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WO2018101541A1 - Procédé de préparation d'une couche de support de filtre d'osmose directe et filtre d'osmose directe l'utilisant - Google Patents

Procédé de préparation d'une couche de support de filtre d'osmose directe et filtre d'osmose directe l'utilisant Download PDF

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Publication number
WO2018101541A1
WO2018101541A1 PCT/KR2017/001909 KR2017001909W WO2018101541A1 WO 2018101541 A1 WO2018101541 A1 WO 2018101541A1 KR 2017001909 W KR2017001909 W KR 2017001909W WO 2018101541 A1 WO2018101541 A1 WO 2018101541A1
Authority
WO
WIPO (PCT)
Prior art keywords
support layer
forward osmosis
osmosis filter
polymer solution
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2017/001909
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English (en)
Korean (ko)
Inventor
양비룡
오영환
김현
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ENH Co Ltd
Industry Academic Cooperation Foundation of Kumoh National Institute of Technology
Original Assignee
ENH Co Ltd
Industry Academic Cooperation Foundation of Kumoh National Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ENH Co Ltd, Industry Academic Cooperation Foundation of Kumoh National Institute of Technology filed Critical ENH Co Ltd
Publication of WO2018101541A1 publication Critical patent/WO2018101541A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01D69/108—Inorganic support material
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • 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

Definitions

  • the present invention is to manufacture a support layer used in the forward osmosis filter, the method of manufacturing a forward osmosis filter support layer to provide a support layer excellent in water permeability through the solidification of the polymer material by maintaining the cast state of the polymer solution on the substrate and It relates to a forward osmosis filter using the same.
  • the separation method using reverse osmosis membrane separates components such as salts dissolved in seawater from water by applying a pressure corresponding to the osmotic pressure caused by dissolved components in the raw water, and a lot of energy is required to produce an appropriate amount of fresh water. .
  • the separation method using the forward osmosis membrane uses the property that the low concentration solution moves to the high concentration solution through the forward osmosis membrane by the osmotic pressure generated by the difference in concentration between the two solutions, and is induced in the raw water part (low concentration) through the forward osmosis membrane. Water is introduced into the solution (high concentration), and conversely, the inducing solution contained in the inducing solution does not escape.
  • the forward osmosis membrane it is important for the forward osmosis membrane to maintain a constant concentration of the inducing solute and at the same time maintain a high osmotic pressure.
  • the osmotic membrane should have a high water permeability in the osmotic direction, and the solute of the inducing solution does not diffuse in the reverse osmosis direction. Most importantly.
  • the forward osmosis filter used in the water treatment method using the forward osmosis membrane generally includes a substrate, a support layer, an active layer, and the like.
  • a forward osmosis membrane In the conventional process of manufacturing a forward osmosis filter, polymers such as polysulfone (PS), polyether sulfone (PES), cellulose acetate (CA), and cellulose triacetate (CTA) are dissolved in a volatile solvent and cast to a predetermined thickness on a substrate, and then After the supporting layer is prepared by a method of supporting and solidifying, a forward osmosis membrane is prepared by applying or coating a solution containing an active layer component on the supporting layer.
  • PS polysulfone
  • PES polyether sulfone
  • CA cellulose acetate
  • CTA cellulose triacetate
  • the support layer in the forward osmosis filter supports the forward osmosis filter
  • the water permeability in the raw water portion must be high, and the inducing solution in the induction solution should not diffuse, so the porosity, shape and size of the pores in the support layer are important factors. Becomes.
  • the support layer manufactured by the above method takes a long time for the solidification process, a separate drying process is required, the manufacturing method is complicated and the productivity is reduced, and the pores of the support layer are very densely implemented in the raw water portion While the removal performance of the contained salt is excellent, the water permeability is low efficiency, thereby causing a high membrane fouling problem.
  • the present invention is to solve the above problems, to maintain the cast state of the polymer solution on the substrate manufacturing method of the forward osmosis filter support layer providing a support layer excellent in water permeability through the solidification of the polymer material and forward osmosis filter using the same
  • the purpose is to provide.
  • the present invention provides a first step of preparing a polymer solution by dissolving a polymer material in a solvent, a second step of casting and casting the polymer solution on a substrate, and casting of the polymer solution on the substrate. And a fourth step of solidifying the polymer material contained in the polymer solution by maintaining the state for a predetermined time and a fourth step of separating the solidified polymer material from the substrate to prepare a support layer of the forward osmosis filter.
  • the method of manufacturing the forward osmosis filter support layer characterized in that, and the forward osmosis filter using the same.
  • the first step after the production of the polymer solution, it is preferable to further perform a process for removing the gas contained in the polymer solution.
  • the polymer solution is cast on the substrate, and is preferably exposed to air for 20 to 450 seconds under 30 to 50% humidity at room temperature.
  • the third step after the solidification of the polymer material, it is preferable to carry out an additional solidification process by supporting the substrate on which the polymer solution is cast in a non-solvent.
  • the solidified polymer material is separated from the substrate, and then washed, and the support layer is stored in a non-solvent.
  • the thickness of the support layer is characterized in that 50 ⁇ 300 ⁇ m, the porosity of the support layer is preferably formed in a columnar shape of 30 to 80%.
  • the polymer solution preferably 10 to 25% by weight of the polymer material in the solvent, the polymer material, Cellulose Acetate, Cellulose Triacetate, Polysulfone, Polyether sulfone, Poly (vinylidine fluoride), Polyetherimide and Polyamide It is preferable to use any one or two or more thereof.
  • the support layer of the forward osmosis filter according to the present invention has an effect of providing a support layer having excellent water permeability and high production efficiency by a simple process through the solidification of the polymer material by maintaining the cast state of the polymer solution on the substrate.
  • the forward osmosis filter according to the present invention can be easily enlarged by a solidification process called a time of exposure to room temperature air of the support layer, and the forward osmosis filter including such a support layer is applicable to not only seawater desalination process, but also to medical drug pads. There is an effect that can be applied to the filter system.
  • Figure 2 is a view measuring the water permeability according to the air exposure time in the solidification process of the support layer prepared according to an embodiment of the present invention.
  • FIG 3 is a view showing an electron micrograph according to the cross section of the support layer according to the air exposure time in accordance with one embodiment of the present invention.
  • the present invention is to provide a support layer used for the forward osmosis filter, to maintain a cast state of the polymer solution on the substrate to provide a support layer excellent in water permeability through the solidification of the polymer material.
  • a support layer having excellent water permeability can be provided by a simple manufacturing method, and while supporting the forward osmosis filter, while ensuring high water permeability, the pollution degree of the forward osmosis filter is reduced, and the inducing solution in the induction solution does not pass through. It is possible to provide a forward osmosis filter useful for desalination of seawater.
  • Figure 1 shows a flow chart for the manufacturing method of the forward osmosis filter support layer according to the present invention.
  • the present invention provides a first step of preparing a polymer solution by dissolving a polymer material in a solvent, a second step of coating and casting the polymer solution on a substrate, and a polymer solution on the substrate.
  • a polymer solution is prepared by dissolving a polymer material in a solvent (first step).
  • the polymer material of the present invention is a material of the support layer in the forward osmosis filter, and in order to minimize the permeation resistance with water, a hydrophilic material may be used, or a synthetic polymer copolymerized with a polymer having a hydrophilic functional group may be used.
  • hydrophilic polymer material any one or two or more of Cellulose Acetate, Cellulose Triacetate, Polysulfone, Polyether sulfone, Poly (vinylidine fluoride), Polyetherimide and Polyamide are used.
  • An additive such as polyvinylpyrrolidone for controlling the viscosity of the polymer material may be further added to the polymer material.
  • the solvent Acetone, Ethyl Acetate, Cyclohexane, N-methyl Pyrrolidone, Dimethyl Formamide, Methylene chloride, Dimethyl sulfoxide, and the like are used, and the polymer material is mixed with 10 to 25% by weight to prepare a polymer solution by stirring.
  • the pore size is formed too small, or pores of a shape that is not suitable for improving water permeability is formed, thereby lowering the membrane separation ability.
  • the polymer solution thus prepared is left at a flat bottom for a predetermined time without stirring at room temperature to remove the gas contained in the polymer solution. This is to facilitate the control of the porosity of the pores, the control of the size and shape of the pores by removing the gas contained in the polymer solution when forming the support layer by the casting and solidification process.
  • the polymer solution is coated on the substrate (dopping) to proceed with the casting process (second step).
  • any material for performing the casting process may be used, and in one embodiment of the present invention, glass is used.
  • the polymer solution is applied onto the glass substrate, and a casting process is performed using a casting knife.
  • the thickness of the cast polymer solution is appropriate about 50 ⁇ 500 ⁇ m, in consideration of the thickness of the support layer to be formed after the solidification process to determine the thickness of the cast polymer solution.
  • the polymer material contained in the polymer solution is solidified by maintaining it for a predetermined time in the casting state (step 3).
  • the solidification process is performed by exposing the polymer solution on the glass substrate to air for 20 to 450 seconds at a humidity of 30 to 50% at room temperature.
  • the above conditions are the most effective conditions for improving the water permeability of the support layer, to maintain the proper porosity inside the support layer, and to control the size and shape of the pores.
  • the solidification process may be slow, or the size and shape of the pores and porosity may be inappropriately formed for improving water permeability and salt separation, and if exposed for too long or too long, the water permeability may be improved. Pore is not formed or does not affect the formation of pores.
  • the substrate on which the polymer solution is cast is supported on a non-solvent to extract the remaining solvent, thereby enabling the further solidification process to be realized, thereby making the solidification process faster. Can be lost.
  • a room temperature exposure solidification process may be carried out, so that it may be carried out in addition to the non-solvent to perform an additional solidification process, while controlling the speed of the solidification process, while improving the water permeability and salt separation according to the concentration of raw water To achieve the optimum pore shape required.
  • the solidified polymer material is separated from the substrate to prepare a support layer of the forward osmosis filter (fourth step).
  • the solidified polymer material is separated from the substrate and washed to obtain the support layer, and the support layer is stored in a non-solvent and stored until use.
  • the thickness of the support layer thus prepared is preferably about 50 ⁇ 300 ⁇ m, the porosity of the pores contained in the support layer is 30 to 80%, preferably formed in a columnar shape.
  • the thickness of the support layer is too thin, the breakage is easily performed, and thus, the support layer cannot function properly in the forward osmosis filter, and the handling of the filter is not easy, and if the thickness of the support layer is too thick, the water permeability is reduced. Will be.
  • the porosity of the pores included in the support layer is too low, the water permeability is lowered. If the porosity of the pores is too high, the water permeability may be improved, but the durability is lowered so that the role of the support layer may not be properly performed. do.
  • the pores included in the support layer is formed in a circular or columnar shape according to the room temperature exposure conditions, the column-shaped pores improve water permeability It is showing characteristics.
  • the support layer thus formed may be formed on top of a porous support such as a nonwoven fabric as needed, and may be used as it is to be used as an forward osmosis filter by further forming an active layer thereon.
  • PVP polyvinylpyrrolidone
  • NMP N-methyl pyrrolidone
  • the polymer solution stirred for 24 hours is placed on a flat bottom for 24 hours without stirring at room temperature to remove gas from the solution.
  • the polymer solution is then applied onto a glass substrate and cast using a casting knife.
  • the thickness of the cast polymer solution at that time is about 300 ⁇ 500 ⁇ m.
  • the solidification process is performed by exposure to room temperature at a relative humidity of 30 to 50% for 20 to 450 seconds while being cast on a glass substrate, and finishes the solidification process by rapidly supporting the cast glass substrate exposed to air in ultrapure water. do.
  • the solidified polymer material is taken out using a tweezer, washed thoroughly with clean ultrapure water, and then stored in clean ultrapure water until the forward osmosis filter is used. If the precipitate melts in the ultrapure water prepared for storage and becomes cloudy, replace the above ultrapure water.
  • the thickness of the support layer thus prepared is about 50 ⁇ 300 ⁇ m.
  • 2 is a measurement of the water permeability according to the air exposure time in the solidification process of the support layer prepared according to an embodiment of the present invention, when the air exposure time is 150 seconds, other conditions (0 seconds, 50 seconds, 100 seconds, 125 seconds, 200 seconds, 250 seconds, 350 seconds, 400 seconds, 450 seconds) was confirmed that the water permeability increased more than four times to 231L / hr ⁇ m 2 .
  • FIG. 3 shows an electron micrograph according to the cross section of the support layer according to the air exposure time.
  • the air exposure time t is 0 ⁇ t ⁇ 150
  • the pores are not directional and are randomly distributed.
  • the partition wall is irregularly formed between the pores, the separation is good, but the pores are dense, so the water molecules have a low permeability.
  • the pore size is formed to a size ( ⁇ 10 ⁇ m) that can prevent the diffusion of salts or inducing solutes while passing water, and the pores in the form of pillars having a certain direction It was confirmed that the pores are formed uniformly as a whole.
  • the form of these pores is to improve the water permeability of the forward osmosis filter while increasing the membrane separation properties to increase the forward osmosis filter efficiency. This is consistent with the water permeability measurement result of FIG. 2.
  • the support layer of the forward osmosis filter according to the present invention maintains the cast state of the polymer solution on the substrate to provide a support layer having excellent water permeability by a simple process through the solidification of the polymer material.
  • the forward osmosis filter is easy to be enlarged by the solidification process of room temperature air exposure time, there is an advantage that can be designed forward osmosis filter module and train
  • the forward osmosis filter including the support layer is applicable to not only seawater desalination process, but also to medical drug pads, and is applicable to various filter systems.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne la préparation d'une couche de support utilisée dans un filtre d'osmose directe, et les objets techniques de la présente invention sont un procédé de préparation d'une couche de support de filtre d'osmose directe et un filtre d'osmose directe l'utilisant. Le procédé comprend: une première étape de dissolution d'un matériau polymère dans un solvant de manière à préparer une solution polymère; une deuxième étape consistant à appliquer la solution de polymère sur un substrat et à couler celle-ci; une troisième étape consistant à maintenir l'état fondu de la solution de polymère sur le substrat pendant une durée prédéterminée de façon à solidifier le matériau polymère inclus dans la solution de polymère; et une quatrième étape de séparation du matériau polymère solidifié du substrat de manière à préparer une couche de support d'un filtre d'osmose directe.
PCT/KR2017/001909 2016-11-30 2017-02-21 Procédé de préparation d'une couche de support de filtre d'osmose directe et filtre d'osmose directe l'utilisant Ceased WO2018101541A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20160161885 2016-11-30
KR10-2016-0161885 2016-11-30

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WO2018101541A1 true WO2018101541A1 (fr) 2018-06-07

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PCT/KR2017/001909 Ceased WO2018101541A1 (fr) 2016-11-30 2017-02-21 Procédé de préparation d'une couche de support de filtre d'osmose directe et filtre d'osmose directe l'utilisant

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008137082A1 (fr) * 2007-05-02 2008-11-13 Yale University Procédé de conception de membranes utiles dans des processus membranaires osmotiques
KR20120078146A (ko) * 2010-12-31 2012-07-10 웅진케미칼 주식회사 비대칭 다공성 멤브레인의 제조방법 및 그로부터 제조되는 비대칭 다공성 멤브레인
KR20130075515A (ko) * 2011-12-27 2013-07-05 웅진케미칼 주식회사 정밀여과막의 평균공경 제어방법 및 그로부터 제조된 정밀여과막으로 이루어진 전처리용 프리필터
KR20140001367A (ko) * 2012-06-26 2014-01-07 웅진케미칼 주식회사 정삼투막 및 그의 제조방법
KR20140072709A (ko) * 2012-12-05 2014-06-13 도레이케미칼 주식회사 폴리술폰계 제균분리막 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008137082A1 (fr) * 2007-05-02 2008-11-13 Yale University Procédé de conception de membranes utiles dans des processus membranaires osmotiques
KR20120078146A (ko) * 2010-12-31 2012-07-10 웅진케미칼 주식회사 비대칭 다공성 멤브레인의 제조방법 및 그로부터 제조되는 비대칭 다공성 멤브레인
KR20130075515A (ko) * 2011-12-27 2013-07-05 웅진케미칼 주식회사 정밀여과막의 평균공경 제어방법 및 그로부터 제조된 정밀여과막으로 이루어진 전처리용 프리필터
KR20140001367A (ko) * 2012-06-26 2014-01-07 웅진케미칼 주식회사 정삼투막 및 그의 제조방법
KR20140072709A (ko) * 2012-12-05 2014-06-13 도레이케미칼 주식회사 폴리술폰계 제균분리막 및 그 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIM, H. ET AL.: "Graphene Oxide Composite Membranes as a Potential Candidate for a Desalination System", TRANSACTIONS ON ECOLOGY AND THE ENVIRONMENT, vol. 209, 27 June 2016 (2016-06-27), pages 1 - 8 *

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