed in a solution of N,N-dimethylformamide (DMF), the stirring speed is maintained to 90 ° C, and a polymer having a mass concentration of 16 wt% to 20 wt% is added thereto, and the balance is N.
  • N-dimethylformamide (DMF) was added to 100% to obtain a solution for preparing a support layer, followed by vacuum defoaming treatment at -80 kPa, followed by filtration, cooling to room temperature, and coating the solution on a nonwoven fabric base.
  • the material enters the coagulation bath and is then placed in deionized water for 200 s to obtain a support layer;
  • the support layer prepared in the step (2) is immersed in deionized water for 30 min, and the support layer is taken out from the deionized water, and contains 0.5 wt% to 5 wt% of m-phenylenediamine, 0.5 wt.
  • the aqueous solution of % ⁇ 5wt% triethylamine and 0.5wt% ⁇ 5wt% phase transfer catalyst is contacted for 40s ⁇ 60s, so that the aqueous phase solution penetrates into the pore of the support layer; the excess aqueous solution is filtered, and the aqueous phase liquid on the surface of the membrane is filtered.
  • the droplet is removed by a rolling rubber roller; the membrane is immersed in the oil phase solution for 30 s to 60 s, and the oil phase solution contains 0.02 wt% to 0.1 wt% of the metal organic framework nanomaterial and 0.005 wt% to 3 wt% of phthaloyl chloride, One of phthaloyl chloride, isophthalic acid chloride, phthaloyl dichloride, and trimesoyl chloride.
  • the membrane was taken out and washed with dilute hydrochloric acid for 5 min, infiltrated with glycerin aqueous solution for 5 min, and placed in an oven at 30 ° C to 90 ° C. Drying in the middle, that is.
  • the preparation ratio of the support layer to the aqueous phase solution and the oil phase solution is 100 g: 4-6 L: 4-6 L.
  • the ultrasound has a power of 24 kHz and an output and pulse of 80 w and 0.6, respectively.
  • the oven temperature is from 30 ° C to 90 ° C, preferably 80 ° C.
  • the coagulation bath is an aqueous solution of N,N-dimethylformamide (DMF) having a mass fraction of 1.0%.
  • DMF N,N-dimethylformamide
  • the dilute hydrochloric acid and the hydrogen chloride have a mass concentration of 2%.
  • the aqueous glycerin solution has a glycerin concentration of 8%.
  • the present disclosure has the following advantages:
  • the present disclosure adds a phase transfer catalyst to the aqueous phase to increase the rate of polymerization, to make the prepared polyamide reverse osmosis membrane have more regular and dense pores, and more importantly, to add metal organic framework nanomaterials to the oil phase.
  • the prepared reverse osmosis membrane is thinner and provides an additional water inlet channel, and the size-regulated nanochannel does not affect the membrane salt rejection rate.
  • the preparation method of the metal organic framework nano material modified polyamide seawater membrane functional layer greatly improves the membrane flux without affecting the seawater membrane salt rejection rate, and the operation is simple and the production cost is low.
  • the presence of the metal organic framework not only provides a large number of hydrogen bonds to the functional layer, but also a free amino group in the functional layer.
  • the cross-linking condensation polymerization is carried out to form a covalent bond, and the produced reverse osmosis membrane has a thickness of about 100 nm.
  • the mass percentage of polysulfone, polyethersulfone, and polyvinylpyrrolidone in the present specification is the mass percentage in the solution for preparing the support layer.
  • the mass percentage of tetrabutylammonium chloride, triethylamine hydrochloride, benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, triethylamine and m-phenylenediamine in the present specification Is the mass percentage in the aqueous phase solution.
  • the metal organic framework nano material phthaloyl chloride, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldichloride, trimesoyl chloride, n-hexane, cyclohexane,
  • the mass percentage of n-heptane and Isopar G are the mass percentages in the oil phase solution.
  • a method for preparing a metal organic framework reverse osmosis membrane comprises the following steps:
  • the solution for preparing the support layer is obtained, and then vacuum defoaming treatment is carried out at -80 kPa, filtered, cooled to room temperature, uniformly coated on the non-woven substrate by a doctor blade system and entered into a coagulation bath, and the coagulation bath is of mass.
  • a 1.0% aqueous solution of DMF was applied at a temperature of 20 ° C; then it was placed in deionized water at a temperature of 20 ° C. After 200 s of treatment, a support layer was obtained.
  • the preparation ratio of the support layer to the aqueous phase solution and the oil phase solution is 100 g: 4 L: 4 L.
  • the ultrasound has a power of 24 kHz and an output and pulse of 80 w and 0.6, respectively.
  • a method for preparing a metal organic framework reverse osmosis membrane comprises the following steps:
  • the solution for preparing the support layer is obtained, and then vacuum defoaming treatment is carried out at -80 kPa, filtered, cooled to room temperature, uniformly coated on the non-woven substrate by a doctor blade system, and entered into a coagulation bath, and the coagulation bath is a mass fraction. It was a 1.0% aqueous solution of DMF at a temperature of 20 ° C; it was then placed in deionized water at a temperature of 20 ° C. After 200 s of treatment, a support layer was obtained.
  • the support layer prepared in the step (2) was immersed in deionized water for 30 min, and the support layer was taken out from the deionized water, and contained with 1 wt% of m-phenylenediamine, 1 wt% of triethylamine, The aqueous phase solution of 1 wt% triethylamine hydrochloride is contacted for 45 s to allow the aqueous phase solution to penetrate into the pores of the support layer; the excess aqueous solution is filtered off, and the aqueous phase droplets on the surface of the membrane are removed by a rolling rubber roller; After immersing in an oil phase solution containing Isopar G as a solvent and containing 0.04 wt% of metal organic framework nanomaterials and 0.5 wt% of terephthalic acid chloride for 40 s, the membrane was taken out and washed with 2.0 wt% of dilute hydrochloric acid for 5 min.
  • the preparation ratio of the support layer to the aqueous phase solution and the oil phase solution is 100 g: 4 L: 5 L.
  • the ultrasound has a power of 24 kHz and an output and pulse of 80 w and 0.6, respectively.
  • a method for preparing a metal organic framework reverse osmosis membrane comprises the following steps:
  • a solution for preparing a support layer was obtained, and then vacuum defoaming treatment was carried out at -80 kPa, followed by filtration, cooling to room temperature, uniform coating on a nonwoven fabric substrate by a doctor blade system, and entering a coagulation bath.
  • the DMF aqueous solution having a mass fraction of 1.0% was at a temperature of 20 ° C; then it was placed in deionized water at a temperature of 20 ° C, and after 200 s of treatment, a support layer was obtained.
  • the support layer prepared in the step (2) was immersed in deionized water for 30 min, and the support layer was taken out from the deionized water, and contained with 2.5% by weight of m-phenylenediamine, 2.5 wt% of three-ethyl
  • An aqueous solution of amine, 2.5 wt% benzyltriethylammonium chloride is contacted for 50 s to allow the aqueous phase solution to penetrate into the pores of the support layer; the excess aqueous solution is filtered off, and the aqueous phase droplets on the surface of the membrane are moved by a rolling rubber roller.
  • the membrane was immersed in a solvent solution of n-hexane, cyclohexane mass ratio 1:1, and containing 0.06 wt% metal organic framework nanomaterial and 1 wt% isophthalic acid chloride for 45 s, and then the membrane was taken out. 2.0wt% dilute hydrochloric acid was washed, the cleaning time was 5min, then placed in 8.0wt% glycerin aqueous solution, glycerin temperature 60°C, infiltration time 5min, finally, the prepared metal organic frame reverse osmosis membrane was in 75°C oven Drying, you get the SWRO-MOFs-3 reverse osmosis membrane.
  • the preparation ratio of the support layer to the aqueous phase solution and the oil phase solution is 100 g: 5 L: 5 L.
  • the ultrasound has a power of 24 kHz and an output and pulse of 80 w and 0.6, respectively.
  • a method for preparing a metal organic framework reverse osmosis membrane comprises the following steps:
  • the solution for preparing the support layer is obtained, and then vacuum defoaming treatment is carried out at -80 kPa, filtered, cooled to room temperature, uniformly coated on the non-woven substrate by a doctor blade system and entered into a coagulation bath, and the coagulation bath is of mass.
  • a 1.0% aqueous solution of DMF was applied at a temperature of 20 ° C; then it was placed in deionized water at a temperature of 20 ° C. After 200 s of treatment, a support layer was obtained.
  • the support layer prepared in the step (2) was immersed in deionized water for 30 min, and the support layer was taken out from the deionized water, and contained with 4 wt% of m-phenylenediamine, 4 wt% of triethylamine, The aqueous phase solution of 4wt% dodecyltrimethylammonium chloride is contacted for 55s to allow the aqueous phase solution to penetrate into the pores of the support layer; the excess aqueous solution is filtered out, and the aqueous phase droplets on the surface of the membrane are removed by rolling rubber rollers.
  • the membrane was immersed in a solvent solution containing cyclohexane and n-heptane in a mass ratio of 1:1, and containing 0.08 wt% of metal organic framework nanomaterial and 2 wt% of 4,4'-diphenyldichloride chloride for 50 s.
  • the membrane was taken out and washed with 2.0 wt% dilute hydrochloric acid for 5 min, then placed in a 8.0 wt% aqueous solution of glycerin, the glycerin temperature was 60 ° C, and the infiltration time was 5 min.
  • the prepared metal organic frame reverse osmosis membrane was prepared. Drying in an oven at 80 ° C gives the SWRO-MOFs-4 reverse osmosis membrane.
  • the preparation ratio of the support layer to the aqueous phase solution and the oil phase solution is 100 g: 6 L: 5 L.
  • the ultrasound has a power of 24 kHz and an output and pulse of 80 w and 0.6, respectively.
  • a method for preparing a metal organic framework reverse osmosis membrane comprises the following steps:
  • metal organic framework nanomaterials silver nitrate and N,N-dimethylformamide (DMF) were ultrasonically dispersed for 10 min at a mass ratio of 1:38, and trimesic acid and N,N-dimethyl
  • the solution for preparing the support layer is obtained, and then vacuum defoaming treatment is carried out at -80 kPa, filtered, cooled to room temperature, uniformly coated on the non-woven substrate by a doctor blade system and entered into a coagulation bath, and the coagulation bath is of mass.
  • a 1.0% aqueous solution of DMF was applied at a temperature of 20 ° C; then it was placed in deionized water at a temperature of 20 ° C. After 200 s of treatment, a support layer was obtained.
  • the support layer prepared in the step (2) is immersed in deionized water for 30 min, the support layer is taken out from the deionized water, and contains 5 wt% of m-phenylenediamine, 5 wt% of triethylamine, 5wt% aqueous solution of tetrabutylammonium chloride is contacted for 60s, so that the aqueous phase solution penetrates into the pores of the support layer; the excess aqueous solution is filtered out, and the aqueous phase droplets on the surface of the membrane are removed by rolling rubber roller; Immersed in an oil phase solution containing n-hexane, n-heptane, Isopar G at a mass ratio of 1:1:1, and containing 0.1 wt% of metal organic framework nanomaterials and 3 wt% of trimesoyl chloride for 60 s, and then taken out the membrane with 2.0.
  • the wt% diluted hydrochloric acid was cleaned for 5 min, then placed in a 8.0 wt% aqueous solution of glycerin, the glycerin temperature was 60 ° C, and the infiltration time was 5 min. Finally, the prepared metal organic frame reverse osmosis membrane was baked in an oven at 90 ° C. Dry, that is, SWRO-MOFs-5 reverse osmosis membrane.
  • the preparation ratio of the support layer to the aqueous phase solution and the oil phase solution is 100 g: 6 L: 6 L.
  • the ultrasound has a power of 24 kHz and an output and pulse of 80 w and 0.6, respectively.
  • a method for preparing a reverse osmosis membrane comprising the steps of:
  • support layer 5 wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) were mixed and dispersed, and stirred at a stirring speed of 90 r/min to make polyvinylpyrrolidone in N , N-dimethylformamide (DMF) solution was uniformly dispersed, maintaining the stirring speed to 90 ° C, adding 18 wt% polysulfone, and the remainder was supplemented with N,N-dimethylformamide (DMF) to 100 wt.
  • N,N-dimethylformamide (DMF) 5 wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) were mixed and dispersed, and stirred at a stirring speed of 90 r/min to make polyvinylpyrrolidone in N , N-dimethylformamide (DMF) solution was uniformly dispersed, maintaining the stirring speed to 90 ° C, adding 18 wt% polysulfone,
  • the solution for preparing the support layer is obtained, and then vacuum defoaming treatment is carried out at -80 kPa, filtered, cooled to room temperature, uniformly coated on the non-woven substrate by a doctor blade system, and entered into a coagulation bath, and the coagulation bath is a mass fraction. It was a 1.0% aqueous solution of DMF at a temperature of 20 ° C; it was then placed in deionized water at a temperature of 20 ° C. After 200 s of treatment, a support layer was obtained.
  • the support layer prepared in the step (1) was immersed in deionized water for 30 min, and the support layer was taken out from the deionized water, and contained with 3 wt% of m-phenylenediamine, 4 wt% of triethylamine, 2wt% aqueous solution of benzyltriethylammonium chloride is contacted for 40s, so that the aqueous phase solution penetrates into the pores of the support layer; the excess aqueous solution is filtered out, and the aqueous phase droplets on the surface of the membrane are removed by rolling rubber rollers; After the membrane was immersed in an oil phase solution containing Iwtar G as a solvent and containing 3 wt% of trimesoyl chloride for 60 s, the membrane was taken out and washed with 2.0 wt% of dilute hydrochloric acid for 5 min, and then placed at 8.0 wt% of glycerol.
  • the glycerin temperature is 60 ° C
  • the infiltration time is 5 min.
  • the prepared reverse osmosis membrane is dried in an oven at 80 ° C to obtain a SWRO reverse osmosis membrane.
  • the preparation ratio of the support layer to the aqueous phase solution and the oil phase solution is 100 g: 5 L: 5 L.
  • the ultrasound has a power of 24 kHz and an output and pulse of 80 w and 0.6, respectively.
  • the SWRO-MOFs-1, SWRO-MOFs-2, SWRO-MOFs-3, SWRO-MOFs-4, SWRO-MOFs-5 and SWRO of Examples 1-5 and Comparative Example 1 were placed in a reverse osmosis membrane test bench.
  • the test was carried out by rinsing with pure water at a working pressure of 500 psi for 15 min and then switching to a 32,000 ppm NaCl aqueous solution as raw water.
  • the temperature was controlled at 25 ° C, the pH was 6.4-7.3, and the pressure was 800 psi.
  • the performance of the reverse osmosis membrane was tested after 30 min. The thickness of each reverse osmosis membrane was recorded, and the results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane d'osmose inverse à structure organométallique et son procédé de préparation. Une couche de support de ladite membrane d'osmose inverse est synthétisée à partir d'un polymère et d'un stabilisant hydrophile actif. Une couche de dessalement sur la couche de support est une couche fonctionnelle qui a une structure de réseau nanocristallin réticulé et est formée en soumettant la couche de support à une réaction de polymérisation interfaciale d'une solution de phase aqueuse et d'une solution de phase huileuse. Le procédé de préparation de ladite membrane d'osmose inverse comprend la préparation d'une couche de support de polymère, la préparation d'un nano-ion de structure organique métallique, et la préparation d'une couche de dessalement. La présence de la structure organométallique fournit un grand nombre de liaisons hydrogène à la couche fonctionnelle, et en même temps, le cadre organométallique peut réticuler et condenser avec des groupes amino libres dans la couche fonctionnelle, ce qui permet d'augmenter le degré de réticulation de la membrane d'osmose inverse. La membrane d'osmose inverse a une faible épaisseur de film, ce qui permet d'économiser considérablement les coûts de fabrication. De manière plus importante, la membrane d'osmose inverse peut considérablement augmenter le flux de membrane sans affecter le taux d'élimination de sel, de telle sorte que la consommation d'énergie de fonctionnement de la membrane est réduite, et ainsi est une membrane de dessalement d'eau de mer à faible consommation d'énergie ayant des propriétés supérieures.
PCT/CN2018/110429 2018-03-20 2018-10-16 Membrane d'osmose inverse à structure organométallique et son procédé de préparation WO2019179082A1 (fr)

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CN114660026A (zh) * 2022-02-26 2022-06-24 安徽大学 非甾体抗炎药dcf检测膜材料及其制备方法与应用
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