WO2020189898A1 - Membrane de séparation par osmose retardée sous pression et son procédé de fabrication - Google Patents

Membrane de séparation par osmose retardée sous pression et son procédé de fabrication Download PDF

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WO2020189898A1
WO2020189898A1 PCT/KR2020/002355 KR2020002355W WO2020189898A1 WO 2020189898 A1 WO2020189898 A1 WO 2020189898A1 KR 2020002355 W KR2020002355 W KR 2020002355W WO 2020189898 A1 WO2020189898 A1 WO 2020189898A1
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pressure
delayed osmosis
osmosis membrane
membrane
polysulfone resin
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PCT/KR2020/002355
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English (en)
Korean (ko)
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한만재
심연주
이종화
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도레이첨단소재 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • 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
    • 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
    • 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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
    • 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
    • B01D69/1216—Three or more layers
    • 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
    • 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
    • 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
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • 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 invention relates to a pressure delayed osmosis (PRO) separator and a method of manufacturing the same, and more particularly, to a high water permeability and high power density PRO separator capable of providing a pressure delayed osmosis module with excellent commerciality and a method of manufacturing the same. .
  • PRO pressure delayed osmosis
  • the osmosis phenomenon as described above is the core of desalination technology using seawater, which is one of the methods that can solve the severe water shortage due to climate change caused by global warming, industrial water increase due to industrialization, and water demand increase due to population increase.
  • seawater desalination process up to now is a highly energy-intensive process, and it still has limitations in terms of economics unless it is a water shortage area such as the Middle East.
  • the reverse osmosis method is a technology that has been used for the past 30 years, and has a high degree of completion. Recently, the development of a technology focusing on improvement of a reverse osmosis membrane capable of obtaining a high recovery rate even at low pressure has been continued. On the other hand, with the continuation of technology development as described above, technologies for recovering high-pressure energy from seawater condensed water discharged from the reverse osmosis process have recently emerged, and as the membrane technology has continued to develop rapidly, the osmotic pressure development introduced in 1976. There is increasing interest in
  • Osmotic power generation means generating electricity by using the osmotic pressure action at the place where two streams with a difference in salinity meet, and where seawater with an osmotic pressure of 27 bar and river water or sewage with an osmotic pressure close to zero meet 27
  • the bar osmotic pressure can be used for power generation.
  • the power generation uses a pressure delayed osmosis (PRO) method different from the reverse osmosis method (RO).
  • Patent Publication No. 2017-1731825 relates to a method of manufacturing a high-performance forward osmosis thin-film composite separator using a hydrophilic porous support layer.
  • a prepolymerization solution is prepared by mixing polyethylene glycol diacrylate, a photoinitiator, and a solvent.
  • Disclosed is a method of preparing a porous support layer by irradiating and polymerizing light and forming a selection layer (active layer) on the support layer to prepare a separator having a high water transmittance.
  • the present invention has been conceived to solve the above-described problems, and the problem to be solved by the present invention is a method of manufacturing a pressure delayed osmosis (PRO) separator and module that can be commercialized more easily and secures high water permeability and high power density. To provide.
  • PRO pressure delayed osmosis
  • the present invention for solving the above problem relates to a pressure delayed osmosis membrane, comprising a porous support layer, a porous hydrophilic polymer layer, and a composite membrane in which an active layer is sequentially stacked, and the porous hydrophilic polymer layer is a polysulfone resin and It may be formed by coating and phase-separating a polymer crude liquid containing at least one selected from among sulfonated polysulfone resins.
  • Another object of the present invention is to provide a pressure delayed osmosis module provided with the pressure delayed osmosis membrane described above.
  • the pressure delayed osmosis (PRO) membrane of the present invention can implement a pressure delayed osmosis membrane and module having high water permeability and high power density.
  • a hydrophilic polymer to the polymer support layer, a high water permeability can be easily achieved, and thus, a pressure delayed osmosis membrane and a manufacturing method of a high power density suitable and practical for a large-capacity separation membrane production process can be provided.
  • FIG. 1 is a schematic diagram showing a cross-sectional view of a separator used in RO and PRO processes and a fouling phenomenon thereof.
  • FIG. 2 is a schematic cross-sectional view of a pressure delayed osmosis (PRO) separation membrane according to an embodiment of the present invention.
  • PRO pressure delayed osmosis
  • FIG. 3 is a SEM measurement photograph of a cross section of a PRO separator according to an embodiment of the present invention.
  • FIG. 4 is a schematic diagram of a pressure delay osmotic membrane module according to an embodiment of the present invention.
  • the method of manufacturing a high-performance forward osmosis thin film composite separator using a conventional hydrophilic porous support layer is to prepare a prepolymerization solution by mixing polyethylene glycol diacrylate, a photoinitiator and a solvent, and irradiate light to the prepolymerization solution.
  • a method of preparing a porous support layer by polymerization and forming a selection layer on the support layer to prepare a separator having a high water permeability is disclosed.
  • the pressure delayed osmosis (hereinafter referred to as "PRO") process differs from the RO (Reverse Osmosis) and FO (Forward Osmosis) processes, and the direction of movement of the flux depends on the osmosis gradient. It moves from the backing layer to the active layer or the selection layer, and accordingly, there is a problem that a fouling phenomenon occurs toward the back side of the PRO separator. Such fouling causes the degradation of the PRO separator and shortens the membrane module replacement and CIP cleaning cycle, thereby increasing the maintenance cost of the process.
  • RO Reverse Osmosis
  • FO Forward Osmosis
  • the present invention is a high water permeability and high power by forming a porous hydrophilic polymer layer 12 on the porous support layer 12 and forming the active layer 13 disposed on the upper surface of the support layer, as shown in the schematic diagram in FIG. It is an invention that can provide a pressure delayed osmosis membrane having a density (hereinafter, PRO membrane, 10) and a manufacturing method that can be easily manufactured and commercialized.
  • PRO membrane a density
  • the PRO separator of the present invention comprises a first step of preparing a polymer crude liquid by mixing a hydrophilic polymer resin and a solvent; A second step of forming a porous hydrophilic polymer layer on the porous support layer by processing the polymer crude liquid on the porous support so that the polymer crude liquid penetrates into the pores of the porous support, and then phase-transferring the polymer crude liquid; And 3 steps of forming an active layer on the porous hydrophilic polymer layer; by performing a process including, a PRO separator having a structure as in the schematic diagram of FIG. 2 may be manufactured.
  • the PRO separation membrane manufacturing method of the present invention may further include a fourth step of washing and drying the laminate having the active layer formed thereon in order to remove the unreacted residue.
  • the hydrophilic polymer resin may include at least one selected from a sulfonated polysulfone resin and a sulfonated polyethersulfone resin, and preferably, based on 100 parts by weight of the polysulfone resin, the sulfonated 4 to 25 parts by weight of the polysulfone resin, more preferably based on 100 parts by weight of the polysulfone resin, may include 5 to 15 parts by weight of the sulfonated polysulfone resin.
  • the amount of the sulfonated polysulfone resin used is less than 4 parts by weight, there may be a problem that the hydrophilicity of the separator may not be expressed, so that the water permeability may be lowered. If it exceeds 25 parts by weight, the structure of the separator is deformed, resulting in low porosity and pressure resistance. There may be a problem with this occurring.
  • the polysulfone resin may include a copolymer including a repeating unit represented by the following Formulas 1-1 and 1-2, and the weight average molecular weight of the polysulfone resin is 15,000 to 100,000 g/mol, preferably May be 20,000 to 65,000 g/mol, more preferably 20,000 to 40,000 g/mol.
  • the degree of sulfonation of the polysulfone resin may be 5 to 40%, preferably 20 to 40%.
  • the degree of sulfonation when the degree of sulfonation is less than 5%, the degree of hydrophilicity of the separation membrane is reduced, resulting in a decrease in water permeability, and the power density of the pressure-delayed osmosis membrane may be lowered. If the degree of sulfonation exceeds 40%, the pressure resistance of the PRO membrane is low. There may be a problem that the salt removal rate is lowered.
  • the sulfonated polysulfone resin may include a copolymer including a repeating unit represented by Formulas 2-1 and 2-2 below.
  • each of R 1 , R 2 , R 3 and R 4 is independently a hydrogen atom, a straight chain alkyl group of C1 to C5, a branched alkyl group of C3 to C5 or an alkyl of C2 to C4. It is a ren group, and preferably each of R 1 , R 2 , R 3 and R 4 may be independently a hydrogen atom, a straight chain alkyl group of C1 to C5 or a branched alkyl group of C3 to C5, and more preferably C1 to C3 It may be a straight-chain alkyl group of.
  • the sulfonated polysulfone resin may have a weight average molecular weight of 100,000 to 200,000 g/mol, preferably 120,000 to 180,000 g/mol, more preferably 130,000 to 165,000 g/mol.
  • the weight average molecular weight of the sulfonated polysulfone resin is less than 100,000 g/mol, the structure of the separator may be affected, and the active layer may become unstable, resulting in a decrease in the salt removal rate, and the weight of the sulfonated polysulfone resin If the average molecular weight exceeds 200,000 g/mol, the hydrophilicity of the porous hydrophilic polymer layer may decrease, resulting in a problem of lowering the water permeability.
  • the polymer crude liquid used to form the porous hydrophilic polymer layer is prepared by mixing the hydrophilic polymer resin and a solvent, and the polymer crude liquid has a viscosity of 500 to 3,000 cP (25°C), preferably 900 to 2,800 cP (25 °C), more preferably 1,250 ⁇ 2,500 cP (25 °C) is good.
  • the viscosity of the polymer crude liquid is less than 500 cP, the water permeability may increase, but the pressure resistance decreases, making it impossible to operate at high pressure.
  • the viscosity of the polymer crude liquid is more than 3,000 cP, the water permeability decreases and the power density of the pressure delayed osmosis membrane decreases.
  • the bonding strength between the porous support layer and the porous hydrophilic polymer layer may be weakened, resulting in a desorption phenomenon, and the surface of the porous hydrophilic polymer layer may become unstable, resulting in a low salt removal rate.
  • the porous support layer may be used without limitation, as long as the support layer is generally used for a pressure delayed osmosis membrane support, and preferably polyester, polypropylene, nylon, polyethylene, acrylic, rayon, acetate and It may include a fabric served with one or more fibers selected from cellulose.
  • the performance of the separator may be improved depending on the porosity and thickness of the porous support. Since the structure and thickness of the support affects the S value, which is the structural constant of the PRO separator, the power density of the separator may change depending on the selection of the support. For example, when a support having excellent air permeability is used, the S value decreases to implement a pressure delayed osmosis membrane having high water permeability and high power density, and when the thickness of the support is decreased, a high performance pressure delayed osmosis membrane can be manufactured.
  • the porous support is used with an air permeability of 50 to 700 cc/m 2 /sec, preferably 80 to 500 cc/m 2 /sec, more preferably 90 to 400 cc/cm 2 ⁇ sec. good.
  • step 2 is a process of forming a porous hydrophilic polymer layer on top of the porous support layer.
  • the polymer crude solution prepared in step 1 After applying the polymer crude solution prepared in step 1 to one side of the porous support, it is immersed in a coagulation bath containing a non-solvent, and phase separation (or A phase transition) is induced to form a porous hydrophilic polymer layer on the porous support layer to prepare a two-layered laminate.
  • the non-solvent at least one selected from water, ethanol, isopropyl alcohol and methanol may be used, and water and/or isopropyl alcohol may be preferably used.
  • the third step is a process of forming an active layer on the porous hydrophilic polymer layer of the laminate prepared in step 2, and the second step is 3 in which the laminate is immersed in an aqueous solution containing a polyfunctional amine or an alkylated aliphatic amine.
  • the active layer may include at least one selected from polyamide-based polymers, polypiperazine-based polymers, polyphenylenediamine-based polymers, polychlorophenylenediamine-based polymers, and polybenzidine-based polymers, and preferably polyamide-based It may be a layer containing a polymer.
  • the active layer in the third step is a polyamide-based active layer composed of a polyamide-based compound, it will be described in detail as follows.
  • Step 3-1 is the multifunctional amine or alkylation of the layered product in an aqueous solution containing 1.5 to 3.8% by weight of a polyfunctional amine or an alkylated aliphatic amine for 30 seconds to 300 seconds, preferably at a concentration of 2.0 to 3.8% by weight. It is carried out by immersing in an aqueous solution containing a polyfunctional amine or an alkylated aliphatic amine at a concentration of 2.5 to 3.5% by weight for 40 seconds to 200 seconds, more preferably in an aqueous solution containing the aliphatic amine.
  • the concentration of the polyfunctional amine or the alkylated aliphatic amine in the aqueous solution is less than 1.5% by weight, there may be a problem in that the interfacial polymerization reaction of 2-3 steps is not sufficiently formed and the active layer is not formed evenly, and the polyfunctionality in the aqueous solution
  • the concentration of amine or alkylated aliphatic amine exceeds 3.8% by weight, the water permeation constant (L/m 2 /hr/bar) of the produced PRO membrane is too low, or the structural constant of the porous hydrophilic polymer layer of the PRO membrane (S , mm) is too high, there may be a problem that the water permeability and/or power density of the PRO separator is very low.
  • the polyfunctional amine is at least one selected from metaphenyldiamine, paraphenyldiamine, orthophenyldiamine, piperazine, and alkylated piperazine, preferably from metaphenyldiamine, paraphenyldiamine and orthophenyldiamine. It may include at least one selected, more preferably at least one selected from metaphenyldiamine and paraphenyldiamine.
  • the aqueous solution containing the polyfunctional amine or the alkylated aliphatic amine of step 3-1 is at least one selected from the group consisting of a hydroxyl group, a sulfonated group, a carbonyl group, a trialkoxysilane group, an anionic group, and a tertiary amino group. It may further contain a hydrophilic compound having a hydrophilic functional group.
  • hydrophilic compound having a hydroxy group examples include 1,3-diamino-2-propanol, ethanolamine, diethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, It may contain at least one selected from 2-amino-1-butanol.
  • hydrophilic compound having a carbonyl group is 1 selected from aminoacetaldehyde dimethylacetal, ⁇ -aminobutylrolactone, 3-aminobenzamide, 4-aminobenzamide and N-(3-aminopropyl)-2-pyrrolidinone It may contain more than one species.
  • hydrophilic compound containing a trialkoxysilane group may include at least one selected from (3-aminopropyl)triethoxysilane or (3-aminopropyl)trimethoxysilane.
  • hydrophilic compounds having an anionic group include glycine, taurine, 3-amino-1-propenesulphonic acid, 4-amino-1-butenesulphonic acid, 2-aminoethyl hydrogen sulfate, and 3-aminobenzenesulphate.
  • hydrophilic compounds having a tertiary amino group 3-(dimethylamino)propylamine, 3-(diethylamino)propylamine, 4-(2-aminoethyl)morpholine, 1-(2-aminoethyl)pipe It may contain at least one selected from ragine, 3,3'-diamino-N-methyldipropylamine, and 1-(3-aminopropyl)imidazole.
  • the method of removing the non-solvent from the surface of the layered product in step 3-2 may be performed by a general method used in the art, and as a preferred example, the non-solvent may be removed by a compression method.
  • Step 3-3 is a step of performing interfacial polymerization, in the organic solution from which the non-solvent has been removed, at room temperature (10 to 35°C) for 30 seconds to 300 seconds, preferably 40 seconds to 180 seconds, more preferably 50 seconds to By immersing for about 120 seconds, the polyfunctional amine or the alkylated aliphatic amine present on the surface of the laminate and the polyfunctional acid halogen compound undergo interfacial polymerization to form an active layer including the polyamide compound.
  • the organic solution includes a polyfunctional acid halogen compound and an organic solvent, wherein the organic solvent may include at least one selected from hexane, toluene, cyclohexane, and heptane.
  • the polyfunctional acid halogen compound may include at least one selected from a polyfunctional acyl halide, a polyfunctional sulfonyl halide, and a polyfunctional isocyanate. More specifically, at least one polyfunctional acyl halide selected from trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride may be included, and preferably trimesoyl chloride may be included.
  • the organic solution may have a concentration of the polyfunctional acid halogen compound of 0.1 to 0.5% by weight, preferably 0.15 to 0.40% by weight, and if the concentration of the polyfunctional acid halogen compound is less than 0.1% by weight, a sufficient interfacial polymerization reaction product Due to the lack of this, the active layer may not be formed well, and if the amount exceeds 0.5% by weight, the active layer may be formed thick and there may be a problem that the water permeability decreases. Therefore, it is preferable to use an organic solution in the above concentration range.
  • the active layer thus formed can be formed as a dense surface layer of the PRO separator to form a structure with strong pressure resistance, and at the same time, the thin-film hydrophilic selective layer can maintain a uniform size of pores to secure a high salt exclusion rate.
  • the step 3-4 is a process of forming an active layer by drying the laminate subjected to the interfacial polymerization reaction.
  • the drying may be performed by a general method used in the art, and a preferred example may be performed by naturally drying for 1 minute to 5 minutes at 15 to 35°C.
  • the PRO separator of the present invention thus prepared has a form in which a porous support layer, a porous hydrophilic polymer layer, and an active layer are sequentially stacked, and the porous support layer may have a thickness of 60 ⁇ m to 80 ⁇ m, preferably 65 ⁇ m to 75 ⁇ m. .
  • the thickness of the porous support layer is less than 60 ⁇ m, and if the thickness of the support is less than 60 ⁇ m, the pressure resistance is low, so that it cannot be utilized under high pressure operation conditions, so that the function as a PRO separator may not be performed properly. If it exceeds, the S value, which is the structural constant of the PRO membrane, increases and the water permeability decreases, resulting in a problem of lowering the power density.
  • the porous hydrophilic polymer layer may have a thickness of 30 ⁇ m to 80 ⁇ m, preferably 35 ⁇ m to 75 ⁇ m, more preferably 40 ⁇ m to 65 ⁇ m.
  • the thickness of the porous hydrophilic polymer layer is less than 30 ⁇ m, the pressure resistance may be weakened, and when the thickness of the porous hydrophilic polymer layer is less than 80 ⁇ m, there may be a problem in that the separator structure constant increases and water permeability decreases.
  • the active layer may have a thickness of 0.1 ⁇ m to 1 ⁇ m, preferably a thickness of 0.2 ⁇ m to 0.8 ⁇ m, and if the thickness of the active layer is less than 0.1 ⁇ m, there may be a problem that the reverse salt transmission constant increases, and the thickness of the active layer is 1 If it exceeds ⁇ m there may be a problem that the water permeability is lowered.
  • the PRO separation membrane of the present invention has an overall thickness of 90.1 ⁇ m to 161 ⁇ m, preferably 95 to 145 ⁇ m, more preferably 100 to 140 ⁇ m, which is good in terms of proper water permeability and power density.
  • the PRO separation membrane of the present invention is subjected to a pressure delayed osmosis experiment at 25° C., a pressure of 20 bar and a flow rate of 0.5 LPM for an aqueous solution of 70,000 ppm sodium chloride, and the water permeability (J W ) is measured according to the following equation
  • the transmittance may be 12 to 40 L/m 2 /hr, preferably 14 to 38 L/m 2 /hr, more preferably 14.5 to 35 L/m 2 /hr.
  • Equation 1 J W is the water permeability, ⁇ draw is the osmotic pressure of the draw solution, ⁇ feed is the osmotic pressure of the influent solution, A is the water permeation constant of the PRO membrane, B is the salt permeation constant of the PRO membrane, and K m is 1 /K R , K R is the salt diffusion resistance coefficient of the porous hydrophilic polymer layer of the PRO membrane, and ⁇ P is the pressure.
  • the PRO separation membrane of the present invention has a water permeability constant value (A) of the PRO separation membrane in Equation 1 from 1 to 3.6 L/m 2 /hr/bar, preferably 1.10 to 3.00 L/m 2 /hr/bar , More preferably, it may satisfy the range of 1.15 to 2.90 L/m 2 /hr/bar.
  • A water permeability constant value of the PRO separation membrane in Equation 1 from 1 to 3.6 L/m 2 /hr/bar, preferably 1.10 to 3.00 L/m 2 /hr/bar , More preferably, it may satisfy the range of 1.15 to 2.90 L/m 2 /hr/bar.
  • the water permeability constant value is less than 1 L/m 2 /hr/bar, the water permeability decreases and the power density decreases. If it exceeds 3.6 L/m 2 /hr/bar, salt The disadvantage of lowering the removal rate may occur.
  • the PRO membrane of the present invention may satisfy a salt permeation constant value (B) of 0.1 to 0.8 L/m 2 /hr in Equation 1, preferably 0.200 to 0.600 L/m 2 /hr, more preferably In other words, the range of 0.300 to 0.550 L/m 2 /hr may be satisfied.
  • B salt permeation constant value
  • the water permeation constant value and the salt permeation constant value can be obtained based on Equation 2 below through an experiment of a salt removal rate under 1,000 ppm NaCl aqueous solution and 10 bar condition.
  • Equation 2 A is the water permeation constant of the PRO membrane, B is the salt permeation constant of the PRO membrane, R is the salt removal rate, ⁇ P is the pressure, and ⁇ is the difference between the osmotic pressure of the draw solution and the osmotic pressure of the input solution. .
  • the PRO separation membrane of the present invention may satisfy a range in which the S value, which is a structural constant in Equation 1, is 6 ⁇ 10 -4 to 3 ⁇ 10 -3 m, and preferably 7 ⁇ 10 -4 to 2.5 ⁇ 10 It can satisfy the range of -3 m.
  • the S value which is a structural constant in Equation 1
  • the pressure resistance of the separator decreases, so durability at high pressure may be lowered, and the operating period may also be reduced, and if it is 3 ⁇ 10 -3 m or more, the resistance inside the separator increases, resulting in water permeability. Reducing disadvantages can occur.
  • the salt diffusion resistance coefficient (K R ) of the porous hydrophilic polymer layer of the PRO separation membrane of Equation 1 and the structural constant (S) of the porous hydrophilic polymer layer of the PRO separation membrane are 70,000 ppm NaCl aqueous solution as a draw solution under a pressure of 20 bar.
  • Equation 3 S (mm) is the structural constant of the porous hydrophilic polymer layer of the PRO membrane, and D s is the salt diffusion coefficient.
  • the power density is the most important performance indicator in pressure delayed osmosis and can be defined as the amount of power that can be produced per unit area of the separator, and the maximum power density is calculated as the product of the water permeability through the separator and the water pressure difference.
  • the pressure-delayed osmosis process the low-concentration influent is moved to the high-concentration draw solution by the osmosis phenomenon. At this time, the turbine is operated using the increased flow rate of the draw solution to generate power. In this case, the power density is expressed by using the permeate flow rate through the separation membrane.
  • the PRO separator of the present invention has a power density of 6 to 25 W/m 2 , preferably 7.0 to 22.5 W/m 2 , more preferably 8.0 to 22.0 W/m when measured according to Equation 4 below. It can be 2 .
  • Equation 4 PRO is the water permeability (L/m 2 /hr), and ⁇ P is the pressure.
  • a fabric with a weft and warp of polyester material in the range of width (2.54 cm) ⁇ length (2.54 cm) and in the range of 300 to 310 plain weaves by carpenters was prepared.
  • the fabric has an air permeability of about 100 to 200 cc/cm 2 ⁇ sec and has a thickness of about 65 ⁇ m.
  • the polysulfone resin is a copolymer having a weight average molecular weight of 25,000 g/mol including a repeating unit represented by the following Chemical Formulas 1-1 and 1-2, and a sulfonation degree of 30%.
  • the sulfonated polysulfone resin is a copolymer having a weight average molecular weight of 145,000 g/mol including a repeating unit represented by the following Chemical Formulas 2-1 and 2-2.
  • R 1 , R 2 , R 3 and R 4 are all methyl groups.
  • the two-layered laminate was immersed in an aqueous solution containing metaphenylenediamine (MPD) in an amount of 3.5% by weight for 1 minute, and then the non-solvent on the surface was removed by a compression method. Thereafter, it was immersed in an organic solution containing 0.1% by weight of trimesoyl chloride (TMC) in an ISOPAR solvent (Exxon Corp.) for 1 minute, followed by interfacial polymerization, and then naturally dried at room temperature (25°C) for 1 minute and 30 seconds to obtain polyamide.
  • TMC trimesoyl chloride
  • ISOPAR solvent Exxon Corp.
  • a pressure delayed osmosis (PRO) membrane having a total thickness of about 120 ⁇ m was prepared by immersing in a 0.2% by weight sodium carbonate solution for 2 hours.
  • the thickness of the porous support layer was 65 ⁇ m
  • the thickness of the porous hydrophilic polymer layer was about 55 ⁇ m
  • the thickness of the active layer was about 0.2 ⁇ m.
  • Preparation was carried out in the same manner as in Example 1, but a polymer crude solution was prepared using 5.6 parts by weight of a sulfonated polysulfone resin based on 100 parts by weight of a polysulfone resin, and then a PRO separator was prepared as shown in Table 1 below. .
  • Preparation was carried out in the same manner as in Example 1, but a polymer crude solution was prepared using 8.3 parts by weight of a sulfonated polysulfone resin based on 100 parts by weight of a polysulfone resin, and then a PRO separator was prepared as shown in Table 1 below. .
  • a PRO separation membrane was prepared as shown in Table 2 below, but a PRO separation membrane having a thickness of 135 ⁇ m was prepared.
  • the thickness of the porous support layer was 65 ⁇ m, and the porosity
  • the thickness of the hydrophilic polymer layer was about 70 ⁇ m, and the thickness of the active layer was about 0.2 ⁇ m.
  • a PRO separation membrane was prepared as shown in Table 2 below, but a polymer crude solution having 3,200 cP was prepared at 25° C. by using less solvent, and then a PRO separation membrane was prepared using this.
  • Example 2 In the same manner as in Example 1, a PRO separator was prepared as shown in Table 2 below, but a PRO separator was prepared using a support having a thickness of 40 ⁇ m.
  • a PRO separation membrane was prepared as shown in Table 2 below by performing the same as in Example 1, but when the active layer was formed, the two-layered laminate was immersed in an aqueous solution containing metaphenylenediamine (MPD) at 4.0% by weight for 1 minute. After that, the non-solvent on the surface was removed by a pressing method. Thereafter, it was immersed in an organic solution containing 0.1% by weight of trimesoyl chloride (TMC) in an ISOPAR solvent (Exxon Corp.) for 1 minute, followed by interfacial polymerization, and then naturally dried at room temperature (25°C) for 1 minute and 30 seconds to obtain polyamide. The configured active layer was formed. Other procedures were carried out in the same conditions and method as in Example 1 to prepare a PRO separator.
  • MPC metaphenylenediamine
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Polymer bath liquid A 100 parts by weight 100 parts by weight 100 parts by weight 100 parts by weight 100 parts by weight 100 parts by weight 100 parts by weight B 11 parts by weight 11 parts by weight 5.6 parts by weight 8.3 parts by weight 11 parts by weight 11 parts by weight 11 parts by weight 11 parts by weight menstruum 444 parts by weight 326 parts by weight 450 parts by weight 447 parts by weight 444 parts by weight 444 parts by weight Viscosity (25°C) 2,000 cP 2,500 cP 1,950 cP 2,010 cP 2,000 cP 2,000 cP 2,000 cP Each layer thickness Porous support layer 68 ⁇ m 68 ⁇ m 68 ⁇ m 68 ⁇ m 68 ⁇ m 68 ⁇ m 68 ⁇ m 68 ⁇ m Porous hydrophilic polymer layer 50 ⁇ m 50 ⁇ m 50 ⁇ m 50 ⁇ m 38 ⁇ m 74 ⁇ m Active layer 0.2 ⁇ m 0.2 ⁇ m 0.2 ⁇ m 0.2
  • the active layer of the PRO separation membrane is mounted in the direction of the draw solution (aqueous sodium chloride solution) (direction in contact with the pressure), and under the conditions of 25°C temperature, 20bar pressure and 0.5 LPM flow rate, 70,000 ppm NaCl aqueous solution and distilled water as the supply solution
  • draw solution aqueous sodium chloride solution
  • Equation 1 J W is the water permeability, ⁇ draw is the osmotic pressure of the draw solution, ⁇ feed is the osmotic pressure of the influent solution, A is the water permeation constant of the PRO membrane, B is the salt permeation constant of the PRO membrane, and K m is 1 /K R , K R is the salt diffusion resistance coefficient of the porous hydrophilic polymer layer of the PRO membrane, and ⁇ P is the pressure.
  • a (L/m 2 /hr/bar), the water permeation constant of the PRO membrane and B (L/m 2 /hr), the salt permeation constant of the PRO membrane were 1,000 ppm NaCl aqueous solution, and the salt removal rate was tested under 10 bar conditions. Through, it can be obtained based on Equation 2 below.
  • Equation 2 A is the water permeation constant of the PRO membrane, B is the salt permeation constant of the PRO membrane, R is the salt removal rate, ⁇ P is the pressure, and ⁇ is the difference between the osmotic pressure of the draw solution and the osmotic pressure of the input solution. .
  • the salt diffusion resistance coefficient (K R ) of the porous hydrophilic polymer layer of the PRO separation membrane of Equation 1 and the structural constant (S) of the porous hydrophilic polymer layer of the PRO separation membrane are 70,000 ppm NaCl aqueous solution as a draw solution under a pressure of 20 bar. And through a pressure delayed osmosis experiment using distilled water as a feed solution, it can be calculated based on Equation 3 below.
  • Equation 3 S (mm) is the structural constant of the porous hydrophilic polymer layer of the PRO membrane, and D s is the salt diffusion coefficient.
  • the power density (W) of the PRO separator was calculated based on Equation 4 below.
  • Equation 4 PRO is the water permeability (L/m 2 /hr), and ⁇ P is the pressure.
  • Example 1 2.85 0.466 0.93 31.4 17.1
  • Example 2 1.35 0.400 1.19 17.04 9.5
  • Example 3 1.15 0.337 1.57 16 8.7
  • Example 4 1.47 0.435 1.51 17 9.3
  • Example 5 1.90 0.625 1.08 15 7.4
  • Example 6 1.51 0.481 2.16 12 6.7
  • Comparative Example 1 1.8 0.714 4.29 6 3.3
  • Comparative Example 2 1.84 0.707 2.83 9 4.9 Comparative Example 3 Not measurable Comparative Example 4 0.73 0.069 6.12 5.4 2.9
  • Comparative Example 5 1.4 0.710 2.8 8 4.1 Comparative Example 6 2.1 1.115 2.8 7 3.8 Comparative Example 7 1.7 0.711 4.1 6.5 3.6
  • Example 1 the pressure-delayed osmosis membrane prepared in Example 1 has higher water permeability and higher power density than the separation membranes prepared in Examples 2 to 4 and Comparative Examples 1 to 4.
  • Example 2 which has a higher viscosity than Example 1, it can be seen that the water permeability constant A value and the water permeability decreased, and thus the power density was also lowered. It is believed that the thickness of the separator increased as the viscosity of the polymer crude liquid increased.
  • Comparative Example 1 it was confirmed that the thickness of the support layer was increased compared to Example 1, so that the S value, which is the separator structural constant, was increased, and the water permeability was decreased, thereby lowering the power density, and Comparative Example 2 had a viscosity of 3,000 cP or more.
  • the salt permeation constant B value increased to 0.8 L/m 2 /hr or more
  • the separator structural constant S value increased, and the power density decreased.
  • Comparative Example 3 had a problem in that the thickness of the separator was decreased compared to Example 1, and the separator was compressed due to low durability, making it impossible to measure physical properties.
  • Comparative Example 4 as the content of metaphenylenediamine (MPD) in the active layer was increased, the salt removal rate was increased, so that the salt permeability constant B value decreased to 0.1 L/m 2 /hr or less. It was confirmed that the water permeability decreased and the water permeability constant A value was lowered to 1 L/m 2 /hr/bar or less, resulting in a problem of decreasing power density.
  • MPD metaphenylenediamine

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Abstract

La présente invention concerne une membrane de séparation par osmose retardée sous pression ayant une perméabilité à l'eau élevée et une densité de puissance élevée, et son procédé de fabrication. Plus spécifiquement, afin de commercialiser un processus d'osmose retardée par pression (PRO), il est essentiel de développer un module d'osmose à pression retardée ayant une perméabilité à l'eau élevée et une densité de puissance élevée. A cet effet, la présente invention concerne un procédé de fabrication d'une membrane de séparation ayant une perméabilité à l'eau élevée et une densité de puissance élevée.
PCT/KR2020/002355 2019-03-18 2020-02-19 Membrane de séparation par osmose retardée sous pression et son procédé de fabrication WO2020189898A1 (fr)

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KR20130131758A (ko) * 2012-05-24 2013-12-04 삼성전자주식회사 분리막 및 상기 분리막을 포함하는 수처리 장치
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