KR102010402B1 - Molecular additive, manufacturing method for water-treatment membrane using by the same and water-treatment membrane comprising the same - Google Patents
Molecular additive, manufacturing method for water-treatment membrane using by the same and water-treatment membrane comprising the same Download PDFInfo
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- KR102010402B1 KR102010402B1 KR1020150134109A KR20150134109A KR102010402B1 KR 102010402 B1 KR102010402 B1 KR 102010402B1 KR 1020150134109 A KR1020150134109 A KR 1020150134109A KR 20150134109 A KR20150134109 A KR 20150134109A KR 102010402 B1 KR102010402 B1 KR 102010402B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- 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
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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Abstract
The present specification relates to a molecular additive, a method for preparing a water treatment membrane using the same, and a water treatment membrane including the same.
Description
The present specification provides a molecular additive, a method of preparing a water treatment membrane using the same, and a water treatment membrane including the same.
Due to the recent severe pollution and lack of water in the water environment, the development of new water resources is an urgent challenge. Water pollution research aims to treat high quality living and industrial water, various kinds of domestic sewage and industrial wastewater, and interest in water treatment processes using membranes has advantages of energy saving. In addition, accelerating environmental regulations are expected to accelerate membrane technology. Conventional water treatment processes are difficult to meet the tightening regulations, but the membrane technology is expected to become a leading technology in the future because of the excellent treatment efficiency and stable treatment.
Liquid separation is classified into Micro Filtration, Ultra Filtration, Nano Filtration, Reverse Osmosis, Sedimentation, Active Transport and Electrodialysis depending on the pore of the membrane. The reverse osmosis method refers to a process of desalting using a semipermeable membrane that transmits water but is impermeable to salt. When the high pressure water in which the salt is dissolved flows into one side of the semipermeable membrane, the pure water is removed. Will come out on the other side at low pressure.
In recent years, about 1 billion gal / day of water worldwide has undergone desalination through reverse osmosis, and since the first desalination using reverse osmosis was introduced in the 1930s, many of the The study was conducted. Among them, the main successes of commercial success are cellulose-based asymmetric membranes and polyamide-based composite membranes. Cellulose membranes developed in the early stages of reverse osmosis membranes have suffered from several shortcomings due to their narrow operating pH range, their deformation at high temperatures, the high cost of operation using high pressure, and their vulnerability to microorganisms. This is a rarely used trend.
On the other hand, in the polyamide composite membrane, a polysulfone layer is formed on a nonwoven fabric to form a microporous support, and the microporous support is immersed in an aqueous solution of m-phenylenediamine (mPD) to form an mPD layer. After forming, it is immersed or coated in a trimesoyl chloride (TMC) organic solution, and the mPD layer is contacted with TMC to prepare a polyamide active layer by interfacial polymerization. By contacting the nonpolar and polar solutions, the polymerization takes place only at the interface to form a very thin polyamide layer. The polyamide-based composite membrane has high stability against pH change, can be operated at low pressure, and excellent salt removal rate, compared to existing cellulose-based asymmetric membranes, and is currently the main species of water treatment membranes.
Research on increasing the salt removal rate and permeation flow rate of such polyamide composite membranes has been continuously conducted.
The present specification is to provide a molecular additive, a method for preparing a water treatment membrane using the same, and a water treatment membrane including the same.
One embodiment of the present specification, a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And crown ether derivatives wherein at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed.
One embodiment of the present specification, preparing a porous support; And forming a polyamide active layer on the porous support using interfacial polymerization of an aqueous solution including an amine compound and an organic solution including an acyl halide compound, wherein at least one of the aqueous solution and the organic solution is Includes molecular additives,
The molecular additive may include a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And a crown ether derivative in which at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed.
One embodiment of the present specification, a porous support; And a polyamide active layer provided on the porous support.
The polyamide active layer may include a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And a molecular additive including a crown ether derivative wherein at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed.
An exemplary embodiment of the present specification provides a water treatment module including at least one of the water treatment separation membranes.
The water treatment membrane manufactured using the molecular additive according to the exemplary embodiment of the present specification may implement an excellent permeate flow rate.
The water treatment membrane according to one embodiment of the present specification can achieve a high permeate flow rate while minimizing the reduction of the salt removal rate.
1 illustrates a water treatment separation membrane according to an exemplary embodiment of the present specification.
In this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.
In the present specification, when a part "contains" a certain component, this means that the component may further include other components, except for the case where there is no contrary description.
The present inventors have completed the present invention in order to improve the performance of the polyamide active layer of the water treatment separation membrane. Specifically, the present inventors have developed a molecular additive containing a metal chelate compound and a crown ether derivative, and when using it in the preparation of the water treatment membrane, it was confirmed that excellent permeate flow rate is secured while minimizing the reduction of the salt removal rate. Specifically, in the case of forming the polyamide active layer through interfacial polymerization with the molecular additive, it was found that the production of a water treatment separation membrane having excellent performance is possible.
Hereinafter, this specification is demonstrated in detail.
One embodiment of the present specification, a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And crown ether derivatives wherein at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed.
The crown ether refers to a macrocyclic polyether molecule containing repeating units of the CR c 2 -CR c 2 O- structure wherein R c is H or alkyl and forms a cavity.
According to an exemplary embodiment of the present specification, the metal chelate compound may be located in the cavity of the crown ether derivative. Specifically, the molecular additive may be a structure in which a metal atom or metal ion of the metal chelate compound is bonded to the crown ether derivative.
According to one embodiment of the present specification, the aliphatic ring or the aromatic ring may be condensed to two consecutive carbon chains of the crown ether.
The crown ether may be a structure in which two or more 1,2-dimethoxyethanes referred to as two or more glymes are bonded. The aliphatic ring or the aromatic ring may be condensed to two consecutive carbon chains in the glyme structure in the crown ether. Specifically, two consecutive carbon chains in the glyme structure in the crown ether may constitute the aliphatic ring or the aromatic ring.
The crown ether derivative may have a structure in which an aliphatic ring or the aromatic ring is condensed to a crown ether, as shown in the following structure. However, the present invention is not limited to the following structure, and further substituents may be substituted, or the number of oxygen and carbon of the base crown ether may be adjusted.
According to an exemplary embodiment of the present specification, the crown ether is 12-crown-4, 15-crown-5, 18-crown-6, 20-crown-6, 21-crown-7, 24-crown-8 or 30 It may be crown-10.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring are each independently hydrogen; heavy hydrogen; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; Substituted or unsubstituted aldehyde group; Substituted or unsubstituted alkyl ketone group; Substituted or unsubstituted amine group; Nitrile group; Hydroxyl group; Thiol group; It may be substituted or unsubstituted with a carboxy group or nitric oxide.
According to an exemplary embodiment of the present specification, the aliphatic ring may be cycloalkyl. The cycloalkyl may have 3 to 60 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclo Hexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like. Specifically, according to one embodiment of the present specification, the aliphatic ring may be cyclohexane.
According to an exemplary embodiment of the present specification, the aromatic ring may be a monocyclic or polycyclic aromatic ring having 6 to 25 carbon atoms. Specifically, the aromatic ring may be benzene, naphthalene, anthracene, phenylene, tetracene, and the like, but is not limited thereto. More specifically, according to one embodiment of the present specification, the aromatic ring may be benzene.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may each be independently unsubstituted.
As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Cyano group; Nitro group; Hydroxyl group; An alkyl group; Cycloalkyl group; Alkenyl groups; An alkoxy group; Aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group or substituted with a substituent to which two or more substituents in the above-described substituents are connected, or does not have any substituents. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.
In the present specification, when the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-24. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number of a heterocyclic group is not specifically limited, It is preferable that it is C2-C60. Examples of the heterocyclic group include thiophenyl group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl Group, acridil group, hydroacridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazin Ginopyrazinyl group, isoquinolinyl group, indole group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, benzothiophenyl group, dibenzo Thiophenyl group, benzofuranyl group, dibenzofuranyl group; Benzosilol group; Dibenzosilol group; Phenanthrolinyl group, thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, phenooxazinyl group, and condensation structures thereof, It is not limited only to these.
In the present specification, the alkyl ketone group may mean that an alkyl group is bonded to one functional group of the ketone, and the remaining functional group of the ketone may be a bonding position.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with an alkyl group having 1 to 10 carbon atoms. Specifically, according to one embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with tertiary butyl.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with an aldehyde group.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with a substituted or unsubstituted benzimidazole group.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with a secondary nitrogen oxide.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with a propanone group.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with fluorine.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with bromine.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with chlorine.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with a nitrile group.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with a hydroxyl group.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with a thiol group.
According to an exemplary embodiment of the present specification, the aliphatic ring and the aromatic ring may be each independently substituted with a carboxy group.
According to an exemplary embodiment of the present specification, the crown ether derivative may be any one of the following structures. However, the crown ether derivative is not limited to the following structure, and further substituents may be substituted, or the number of oxygen and carbon of the crown ether as a base may be controlled. In addition, the substitution position of the substituent of the following structural formula is not limited to the following structure, and the substitution position may be adjusted.
In the above structural formula, R1 and R2 are each independently hydrogen; heavy hydrogen; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; Substituted or unsubstituted aldehyde group; Substituted or unsubstituted alkyl ketone group; Substituted or unsubstituted amine group; Nitrile group; Hydroxyl group; Thiol group; Carboxyl groups or nitric oxide.
According to an exemplary embodiment of the present specification, the metal atom or metal ion of the metal chelate compound may be selected from Group 1, Group 2, Group 13 and a transition metal. Specifically, according to one embodiment of the present specification, the metal atoms or metal ions of the metal chelate compound may be selected from Group 1, Group 2 or 13 of the periodic table, respectively. More specifically, according to one embodiment of the present specification, the metal atom or metal ion of the metal chelate compound may be selected from Group 2 or Group 13 of the periodic table, respectively.
According to an exemplary embodiment of the present specification, the metal atoms or metal ions of the metal chelate compound may be selected from alkaline earth metals, respectively.
According to an exemplary embodiment of the present specification, the metal atom or metal ion of the metal chelate compound may be any one of the metal atoms or metal ions of Mg, Ca and Sr.
According to an exemplary embodiment of the present specification, the ligand of the metal chelate compound may be a fluorinated diketonate.
According to an exemplary embodiment of the present specification, the diketonate may be beta-diketonate. Specifically, according to one embodiment of the present specification, the diketonate may be a fluorinated beta-diketonate.
In the present specification, the fluorination may be a combination of at least one -F or -CF 3 .
According to an exemplary embodiment of the present specification, the metal chelate compound is Al (acac) 3 , Al (F 6 acac) 3 , Be (acac) 2 , Be (F 6 acac) 2 , Be (acac) 2 , Be ( F 6 acac) 2 , Ca (acac) 2 , Ca (F 6 acac) 2 , Cd (acac) 2 , Cd (F 6 acac) 2 , Ce (acac) 3 , Ce (F 6 acac) 3 , Cr ( acac) 3 , Co (acac) 3 , Cu (acac) 2 , Cu (F6acac) 2 , Dy (acac) 3 , Er (acac) 3 , Fe (acac) 2 , Fe (acac) 3 , Ga (acac) 3 , Hf (acac) 4 , In (acac) 3 , K (acac), Li (acac), Mg (acac) 2 , Mg (F 6 acac) 2 , Mn (acac) 2 , Mn (acac) 3 , MoO 2 (acac) 2 , MoO 2 (F6acac) 2 , Na (acac), Nd (acac) 3 , Nd (F 6 acac) 3 , Ni (acac) 2 , Ni (F6acac) 2 , Pd (acac) 2 , Pr (acac) 3 , Pr (F6acac) 3 , Ru (acac) 3 , Ru (F 6 acac) 3 , Sc (acac) 2 , Sc (F 6 acac) 2 , Sm (acac) 3 , Sn (acac ) 2 , Sn (acac) 2 Cl 2 , t-butyl-Sn (acac) 2 , t-butyl-Sn (acac) 2 Cl 2 , Sn (F 6 acac) 2 , Sr (acac) 2 , Sr (F 6 acac) 2 , Tb (acac) 3 , V (acac) 3 , Y (acac) 3 , Y (F 6 acac) 3 , Zn (acac) 2 , Zn (F 6 acac) 2 , and Zr (acac) It may include at least one or more of four .
In the present specification, acac means acetylacetonate.
One embodiment of the present specification, preparing a porous support; And forming a polyamide active layer on the porous support using interfacial polymerization of an aqueous solution including an amine compound and an organic solution including an acyl halide compound, wherein at least one of the aqueous solution and the organic solution is Includes molecular additives,
The molecular additive may include a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And a crown ether derivative in which at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed.
The content of the molecular additive in the method of producing the water treatment separation membrane is the same as the content of the above-described molecular additive.
According to an exemplary embodiment of the present specification, the molecular additive may be included in the organic solution.
The molecular additive may be included as an additive when the polyamide active layer is formed through interfacial polymerization, thereby controlling the pore size of the polymer matrix of the polyamide active layer. Specifically, the molecular additive may be bonded to some of the hydrated acyl halide compounds contained in the organic solution by attraction such as hydrogen bonding, so that some pores of the network structure of the polyamide polymer formed by interfacial polymerization are largely formed. . Through this, the permeation flow rate of the water treatment separation membrane can be increased.
According to an exemplary embodiment of the present specification, the content of the molecular additive in the aqueous solution or the organic solution may be 0.001 wt% or more and 2 wt% or less. Specifically, according to the exemplary embodiment of the present specification, the content of the molecular additive of the aqueous solution or the organic solution may be 0.001 wt% or more and 1 or less, or 0.001 wt% or more and 0.5 wt% or less. Specifically, according to one embodiment of the present specification, the content of the molecular additive in the aqueous solution or the organic solution may be 0.01 wt% or more and 0.1 wt% or less. More specifically, according to the exemplary embodiment of the present specification, the content of the molecular additive of the aqueous solution or the organic solution may be 0.02 wt% or more and 0.07 wt% or less, or 0.02 wt% or more and 0.05 wt% or less.
When the content of the molecular additive is within the above range, the pore size of the polyamide active layer can be appropriately adjusted, thereby minimizing the reduction of the salt removal rate and at the same time can implement a high permeation.
According to one embodiment of the present specification, the molecular additive may be prepared by adding a salt, a diketonate compound, and a crown ether containing a metal ion to an organic solvent, and then refluxing for 12 hours or more. However, the method of preparing the molecular additive is not limited thereto, and may be prepared by appropriately adjusting it as necessary.
One embodiment of the present specification, a porous support; And a polyamide active layer provided on the porous support.
The polyamide active layer may include a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And a molecular additive including a crown ether derivative wherein at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed.
The content of the molecular additive in the water treatment membrane is the same as the content of the molecular additive described above.
According to an exemplary embodiment of the present specification, the molecular additive may be located in the pores of the polymer matrix of the polyamide active layer.
The molecular additives may act together during interfacial polymerization to form the polyamide active layer, thereby increasing the voids of the polymer matrix in the region where the molecular additives are located. Through this, relatively large voids are formed in a portion of the polyamide active layer, thereby increasing the permeate flow rate of the water treatment separation membrane.
1 illustrates a water treatment separation membrane according to an exemplary embodiment of the present specification. Specifically, FIG. 1 illustrates a water treatment separator in which the nonwoven fabric 100, the porous support 200, and the polyamide
According to one embodiment of the present specification, as the porous support, a coating layer of a polymer material may be used on a nonwoven fabric. Examples of the polymer material include polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyether ether ketone, polypropylene, polymethylpentene, polymethyl chloride and polyvinylidene fluorine. Ride or the like may be used, but is not necessarily limited thereto. Specifically, polysulfone may be used as the polymer material.
According to one embodiment of the present specification, the polyamide active layer may be formed through interfacial polymerization of an aqueous solution containing an amine compound and an organic solution containing an acyl halide compound. Specifically, the polyamide active layer comprises the steps of forming an aqueous layer including an amine compound on the porous support; And an organic solution including an acyl halide compound and an organic solvent on the aqueous solution layer including the amine compound, to form a polyamide active layer.
Upon contact between the aqueous solution layer containing the amine compound and the organic solution, the amine compound and acyl halide compound coated on the surface of the porous support react with each other to generate polyamide by interfacial polymerization, and are adsorbed onto the microporous support to form a thin film. Is formed. In the contact method, the polyamide active layer may be formed through a method such as dipping, spraying or coating.
According to one embodiment of the present specification, a method of forming an aqueous solution layer including an amine compound on the porous support is not particularly limited, and any method capable of forming an aqueous solution layer on the support may be used without limitation. Specifically, the method of forming the aqueous solution layer containing an amine compound on the porous support may be sprayed, applied, immersed, dripping and the like.
At this time, the aqueous solution layer may be further subjected to the step of removing the aqueous solution containing the excess amine compound as necessary. The aqueous solution layer formed on the porous support may be unevenly distributed when there are too many aqueous solutions present on the support. When the aqueous solution is unevenly distributed, a non-uniform polyamide active layer may be formed by subsequent interfacial polymerization. have. Therefore, it is preferable to remove excess aqueous solution after forming an aqueous solution layer on the said support body. The removal of the excess aqueous solution is not particularly limited, but may be performed using, for example, a sponge, air knife, nitrogen gas blowing, natural drying, or a compression roll.
According to an exemplary embodiment of the present specification, the amine compound in the aqueous solution containing the amine compound is not limited if the amine compound used in the water treatment separation membrane manufacturing, to give a specific example, m-phenylenediamine, p -Phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylene diamine Or a mixture thereof.
According to an exemplary embodiment of the present specification, the acyl halide compound is not limited thereto, but may be, for example, an aromatic compound having 2 to 3 carboxylic acid halides, such as trimezoyl chloride, isophthaloyl chloride and At least one mixture selected from the group of compounds consisting of terephthaloyl chloride.
According to an exemplary embodiment of the present specification, the organic solvent is an aliphatic hydrocarbon solvent, for example, a hydrophobic liquid which is not mixed with freons and water such as hexane, cyclohexane, heptane, and alkanes having 5 to 12 carbon atoms, for example. For example, alkanes having 5 to 12 carbon atoms and mixtures thereof, such as IsoPar (Exxon), ISOL-C (SK Chem), ISOL-G (Exxon), and the like may be used, but are not limited thereto.
According to one embodiment of the present specification, the water treatment separation membrane may be used as a micro filtration membrane, an ultra filtration membrane, an ultra filtration membrane, a nano filtration membrane, a reverse osmosis membrane, or a reverse osmosis membrane. Can be used.
In addition, an exemplary embodiment of the present specification provides a water treatment module including at least one of the water treatment separation membrane.
A specific kind of the water treatment module is not particularly limited, and examples thereof include a plate & frame module, a tubular module, a hollow & fiber module or a spiral wound module. In addition, as long as the water treatment module includes the water treatment separation membrane according to one embodiment of the present specification described above, other configurations and manufacturing methods are not particularly limited, and general means known in the art may be employed without limitation. have.
Meanwhile, the water treatment module according to one embodiment of the present specification has excellent salt removal rate and permeation flow rate, and has excellent chemical stability, and thus may be usefully used for water treatment devices such as household / industrial water purification devices, sewage treatment devices, seawater treatment devices, and the like. have.
Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.
[ Comparative example ]
18 wt% of polysulfone solids was added to a DMF (N, N-dimethylformamide) solution and dissolved at 80 to 85 for 12 hours or more to obtain a uniform liquid phase. This solution was cast 150 μm thick on a 95 μm to 100 μm thick nonwoven fabric made of polyester. Then, the cast nonwoven fabric was put in water to prepare a porous polysulfone support.
The porous polysulfone support prepared by the above method was soaked for 2 minutes in an aqueous solution containing 2 wt% of metaphenylenediamine (mPD), and then the excess aqueous solution on the support was removed by using a 25 psi roller, and at room temperature. It dried for 1 minute.
Subsequently, the support was immersed in 0.1 wt% of trimethoyl chloride (TMC) organic solution using ISOL-C (SK Chem) solvent for 1 minute, then taken out, dried in 60 oven for 10 minutes, and then 200 nm thick polyamide active layer. A water treatment separation membrane was prepared.
[ Example One]
18 wt% of polysulfone solids were added to a DMF (N, N-dimethylformamide) solution and dissolved at 80 to 85 for 12 hours or longer to obtain a uniform liquid phase. This solution was cast 150 μm thick on a 95 μm to 100 μm thick nonwoven fabric made of polyester. Then, the cast nonwoven fabric was put in water to prepare a porous polysulfone support.
The porous polysulfone support prepared by the above method was immersed in an aqueous solution containing 2 wt% of metaphenylenediamine and 0.025 wt% of Ca (acac) 2 (dibenzo-18-crown-6) for 2 minutes, and then removed. Excess aqueous solution of the phase was removed using a 25 psi roller and dried at room temperature for 1 minute.
Subsequently, the support was immersed in 0.1 wt% of trimethoyl chloride (TMC) organic solution using ISOL-C (SK Chem) solvent for 1 minute, then taken out, dried in 60 oven for 10 minutes, and then 200 nm thick polyamide active layer. A water treatment separation membrane was prepared.
[ Example 2]
A water treatment separation membrane was manufactured in the same manner as in Example 1, except that the content of Ca (acac) 2 (dibenzo-18-crown-6) in the aqueous solution was adjusted to 0.05 wt%.
[ Example 3]
A water treatment separation membrane was prepared in the same manner as in Example 1, except that the content of Ca (acac) 2 (dibenzo-18-crown-6) in the aqueous solution was adjusted to 0.1 wt%.
[ Example 4]
A water treatment membrane was prepared in the same manner as in Example 1, except that the content of Ca (acac) 2 (dibenzo-18-crown-6) in the aqueous solution was adjusted to 1 wt%.
[ Example 5]
18 wt% of polysulfone solids were added to a DMF (N, N-dimethylformamide) solution and dissolved at 80 to 85 for 12 hours or longer to obtain a uniform liquid phase. This solution was cast 150 μm thick on a 95 μm to 100 μm thick nonwoven fabric made of polyester. Then, the cast nonwoven fabric was put in water to prepare a porous polysulfone support.
The porous polysulfone support prepared by the above method was immersed in an aqueous solution containing 2 wt% of metaphenylenediamine and 0.025 wt% of Ca (F 6 acac) 2 (dibenzo-18-crown-6) for 2 minutes, and then taken out. Excess aqueous solution on the support was removed using a 25 psi roller, and dried at room temperature for 1 minute.
Subsequently, the support was immersed in 0.1 wt% of trimethoyl chloride (TMC) organic solution using ISOL-C (SK Chem) solvent for 1 minute, then taken out, dried in 60 oven for 10 minutes, and then 200 nm thick polyamide active layer. A water treatment separation membrane was prepared.
[ Example 6]
A water treatment membrane was prepared in the same manner as in Example 5, except that the content of Ca (F 6 acac) 2 (dibenzo-18-crown-6) in the aqueous solution was adjusted to 0.05 wt%.
[ Example 7]
A water treatment membrane was prepared in the same manner as in Example 5, except that the content of Ca (F 6 acac) 2 (dibenzo-18-crown-6) in the aqueous solution was adjusted to 0.1 wt%.
[ Example 8]
A water treatment membrane was prepared in the same manner as in Example 5, except that the content of Ca (F 6 acac) 2 (dibenzo-18-crown-6) in the aqueous solution was adjusted to 1 wt%.
In order to measure the rejection rate and permeation flow rate (gfd) of the water treatment membranes prepared according to Comparative Examples and Examples 1 to 4, a water treatment module including a flat permeation cell, a high pressure pump, a reservoir and a cooling device Was used. The structure of the plate-shaped transmission cell was 28 cm 2 in an effective cross-flow (cross-flow) manner. The reverse osmosis membrane was installed in the permeation cell, and then preliminarily operated for about 1 hour using tertiary distilled water to stabilize the evaluation equipment. Then, after confirming that the 250 ppm aqueous sodium chloride solution was stabilized by running the equipment for about 1 hour at a flow rate of 60 psi and 4.5 L / min, the flux was calculated by measuring the amount of water permeated at 25 ° C. for 10 minutes. Rejection was calculated by analyzing the salt concentration before and after permeation using a conductivity meter.
The salt removal rate and the permeate flow rate thus measured are shown in Table 1 below.
(wt%)
(wt%)
(%)
(gfd)
According to the table, in the case of the water treatment separation membrane according to the embodiment, although the salt removal rate slightly decreased compared to the comparative example, it can be seen that the permeate flow rate is significantly improved. Through this, the water treatment membrane according to one embodiment of the present specification, it can be inferred that by appropriately adjusting the type and content of molecular additives, it is possible to minimize the reduction of the salt removal rate, significantly improving the permeate flow rate.
100: nonwoven
200: porous support
300: polyamide active layer
400: brine
500: purified water
600: concentrated water
Claims (12)
A molecular additive comprising a crown ether derivative wherein at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed,
The crown ether refers to a macrocyclic polyether molecule containing repeating units of a CR c 2 -CR c 2 O- structure wherein R c is H or alkyl, and forms a cavity,
And said metal chelate compound is located in a cavity of said crown ether derivative.
The aliphatic ring or the aromatic ring is condensed to two consecutive carbon chains of the crown ether.
The crown ether is a molecular additive of 12-crown-4, 15-crown-5, 18-crown-6, 20-crown-6, 21-crown-7, 24-crown-8 or 30-crown-10. .
The aliphatic ring and the aromatic ring are each independently hydrogen; heavy hydrogen; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; Substituted or unsubstituted aldehyde group; Substituted or unsubstituted alkyl ketone group; Substituted or unsubstituted amine group; Nitrile group; Hydroxyl group; Thiol group; A molecular additive which is unsubstituted or substituted with a carboxyl group or nitric oxide.
The metal atom or metal ion of the said metal chelate compound is respectively chosen from group 1, 2, 13, and a transition metal of a periodic table.
The ligand of the metal chelate compound is a fluorinated diketonate.
The metal chelate compound may be Al (acac) 3 , Al (F 6 acac) 3 , Be (acac) 2 , Be (F 6 acac) 2 , Be (acac) 2 , Be (F 6 acac) 2 , Ca (acac ) 2 , Ca (F 6 acac) 2 , Cd (acac) 2 , Cd (F 6 acac) 2 , Ce (acac) 3 , Ce (F 6 acac) 3 , Cr (acac) 3 , Co (acac) 3 , Cu (acac) 2 , Cu (F6acac) 2 , Dy (acac) 3 , Er (acac) 3 , Fe (acac) 2 , Fe (acac) 3 , Ga (acac) 3 , Hf (acac) 4 , In (acac) 3 , K (acac), Li (acac), Mg (acac) 2 , Mg (F 6 acac) 2 , Mn (acac) 2 , Mn (acac) 3 , MoO 2 (acac) 2 , MoO 2 (F6acac) 2 , Na (acac), Nd (acac) 3 , Nd (F 6 acac) 3 , Ni (acac) 2 , Ni (F6acac) 2 , Pd (acac) 2 , Pr (acac) 3 , Pr ( F6acac) 3 , Ru (acac) 3 , Ru (F 6 acac) 3 , Sc (acac) 2 , Sc (F 6 acac) 2 , Sm (acac) 3 , Sn (acac) 2 , Sn (acac) 2 Cl 2 , t-butyl-Sn (acac) 2 , t-butyl-Sn (acac) 2 Cl 2 , Sn (F 6 acac) 2 , Sr (acac) 2 , Sr (F 6 acac) 2 , Tb (acac) At least one of 3 , V (acac) 3 , Y (acac) 3 , Y (F 6 acac) 3 , Zn (acac) 2 , Zn (F 6 acac) 2 , and Zr (acac) 4 Phosphorus Molecular Additives.
Using interfacial polymerization of an aqueous solution containing an amine compound and an organic solution containing an acyl halide compound, forming a polyamide active layer on the porous support,
At least one of the aqueous solution and the organic solution includes a molecular additive,
The molecular additive may include a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And a crown ether derivative in which at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed, comprising: a crown ether derivative;
The crown ether refers to a macrocyclic polyether molecule containing repeating units of a CR c 2 -CR c 2 O- structure wherein R c is H or alkyl, and forms a cavity,
The metal chelate compound is located in the cavity of the crown ether derivative is a method for producing a water treatment membrane.
The content of the molecular additive in the aqueous solution or the organic solution is 0.001 wt% or more 2 wt% or less manufacturing method of the water treatment membrane.
The polyamide active layer may include a metal chelate compound including a metal atom or a metal ion and a diketonate ligand; And a molecular additive comprising a crown ether derivative wherein at least one of an aliphatic ring substituted or unsubstituted in the crown ether and a substituted or unsubstituted aromatic ring is condensed.
The crown ether refers to a macrocyclic polyether molecule containing repeating units of a CR c 2 -CR c 2 O- structure wherein R c is H or alkyl, and forms a cavity,
The metal chelate compound is located in the cavity of the crown ether derivative.
Wherein said molecular additive is located within the pores of the polymer matrix of said polyamide active layer.
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| JP2004231878A (en) * | 2003-01-31 | 2004-08-19 | Tosoh Corp | Catalyst composition for producing polyurethane resin and method for producing polyurethane resin |
| US20100062156A1 (en) * | 2008-04-15 | 2010-03-11 | NanoH+hu 2+l O, Inc. NanoH+hu 2+l O Inc. | Reverse Osmosis Membranes |
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| US5252733A (en) * | 1990-06-05 | 1993-10-12 | Air Products And Chemicals, Inc. | Volatile crown ligand β-diketonate alkaline earth metal complexes |
| KR19990019008A (en) | 1997-08-28 | 1999-03-15 | 한형수 | Manufacturing method of high flow rate reverse osmosis membrane |
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| JP2004231878A (en) * | 2003-01-31 | 2004-08-19 | Tosoh Corp | Catalyst composition for producing polyurethane resin and method for producing polyurethane resin |
| US20100062156A1 (en) * | 2008-04-15 | 2010-03-11 | NanoH+hu 2+l O, Inc. NanoH+hu 2+l O Inc. | Reverse Osmosis Membranes |
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