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WO2016036125A1 - Récipient à pression à membrane d'oi en ntc hybride - Google Patents

Récipient à pression à membrane d'oi en ntc hybride Download PDF

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Publication number
WO2016036125A1
WO2016036125A1 PCT/KR2015/009225 KR2015009225W WO2016036125A1 WO 2016036125 A1 WO2016036125 A1 WO 2016036125A1 KR 2015009225 W KR2015009225 W KR 2015009225W WO 2016036125 A1 WO2016036125 A1 WO 2016036125A1
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Prior art keywords
carbon nanotubes
reverse osmosis
osmosis membrane
pressure vessel
module
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English (en)
Korean (ko)
Inventor
정준교
김상현
김홍석
오세진
김보람
김선규
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Hyundai Engineering and Construction Co Ltd
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Hyundai Engineering and Construction Co Ltd
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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
    • B01D61/08—Apparatus therefor
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/138—Water desalination using renewable energy
    • Y02A20/144—Wave energy

Definitions

  • the present invention relates to a pressure vessel of the hybrid CNT-RO membrane, and more particularly, a reverse osmosis membrane module having a higher salt rejection rate than the reverse osmosis membrane disposed at the rear end is disposed at the front end of the pressure vessel to increase the freshwater recovery rate. It relates to a pressure vessel.
  • Seawater desalination refers to a series of water treatment processes that removes dissolved substances, including salts, from seawater, which cannot be directly used for domestic or industrial water, to obtain high-purity drinking water, domestic water, and industrial water. Also called seawater desalination, the facilities used to produce seawater as freshwater are called seawater desalination plants or seawater desalination plants.
  • the desalination plant is a facility that removes salt in an economic way to make fresh water using 98% of sea water or brackish water useful for human life.
  • rain falls on the ground, it flows into the sea through various paths, while salts and other substances dissolve as water flows on and into the ground, increasing salinity.
  • Water arriving at sea or in lowlands is evaporated by solar energy, leaving salts in the evaporation process, and only pure water forms clouds and rains. This shows the evaporation process where physical separation takes place and the condensation process where water vapor meets cold air and turns into rainwater, which is a representative desalination seen in natural phenomena.
  • Desalination methods are largely classified according to their basic principles.
  • the reverse osmosis method is used to heat seawater using a heat source and condense the generated steam to obtain fresh water, and reverse osmosis, which produces fresh water by passing the seawater through a semi-permeable membrane using osmosis. It is a representative method of seawater desalination.
  • the evaporation method using a heat source is classified into multi-stage flash (MSF) and multi-effect distillation (MED) according to the fluid flow pattern.
  • MSF multi-stage flash
  • MED multi-effect distillation
  • crystallization method, ion exchange membrane method, solvent extraction method, and pressure adsorption method are applied to seawater desalination.
  • the widely used seawater desalination method is MSF, MED and RO.
  • a hybrid method is used to produce.
  • Reverse osmosis membrane pressure vessels are used for desalination of seawater using reverse osmosis among various seawater desalination systems.
  • the pressure vessel has a plurality of reverse osmosis membrane modules connected in series, raw water flows into the inlet of the front end of the pressure vessel, and desalination of the produced water is discharged into the product outlet located at the rear end of the pressure vessel, and the rear end of the pressure vessel.
  • the brine is located at the brine and the brine is desalted.
  • a plurality of reverse osmosis membrane modules are arranged in series. Since the modules are connected in series, the salinity of seawater that has not been desalted in the reverse osmosis membrane module located at the front end becomes darker as it flows to the rear end.
  • the present invention has been made to solve the conventional problems as described above, the object is to provide a user with a hybrid CNT-RO membrane pressure vessel with a high fresh water recovery.
  • the purpose is to reduce the difference between the fresh water production of the reverse osmosis membrane module disposed in the front end and the fresh water production of the reverse osmosis membrane module disposed in the rear end.
  • the purpose is to increase the water permeability of the reverse osmosis membrane module by mixing the carbon nanotubes in the reverse osmosis membrane module 50% or more.
  • the aim is to reduce the amount of incoming seawater and to reduce the cost of operating a freshwater production system.
  • Reverse osmosis membrane pressure vessel for realizing the above object is a reverse osmosis membrane pressure vessel for desalination of sea water, the seawater inlet is located at at least part of the front end of the pressure vessel; A plurality of reverse osmosis membrane modules disposed in series in the pressure vessel; A permeate flow path passing through a central portion of each of the plurality of reverse osmosis membrane modules and having a plurality of holes formed in contact with the plurality of reverse osmosis membrane modules; A permeate water outlet located at least a portion of the rear end of the pressure vessel; And a concentrated water outlet positioned at at least a portion of the rear end of the pressure vessel, wherein the seawater is introduced through the seawater inlet, and the introduced seawater is desalted while passing through the plurality of reverse osmosis membrane modules.
  • the seawater that has passed through the reverse osmosis membrane module is introduced into the permeate flow path through the plurality of holes, and the seawater introduced into the permeate flow path is discharged through the permeate discharge port and cannot flow into the permeate flow path.
  • Sea water is discharged through the concentrated water outlet, at least one module located at the front end of the pressure vessel of the plurality of reverse osmosis membrane module constitutes a first module portion, the module located at a rear end than the first module portion
  • the flow rate of each module constituting the second module unit, the flow rate of each module constituting the first module unit than There can be many.
  • the salt rejection rate of each module constituting the first module unit may be higher than the salt rejection rate of each module constituting the second module unit.
  • carbon nanotubes may be mixed in the separator of at least one of the first module unit and the second module unit.
  • the carbon nanotubes may be mixed in at least one layer of the polyamide layer and the support layer of the separator.
  • poly dopamine is coated on the carbon nanotubes so that the carbon nanotubes may be uniformly coated.
  • module of the first module unit may be two, and the module of the second module unit may be four.
  • the material of the pressure vessel may be fiber reinforced plastics (FRP, Fiber Reinforced Plastics).
  • the module located at a rear end of the first module unit may constitute a second module unit, and the flow rate of each module constituting the second module unit may be greater than the flow rate of each module constituting the first module unit.
  • the salt rejection rate of each module constituting the first module unit may be higher than the salt rejection rate of each module constituting the second module unit.
  • the second reverse osmosis membrane module may further include a carbon nanotube layer, and the second step may further include transmitting the seawater through the carbon nanotube layer.
  • the pressure vessel stage according to an embodiment of the present invention for realizing the above problems may be a plurality of reverse osmosis membrane pressure vessel connected in parallel.
  • Seawater desalination apparatus for realizing the above problem may be a plurality of reverse osmosis membrane pressure vessel stage connected in series.
  • the carbon nanotubes the step of maintaining the carbon nanotubes in a H 2 O 2 solution of 50 ⁇ 70 °C for 30 minutes ⁇ 2 hours; Evaporating the H 2 O 2 solution and oxidizing the carbon nanotubes for 1 to 3 hours while injecting an inert gas at 800 to 1000 ° C .; Cooling the carbon nanotubes to 25 to 40 ° C. at room temperature; Heating the carbon nanotubes at 300 to 600 ° C. for 2 to 4 hours; And injecting an inert gas to cool the carbon nanotubes to room temperature to open the ends through a thermal oxidation method.
  • the average length obtained through the inert gas may be 1 to 2 ⁇ m, and the average diameter may be 5 to 8 nm. .
  • the carbon nanotubes may be dispersed in the amine solution and mixed with the separator by interfacial polymerization.
  • the amine contained in the amine solution is ortho-phenylenediamine (ortho-phenylenediamine), meta-phenylenediamine (meta-phenylenediamine), para-phenylenediamine (para-phenylenediamine), piperazine ( piperazine, ethylene diamine, cadaverine, and any one selected from the group consisting of a mixture thereof.
  • the poly dopamine is coated, the first step of ultrasonically dispersing the carbon nanotubes in a tris-buffer solution; A second step of prepurging oxygen in the tris-buffer solution in which the carbon nanotubes are mixed; Injecting dopamine into the oxygen pre-purged tris-buffer solution; A fourth step of reacting the carbon nanotubes with the dopamine by injecting oxygen into the dopamine-infused tris-buffer solution; A fifth step of applying ultrasonic dispersion to the tris-buffer solution in which the carbon nanotubes and the dopamine are reacted; A sixth step of reacting the carbon nanotubes with the dopamine by injecting oxygen into the ultrasonically dispersed tris-buffer solution; A seventh step of lowering the pH of the tris-buffer solution; And an eighth step of drying the tris-buffer solution.
  • the tris-buffer solution may be adjusted to a pH of 8.5 or more.
  • the reverse osmosis membrane pressure vessel manufacturing method for realizing the above object in the method for producing a pressure vessel using a reverse osmosis membrane in which carbon nanotubes are mixed, the carbon nanotube 50 Holding in a H 2 O 2 solution at ⁇ 70 ° C. for 30 minutes to 2 hours; Evaporating the H 2 O 2 solution and oxidizing the carbon nanotubes for 1 to 3 hours while injecting an inert gas at 800 to 1000 ° C .; Cooling the carbon nanotubes to 25 to 40 ° C. at room temperature; Heating the carbon nanotubes at 300 to 600 ° C.
  • the average length of the carbon nanotubes is 1 to 2 ⁇ m and the average diameter is 5 to 8 nm. Can be.
  • the present invention can be provided to users of a hybrid CNT-RO membrane pressure vessel having a high freshwater recovery rate.
  • the water permeability of the reverse osmosis membrane module can be increased by 50% or more by mixing carbon nanotubes in the reverse osmosis membrane module.
  • FIG. 1 is a perspective view showing an example of a spiral wound separator module.
  • Figure 2 shows a cross-sectional view of a conventional reverse osmosis membrane pressure vessel.
  • FIG 3 is a cross-sectional view of the hybrid reverse osmosis membrane pressure vessel according to an embodiment of the present invention.
  • Figure 4 shows a cross-section of the reverse osmosis membrane used in the reverse osmosis membrane module according to an embodiment of the present invention.
  • Figure 5 shows that the carbon nanotubes mixed in the reverse osmosis membrane according to an embodiment of the present invention is disproportionately dispersed.
  • FIG. 6 shows a reverse osmosis membrane in which carbon nanotubes coated with poly dopamine are mixed according to one embodiment of the present invention.
  • FIG. 7 is a flowchart illustrating a method of desalination of seawater according to an embodiment of the present invention.
  • Figure 8 is a graph showing the flow rate according to the module position when desalination of sea water using a hybrid CNT reverse osmosis membrane pressure vessel according to an embodiment of the present invention and a conventional reverse osmosis membrane pressure vessel.
  • FIG. 9 shows a stage (Stage) connected in parallel to the reverse osmosis membrane module according to an embodiment of the present invention.
  • FIG. 10 illustrates a multi-stage system in which reverse osmosis membrane pressure vessel stages are connected in series according to an embodiment of the present invention.
  • FIG. 11 is a photograph showing a dispersion result according to Preparation Example 2 and a figure showing the results of a UV spectrometer analysis.
  • FIG. 13 is a photograph showing carbon nanotubes whose ends are opened by treating with thermal oxidation in Example 1.
  • FIG. 14 is a photograph showing carbon nanotubes whose ends are not opened because the thermal oxidation method is not treated by Comparative Example 1.
  • FIG. 14 is a photograph showing carbon nanotubes whose ends are not opened because the thermal oxidation method is not treated by Comparative Example 1.
  • TGA thermogravimetric analysis
  • FIG. 18 is a graph showing the changing peak pattern in atomic absorption analysis by thermal oxidation treatment.
  • 19 is a TEM image showing dopamine-coated carbon nanotubes.
  • Example 20 is a process chart for preparing a carbon nanotube-polyamide composite separator according to Example 1 of the present invention.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • FIG. 23 is a scanning electron microscope (SEM) (a) and transmission electron microscope (TEM) image (b) of a polydopamine-coated carbon nanotube according to Example 2 of the present invention.
  • FIG. 24 is a scanning electron microscope (SEM) (a) and transmission electron microscope (TEM) photograph (b) of a polydopamine-coated carbon nanotube according to a comparative example of the present invention.
  • FIG. 26 shows infrared spectroscopy (FT-IR) results of carbon nanotubes not coated with polydopamine and carbon nanotubes coated with polydopamine according to Examples 1, 2 and Comparative Examples of the present invention.
  • XPS photoelectron spectroscopy
  • FIG. 28 shows spectrophotometric analysis (UV-vis) results of polydopamine-coated carbon nanotubes according to a comparative example of the present invention (a) and spectroscopy of polydopamine-coated carbon nanotubes according to Example 1 of the present invention. Photometric analysis (UV-vis) results (b).
  • FIG. 29 is a photograph of dispersibility in various solvents of carbon nanotubes not coated with polydopamine.
  • Example 30 is a photograph of dispersibility in various solvents of polydopamine-coated carbon nanotubes according to Example 1 of the present invention.
  • FIG. 31 illustrates an aqueous dispersion image and UV-vis analysis result of CNTs having improved aqueous dispersibility according to an embodiment of the present invention.
  • FIG 32 is a graph comparing the power consumption for the same flow rate when desalination using the reverse osmosis membrane pressure vessel according to an embodiment of the present invention and the conventional reverse osmosis membrane pressure vessel.
  • Reverse osmosis membranes are used for desalination with large amounts of water with relatively low salts such as industrial water, agricultural water, and household water by removing salts such as brine or seawater.
  • Semi-saline desalination using reverse osmosis membrane or desalination of seawater means that the salt or ions in the aqueous solution cannot pass through the membrane when the aqueous solution containing salt or ions is pressurized and filtered. It means passing through and becoming constant water.
  • the pressure applied should be more than the osmotic pressure of the aqueous solution, the action is the reverse of the osmotic process, and the higher the concentration of the aqueous solution, the greater the osmotic pressure, the higher the pressure applied to the feed water.
  • the permeate flow rate of the membrane may be more important than the salt rejection rate depending on the use, or vice versa.
  • a large membrane area is required to apply the separator to industrial scale liquid separation.
  • a device unit that integrates a large membrane area on a compact scale is called a membrane module, and various types of membrane modules such as flat module, tubular module, hollow fiber module, spiral wound module have been developed.
  • commercially available reverse osmosis membrane modules are mainly used as spiral wound type membrane modules.
  • FIG. 1 is a perspective view showing an example of a spiral wound membrane module, wherein the spiral wound module uses a flat sheet membrane as a separator.
  • a mesh (9) and a separator (feed spacer) may be used.
  • 7) and the permeate spacer (8), another membrane (7) is bonded by a sandwich method, and then wound in the form of a roll (roll) on the porous central pipe (10) located in the center Form a module.
  • the inflow water under a constant pressure is passed through the membrane (7) through the inlet flow channel (9).
  • the membrane In the passage of the membrane, dissolved salts and organic substances are excluded and pure water is separated.
  • the separated water flows along the permeate flow path 8 located between the separation membranes, and the permeate is discharged out of the pressure vessel through the permeate outlet 5.
  • the concentrated water discharged from the reverse osmosis membrane module located at the front end flows into the reverse osmosis membrane module located at the rear end, so that the salt concentration of the seawater increases as the seawater flows to the rear end.
  • Figure 2 shows a cross-sectional view of a conventional reverse osmosis membrane pressure vessel
  • a reverse osmosis membrane module inherent in the conventional reverse osmosis membrane pressure vessel all the same type of modules are arranged to treat a high concentration of concentrated water
  • the production water flow rate of the reverse osmosis membrane module of the rear end is very low compared to the front end module has become a problem.
  • the present invention is to provide a reverse osmosis membrane pressure vessel with a high fresh water recovery rate by arranging the reverse osmosis membrane module of other characteristics in the reverse osmosis membrane pressure vessel to solve this problem.
  • FIG 3 is a cross-sectional view of the hybrid reverse osmosis membrane pressure vessel according to an embodiment of the present invention.
  • the hybrid reverse osmosis membrane pressure vessel is a pressure vessel 100, inlet 200, a plurality of reverse osmosis membrane module 300, porous outlet pipe 400, permeate outlet 500 and concentrated water outlet 600 and the like.
  • the pressure vessel 100 is a vessel in which other components are mounted.
  • Pressure vessel 100 It can be manufactured by filament winding method using raw materials such as epoxy resin and glass fiber as pressure vessel 100, and there is no liner inside, and it is light without gel coating and can withstand high pressure FRP (Fiber Reinforced Plastics) ) Pressure vessel 100 may be used.
  • FRP Fiber Reinforced Plastics
  • the inlet 200 is located in the front end of the pressure vessel 100 is a hole in which seawater is introduced.
  • the plurality of reverse osmosis membrane module 300 serves to desalination of the introduced seawater, a spiral wound reverse osmosis membrane module as shown in FIG. 1 is used.
  • Figure 4 shows a cross-section of the reverse osmosis membrane used in the reverse osmosis membrane module according to an embodiment of the present invention
  • the reverse osmosis membrane 310 is a polyamide (PA) layer 311, the support layer 312 And nonwoven fabric 313.
  • the support layer 312 may be made of poly ethersulfone (PES).
  • the reverse osmosis membrane module 300 may be classified according to the salt excretion rate of the reverse osmosis membrane (310).
  • the reverse osmosis membrane module with high salt rejection rate and low production water flow rate is called the high salt rejection type reverse osmosis membrane module (HR type high osmosis membrane module) (320).
  • the high flow rate reverse osmosis membrane module is called a high flow rate reverse osmosis membrane module (HF type reverse osmosis membrane module, High Flux Membrane) (330).
  • the HR type reverse osmosis membrane module 320 is disposed at the front end of the hybrid reverse osmosis membrane pressure vessel, and the HF type reverse osmosis membrane module 330 is disposed at the rear end thereof.
  • the HR type reverse osmosis membrane module 320 is disposed at the front end of the pressure vessel 100 with a relatively low flow rate and high salt rejection rate.
  • the salt concentration is increased toward the end of the.
  • the reverse osmosis membrane module 300 disposed at the rear end of the pressure vessel 100 has to process high concentrations of seawater, so the freshwater production is less than the reverse osmosis membrane module 300 disposed at the front end.
  • the HF-type reverse osmosis membrane module 330 having a relatively high transmittance is disposed at the rear end of the pressure vessel 100.
  • the fresh water recovery rate is increased as compared with the conventional reverse osmosis membrane module.
  • the number of the plurality of reverse osmosis membrane modules 300 used in the pressure vessel 100 is two HR type reverse osmosis membrane modules 320 and four HF type reverse osmosis membrane modules 330 as shown in FIG. 3. It is not limited to, the number can be changed as needed.
  • carbon nanotubes (CNT) 314 may be mixed in the reverse osmosis membrane.
  • the carbon nanotubes 314 may be coated on a polyamide (PA) layer 311 or a poly ethersulfone (PES) layer 312 of the reverse osmosis membrane.
  • PA polyamide
  • PES poly ethersulfone
  • the HF-type reverse osmosis membrane module 330 disposed at the rear end of the reverse osmosis membrane pressure vessel of the present invention requires high permeability in order to desalination seawater quickly. Therefore, when carbon nanotubes 314 are mixed in the reverse osmosis membrane 310 of the HF type reverse osmosis membrane module 330, the production water recovery rate may be further increased. However, the carbon nanotubes 314 may not only be applied to the HF type reverse osmosis membrane module 320 but may also be applied to the HR type reverse osmosis membrane module 330.
  • Figure 5 shows that the carbon nanotubes mixed in the reverse osmosis membrane according to an embodiment of the present invention is disproportionately dispersed.
  • the performance of the reverse osmosis membrane module 300 may be degraded and thus may not normally be desalted.
  • the poly dopamine 315 may be coated on the carbon nanotubes mixed in the reverse osmosis membrane 310.
  • FIG. 6 illustrates a reverse osmosis membrane in which carbon nanotubes coated with poly dopamine are mixed according to an embodiment of the present invention.
  • poly dopamine 315 coated on carbon nanotubes 314 may be used.
  • the carbon nanotubes 314 may be uniformly dispersed in the reverse osmosis membrane 310.
  • the porous outflow pipe 400 connects the plurality of reverse osmosis membrane modules 300 in series, passes through the plurality of reverse osmosis membrane modules 300, and is a passage through which desalination water flows.
  • the permeated water outlet 500 is a hole through which the water introduced into the porous outlet pipe 400 is discharged, and the concentrated water outlet 600 is concentrated in the saltwater which is not fresh water due to the inflow into the porous outlet pipe 400. It is a hole through which concentrated water is discharged.
  • the permeate outlet 500 and the concentrated water outlet 600 are located at the rear end of the pressure vessel 100.
  • FIG. 7 is a flowchart illustrating a method of desalination of seawater according to an embodiment of the present invention.
  • the introduced seawater is desalted by passing through a plurality of reverse osmosis membrane modules in the pressure vessel (S200).
  • At least one module positioned at the front end of the pressure vessel among the plurality of reverse osmosis membrane modules constitutes a first module portion, and the remaining modules positioned at a rear end of the first module portion constitute a second module portion.
  • the reverse osmosis membrane module of the first module unit is an HR type reverse osmosis membrane module 320
  • the reverse osmosis membrane module of the second module unit is an HF type reverse osmosis membrane module 330.
  • the reverse osmosis membrane module of the first module unit may include a plurality of HR type reverse osmosis membrane modules 320
  • the reverse osmosis membrane module of the second module unit includes a plurality of HF type reverse osmosis membrane modules 330. can do.
  • the desalted seawater is discharged through the permeate outlet of the pressure vessel (S300).
  • the Y axis represents the flow rate by position in the pressure vessel, and the area formed by each graph and the X axis is the total freshwater production amount when each separator is used.
  • the flow rate decreases toward the rear end of the pressure vessel 100.
  • the membrane of the present invention the flow rate decreases to the second module, but in the third module, the HF type reverse osmosis membrane module 330 increases the flow rate even when desalination of high concentration seawater. And the flow rate decreases toward the rear end.
  • the freshwater production up to the second module is higher when using the conventional reverse osmosis membrane pressure vessel, but the third to sixth modules are used.
  • Freshwater production up to the first module is more when the hybrid CNT reverse osmosis membrane of the present invention is used.
  • FIG. 9 shows a stage connected in parallel with the reverse osmosis membrane module 300 according to an embodiment of the present invention.
  • the pressure vessel 100 is connected in parallel to a plurality of stages (Stage) 700 is called.
  • Stage 700 is formed by connecting the pressure vessels 100 in parallel, the desalination capacity is increased by the number of the pressure vessels 100 connected thereto.
  • FIG. 10 illustrates a multi-stage system in which reverse osmosis membrane pressure vessel stages are connected in series according to an embodiment of the present invention.
  • a system in which a plurality of stages 700 connected with a plurality of pressure vessels 100 are connected in series may be used.
  • the first stage becomes the first stage and the second stage becomes the second stage.
  • the thermal oxidation method refers to a method of oxidizing by applying high temperature heat, and the reverse osmosis membrane may include carbon nanotubes coated with dopamine.
  • the dopamine is one of the biomimetic substances found in mussel extracts. Dopamine spontaneously adsorbs on a variety of materials under specific conditions and has hydroxyl group (-OH) and amine (-NH2) functional groups to improve the hydrophilicity of the adsorbed material.
  • Dopamine is coated on the carbon nanotubes, thereby improving dispersibility of the carbon nanotubes in the solution used in the preparation of the reverse osmosis membrane.
  • the carbon nanotubes used in the present invention are unopened and coated with dopamine, and the average length of the carbon nanotubes is 1 to 2 ⁇ m, and the average diameter is 5 to 8 nm.
  • the ends of the carbon nanotubes are preferably opened by treating the carbon nanotubes by thermal oxidation.
  • the average length of the ends of the carbon nanotubes before the treatment is shortened to 1 to 2 ⁇ m after the treatment.
  • the carbon nanotubes having an average diameter of 6 to 10 nm before treatment are reduced to 5 to 8 nm after the treatment.
  • the length of the open end of the carbon nanotube is less than 1 ⁇ m the length is too short, it is difficult to expect the improvement of water permeation performance through the inside of the carbon nanotube in the selection layer is not preferable.
  • the length of the open end of the carbon nanotube exceeds 2 ⁇ m the length is too long is not preferable because the protruding portion in the selection layer occurs.
  • the performance is generally improved, but less than 5 nm is not preferable because the water transmittance is too low, if more than 8 nm salt rejection to be achieved in the present invention is It is not preferable to fall too much.
  • the dopamine is coated to improve the dispersibility of the carbon nanotubes in the solution used in the preparation of the reverse osmosis membrane.
  • the binding energy due to the bond between carbon and oxygen forms a peak at 288 to 290 eV.
  • characteristic peaks such as those after the thermal oxidation process are not observed at 288 to 290 eV.
  • the reverse osmosis membrane mixed with carbon nanotubes having such characteristics has excellent water permeability and salt rejection rate.
  • step 2) coating the carbon nanotubes whose end is opened by step 1) with dopamine;
  • step 2) dispersing the carbon nanotubes obtained in step 2) in the amine solution to prepare a carbon nanotube-polyamide composite membrane by interfacial polymerization;
  • the carbon nanotubes are opened at their ends by the thermal oxidation method of step 1).
  • the thermal oxidation method is not particularly limited as long as the carbon nanotubes are opened by oxidizing the carbon nanotubes by injecting heat, but preferably, the carbon nanotubes are oxidized for 1 to 3 hours while injecting an inert gas at 800 to 1,000 ° C. Then, it is cooled to 25 ⁇ 40 °C at room temperature, after which it is heated to 300 ⁇ 600 °C and maintained for 2 to 4 hours, it is characterized in that the inert gas is injected to cool to room temperature.
  • the ends of the carbon nanotubes are opened.
  • Producing a reverse osmosis membrane including the open end of the carbon nanotube enables a fast water permeation phenomenon into the inside of the carbon nanotube, and provides a reverse osmosis membrane having an excellent water permeability compared to before the end is opened. This becomes possible.
  • the average diameter of the carbon nanotubes is reduced to 5 to 8 nm, thereby reducing the effect of reducing the salt excretion rate in the active layer.
  • the average length of the carbon nanotubes becomes 1 to 2 ⁇ m, and there is no protruding portion, and at the same time, the carbon nanotubes are completely enclosed in the separator to reduce the water permeability. This phenomenon is preferable because it can prevent the phenomenon.
  • the amount of dopamine used to coat the carbon nanotubes in the step 2) is characterized in that the coating by using 1,000 parts by weight based on 100 parts by weight of the carbon nanotubes the end is opened.
  • a carbon nanotube-polyamide composite separator is formed by interfacial polymerization.
  • the carbon nanotubes are coated with dopamine, so that the dispersibility is excellent in the amine solution, and the aggregation phenomenon is significantly reduced.
  • the amine contained in the amine solution is ortho-phenylenediamine, ortho-phenylenediamine, meta-phenylenediamine, para-phenylenediamine, and piperazine. ), Ethylene diamine, cadaverine, and mixtures thereof.
  • the thermal oxidation process was the first step through a thermal annealing process to remove amorphous carbon and impurities.
  • the carbon nanotubes were placed in a furnace, and the reaction was performed at 900 ° C. for 2 hours in an argon atmosphere.
  • a thermal oxidation reaction process was performed to open the ends of the carbon nanotubes.
  • Fill the furnace with high-purity air heat the carbon nanotubes to 400 ° C at 10 ° C / min in air condition, maintain 3 hours at isothermal temperature at 400 ° C, and raise the furnace temperature to 500 ° C at 10 ° C / min.
  • inert gas argon
  • a polydopamine coating process was introduced to increase the dispersing performance of the end-opened carbon nanotubes.
  • Dopamine solution 2,000 ppm Dopamine hydrochloride
  • a precursor of polydopamine was prepared under specific conditions (using a 1 M NaOH solution in 15 mM Trizma solution to adjust the pH to pH 8.5 or higher), and then using a known stirring coating method. The reaction proceeded with the nanotubes.
  • the coating process was performed while reacting with an ultrasonic homogeneous system for uniform coating, and the polydopamine was purified by centrifugation to separate the carbon nanotubes uniformly coated.
  • 19 shows the structure of poly dopamine-coated carbon nanotubes through TEM analysis.
  • the dopamine-coated carbon nanotubes according to Preparation Example 2 was dispersed in a water system with a surfactant and stirred with meta-phenylenediamine (MPD) to obtain an MPD solution, TMC After dissolving (Trimesoyl chloride) in a Dodecane solvent to obtain an organic solution, a carbon nanotube-polyamide composite membrane having open ends was prepared by interfacial polymerization. In addition, UV-vis spectroscopy was performed while increasing the concentration of carbon nanotubes to confirm the dispersion performance.
  • MPD meta-phenylenediamine
  • a carbon nanotube-polyamide composite separator was prepared in the same manner as in Example 1 except that the processes of Preparation Example 1 and Preparation Example 2 were not performed.
  • a carbon nanotube-polyamide composite separator was prepared in the same manner as in Example 1 except that the procedure of Preparation Example 1 was not performed.
  • a carbon nanotube-polyamide composite separator was prepared in the same manner as in Example 1 except that the process of Preparation Example 2 was not performed.
  • Figure 14 is a TEM photograph of the end of the carbon nanotubes when the thermal oxidation method is not performed.
  • the average length is 3 to 5 ⁇ m, and when the terminals are opened by the thermal oxidation method, the average length is 1 to 2 ⁇ m.
  • the average length of the carbon nanotubes was also shortened.
  • the average diameter is 6 to 10 nm, and when the terminal is opened by the thermal oxidation method, the average diameter is 5 to 8 nm. It was confirmed that the average diameter of the carbon nanotubes is also reduced due to the terminal opening according to the oxidation method.
  • FIG. 15 is a case in which the end is not opened and the dopamine is coated with carbon nanotubes according to Comparative Example 1
  • FIG. 16 is the dopamine coated in Comparative Example 3 If not, but the end is used to open the carbon nanotubes.
  • the permeability increased when the ends of the carbon nanotubes were unopened than when the terminals were not opened.
  • Table 2 shows the results obtained by measuring the water permeability and salt rejection of the membrane as the content of carbon nanotubes is increased using the separator prepared in Example 1.
  • Table 3 below is a result of measuring the water permeability and salt rejection of the separator prepared from Comparative Example 3.
  • Example 1 in the case of Example 1 according to the present invention, as can be seen in Table 2, it was confirmed that the water permeability and the salt rejection rate were excellently improved or maintained even though the content of carbon nanotubes was increased. On the contrary, in Table 3, even in the case of increasing the content of carbon nanotubes in Comparative Example 3, the water permeability did not increase, and the salt excretion rate also decreased. Through this, it was confirmed that the coating of dopamine on the end-opened carbon nanotubes contributes to the improvement of water transmittance and salt rejection rate.
  • the following process may be added to improve the rate at which the end of the carbon nanotubes open in the step of the reverse osmosis membrane manufacturing method described above.
  • Preparation Example 1 Before performing the process of Preparation Example 1 is a process of injecting carbon nanotubes in a 30% solution of H 2 O 2 at 60 ° C. This process is to pretreat under H 2 O 2 weak oxidation conditions to increase the terminal opening effect during the heat treatment in the subsequent process.
  • the intensity value for the pore size was higher than that obtained by oxidizing under the conventional air condition.
  • the x-axis represents the pore diameter
  • the y-axis represents the volume of the pore, which can be viewed as an intensity value.
  • the y-axis value of the CNTs that were not pretreated was low, but the intensities corresponding to 2.6 nm and 3.3 nm were significantly increased in the case of oxidation treatment under air condition, and the intensity was further increased by H 2 O 2 treatment. You can see the increase. Therefore, the H 2 O 2 treatment can be seen that the highest open rate.
  • the neutral solution of dopamine oxidizes immediately upon contact with air, which can be converted to polydopamine by substantially spontaneous oxidative polymerization and coated on the surface of a material such as carbon nanotubes.
  • the coating process was carried out in an air atmosphere to sufficiently coat polydopamine on carbon nanotubes, but the coating process took 12 to 24 hours, and compared to 6 to 20 nm, which is the thickness of conventional carbon nanotubes. There is a problem that it is difficult to obtain a relatively thick and uniform coating with a thickness of 6 ⁇ 12 nm.
  • dopamine is dissolved in a tris-buffer solution to obtain a precursor solution of polydopamine.
  • the precursor solution of polydopamine is preferably adjusted to a pH of 8.5 or more using 1M NaOH solution in Trizma solution. Can be used.
  • carbon nanotubes are added to the precursor solution of polydopamine to perform a coating process under an oxygen atmosphere.
  • the carbon nanotubes are single wall carbon nanotubes, double wall carbon nanotubes, It may be any one selected from the group consisting of multiwall carbon nanotubes, and rope carbon nanotubes, and multiwall carbon nanotubes may be more preferably used.
  • the coating process may be carried out in an oxygen atmosphere over 15 minutes to 1 hour, but if the coating process time is less than 15 minutes, it is difficult to obtain a uniform coating layer, and if it exceeds 1 hour, the thickness of the coating layer becomes thick. To control the coating time within the above range, it is more preferable to perform the coating process for 30 minutes.
  • the polydopamine-coated carbon nanotubes according to the present invention is prepared.
  • Polydopamine-coated carbon nanotubes were prepared in the same manner as in Example 1, except that the coating process was performed at room temperature in an air atmosphere for 12 hours.
  • FIG. 22 shows a scanning electron microscope (SEM) (a) and a transmission electron microscope (TEM) photograph (b) of a polydopamine-coated carbon nanotube according to Example 1 of the present invention.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • FIG. 23 is a scanning electron microscope (SEM) (a) and a transmission electron microscope (TEM) photograph of a polydopamine-coated carbon nanotube prepared by performing a coating process for 15 minutes according to Example 2 of the present invention. As shown, it can be confirmed that the coating layer has a thickness of 1.7 nm.
  • FIG. 24 shows a scanning electron microscope (SEM) (a) and a transmission electron microscope (TEM) photograph (b) of a polydopamine-coated carbon nanotube according to a comparative example of the present invention, the coating process is carried out for 12 hours Even if a uniform coating layer is not formed, it can be confirmed that the thickness of the coating layer is also relatively thick as 10 nm.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • Figure 25 is thermogravimetrically weighted carbon nanotubes coated with polydopamine according to Examples 1, 2, and Comparative Examples of the present invention together with carbon nanotubes not coated with polydopamine at a temperature of 10 ° C./min under a nitrogen atmosphere.
  • TGA thermogravimetrically weighted carbon nanotubes coated with polydopamine according to Examples 1, 2, and Comparative Examples of the present invention together with carbon nanotubes not coated with polydopamine at a temperature of 10 ° C./min under a nitrogen atmosphere.
  • TGA thermogravimetrically weighted carbon nanotubes coated with polydopamine according to Examples 1, 2, and Comparative Examples of the present invention together with carbon nanotubes not coated with polydopamine at a temperature of 10 ° C./min under a nitrogen atmosphere.
  • TGA thermogravimetrically weighted carbon nanotubes coated with polydopamine according to Examples 1, 2, and Comparative Examples of the present invention together with carbon nanotubes not coated with polydopamine at
  • Fig. 26 shows the results of infrared spectroscopy (FT-IR) of carbon nanotubes not coated with polydopamine and carbon nanotubes coated with polydopamine according to Examples 1, 2 and Comparative Examples of the present invention.
  • the carbon nanotubes not coated with polydopamine do not show a specific peak in the range of 1,000 to 2,000 (cm ⁇ 1) because there are almost no functional groups.
  • the polydopamine particles exhibit characteristic peaks of dopamine in the 1610 and 1500 (cm-1) sections. The peaks of polydopamine were measured for both carbon nanotubes according to Examples 1, 2 and Comparative Example, which shows that the polydopamine was well coated on the carbon nanotubes.
  • Figure 27 shows the photoelectron spectroscopy (XPS) results of the polydopamine-coated carbon nanotubes according to the comparative example of the present invention (a) and the optoelectronics of the polydopamine-coated carbon nanotubes according to Example 1 of the present invention
  • Spectroscopic analysis (XPS) shows (b).
  • XPS photoelectron spectroscopy
  • the ratio of O and N elements increases, which increases with the coating amount of dopamine relative to the carbon nanotubes.
  • the ratio of the O element was 20.57% and the ratio of the N element was 7.38%
  • Example 1 the ratio of the O element was 11.56% and the ratio of the N element was 3.27%.
  • the element ratio result was shown. This shows that the carbon nanotubes coated under oxygen conditions have a low coating amount of polydopamine, and also show a quantitative value for the coating amount of thinly coated carbon nanotubes.
  • FIG. 28 shows spectrophotometric analysis (UV-vis) results of polydopamine-coated carbon nanotubes according to a comparative example of the present invention (a) and spectroscopy of polydopamine-coated carbon nanotubes according to Example 1 of the present invention.
  • Photometric analysis (UV-vis) result (b) is shown.
  • the polydopamine-coated carbon nanotube shows an absorption peak at about 260-270 nm in UV-vis. Absorbance increases as the dispersion is better in the solution, and the carbon nanotubes coated under oxygen conditions are more than the entire range (0.25, 0.75, 1.25 mg / 100g, carbon nanotubes) compared to carbon nanotubes coated under air conditions.
  • the manufacturing method of the polydopamine-coated carbon nanotube of the present invention by coating the polydopamine on the carbon nanotubes in a short time under an oxygen atmosphere, it is possible to achieve a uniform shortening of the coating and coating process time, thereby
  • the polydopamine-coated carbon nanotubes produced are very thin, with a thickness of 1.7 to 2 nm, and the dispersibility is improved in an aqueous system, and includes carbon nanotubes coated with polydopamine, including carbon nanotubes / polymer composite membranes. Applicable to mass production of polymer composites.
  • the process can be further modified as follows to maintain the dispersion degree of carbon nanotubes over time.
  • the conventional dopamine coating process (i) ultrasonic dispersion of carbon nanotubes with a concentration of 200 mg / 1L in a 15 mM tris-buffer solution at pH 8.5 for 1 hour, (ii) dopamine is injected into the solution at a concentration of 2000 ppm, ( iii) reacted with O 2 for 15 minutes, (iv) lowered the pH, terminated the reaction, and (v) dried, but the process for increasing the dispersion was further modified to (i) 200 mg / 1L carbon nano The tube was sonicated for 1 hour in a 15 mM tris-buffer solution at pH 8.5, (ii) pre-purged O 2 in the solution for 5-10 minutes, and (iii) 2000 ppm concentration of dopamine in the solution.
  • FIG. 31 illustrates an aqueous dispersion image and UV-vis analysis result of CNTs having improved aqueous dispersibility according to an embodiment of the present invention.
  • O 2 gas was pre-injected into the solution so that the O 2 was dissolved in the solution in advance, thereby rapidly contacting with dopamine.
  • FIG 32 is a graph comparing the power consumption for the same flow rate when desalination using the reverse osmosis membrane pressure vessel according to an embodiment of the present invention and the conventional reverse osmosis membrane pressure vessel.
  • the power used to obtain the same amount of fresh water was less when using the reverse osmosis membrane pressure vessel according to an embodiment of the present invention, which means that more desalination can be performed using the same power. .
  • the hybrid reverse osmosis membrane pressure vessel described above is not limited to the configuration and method of the above-described embodiments, the embodiments may be selectively all or part of each embodiment so that various modifications can be made It may be configured in combination.
  • the present invention applying the above-described configuration can be provided to users of a hybrid CNT-RO membrane pressure vessel with a high freshwater recovery.
  • the water permeability of the reverse osmosis membrane module can be increased by 50% or more by mixing carbon nanotubes in the reverse osmosis membrane module.

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

Abstract

La présente invention concerne un récipient à pression à membrane d'OI en NTC hybride Le récipient à pression à membrane de séparation par osmose inverse récipient selon un mode de réalisation de la présente invention comprend une entrée d'eau de mer, de multiples modules de membrane de séparation par osmose inverse, un canal d'écoulement d'eau de perméat, une sortie d'eau de perméat, et une sortie d'eau concentrée, et un ou plusieurs modules des multiples modules de membrane de séparation par osmose inverse, qui sont situés à l'extrémité avant du récipient à pression, constituent une première unité de module, et des modules situés derrière la première unité de modules constituent une seconde unité de modules, et le débit des modules respectifs constituant la seconde unité de module peut être supérieur à celui des modules respectifs constituant la première unité de module.
PCT/KR2015/009225 2014-09-02 2015-09-02 Récipient à pression à membrane d'oi en ntc hybride Ceased WO2016036125A1 (fr)

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CN106925121A (zh) * 2017-05-02 2017-07-07 华东理工大学 一种Mg2+和Li+分离三通道内皮层荷正电纳滤膜及其制备方法
ES2680904A1 (es) * 2017-03-06 2018-09-11 Manuel Lahuerta Romeo Desalinizadora submarina
CN113101807A (zh) * 2021-04-06 2021-07-13 九章膜(北京)科技有限公司 一种膜组件、具有该膜组件的膜设备及膜系统
CN113121859A (zh) * 2021-04-22 2021-07-16 哈尔滨工业大学 一种电聚合聚多巴胺-碳纳米管复合膜的制备方法

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CN113121859B (zh) * 2021-04-22 2022-09-02 哈尔滨工业大学 一种电聚合聚多巴胺-碳纳米管复合膜的制备方法

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