WO2010082710A1 - Method for preparing a highly durable reverse osmosis membrane - Google Patents

Method for preparing a highly durable reverse osmosis membrane Download PDF

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Publication number
WO2010082710A1
WO2010082710A1 PCT/KR2009/001713 KR2009001713W WO2010082710A1 WO 2010082710 A1 WO2010082710 A1 WO 2010082710A1 KR 2009001713 W KR2009001713 W KR 2009001713W WO 2010082710 A1 WO2010082710 A1 WO 2010082710A1
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Prior art keywords
silane
reverse osmosis
osmosis membrane
preparing
membrane
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PCT/KR2009/001713
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English (en)
French (fr)
Inventor
Yong Taek Lee
No Won Kim
Dong Ho Shin
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University-Industry Cooperation Group Of Kyung Hee University
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Publication of WO2010082710A1 publication Critical patent/WO2010082710A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • 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

Definitions

  • the present invention relates to a method for preparing a reverse osmosis membrane with improved durability and a reverse osmosis membrane obtained thereby.
  • dissolved substances can be separated from their solvents by use of selective membranes.
  • membranes such as microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, reverse osmosis membranes and the like.
  • the reverse osmosis membranes are particularly useful in the desalination of brackish water or sea water.
  • the desalination process of brackish water or sea water using reverse osmosis membranes involves a filtration process for separation by applying pressure to the feed water and forcing the water through the membrane, so that purified water passes through the membrane and the salts or other dissolved substances or molecules are filtered out.
  • osmotic pressure naturally occurs, and the more concentrated the feed water, the greater the osmotic pressure, which requires higher pressure applied from outside.
  • Tap water should be treated by chlorination for sterilization.
  • Water for industrial use or desalinated water from sea water should also be treated with chlorine so as to prevent water from being contaminated by bacteria present on a reverse osmosis membrane, and then undergone a dechlorination process.
  • Such dechlorination is generally done by use of activated charcoal or chemical agents, thus having many difficulties in their maintenance.
  • Reverse osmosis membranes prepared from a porous supporting layer and a polyamide membrane formed on said supporting layer have been widely used.
  • the polyamide membrane can be obtained by interfacial polymerization between polyfunctional amines and polyfunctional acyl halides.
  • US patent No. 5,614,099 issued to Hirose discloses a technique of adjusting a polyamide surface structure.
  • the invention is to provide a process for preparing a membrane having at least a certain degree of surface roughness, from the finding that the surface roughness is closely related to a flow rate increase, based on the Tomashke's method of membrane preparation.
  • the present inventors have continued researches to develop polyamide membranes having greater resistance to both chlorine and fouling, and excellent permeation performance.
  • the present inventors have developed a method for preparing a highly durable reverse osmosis membrane having both satisfying chlorine resistance and fouling resistance by primarily coating the surface of a polyamide membrane with an aqueous solution of silane derivatives having chlorine resistance, followed by second coating process using an aqueous solution of glycidyl compounds having fouling resistance, as well as a composite reverse osmosis membrane prepared therefrom.
  • the present invention is to provide a method for preparing a highly durable reverse osmosis membrane having both fouling resistance and chlorine resistance by primarily coating the polyamide membrane surface with an aqueous solution of silane derivatives and then secondly coating the resulted surface with an aqueous solution of glycidyl compounds.
  • the present invention is to provide a reverse osmosis membrane having improved durability prepared by the said method.
  • the present invention is to provide a reverse osmosis membrane having excellent permeability.
  • the present invention provides a method for preparing a reverse osmosis membrane having improved durability, characterized by comprising the steps of: forming a polyamide thin film on a porous supporting layer; primarily coating the surface of the polyamide thin film with an aqueous solution of silane derivatives; secondly coating the primarily coated polyamide thin film surface with an aqueous solution of glycidyl compounds and drying the resulted membrane; and washing the dried membrane with a basic aqueous solution.
  • the silane derivatives are alkoxyalkylsilanes represented by the following chemical figure 1:
  • R 1 is selected from the group consisting of substituted or unsubstituted C1 ⁇ C18 alkyl group, substituted or unsubstituted vinyl group, substituted or unsubstituted aromatic group, and substituted or unsubstituted phenyl group;
  • R2 is C1-C4 alkyl; and
  • n is an integer of 1, 2 or 3.
  • the glycidyl compounds may include 3 ⁇ 4 three-membered cyclic epoxy groups, and at least one functional group selected from the group consisting of ether group, glyceryl group and sorbitol group.
  • the method further includes, after secondly coating the polyamide thin film with the aqueous solution of glycidyl compounds and drying it, a step of drying the resulted membrane with hot air at the temperature range of 25 ⁇ 100°C.
  • the present invention provides a reverse osmosis membrane with improved durability prepared by the foregoing method.
  • the reverse osmosis membrane according to the present invention has improved resistance to chlorine and fouling, as well as excellent permeation performance, by primarily coating the surface of a polyamide thin film with an aqueous solution of silane derivatives having chlorine resistance, and secondly coating the surface with an aqueous solution of glycidyl compounds having fouling resistance.
  • the method for preparing a reverse osmosis membrane of the present invention includes the steps of:
  • the step of forming a polyamide thin film on a porous supporting layer may be carried out by well-known methods in this field of art.
  • the polyamide thin film is generally formed by: spreading an aqueous polyfunctional amine solution over the microporous supporting layer; removing the excess solution therefrom; contacting the resulted surface with an organic solvent containing amine-reactive compounds selected from the group consisting of polyfunctional acylhalide, polyfunctional sulfonylhalide and polyfunctional isocyanate; and carrying out interfacial polymerization.
  • the porous supporting layer used herein refers to a microporous supporting layer. Any well-known materials and production methods for the porous supporting layer in this field of art may be used herein without being specifically limited.
  • the dimension of a micropore should be large enough for the feed water to permeate, but not too much to hinder the crosslinking of a thin film formed on the micropores.
  • the hole diameter of the porous supporting layer is desirably 1 ⁇ 500 nm, without being specifically limited to this. When the hole diameter of the porous supporting layer is more than 500 nm, the surface membrane obtained from the interfacial polymerization permeates through the holes on the supporting layer, being difficult to form a normal flat membrane.
  • microporous supporting layer there is no specific restriction on materials for the microporous supporting layer, any materials generally used in this field of art may be employed. For instance, polymers such as polysulfone, polyether sulfone, polyimide, polyamide, polyether amide, polyacrylonitrile, polymethylmethacrylate, polyethylene, polypropylene, polyvinylidene fluoride and the like may be desirably mentioned. Although thickness of the microporous supporting layer is not specifically limited, 25 ⁇ 130 ⁇ m is desirable.
  • the species of polyfunctional amines are not specifically limited, and any types well-known in this field of art may be used, for example, such as one polyfunctional amine or mixtures thereof.
  • examples include aromatic primary diamines of methylphenyldiamine or para-phenyl diamine, or substituted derivatives thereof; analogues having N-alkyl or aryl substituents; and alkane diamines or cycloaliphatic primary amines such as cyclohexane diamine, cycloaliphatic secondary amines such as piperazine and alkyl derivatives thereof, and aromatic secondary diamines.
  • the substituent for the substituted aromatic primary amines includes an alkyl group, an alkoxy group, a hydroxyalkyl group or a halogen atom.
  • the polyfunctional amine is used in the form of an aqueous solution.
  • the amine may be contained in the aqueous solution at the amount of 0.1 ⁇ 30 wt%.
  • the aqueous solution of the polyfunctional amine has a pH of 7 ⁇ 13.
  • Acid acceptors such as hydroxide, carboxylate, carbonate, borate, alkali metal phosphate, trialkyl amine and the like may be further added to the aqueous solution of the polyfunctional amine, so as to neutralize acids (hydrochloric acid, etc.) generated during the interfacial polymerization.
  • the polyfunctional amine solution i.e. aqueous polyamine solution may be used alone or with other additives described in conventional arts.
  • a polar protic solvent and a mixture thereof a mixture of polar protic solvent and polar aprotic solvent may be used.
  • the polar protic solvent include alcohol, dialcohol, alcohol-ether and the like
  • examples of the polar aprotic solvent include diethyleneglycol, ether derivatives such as di(ethylene glycol) tertiary butylmethylether, and sulfoxide derivatives such as dimethylsulfoxide, butylsulfoxide, tetramethylenesulfoxide.
  • Other additives containing monomeric amine salts may be used for increasing the flow rate.
  • the polyfunctional acyl halide used in the interfacial polymerization is an aromatic compound having 2 ⁇ 3 carboxylic acid halides, and for example, trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and mixtures thereof may be widely used.
  • the aromatic polyfunctional acylhalide may be used alone or as a mixture, for example such as trimesoyl chloride, a mixture of trimesoyl chloride and isophthaloyl chloride and a mixture of trimesoyl chloride and terephthaloyl chloride.
  • the content of whole carboxylic acid halides in organic solvent may be 0.005 ⁇ 5 wt%.
  • silane derivatives As for the silane derivatives, alkoxyalkyl silane compounds represented by the following chemical figure 1 may be used.
  • R 1 is selected from the group consisting of substituted or unsubstituted C1 ⁇ C18 alkyl group, substituted or unsubstituted vinyl group and substituted or unsubstituted phenyl group;
  • R 2 is C1 ⁇ C4 alkyl group; and
  • n is an integer of 1, 2 or 3.
  • alkoxyalkylsilane compounds used in the present invention are preferably compounds represented by the chemical figure 1, wherein R 1 is a substituted or unsubstituted C8-C18 alkyl group, in terms of chlorine resistance. More preferred is alkoxyalkylsilane compounds represented by the chemical figure 1, wherein R 1 is a substituted or unsubstituted C8 alkyl group.
  • Alkoxyalkylsilane compounds used in the present invention may include trialkoxyalkyl silane, dialkoxydialkyl silane, alkoxytrialkyl silane and mixtures thereof.
  • the alkyl group may further contain at least one functional group selected from the group consisting of amine, aldehyde, acid, ether, ketone, alcohol, ester, halogen and aromatic group.
  • the alkoxyalkyl silane compounds which can be used in the present invention is at least one selected from the group consisting of trimethylmethoxy silane, trimethylethoxy silane, trimethylpropoxy silane, dimethylethylmethoxy silane, dimethylethylethoxy silane, dimethylethylpropoxy silane, diethylmethylmethoxy silane, diethylmethylethoxy silane, diethylmethylpropoxy silane, methyltrimethoxy silane, ethyltrimethoxy silane, propyltrimethoxy silane, ethyltriethoxy silane, propyltriethoxy silane, methyltripropoxy silane, ethyltripropoxy silane, propyltripropoxy silane, pentyltriethoxy silane, octyltrimethoxy silane, octyltriethoxy silane, octadecyltrimethoxy silane, o
  • aqueous solution of silane derivatives After preparing an aqueous solution of silane derivatives by mixing 0.1 ⁇ 4 wt% of above-described silane derivatives with 96 ⁇ 99.9 wt% of a coating solvent, it is applied to the surface of the polyamide thin film so as to form a primary coat thereon through a self-assembly method.
  • Ethanol is preferably used as a coating solvent, without being limited to this.
  • the content of the silane derivatives is less than 0.1 wt%, a sol-gel reaction of silane on the membrane surface is so negligible that it cannot cover the entire polyamide surface, which may cause poor resistance to chlorine or fouling.
  • the sol-gel reaction of silane on the membrane surface occurs excessively, forming a thick coat, which may cause a significant decrease in the flow rate, making the resulting membrane inefficient, although resistance to chlorine and fouling can be obtained.
  • the aqueous solution of silane derivatives forms a polymer through a sol-gel reaction in the way of self-assembly, being evenly distributed to the polyamide surface.
  • self-assembly refers that monomers are arranged to form a thermodynamically stable structure before the sol-gel polymerization reaction via n-alkyl silane coupling agents, wherein the polymerization is carried out by hydrolysis between adjacent silane monomers.
  • one alkoxide of silane reacts with a polar atom on the surface of the polyamide thin film, achieving polyamide-polysiloxane immobilization. Since the non-polar functional groups are arranged before the polymerization reaction, it is easy to adjust the non-polar nanostructure.
  • the glycidyl compounds contain 3 ⁇ 4 three-membered cyclic epoxy groups, and at least one functional group selected from the group consisting of ether, glyceryl and sorbitol group.
  • the glycidyl compounds containing 3 epoxy groups may be selected from the group consisting of glycerol triglycidyl ether, diglycerol triglycidyl ether, pentaerythritol triglycidyl ether, sorbitol triglycidyl ether, glycerolpropoxylate triglycidyl ether, trimethylolpropane triglycidyl ether, 1,1,1-tris(hydroxymethy)ethane triglycidyl ether, 1,1,1-tris(hydroxypenyl)ethane triglycidyl ether, tris-hydroxymethylnitromethane triglycidyl ether, tris-(2,3-epoxypropyl)isocyanurate, fluoroglucynol triglycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline, a product obtained from a
  • the glycidyl compounds having 4 epoxy groups may be selected from the group consisting of sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycerol tetraglycidyl ether, and 4,4'-methylenebis(N,N-diglycidylaniline).
  • the glycidyl compounds used herein may be water-soluble or soluble in a mixed solution of water and ethanol, wherein the water content is not less than 50 vol%.
  • the layer coated primarily with the aqueous solution of silane derivatives is again secondly coated with an aqueous solution of glycidyl compounds prepared by mixing 0.1 ⁇ 4 wt% of glycidyl compounds with 96 ⁇ 99.9 wt% of a coating solvent.
  • Water is generally used as a solvent for the coating solution, without being limited to this.
  • the second coating of the nanostructure formed by primarily coating the surface of the polyamide thin film with an aqueous silane derivative solution, with an aqueous glycidyl compound solution rigidly fixes said nanostructure by being served as a bridge, and helps to reduce fouling of the membrane surface by allowing the hydrophilic groups located on the primarily coated polyamide thin film.
  • the hot-air or air drying process increases the effective concentration of the materials for a sol-gel reaction.
  • the present invention further comprises, after primarily coating the surface of the polyamide thin film with an aqueous silane derivative solution and then secondly coating the resulted surface with an aqueous glycidyl compound solution, a step of drying the resulted membrane with hot air at the temperature range of 25 ⁇ 100°C.
  • the hot air drying process effectively fixes the first and the second coating layers formed by each silane derivatives and glycidyl compounds to the surface of the polyamide thin film.
  • hot air drying process is generally well known in this field of art, further detailed description is eliminated herein.
  • the resulted polyamide membrane is washed with a basic aqueous solution.
  • a basic aqueous solution Any types of basic aqueous solutions generally used in this field of art may be used without specific restriction. In this specification, a sodium carbonate or sodium hydroxide solution was used.
  • the method for preparing a reverse osmosis membrane includes the steps of:
  • the present invention can provide a highly durable reverse osmosis membrane having both satisfying chlorine resistance and fouling resistance, prepared by primarily coating the surface of a polyamide thin film with an aqueous solution of glycidyl compounds and then secondly coating it with an aqueous solution of silane derivatives.
  • the each step can be carried out as described in the above.
  • the present invention provides a reverse osmosis membrane prepared by said method.
  • the reverse osmosis membrane is comprised of: a porous supporting layer; a polyamide thin film formed on the porous supporting layer; and a silane derivative layer and a glycidyl compound layer both of which are coated on the surface of the polyamide thin film.
  • the present invention used a disassembled commercial membrane as a substrate to minimize the changes in physical properties in the course of preparing a polyamide membrane, wherein the commercial membrane was originally manufactured as a module.
  • a reverse osmosis membrane for brackish water (CPA2-4040), manufactured by Hydranautics corp. USA was selected.
  • a thin film made of polyester unwoven fabric casted with polysulfone was used, wherein the thickness of the thin film was 100-150 ⁇ m and the pore size was 0.01 ⁇ m.
  • the reverse osmosis membrane used herein was a polyamide reverse osmosis membrane for industrial use, made of about 90-95 ⁇ m of a reinforcing layer made of polyester unwoven fabric, 40-50 ⁇ m of a polysulfone support casted on said reinforcing layer, and about not more than 2 ⁇ m of polyamide polymer coated on the polysulfone support.
  • the initial salt rejection rate and permeation flow rate in the present invention were measured by using 2,000 ppm of an aqueous NaCl solution.
  • a system used for estimation of a reverse osmosis membrane was comprised of a permeation cell in the form of a flat panel, a high pressure pump, a reservoir and a cooling device.
  • the structure of the permeation cell in the form or a flat panel employs a cross-flow type, having an effective permeation area being 27.01 cm 2 .
  • warm-up operation of the system was carried out sufficiently for about 1 hour until the pressure and water permeation becomes regular.
  • Water permeation degree was determined by measuring the amount of permeated water at an interval of 30 minutes.
  • Salt rejection was determined by analyzing the salt concentration before and after permeation, by using a conductivity meter.
  • the resistance to chlorine was determined in a mixed aqueous solution of 2,000 ppm of NaCl and 2,000 ppm of NaOCl.
  • the mixed solution was allowed to flow through the inside of the system for 10 to 30 seconds and maintained as being a stationary phase so that the salt permeation only occurs through the polyamide surface. Changes in salt rejection and flow rate were practically measured by operating time.
  • aqueous solution 2,000 ppm of NaCl and 100 ppm of casein was used. After determination of the initial permeation property, 100 ppm of the aqueous casein solution was directly fed to a tank, and then the permeation property was immediately determined. The changes in water permeation before and after the introduction of the casein-containing solution were plotted, and the slope at the time of change was calculated by using a computer program, determining the level of fouling.
  • the surface of the above-mentioned polyamide membrane (CPA2-4040) was coated with 1.5 wt% of an aqueous solution of octyltriethoxy silane (OcTES), wherein ethanol was used as a solvent, and dried with hot air at 70°C for 10 minutes, forming a primary coat.
  • OcTES octyltriethoxy silane
  • the octyltriethoxy silane-polyamide reverse osmosis membrane surface was secondly coated with 1.0 wt% of sorbitoltriglycidyl ether, wherein water was used as a solvent, and dried with hot air at 70°C for 10 minutes.
  • the performance of the resulted membrane was measured by using 2,000 ppm of an aqueous NaCl solution under pressure of 225 psi, and the results were represented in Table 1.
  • a reverse osmosis membrane was prepared as in Example 1, except that 1.0 wt% of polyglycerol triglycidyl ether was used for the secondary coating process.
  • the performance of the resulted membrane was measured by using 2,000 ppm of an aqueous NaCl solution under pressure of 225 psi, and the results were represented in Table 1.
  • a reverse osmosis membrane was prepared as in Example 1, except that 1.0 wt% of diglycerol triglycidyl ether was used for the secondary coating process.
  • the performance of the resulted membrane was measured by using 2,000 ppm of an aqueous NaCl solution under pressure of 225 psi, and the results were represented in Table 1.
  • the polyamide membrane (CPA2-4040) was not subjected to any surface treatment, but only soaked in distilled water 1 hour or more. Then, its permeation performance was estimated under the same conditions as described in Examples 1 to 3, and the results were represented in Table 1.
  • Test examples 1 to 3 Estimation of chlorine resistance
  • the initial permeation property of each reverse osmosis membrane was determined by operating the system with a mixture of 2,000 ppm of an aqueous NaCl solution and 2,000 ppm of an aqueous NaOCl solution under pressure of 225 psi, and the results were represented in Table 2.
  • the polyamide membrane (CPA2-4040) was not subjected to any surface treatment, but only soaked in distilled water 1 hour or more. Then, it was estimated under the same conditions as described in test Examples 1 to 3.
  • Test examples 4 to 6 Estimation of fouling resistance
  • the salt rejection and permeation flow rate of the reverse osmosis membranes obtained from Examples 1 to 3 were measured by using a mixed aqueous solution of 2,000 ppm NaCl and 100 ppm casein.
  • the salt rejection and flow rate before and after the introduction of the casein-containing solution were determined and compared.
  • the permeation flow rate was converted to MFI, an index of membrane fouling, and the results were disclosed in Table 5.
  • MFI defined by the following math figure, is mainly used for measuring a fouling level in a microfiltration membrane.
  • the MFI can be represented by the above math figure, provided that the thickness of a cake layer formed on the membrane surface (fouling) is in proportion to the filtered amount.
  • the flow rate (Q) is obtained by multiplying the measured permeation flux by the membrane area (A).
  • the resulted value is multiplied by filtration time (t) to obtain the filtered amount (V).
  • t filtration time
  • V the slope of t/V to V curve is a MFI value.
  • MFI is applied to a reverse osmosis membrane process
  • the change in permeation before and after introduction of fouling materials can be expressed as a change in the slope, helping to understand the level of fouling on the reverse osmosis membrane by comparing the slopes.
  • the higher the MFI value of a reverse osmosis membrane the greater the membrane fouling occurred.
  • the polyamide membrane (CPA2-4040) was not subjected to any surface treatment, but only soaked in distilled water 1 hour or more. Then, its permeation performance was estimated under the same conditions as in test examples 4 to 6. The change in permeation flow rate represented by MFI was disclosed in Table 5.
  • the reverse osmosis membranes of the present invention exhibit excellent chlorine and fouling resistance, at the same time.
  • the reverse osmosis membranes according to the present invention also show strong resistance to cleaning agents such as sodium hypochlorite(NaOCl) that is generally introduced to reduce the membrane fouling, and are capable of reducing fouling of the membrane surface, thereby being advantageously applicable to a sea water desalination system or ultrapure water system.

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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)
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