WO2020145401A1 - 膜蒸留用モジュール及びそれを用いた膜蒸留装置 - Google Patents
膜蒸留用モジュール及びそれを用いた膜蒸留装置 Download PDFInfo
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- WO2020145401A1 WO2020145401A1 PCT/JP2020/000744 JP2020000744W WO2020145401A1 WO 2020145401 A1 WO2020145401 A1 WO 2020145401A1 JP 2020000744 W JP2020000744 W JP 2020000744W WO 2020145401 A1 WO2020145401 A1 WO 2020145401A1
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- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- hollow fiber
- porous hollow
- hydrophobic polymer
- fiber membrane
- Prior art date
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Images
Classifications
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
- B01D61/3641—Membrane distillation comprising multiple membrane distillation steps
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/366—Apparatus 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
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/08—Hollow fibre membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/04—Specific sealing means
- B01D2313/042—Adhesives or glues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/22—Cooling or heating elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/04—Hydrophobization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/004—Seals, connections
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a membrane distillation module and a membrane distillation apparatus equipped with the module.
- the membrane distillation method uses a porous membrane that allows only water vapor to permeate out of the water to be treated, and condenses the steam that has passed through the porous membrane due to the saturated water vapor pressure difference from the heated raw water (high temperature water) to obtain distilled water. Is the way to get.
- the membrane distillation method does not require a high driving force, and therefore the power energy can be reduced.
- the membrane distillation method has an extremely high separation performance for non-volatile solutes such as salt, so that high-purity water can be obtained.
- Patent Document 1 has an outer surface opening ratio of 20% or more and less than 50%, and is composed of a polyolefin, an olefin-halogenated olefin copolymer, a halogenated polyolefin, or the like, from the viewpoint of water permeability retention and membrane scratch resistance. Porous hollow fiber membranes are described.
- Patent Document 2 discloses a hydrophobic porous hollow fiber having a surface opening ratio of 20% or more and 70% or less on the surface of a membrane in contact with water to be treated as a membrane used in a membrane distillation apparatus having water treatment capacity and compactness. Membranes have been described and an average pore size of 10 ⁇ m or less has been investigated from the viewpoint of suppressing wetting.
- Patent Document 3 It is also known to modify the surface of the porous membrane in order to suppress wetting in membrane distillation (Patent Document 3).
- Patent Document 3 in order to prevent the surface of a porous film made of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) or the like from being covered with oil and easily wetted, a fluorinated monomer or It is described that the surface of the porous membrane is treated with the polymer to make it liquid repellent.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- wetting is likely to occur near the boundary between the adhesive fixing part and the non-adhesive fixing part.
- the first reason is that the starting point of wetting is formed in the subsequent process of manufacturing the membrane module even if the wetting countermeasure is applied to the porous membrane.
- the adhesive resin before curing penetrates into the porous membrane, and the adhesive fixing part and the non-adhesive fixing part after curing.
- a phenomenon occurs in which the adhesive resin coats the surface of the film near the interface with and the surface of the pores inside.
- the resin used for adhesive fixation is a resin with low hydrophobicity such as epoxy resin and urethane resin, so even if the porous film itself has the ability to suppress wetting, the properties of the film adhere near the adhesive resin. It becomes close to that of resin and wetting occurs.
- the second reason is that the amount of steam generated during the operation of the membrane distillation module is not uniform depending on the location of the membrane, and wetting occurs at the location where evaporation is active.
- the raw water consumes heat of vaporization when it is delivered as steam through the membrane, so the raw water temperature is highest at the site where the raw water is introduced. Decreases as it goes in the longitudinal direction of the film.
- the temperature of the raw water introduced into the module may be 90°C and the temperature of the raw water discharged from the module may be 70°C. In such a case, the amount of steam generated at the raw water inlet portion is large, and wetting is likely to occur at this portion.
- One aspect of the present invention is to solve the above problems, and an object of the present invention is to provide a membrane distillation module having excellent temporal stability of water treatment capacity by suppressing wetting, and a membrane distillation apparatus including the module. To do.
- the present inventor has conducted extensive studies and experiments to solve the above-mentioned two problems that are the main causes of wetting, and as a result, in one aspect, by attaching a hydrophobic polymer in the vicinity of an adhesive fixing site by an adhesive resin, It has been found that penetration of the adhesive resin into the hollow fiber membrane is prevented, the hydrophobicity of the hollow fiber membrane is maintained, and the evaporation amount at this portion is reduced, so that wetting can be suppressed. Further, in one aspect, the inventors have found an optimal structure of a membrane distillation apparatus that does not deteriorate the quality of the produced water in pure water production even if slight wetting occurs. That is, the present invention includes the following aspects.
- a membrane module for membrane distillation comprising a housing and a plurality of porous hollow fiber membranes having both ends bonded and fixed to the housing,
- the water contact angle of the outer surface of the porous hollow fiber membrane is 90° or more
- a hydrophobic polymer is attached to at least a part of the non-adhesive fixing part of the porous hollow fiber membrane,
- For each of the inner surface and the outer surface of the porous hollow fiber membrane when the portion from one end to the other end in the longitudinal direction of the non-adhesive fixed portion is expressed as 0% to 100%, 0% to 5% from the one end
- At least one of the amount of the hydrophobic polymer adhering to the site per membrane area and the amount of the hydrophobic polymer adhering to the site at 95 to 100% from the one end is 40 or more from the one end.
- a membrane module for membrane distillation comprising: a housing; and a plurality of porous hollow fiber membranes, both ends of which are adhesively fixed to the housing.
- a hydrophobic polymer is attached to at least a part of the non-adhesive fixing part of the porous hollow fiber membrane, For each of the inner surface and the outer surface of the porous hollow fiber membrane, when the portion from one end to the other end in the longitudinal direction of the non-adhesive fixed portion is expressed as 0% to 100%, 0% to 5% from the one end Both the amount of the hydrophobic polymer adhering to the site per membrane area and the amount of the hydrophobic polymer adhering to the site at 95 to 100% from the one end are 40 to 40% from the one end.
- a module for membrane distillation that has more than the amount of hydrophobic polymer per membrane area present at 60% site.
- the raw water introduction part is arranged so that the non-adhesive fixed part of the porous hollow fiber membrane is closest to the raw water introduction part at a site of less than 50% from the one end, and the membrane area of the porous hollow fiber membrane is
- the amount of said hydrophobic polymer per unit has the following relationship: [Amount of hydrophobic polymer at 0 to 20% site from the one end]>[Amount of hydrophobic polymer at 95 to 100% site from the one end]>[Hydrophobic polymer at 40 to 60% site from the one end] Amount of]
- the membrane distillation module according to Aspect 1 or 2, which satisfies the above condition.
- a membrane distillation apparatus for producing water comprising: A membrane distillation apparatus comprising the membrane distillation module according to any one of aspects 1 to 4 above.
- the membrane distillation apparatus further includes a cooling device connected to the membrane distillation module, The membrane distillation module is configured such that the porous hollow fiber membrane is fixed in a substantially vertical direction with the one end facing down, and raw water is introduced into the porous hollow fiber membrane from the one end, 6.
- the membrane distillation module is configured such that the porous hollow fiber membrane is fixed in a substantially vertical direction with the one end facing down, and raw water is introduced into the porous hollow fiber membrane from the one end.
- 7. The membrane distillation apparatus according to the above aspect 5 or 6, wherein the module for membrane distillation has a discharge port at a vertical position corresponding to a position lower than 1 ⁇ 2 of the total height of the non-adhesive fixed portion of the porous hollow fiber membrane.
- a membrane distillation module that is excellent in temporal stability of water treatment capacity by suppressing wetting, and a membrane distillation apparatus including the module.
- FIG. 1A is a schematic diagram showing a membrane distillation module according to an aspect of the present disclosure.
- FIG. 1B is a schematic diagram showing a membrane distillation module according to an aspect of the present disclosure.
- FIG. 2A is a schematic diagram showing the vicinity of the boundary between the adhesive fixation site A and the adhered fixation site NA of the porous hollow fiber membrane to which the hydrophobic polymer is not applied.
- FIG. 2B is a schematic diagram showing the vicinity of the boundary between the adhesive fixation site A and the adhered fixation site NA of the porous hollow fiber membrane to which the hydrophobic polymer is not applied.
- FIG. 1A is a schematic diagram showing a membrane distillation module according to an aspect of the present disclosure.
- FIG. 1B is a schematic diagram showing a membrane distillation module according to an aspect of the present disclosure.
- FIG. 2A is a schematic diagram showing the vicinity of the boundary between the adhesive fixation site A and the adhered fixation site NA of the porous hollow fiber membrane to which the hydrophobic poly
- FIG. 3A is a schematic diagram showing the vicinity of the boundary between the adhesive fixation site A and the adhered fixation site NA of the porous hollow fiber membrane to which the hydrophobic polymer is applied.
- FIG. 3B is a schematic diagram showing the vicinity of the boundary between the adhesive fixation site A and the adhered fixation site NA of the porous hollow fiber membrane to which the hydrophobic polymer is applied.
- FIG. 4 is an image diagram showing the relationship between the position in the longitudinal direction of the porous hollow fiber membranes in the membrane distillation modules 10A and 10B and the vapor permeation amount.
- FIG. 5A is a diagram showing a radial cross section of a porous hollow fiber membrane according to an aspect of the present disclosure.
- FIG. 5B is a view showing a longitudinal cross section of the porous hollow fiber membrane shown in FIG. 5A.
- FIG. 6A is a schematic diagram showing an example of a membrane distillation apparatus according to an aspect of the present disclosure.
- FIG. 6B is a schematic diagram showing an example of a membrane distillation apparatus according to an aspect of the present disclosure.
- FIG. 7 is a schematic diagram illustrating various membrane distillation methods.
- FIG. 8 is a schematic diagram showing the configuration of the membrane distillation apparatus used in Example 1.
- this embodiment A mode for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail below.
- the present invention is not limited to the following embodiments, and various modifications can be carried out within the scope of the gist.
- One aspect of the present invention includes a housing and a plurality of porous hollow fiber membranes whose both ends are adhesively fixed to the housing (in the present disclosure, the term may be referred to as “hollow fiber membrane” or “membrane” without special mention).
- a membrane module for membrane distillation having: A hydrophobic polymer is attached to at least a part of the non-adhesive fixing part of the porous hollow fiber membrane, When the portion from one end to the other end in the longitudinal direction of the non-adhesive fixed portion of the porous hollow fiber membrane is expressed as 0% to 100%, the membrane area attached to the portion 0 to 5% from the one end At least one, preferably both, of the amount of the hydrophobic polymer and the amount of the hydrophobic polymer per membrane area adhered to the site of 95 to 100% from the one end to the site of 40 to 60%.
- a module for membrane distillation is provided that has a greater amount of hydrophobic polymer per membrane area present in.
- the water contact angle of the outer surface of the porous hollow fiber membrane is 90° or more.
- the “non-adhesive fixing part” means a part of the porous hollow fiber membrane excluding the adhesive fixing parts at both ends.
- the “inner surface” means the portion of the surface of the porous hollow fiber membrane (that is, the exposed surface of the membrane constituent member) that faces the hollow portion of the membrane, and the “outer surface”. "Means the part of the surface facing the outside of the film (that is, the facing surface of the inner surface), and the "pore surface” means the part of the surface excluding the inner surface and the outer surface (that is, the thickness of the film). The part facing the pores inside the direction).
- the amount of the hydrophobic polymer defined in the present disclosure may be satisfied on at least one of the “inner surface” and the “outer surface” of the porous hollow fiber membrane, and preferably at least on the surface in contact with raw water. And more preferably both surfaces are filled.
- the “membrane area” means the area of the surface (that is, the exposed surface of the membrane constituent member).
- the module for membrane distillation of the present embodiment is excellent in stability over time of water treatment capacity because the wetting is suppressed.
- FIGS. 1A and 1B are schematic views showing a module for membrane distillation according to an aspect of the present disclosure.
- the membrane distillation modules 10A and 10B have a housing 11 and a plurality of porous hollow fiber membranes 12 housed in the housing 11, Both ends of the thread film 12 are adhesively fixed to the housing 11 with an adhesive resin 13 (adhesive fixing portion A in FIGS. 1A and 1B).
- the porous hollow fiber membrane 12 the parts other than the adhesion fixing part A are not fixed with the adhesive resin 13 (non-adhesion fixing part NA in FIGS. 1A and 1B).
- raw water is introduced into the inside of the porous hollow fiber membrane 12, and pure water as steam is delivered from the outside of the porous hollow fiber membrane 12 as generated water.
- the membrane distillation module 10B shown in FIG. 1B raw water is introduced to the outside of the porous hollow fiber membrane 12 and produced water (as steam) is delivered from the inside of the porous hollow fiber membrane 12.
- one surface of the porous hollow fiber membrane 12 comes into contact with raw water, and steam is generated from the other surface.
- the adhesive resin 13 has a thickness (that is, the longitudinal length of the membrane) that can fix both end portions of the membrane with a predetermined length.
- the thickness of the adhesively fixed portion A by the adhesive resin 13 is determined by the temperature and pressure inside and outside the hollow fiber membrane (that is, the raw water side and the reduced pressure side), the stress applied to the membrane, and the like.
- FIGS. 2A and 2B are schematic diagrams showing the vicinity of the boundary between the adhesive fixation site A and the adhered fixation site NA of the porous hollow fiber membrane to which the hydrophobic polymer is not applied, and FIGS. It is a schematic diagram which shows the boundary vicinity of the adhesion
- the porous hollow fiber membrane 12 when the porous hollow fiber membrane 12 is adhesively fixed to the housing 11 with the adhesive resin 13, the hollow fiber membrane 12 is formed near the boundary between the adhesive fixing portion A and the non-adhesive fixing portion NA.
- a phenomenon called “elevation” (the elevation 13A in FIGS. 2A and 2B) that covers the exposed portion of the outer surface of the adhesive resin may occur.
- the rising means that the adhesive resin 13 contacts the porous hollow fiber membrane 12 in a fluid state before curing, and the adhesive resin 13 enters the pores of the porous hollow fiber membrane 12 during the time until curing. Is formed by. In the normal case, the rising range is within 30 mm in the longitudinal direction of the film from the boundary between the adhesive fixing site A and the non-adhesive fixing site NA.
- porous hollow fiber membrane used in the module for membrane distillation according to the present embodiment needs to have pores (communication holes) communicating in the thickness direction from one surface of the membrane to the other surface.
- the communication holes may be voids in a network of membrane materials such as polymers, and may be branched or direct (ie, unbranched).
- the pores must be permeable to steam but impermeable to raw water (liquid).
- the water contact angle of the outer surface of the porous hollow fiber membrane is 90° on the outer surface of substantially all regions of the membrane from the viewpoint of avoiding wetting due to the hydrophobic nature of the porous hollow fiber membrane. It is at least 110°, preferably at least 120°.
- the water contact angle represents hydrophobicity, and there is no particular upper limit, but the upper limit is actually about 150°.
- a hydrophobic polymer is attached to the entire length or part of the membrane so that the membrane surface exhibits stable hydrophobicity. In the cross-sectional direction of the membrane, the hydrophobic polymer may be attached to at least a part of at least one of the inner surface, the outer surface and the surface of the communicating hole.
- the water contact angle is a value measured by the droplet method.
- the droplet method for example, 2 ⁇ L of pure water is dropped on the measurement target (that is, the outer surface of the porous hollow fiber membrane), and the angle formed by the measurement target and the droplet is analyzed from the projection image to obtain a numerical value. Turn into.
- the portion from one end E1 to the other end E2 in the longitudinal direction of the non-adhesive fixed portion NA of the porous hollow fiber membrane 12 is expressed as 0% to 100%.
- At least one, and preferably both, is greater than the amount of hydrophobic polymer per membrane area attached to 40-60% of the sites from the one end.
- the hydrophobic polymer is attached in an appropriate amount other than at the boundary between the adhesive fixing site A and the non-adhesive fixing site NA.
- the hydrophobic polymer is attached in an appropriate amount other than at the boundary between the adhesive fixing site A and the non-adhesive fixing site NA.
- a hydrophobic polymer may or may not be attached to the central portion, and the water contact angle may be 90° or more throughout the entire length of the membrane.
- the hydrophobic polymer includes the entire non-adhesive fixing part A and the non-adhesive fixing part NA from one end E1 and the other end E2 of the non-adhesive fixing part NA to the longitudinal center side.
- the raw water introducing part is arranged so that the non-adhesive fixing part of the porous hollow fiber membrane is the closest to the raw water introducing part at a part less than 50% from one end E1. Is a portion of the porous hollow fiber membrane where the amount of the hydrophobic polymer adhering to the region of 0 to 20% from the one end E1 is 40 to 60% from the one end E1 (that is, the length of the membrane).
- the amount of the hydrophobic polymer per membrane area adhered to the central portion of the direction) is more preferable, and more preferably, the amount of the hydrophobic polymer per membrane area of the porous hollow fiber membrane has the following relationship: [Amount of hydrophobic polymer at 0 to 20% from one end E1]> [Amount of hydrophobic polymer at 95 to 100% from one end E1]> [Hydrophobic polymer at 40 to 60% from one end E1] Amount of] Meet
- the numerical value (%) shown for the portion of the porous hollow fiber membrane may have an error of about ⁇ 2% in consideration of coating unevenness of the hydrophobic polymer that may occur in the actual module manufacturing process.
- wetting is suppressed by equalizing the amount of steam generated in the longitudinal direction of the membrane.
- the high temperature raw water introduced into the membrane module is deprived of heat of vaporization when part of the raw water is converted into steam, so the raw water temperature decreases as the raw water flows through the membrane module. Since the amount of steam generated is small in the part of the membrane that comes into contact with the raw water whose temperature has decreased, the amount of steam generated in the membrane module varies depending on the part of the membrane, resulting in a distribution.
- FIG. 4 is an image diagram showing the relationship between the position in the longitudinal direction of the porous hollow fiber membranes in the membrane distillation modules 10A and 10B and the vapor permeation amount.
- the hydrophobic polymer is not used in the configuration of the membrane distillation module 10A shown in FIG. 1A, raw water is introduced into the module from one end side of the membrane, so that the one end side of the adhesive fixing part and the non-adhesive fixing part A large amount of steam is generated near the boundary.
- the hydrophobic polymer is not used in the membrane distillation module 10B shown in FIG. 1B, the pressure loss inside the hollow fiber membrane inside the hollow fiber membrane is small near the one end and the other end of the membrane. There is a large amount of vapor permeation near the site.
- the present inventor has found from a number of experiments that wetting is likely to occur in a portion of the membrane where a large amount of vapor is generated.
- a hydrophobic polymer is attached to a site where a large amount of vapor is generated to reduce the amount of vaporization at that site, and the amount of vapor permeation in the longitudinal direction of the membrane is made as uniform as possible, thereby preventing wetting satisfactorily. be able to.
- FIG. 4 as shown in FIG. 3A, the relationship between the position in the longitudinal direction of the porous hollow fiber membrane and the amount of vapor permeation in the membrane distillation module 10A having the hydrophobic polymer 14 (the vapor in the vicinity of the raw water inlet in the longitudinal direction of the membrane). The transmission amount is decreasing).
- the hydrophobic polymer is preferably provided near the raw water introduction part.
- the hydrophobic polymer may be selectively applied to the raw water introducing part and the vicinity of the boundary between the adhesive fixing part and the non-adhesive fixing part.
- the hydrophobic polymer may be applied to the entire hollow fiber membrane, and then the amount of the hydrophobic polymer applied in the raw water introduction section may be further increased. A large coating amount of the hydrophobic polymer over the entire hollow fiber membrane is not preferable because the entire vapor generation amount decreases.
- the amount of the hydrophobic polymer attached may have a gradient in the thickness direction of the porous hollow fiber membrane. In a preferred embodiment, the amount of the hydrophobic polymer is gradually reduced from the raw water introduction side to the produced water delivery side.
- FIG. 5A is a diagram showing a radial cross section of a porous hollow fiber membrane according to one embodiment of the present disclosure
- FIG. 5B is a diagram showing a longitudinal cross section of the porous hollow fiber membrane shown in FIG. 5A. 5A and 5B
- the amount of hydrophobic polymer per membrane area is highest on the inner surface and gradually decreases towards the outer surface.
- Such a gradient is suitable for a configuration in which raw water passes through the inside of the porous hollow fiber membrane.
- the amount of the hydrophobic polymer per membrane area is preferably gradually increased from the inner surface to the outer surface of the porous hollow fiber membrane.
- raw water is introduced into the porous hollow fiber membrane from one end of the non-adhesive fixing portion of the membrane, preferably at 0 to 20% portion, or 0 to 25% portion, or 0 to 30% portion.
- the amount of hydrophobic polymer on the side surface is larger than the amount of hydrophobic polymer on the surface of the porous hollow fiber membrane on the vapor delivery side.
- the average pore diameter of the hollow fiber membrane is preferably within the range of 0.01 ⁇ m to 1.0 ⁇ m, more preferably within the range of 0.03 ⁇ m to 0.6 ⁇ m.
- the average pore diameter is a value measured by the half dry method according to ASTM:F316-86.
- the pore size distribution of the membrane is narrow.
- the pore size distribution which is the ratio of the maximum pore size to the average pore size, is preferably in the range of 1.2 to 2.5, more preferably 1.2 to 2.0.
- the maximum pore size is a value measured by the bubble point method.
- the porosity of the hollow fiber membrane is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, from the viewpoint of obtaining a good pure water production rate, and the strength of the membrane itself is kept good. It is preferably 85% or less, more preferably 83% or less, still more preferably 80% or less, since problems such as breakage hardly occur during long-term use.
- the porosity is a value measured by the method described in the [Example] section of the present disclosure.
- the surface aperture ratio of the hollow fiber membrane is preferably 15% or more, more preferably 18% or more, still more preferably 20% or more for each of the inner surface and the outer surface from the viewpoint of obtaining a good pure water production rate. From the viewpoint that the strength of the film itself is maintained well and problems such as breakage are unlikely to occur during long-term use, it is preferably 60% or less, more preferably 55% or less, still more preferably 50% or less.
- the surface aperture ratio is a value obtained by detecting a hole with image analysis software in an observation image of each of the inner surface and the outer surface by a scanning electron microscope (SEM).
- the outer diameter of the hollow fiber membrane is, for example, 300 ⁇ m or more and 5,000 ⁇ m or less, preferably 350 ⁇ m or more and 4,000 ⁇ m or less, and the inner diameter of the hollow fiber membrane is, for example, 200 ⁇ m or more and 4,000 ⁇ m or less, preferably 250 ⁇ m or more 3, It is 000 ⁇ m or less.
- the film thickness of the porous film is preferably 10 ⁇ m to 1000 ⁇ m, and more preferably 15 ⁇ m to 1000 ⁇ m, from the viewpoint of achieving both water permeability in membrane distillation and mechanical strength of the film.
- the film thickness is 1000 ⁇ m or less, it is possible to suppress a decrease in production efficiency of permeated water.
- the film thickness is 10 ⁇ m or more, it is possible to prevent the film from being deformed during use under reduced pressure.
- the main constituent material of the porous hollow fiber membrane according to the present embodiment is a relatively hydrophobic material (that is, a material having a relatively low affinity for water).
- the constituent material of the membrane is, for example, at least selected from the group consisting of polysulfone, polyether sulfone, polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, ethylene/tetrafluoroethylene copolymer, and polychlorotrifluoroethylene. It may contain one resin. From the viewpoint of hydrophobicity, film-forming property, and mechanical and thermal durability, polyvinylidene fluoride, ethylene/tetrafluoroethylene copolymer, and polychlorotrifluoroethylene are preferable. It is more preferable to remove impurities such as plasticizers after resin production (that is, after polymerization) or by scouring after film formation.
- the hydrophobic polymer is attached to at least a part of the porous hollow fiber membrane.
- the hydrophobic polymer can form a hydrophobic coating on the inner surface, the outer surface and/or the inside of the porous hollow fiber membrane to impart water repellency to the membrane or improve the water repellency of the membrane.
- the “hydrophobic polymer” means a polymer having a property of low affinity with water, for example, a hydrophobic structure (for example, a non-(low) polar group such as a hydrocarbon group or a fluorine-containing group, It is a polymer having a non-(low) polar skeleton such as a hydrocarbon main chain and a siloxane main chain.
- Hydrophobic polymers include hydrocarbon-based polymers, unmodified or modified (eg, hydrocarbon-modified and/or amino-modified) silicone-based polymers, fluorine-containing polymers (eg, polymers having fluorine-containing side groups), and the like.
- Specific examples include the following: (A) By reacting with a polymer having a siloxane bond (for example, dimethyl silicone gel, methylphenyl silicone gel, reactive modified silicone gel having an organic functional group (amino group, fluoroalkyl group, etc.) introduced, or a silane coupling agent Silicone-based polymers that form cross-linked structures and polymer gels (a) Polymers that have (per)fluoroalkyl groups, (per)fluoropolyether groups, alkylsilyl groups, fluorosilyl groups, etc.
- the hydrophobic polymer is a polymer of a (meth)acrylate-based monomer and/or a vinyl-based monomer having a (per)fluoroalkyl group and/or (per)fluoropolyether group having 1 to 12 carbon atoms. Is preferred.
- the amount of the hydrophobic polymer attached per membrane area of the hollow fiber membrane can be directly obtained as the weight by removing the solvent by an operation such as evaporation after extraction with a solvent capable of dissolving the hydrophobic polymer. This weight is divided by the membrane area obtained from the inner diameter or outer diameter of the hollow fiber membrane and the length to calculate the amount of hydrophobic polymer per membrane area.
- the adhesion amount is determined by an analyzer
- the adhesion is determined from the signal intensity ratio between the porous hollow fiber membrane and the hydrophobic polymer using a surface analysis device for each of the inner surface and the outer surface of the porous hollow fiber membrane.
- the quantity can be calculated.
- the amount of hydrophobic polymer per membrane area is defined as being represented by the average value of the inner surface and the outer surface. Since the surface analysis device can analyze the composition of only the surface layer of the hollow fiber membrane having a porous structure, the hydrophobic polymer adhesion amount per membrane area of the hollow fiber membrane can be estimated by the signal intensity ratio.
- the adhesion amount can be quantitatively determined from the calibration curve.
- the intensity ratio of the signal derived from the hydrophobic polymer/the signal derived from the porous hollow fiber membrane is arbitrarily calculated among a plurality of arbitrarily selected parts of the porous hollow fiber membrane.
- the site where the signal intensity ratio is larger than 1.2 times can be judged to be the site where the amount of the hydrophobic polymer applied is large.
- analysis equipment include surface analysis equipment such as IR (infrared spectrum absorption) equipment, XPS (X-ray photoelectron spectroscopy) equipment, and TOF-SIMS (time-of-flight secondary ion analysis) equipment.
- the adhesive resin for adhesively fixing the porous hollow fiber membrane is desired to have good mechanical strength and heat resistance at 100°C.
- the resin that can be used as the adhesive resin include a thermosetting epoxy resin and a thermosetting urethane resin.
- Epoxy resin is preferable from the viewpoint of heat resistance, but urethane resin is preferable from the viewpoint of handling property.
- the method of adhesion and fixing may be according to the known adhesion method for producing a module for membrane distillation.
- the material of the housing is selected from the viewpoint of pressure resistance, heat resistance, impact resistance, weather resistance and the like.
- resin, metal, etc. can be used, but from the above viewpoint, a group of resins consisting of polypropylene, polysulfone, polyether sulfone, polyvinylidene fluoride, ABS resin, fiber reinforced plastic and vinyl chloride resin, or stainless steel, brass, titanium, etc. are preferably selected from the following metals.
- the housing can also have a cooling function that cools the generated steam and turns it into pure water.
- a pipe through which steam passes can be eliminated.
- the membrane distillation module is installed so that the hollow fiber membranes are substantially vertical (that is, in a vertical state or a state close to that), and the hollow fiber membranes are placed between the hollow fiber membranes and the cooler.
- a membrane distillation apparatus for producing water, the membrane distillation apparatus including the membrane distillation module of the present disclosure.
- a membrane distillation apparatus includes a porous hollow fiber membrane and a heating unit that heats raw water or an evaporation unit that evaporates raw water.
- the membrane distillation apparatus if desired, in addition to a porous hollow fiber membrane, a heating section or an evaporation section, a condensation section for condensing water vapor that has passed through the porous hollow fiber membrane, a pipe for delivering raw water or permeated water, A vapor phase part or the like for delivering water vapor may be provided.
- the membrane distillation apparatus 100 preferably includes a membrane distillation module 10A and a cooling device 20 connected to the module 10A.
- the membrane distillation module 10A is configured so that the porous hollow fiber membrane 12 is fixed in a substantially vertical direction with one end facing down, and raw water is introduced into the porous hollow fiber membrane 12 from the one end side. It is configured, and the lower end of the connecting portion C (connecting port) between the porous hollow fiber membrane 12 and the cooling device 20 is located at a position higher than 1 ⁇ 2 of the total height of the non-adhesive fixing portion of the porous hollow fiber membrane. ..
- the connecting part C When the lower end of the connecting part C is located at a position higher than 1 ⁇ 2 of the total height of the non-adhesive fixing part of the porous hollow fiber membrane 12, the connecting part C has a long distance from the raw water introducing part I, so that Even if the raw water leaches out of the hollow fiber membrane by the coating, the raw water and its droplets do not reach the connecting portion, and only the steam reaches the cooling device 20 and desired pure water can be obtained.
- the membrane distillation apparatus 100, 200 corresponds to a lower portion of the membrane distillation module 10A (specifically, a position lower than 1 ⁇ 2 of the total height of the non-adhesive fixing portion of the porous hollow fiber membrane). It is preferable to have a discharge port D for discharging the wetted liquid in the housing at the vertical position). According to the discharge port D, the raw water leached out of the porous hollow fiber membrane can be manually or automatically excluded during operation, and the operation can be continued for a longer period even when wetting occurs. You can The outlet D may be connected to the drain tank 30 like the membrane distillation apparatus 200 shown in FIG. 6B.
- FIG. 7 is a schematic diagram illustrating various membrane distillation methods.
- A DCMD method (Direct Contact Membrane Distillation) in which water vapor generated from the evaporation section is directly taken into the condensation section (cooling device) through the porous hollow fiber membrane 1
- B AGMD method (Air Gap Membrane Distillation) in which a third gas phase section is provided between the evaporation section and the condensation section, and water vapor from the evaporation section is condensed on the surface of the cooling body 2 to obtain distilled water.
- A DCMD method (Direct Contact Membrane Distillation) in which water vapor generated from the evaporation section is directly taken into the condensation section (cooling device) through the porous hollow fiber membrane 1
- B AGMD method (Air Gap Membrane Distillation) in which a third gas phase section is provided between the evaporation section and the condensation section, and water vapor from the evaporation section is condensed on the surface of the cooling body 2 to obtain distilled water.
- a VMD method (Vacuum Membrane Distillation) in which a vacuum gap is provided in the third vapor phase portion and water vapor from the evaporation portion is moved to the condensation portion to obtain distilled water
- D SGMD method (Sweeping Gas Membrane Distillation) in which a sweeping gas is caused to flow in the third vapor phase portion and steam from the evaporation portion is moved to the condensation portion to obtain distilled water
- the VMD method shown in FIG. 7(c) is the most preferable, because stable permeated water quality can be obtained.
- high temperature water is shown as the raw water in FIG. 7, the raw water may be at a temperature near room temperature and the low temperature water, the condensation part, etc. may be lower than room temperature.
- the membrane can be regenerated to the initial state.
- the substance causing the clogging is an inorganic salt or a metal
- an acid having the ability to dissolve them can be used.
- the membrane may be washed with a solution of hydrochloric acid, citric acid or the like.
- the substance causing the clogging is an organic substance or a microorganism (slime)
- it may be washed using, for example, an aqueous solution of sodium hypochlorite as an oxidizing agent.
- the washing solvent may be flown at a high flow rate to remove the fine particles from the membrane surface.
- washing the clogging-causing substance deposited in the pores of the membrane and adhering to the membrane for example, after hydrophilizing the membrane with alcohol or a mixed solution of alcohol and water to wet it, washing with a washing solvent is performed.
- the membrane may be washed by applying pressure to the membrane and flowing a solvent into the pores.
- the clogging-causing substance may be removed by performing membrane distillation with fresh water as the water to be treated (raw water) to move the clogging-causing substance to the membrane surface and then washing the membrane surface.
- the module for membrane distillation and the membrane distillation apparatus according to the present embodiment are used for highly removing and purifying ions, organic substances, and inorganic substances contained in the water to be treated, or for removing water from the water to be concentrated and concentrating it. Can be suitably used. These applications include, for example, desalination of seawater, water production for ships, ultrapure water production (semiconductor factories, etc.), boiler water production (thermal power plants, etc.), water treatment in fuel cell systems, industrial wastewater treatment (food factories, chemicals).
- the produced water contains an inorganic salt content of several% to ten and several percent and an oil content of several ppm to several tens ppm on a mass basis.
- natural gas include conventional natural gas obtained from conventional gas fields, as well as non-conventional natural gas represented by coal bed methane (also known as coal seam gas).
- the module for membrane distillation according to the present embodiment and the membrane distillation apparatus equipped with the module may be used as a combined system combined with another water treatment technology.
- the membrane distillation apparatus according to the present embodiment can also be used as a means for collecting DS (Draw Solution) used in the FO (Forward Osmosis) method.
- the maximum pore diameter of the porous hollow fiber membrane was measured using the bubble point method.
- One end of a porous hollow fiber membrane having a length of 8 cm was closed, and a nitrogen gas supply line was connected to the other end via a pressure gauge.
- nitrogen gas was supplied to replace the inside of the line with nitrogen, and then the porous hollow fiber membrane was immersed in ethanol.
- the porous hollow fiber membrane was immersed in a state where pressure was slightly applied with nitrogen so that ethanol did not flow back into the line.
- the pressure of nitrogen gas was slowly increased while the porous hollow fiber membrane was immersed, and the pressure P at which bubbles of nitrogen gas began to stably emerge from the porous hollow fiber membrane was recorded.
- the porosity of the porous hollow fiber membrane was calculated from the weight of the hollow fiber membrane and the density of the material constituting the hollow fiber membrane according to the method described below.
- the hollow fiber membrane is cut into a certain length, the weight is measured, and the porosity is calculated by the following formula (5): Sought by.
- ⁇ C O / ( ⁇ C- F + ⁇ C -O)
- ⁇ C O / ( ⁇ C- F + ⁇ C -O)
- FIG. 8 is a schematic diagram showing the configuration of the membrane distillation apparatus 300 used in Example 1.
- the porous hollow fiber membrane 12 was completely immersed once in a fluororesin-based water repellent FG-1610-F130 (0.5) manufactured by Fluoro Technology Co., which was a hydrophobic polymer, and was then pulled up and dried. ..
- the hydrophobic polymer was re-applied to each of the both ends of the 15 cm-long film toward the center of the longitudinal direction up to about 4 cm and dried, and 7 cm of the longitudinal central part was not re-applied.
- a hydrophobic polymer for recoating a fluororesin water repellent SFE-DP02H manufactured by AGC Seimi Chemical Co. was used.
- thermosetting epoxy resin was used as the adhesive resin, and the hollow fiber membrane was adhesively fixed in the housing by centrifugal adhesion.
- the hollow fiber membrane was fixed so that the length of the non-adhesive fixing portion was about 10 cm, and 7 cm where the hydrophobic polymer was not recoated was located at the center in the longitudinal direction of the module.
- the number of hollow fiber membranes was adjusted so that the total membrane area of the inner surface (that is, the inner surface) of the hollow fiber membranes was about 50 cm 2 .
- Three membrane distillation modules 10A having this specification were produced.
- the module 10A for membrane distillation obtained by the above method one module was disassembled and the properties of the porous hollow fiber membrane were measured.
- the water contact angle of the porous hollow fiber membrane was 23° C. and 50% relative humidity, and 2 ⁇ L of deionized water was dropped, and the angle formed by the droplet and the outer surface of the hollow fiber membrane was analyzed by image analysis.
- the contact angle was calculated and calculated.
- the measurement was performed 5 times, and the number average value was calculated.
- the contact angle of the outer surface of the hollow fiber membrane is 113° in the portion 5 mm from the respective adhesive interfaces at both ends of the module (that is, the boundary between the adhesive fixing portion and the non-adhesive fixing portion of the membrane) toward the center in the longitudinal direction.
- the central portion in the longitudinal direction was 108°.
- a membrane distillation apparatus 300 having the configuration shown in FIG. 8 was formed using the produced membrane distillation module.
- the MD operation was evaluated for 1000 hours under the following conditions, and the conductivity of the produced water was measured. At that time, when the conductivity exceeded 500 ⁇ S/cm, it was determined that wetting had occurred, and the evaluation was completed.
- Table 1 shows the conductivity of the produced water when the membrane distillation apparatus was operated for 1000 hours.
- the conductivity of the generated water after a lapse of 1000 hours under conditions of raw water temperature of 90° C. under condition 2 has a good water quality of 10 ⁇ S/cm. It was found that wetting did not occur.
- Example 2 The same porous hollow fiber membrane as in Example 1 was cut into a length of 15 cm. This porous hollow fiber membrane was completely immersed once in a fluororesin-based water repellent FG-1610-F130 (0.5) manufactured by Fluoro Technology Co., which was a hydrophobic polymer, and was then pulled up and dried. After that, the hydrophobic polymer was re-applied to each of the both ends of the 15 cm-long film toward the center of the longitudinal direction up to about 4 cm and dried, and 7 cm of the longitudinal central part was not re-applied. Similarly, FG-1610-F130 (0.5) was used as the hydrophobic polymer for recoating.
- FG-1610-F130 0.5
- the module was manufactured in the same manner as in Example 1.
- a thermosetting epoxy resin was used as the adhesive resin, and the hollow fiber membrane was adhesively fixed in the housing by centrifugal adhesion.
- the hollow fiber membrane was fixed so that the length of the non-adhesive fixing portion was about 10 cm, and 7 cm where the hydrophobic polymer was not recoated was located at the center in the longitudinal direction of the module.
- the number of hollow fiber membranes was adjusted so that the total inner membrane area of the hollow fiber membranes was about 50 cm 2 .
- Three membrane distillation modules of this specification were produced.
- the module 10A for membrane distillation obtained by the above method one module was disassembled and the properties of the porous hollow fiber membrane were measured.
- the water contact angle of the porous hollow fiber membrane was 23° C. and 50% relative humidity, and 2 ⁇ L of deionized water was dropped, and the angle formed by the droplet and the outer surface of the hollow fiber membrane was analyzed by image analysis.
- the contact angle was calculated and calculated.
- the measurement was performed 5 times, and the number average value was calculated.
- the contact angle of the outer surface of the hollow fiber membrane is 110° in each of 5 mm portions from the adhesive interfaces at both ends of the module (that is, the boundary between the adhesive fixing portion and the non-adhesive fixing portion of the membrane) toward the center in the longitudinal direction.
- the central portion in the longitudinal direction was 108°.
- Example 3 The same porous hollow fiber membrane as in Example 1 was cut into a length of 15 cm.
- the porous hollow fiber membrane was completely immersed once in a fluororesin-based water repellent FS-392B manufactured by Fluoro Technology Co., which was a hydrophobic polymer, and was then pulled up and dried. After that, the hydrophobic polymer was re-applied to each of the both ends of the 15 cm-long film toward the center of the longitudinal direction up to about 4 cm and dried, and 7 cm of the longitudinal central part was not re-applied.
- a fluororesin water repellent SFE-DP02H manufactured by AGC Seimi Chemical Co. was used as a hydrophobic polymer for recoating.
- the module was manufactured in the same manner as in Example 1.
- a thermosetting epoxy resin was used as the adhesive resin, and the hollow fiber membrane was adhesively fixed in the housing by centrifugal adhesion.
- the hollow fiber membrane was fixed so that the length of the non-adhesive fixing portion was about 10 cm, and 7 cm where the hydrophobic polymer was not recoated was located at the center in the longitudinal direction of the module.
- the number of hollow fiber membranes was adjusted so that the total inner membrane area of the hollow fiber membranes was about 50 cm 2 .
- Three membrane distillation modules of this specification were produced.
- the water contact angle of the porous hollow fiber membrane was 23° C. and 50% relative humidity, 2 ⁇ L of pure water was dropped, and the angle formed by the droplet and the outer surface of the hollow fiber membrane was calculated by image analysis. The contact angle was determined. The measurement was performed 5 times, and the number average value was calculated.
- the contact angle of the outer surface of the hollow fiber membrane is 125° at a portion 5 mm from the adhesive interface on the side where raw water flows in toward the center in the longitudinal direction, and 115 at a portion 5 mm from the adhesive interface on the opposite side toward the center in the longitudinal direction. And 110° in the central portion in the longitudinal direction.
- the peak intensity ratio in the range of 40 to 60% from the one end is 0.02 in the intensity ratio of the outer surface and the inner surface, and the peak intensity ratio in the range of 95 to 100% from the one end is the outer surface.
- the strength ratio of the inner surface were both 0.05.
- Example 4 The same porous hollow fiber membrane as in Example 1 was cut into a length of 15 cm.
- the porous hollow fiber membrane was completely immersed once in a fluororesin-based water repellent FS-392B manufactured by Fluoro Technology Co., which was a hydrophobic polymer, and was then pulled up and dried. After that, the hydrophobic polymer was re-applied to each of the both ends of the 15 cm-long film toward the center of the longitudinal direction up to about 4 cm and dried, and 7 cm of the longitudinal central part was not re-applied.
- a fluororesin water repellent SFE-DP02H manufactured by AGC Seimi Chemical Co. was used as a hydrophobic polymer for recoating.
- the module was manufactured in the same manner as in Example 1.
- a thermosetting epoxy resin was used as the adhesive resin, and the hollow fiber membrane was adhesively fixed in the housing by centrifugal adhesion.
- the hollow fiber membrane was fixed so that the length of the non-adhesive fixing portion was about 10 cm, and 7 cm where the hydrophobic polymer was not recoated was located at the center in the longitudinal direction of the module.
- the number of hollow fiber membranes was adjusted so that the total inner membrane area of the hollow fiber membranes was about 50 cm 2 .
- Three membrane distillation modules of this specification were produced.
- the part of the manufactured module up to 3 cm in the longitudinal direction from the end surface on the side where raw water flows in is completely covered with fluororesin water repellent FG-1610-F130 (2.0) manufactured by Fluoro Technology. After soaking and draining, air was flown only inside the hollow fiber membrane at a rate of 30 L/min for drying.
- the water contact angle of the porous hollow fiber membrane was 23° C. and 50% relative humidity, 2 ⁇ L of pure water was dropped, and the angle formed by the droplet and the outer surface of the hollow fiber membrane was calculated by image analysis. The contact angle was determined. The measurement was performed 5 times, and the number average value was calculated.
- the contact angle of the outer surface of the hollow fiber membrane is 127° at a portion 5 mm from the adhesive interface on the side where raw water flows in toward the center in the longitudinal direction, and 115 at a portion 5 mm from the adhesive interface on the opposite side toward the center in the longitudinal direction. And 110 at the central portion in the longitudinal direction.
- Example 1 A module was prepared in the same manner as in Example 1 except that the hydrophobic polymer was not applied to the membrane distillation module of Example 1.
- the modules for membrane distillation obtained by the above method one module was disassembled and the properties of the porous hollow fiber membrane were measured.
- the water contact angle of the porous hollow fiber membrane was 23° C. and 50% relative humidity, 2 ⁇ L of pure water was dropped, and the angle formed by the droplet and the outer surface of the hollow fiber membrane was calculated by image analysis. The contact angle was determined. The measurement was performed 5 times, and the number average value was calculated.
- the contact angle of the outer surface of the hollow fiber membrane was 95° at the portion 5 mm from the adhesive interface at both ends toward the center in the longitudinal direction, and 95° at the central portion in the longitudinal direction. Further, the peak intensity ratio of IR measured by the ATR method as in Example 1 was 0 at all the sites.
- the membrane distillation apparatus was constructed and operated for 1000 hours in the same manner as in Example 1, and the conductivity of the produced water was measured.
- Example 2 As in Example 1, a PVDF porous hollow fiber membrane having an inner diameter of 0.7 mm, an outer diameter of 1.3 mm, an average pore diameter of 0.21 ⁇ m, a maximum pore diameter of 0.29 ⁇ m, and a porosity of 72% was cut into a length of 15 cm. This porous hollow fiber membrane was once dipped in a fluoropolymer water repellent FG-1610-F-130 (0.5) manufactured by Fluoro Technology Co., which was a hydrophobic polymer, and was coated and dried.
- FG-1610-F-130 0.5
- thermosetting epoxy resin was used as the adhesive resin, and the hollow fiber membrane was adhesively fixed in the housing by centrifugal adhesion.
- the membrane distillation module was produced in the same manner as in Example 1.
- the water contact angle of the porous hollow fiber membrane was 23° C. and 50% relative humidity, 2 ⁇ L of pure water was dropped, and the angle formed by the droplet and the outer surface of the hollow fiber membrane was calculated by image analysis. The contact angle was determined. The measurement was performed 5 times, and the number average value was calculated.
- the contact angle of the outer surface of the hollow fiber membrane is 110° at a portion 5 mm from the adhesive interface on the side where raw water flows in toward the center in the longitudinal direction, and 110° at a portion 5 mm from the adhesive interface on the opposite side toward the center in the longitudinal direction.
- the water contact angle was the same at 110° at the central portion in the longitudinal direction at all the portions.
- the membrane distillation apparatus was constructed and operated for 1000 hours in the same manner as in Example 1, and the conductivity of the produced water was measured.
- Example 5 A membrane distillation apparatus was constructed in the same manner as in Example 1 using the membrane distillation module of Example 1, and a simulated liquid of mixed water (mixed liquid of heavy oil and salt) was used as raw water.
- the composition of the simulated liquid was as follows.
- Comparative Example 3 Using the module for membrane distillation of Comparative Example 1, a membrane distillation apparatus was constructed in the same manner as in Example 1, and the same simulated water as in Example 5 (mixed solution of heavy oil and salt) was used as raw water. And evaluated in the same manner as in Example 5.
- Table 3 shows the conductivity of the produced water when the membrane distillation apparatus was operated for 1000 hours. At the raw water temperature of 70° C. under condition 1, the conductivity exceeds 500 ⁇ S/cm in 36 hours and the wetting occurs, and under the raw water temperature of 90° C. under condition 2, the conductivity exceeds 500 ⁇ S/cm after 4 hours, and wetting occurs. I understood it.
- the membrane distillation module according to one aspect of the present invention can suppress wetting, provide generated water of good water quality, and contribute to stable operation and a longer product life.
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Abstract
Description
すなわち、本発明は以下の態様を包含する。
多孔質中空糸膜の外側表面の水接触角が90°以上であり、
多孔質中空糸膜の非接着固定部位の少なくとも一部の部位に疎水性ポリマーが付着しており、
多孔質中空糸膜の内側表面及び外側表面の各々について、非接着固定部位の長手方向における一端から他端までの部位を0%から100%と表したときに、前記一端から0~5%の部位に付着している膜面積当たりの疎水性ポリマーの量と、前記一端から95~100%の部位に付着している膜面積当たりの疎水性ポリマーの量との少なくとも一方が、前記一端から40~60%の部位に存在する膜面積当たりの疎水性ポリマーの量よりも多い、膜蒸留用モジュール。
[2] ハウジングと、前記ハウジングに両端部が接着固定されている複数本の多孔質中空糸膜とを有する膜蒸留用膜モジュールであって、
多孔質中空糸膜の非接着固定部位の少なくとも一部の部位に疎水性ポリマーが付着しており、
多孔質中空糸膜の内側表面及び外側表面の各々について、非接着固定部位の長手方向における一端から他端までの部位を0%から100%と表したときに、前記一端から0~5%の部位に付着している膜面積当たりの疎水性ポリマーの量と、前記一端から95~100%の部位に付着している膜面積当たりの疎水性ポリマーの量との両方が、前記一端から40~60%の部位に存在する膜面積当たりの疎水性ポリマーの量よりも多い、膜蒸留用モジュール。
[3] 多孔質中空糸膜の非接着固定部位が前記一端から50%未満の部位で原水導入部と最も近接するように原水導入部が配置されており、多孔質中空糸膜の、膜面積当たりの前記疎水性ポリマーの量が、以下の関係:
[前記一端から0~20%の部位の疎水性ポリマーの量]>[前記一端から95~100%の部位の疎水性ポリマーの量]>[前記一端から40~60%の部位の疎水性ポリマーの量]
を満たす、上記態様1又は2に記載の膜蒸留用モジュール。
[4] 前記一端から0~20%の部位において、前記多孔質中空糸膜の原水導入面の膜面積当たりの疎水性ポリマー量が、前記多孔質中空糸膜の蒸気送出面の膜面積当たりの疎水性ポリマー量よりも多い、上記態様1~3のいずれかに記載の膜蒸留用モジュール。
[5] 水生成用の膜蒸留装置であって、
上記態様1~4のいずれかに記載の膜蒸留用モジュールを備える、膜蒸留装置。
[6] 膜蒸留装置は、膜蒸留用モジュールと連結された冷却装置を更に備え、
膜蒸留用モジュールは、多孔質中空糸膜が前記一端を下にして略垂直方向に固定され、かつ原水が前記一端から多孔質中空糸膜内側に導入されるように構成されており、
膜蒸留用モジュールと冷却装置との連結部の下端は、多孔質中空糸膜の非接着固定部位全高の1/2よりも高い位置にある、上記態様5に記載の膜蒸留用装置。
[7] 膜蒸留用モジュールは、多孔質中空糸膜が前記一端を下にして略垂直方向に固定され、かつ原水が前記一端から多孔質中空糸膜内側に導入されるように構成されており、
膜蒸留用モジュールは、多孔質中空糸膜の非接着固定部位全高の1/2よりも低い位置に対応する垂直方向位置に排出口を有する、上記態様5又は6に記載の膜蒸留装置。
多孔質中空糸膜の非接着固定部位の少なくとも一部の部位に疎水性ポリマーが付着しており、
多孔質中空糸膜の非接着固定部位の長手方向における一端から他端までの部位を0%から100%と表したときに、該一端から0~5%の部位に付着している膜面積当たりの疎水性ポリマーの量と、該一端から95~100%の部位に付着している膜面積当たりの疎水性ポリマーの量との少なくとも一方、好ましくは両方が、該一端から40~60%の部位に存在する膜面積当たりの疎水性ポリマーの量よりも多い、膜蒸留用モジュールを提供する。一態様においては、多孔質中空糸膜の外側表面の水接触角が90°以上である。
本開示で、「非接着固定部位」とは、多孔質中空糸膜のうち両端部の接着固定部位を除く部位を意味する。
本開示の多孔質中空糸膜について、「内側表面」とは、多孔質中空糸膜の表面(すなわち膜構成部材の露出面)のうち膜の中空部に面した部位を意味し、「外側表面」とは上記表面のうち膜外に面した部位(すなわち内側表面の対向面)を意味し、「細孔表面」とは、上記表面のうち内側表面及び外側表面を除く部位(すなわち膜の厚み方向内部で細孔に面した部位)を意味する。
本開示で定義する疎水性ポリマー付着量は、多孔質中空糸膜の「内側表面」及び「外側表面」の少なくとも一方において満たされていればよく、好ましくは少なくとも原水と接する側の表面において満たされており、更に好ましくは、両表面において満たされている。
本開示の多孔質中空糸膜について、「膜面積」とは、上記表面(すなわち膜構成部材の露出面)の面積を意味する。
また多孔質中空糸膜における疎水性ポリマーの付着量を調整することで、多孔質中空糸膜のうち蒸発が特に激しい部位(特に熱水が導入される部位)における蒸発量を低下させ、膜全体の蒸気発生量分布を平坦に近づけることもでき、その結果、ウェッティングを大幅に抑制することができる。したがって、本実施形態の膜蒸留用モジュールは、ウェッティングが抑制されていることで水処理能力の経時安定性に優れる。
図1A及び図1Bは、本開示の一態様に係る膜蒸留用モジュールを示す模式図である。図1A及び図1Bを参照し、一態様において、膜蒸留用モジュール10A,10Bは、ハウジング11と、ハウジング11内に収容された複数本の多孔質中空糸膜12とを有し、多孔質中空糸膜12は、両端部が接着樹脂13でハウジング11に接着固定されている(図1A及びB中の接着固定部位A)。多孔質中空糸膜12のうち、接着固定部位A以外の部位は接着樹脂13で固定されていない(図1A及びB中の非接着固定部位NA)。図1Aに示す膜蒸留用モジュール10Aにおいては、多孔質中空糸膜12の内側に原水が導入され、多孔質中空糸膜12の外側から生成水として純水が蒸気として送出される。図1Bに示す膜蒸留用モジュール10Bにおいては、多孔質中空糸膜12の外側に原水が導入され、多孔質中空糸膜12の内側から生成水(蒸気として)が送出される。膜蒸留用モジュール10A,10Bのいずれも、多孔質中空糸膜12の片側表面が原水に触れ、もう一方の表面からは蒸気が発生する仕組みである。
本実施形態に係る膜蒸留用モジュールにおいて用いる多孔質中空糸膜は、膜の一方の表面から他方の表面まで厚み方向に連通している細孔(連通孔)を有することが必要である。この連通孔は、ポリマー等の膜材料のネットワークの空隙であってよく、枝分かれしていても直通孔でも(すなわち枝分かれしていなくても)よい。細孔は、蒸気を通すが原水(液体)を通さないことが必要である。
[一端E1から0~20%の部位の疎水性ポリマーの量]>[一端E1から95~100%の部位の疎水性ポリマーの量]>[一端E1から40~60%の部位の疎水性ポリマーの量]
を満たす。
なお、本開示で多孔質中空糸膜の部位について示す数値(%)は、実際のモジュール製造過程で起こりうる疎水性ポリマーの塗りムラを考慮し、±2%程度の誤差を有してよいものとする。
一態様においては、多孔質中空糸膜の少なくとも一部の部位に疎水性ポリマーが付着している。疎水性ポリマーは、多孔質中空糸膜の内側表面、外側表面及び/又は膜内部に疎水性の被膜を形成して、膜に撥水性を付与又は膜の撥水性を向上させることができる。
(ア)シロキサン結合を有するポリマー(例えば、ジメチルシリコーンゲル、メチルフェニルシリコーンゲル、有機官能基(アミノ基、フルオロアルキル基等)を導入した反応性変性シリコーンゲル、シランカップリング剤と反応することで架橋構造を形成するシリコーン系ポリマー及びポリマーゲル
(イ)側鎖に(パー)フルオロアルキル基、(パー)フルオロポリエーテル基、アルキルシリル基、フルオロシリル基等を持つポリマー(例えば溶液又は薄膜として)
特に、疎水性ポリマーが、炭素数1~12の(パー)フルオロアルキル基及び/又は(パー)フルオロポリエーテル基を有する、(メタ)アクリレート系モノマー及び/又はビニル系モノマーの重合体であることが好ましい。
中空糸膜の膜面積当たりの疎水性ポリマー付着量は、疎水性ポリマーを溶解できる溶媒での抽出後に溶媒を蒸発等の操作により除去することで、直接重量として、求めることができる。この重量を、中空糸膜の内径又は外径と長さとから求めた膜面積で除して、膜面積当たりの疎水性ポリマー量を算出する。
多孔質中空糸膜を接着固定するための接着樹脂には、機械的強度が良好で、かつ100℃での耐熱性を有することが望まれる。接着樹脂として使用できる樹脂としては、例えば、熱硬化性のエポキシ樹脂、熱硬化性のウレタン樹脂等が挙げられる。耐熱性の観点ではエポキシ樹脂が好ましいが、ハンドリング性の観点ではウレタン樹脂が好ましい。接着固定の方法は、膜蒸留用モジュール作製に関する既知の接着方法に従えばよい。
ハウジングは、耐圧性、耐熱性、耐衝撃性、耐候性等の観点から材料を選定する。例えば、樹脂、金属等が使用できるが、上記の観点から、ポリプロピレン、ポリスルホン、ポリエーテルスルホン、ポリフッ化ビニリデン、ABS樹脂、繊維強化プラスチック及び塩化ビニル樹脂からなる樹脂群、或いはステンレス、真鍮、チタン等の金属から選択されることが好ましい。
本実施形態はまた、水生成用の膜蒸留装置であって、本開示の膜蒸留用モジュールを備える、膜蒸留装置を提供する。一態様において、膜蒸留装置は、多孔質中空糸膜と、原水を加温する加温部又は原水を蒸発させる蒸発部とを備える。膜蒸留装置は、所望により、多孔質中空糸膜と、加温部又は蒸発部とに加えて、多孔質中空糸膜を通過した水蒸気を凝縮させる凝縮部、原水又は透過水を送達する管、水蒸気を送達する気相部等を備えてよい。
本実施形態に係る膜蒸留装置は、膜蒸留(MD)法に利用されることができる。
図7は、各種の膜蒸留法を説明する模式図である。図7を参照し、主な膜蒸留法の原理は以下の4つである。
(a)蒸発部から生成した水蒸気を、多孔質中空糸膜1を通じて直接凝縮部(冷却装置)に取り込むDCMD法(Direct Contact Membrane Distillation)
(b)蒸発部と凝縮部の間に第三の気相部を設け、冷却体2の面上に蒸発部からの水蒸気を凝縮させ蒸留水を得るAGMD法(Air Gap Membrane Distillation)
(c)第三の気相部に真空ギャップを設け、蒸発部からの水蒸気を凝縮部まで移動させ蒸留水を得るVMD法(Vacuum Membrane Distillation)
(d)第三の気相部にスイーピングガスを流し、蒸発部からの水蒸気を凝縮部まで移動させ蒸留水を得るSGMD法(Sweeping Gas Membrane Distillation)
これらのうち、図7(c)に示されるVMD方式が、安定した透過水質を得られるため、最も好ましい。なお、図7においては、原水として高温水を示しているが、原水が室温付近の温度で、低温水、凝縮部等が室温よりも低い態様でも構わない。
本実施形態の膜蒸留用モジュールを用いて透過水を生産する運転を長時間続けると、被処理水に含まれる無機塩、有機物、微粒子、油分、金属等が、多孔質中空糸膜の原水導入側に析出、付着することで、膜の貫通孔が閉塞し、透過水生産効率が低下することがある。その場合、運転を一旦中断し、目詰まりの原因となる物質を溶解し得る溶液を、多孔質中空糸膜の表面及び膜内部に高流量で流す等の洗浄操作を行うことで、多孔質中空糸膜を初期状態に再生することができる場合がある。目詰まりの原因物質が無機塩又は金属の場合、これらを溶解する能力を有する酸などを用いることができる。例えば、スケールとして一般的な炭酸カルシウムの場合、塩酸、クエン酸等の溶液で膜を洗浄してよい。目詰まりの原因物質が有機物又は微生物(スライム)の場合、例えば、酸化剤として次亜塩素酸ナトリウム水溶液を用いて洗浄してよい。目詰まりの原因物質が微粒子の場合、洗浄溶媒を高流速で流すことで膜表面から微粒子を排除してよい。
本実施形態に係る膜蒸留用モジュール及び膜蒸留装置は、被処理水に含まれるイオン、有機物、無機物等を高度に除去して精製する用途、又は被処理水から水を除去して濃縮する用途に好適に用いることができる。これらの用途として、例えば、海水淡水化、船舶用水製造、超純水製造(半導体工場等)、ボイラー水製造(火力発電所等)、燃料電池システム内水処理、産業廃水処理(食品工場、化学工場、電子産業工場、製薬工場及び清掃工場)、透析用水製造、注射用水製造、随伴水処理(例えば、重質油、シェールオイル、シェールガス及び天然ガス等)並びに海水からの有価物回収等が挙げられる。随伴水は、質量基準で数%から十数%の無機塩分と数ppmから数十ppmの油分とを含む。天然ガスとしては、従来のガス田から得られる在来型の天然ガスに加え、コールベッドメタン(別名:コールシームガス)に代表される非在来型の天然ガスも含まれる。
本実施形態に係る膜蒸留用モジュール、及びこれを具備する膜蒸留装置は、他の水処理技術と組み合わせた複合システムとして使用してもよい。例えば、RO(Reverse Osmosis)法で処理した際に生成する濃縮水を、本実施形態に係る膜蒸留装置を用いてさらに精製することにより、水の回収率をより高めることができる。また、FO(Forward Osmosis)法で使用するDS(Draw Solution)の回収手段として本実施形態に係る膜蒸留装置を使用することもできる。
本実施例では、以下に記載する各種の測定方法で多孔質中空糸膜の諸物性を求めた。
[外径、内径、膜厚]
多孔質中空糸膜の外径、内径は、中空糸膜を長手方向に垂直な方向にカミソリ等で薄く切り、顕微鏡を用いて断面の外径、内径をそれぞれ測定して求めた。膜厚は下記式(1)により算出した。
ASTM:F316-86に記載されている平均孔径の測定方法(別称:ハーフドライ法)により測定した。
約10cm長の多孔質中空糸膜に対し、液体としてエタノールを用いて、25℃、昇圧速度0.01atm/秒での標準測定条件で行った。
平均孔径[μm]=2860×(使用液体の表面張力[dyne/cm])/(ハーフドライ空気圧力[Pa]) ・・・(2)
ここでエタノールの25℃における表面張力は21.97dyne/cmであるので、下記式(3)により求めた。
平均孔径[μm]=62834/(ハーフドライ空気圧力[Pa]) ・・・(3)
多孔質中空糸膜の最大孔径は、バブルポイント法を用いて測定した。長さ8cmの多孔質中空糸膜の一方の末端を閉塞し、他方の末端に圧力計を介して窒素ガス供給ラインを接続した。この状態で窒素ガスを供給してライン内部を窒素に置換した後、多孔質中空糸膜をエタノールに浸漬した。この時、エタノールがライン内に逆流しないように極僅かに窒素で圧力を掛けた状態で、多孔質中空糸膜を浸漬した。多孔質中空糸膜を浸漬した状態で、窒素ガスの圧力をゆっくりと増加させ、多孔質中空糸膜から窒素ガスの泡が安定して出始めた圧力Pを記録した。これより、多孔質中空糸膜の最大孔径dを、下記式(4):
d=C1γ/P・・・(4)
{式中、C1は定数、γは表面張力、そしてPは圧力である。}により算出した。エタノールを浸漬液としたときのC1γ=0.632(kg/cm)であり、式(4)にP(kg/cm2)を代入することにより、最大孔径d(μm)を求めた。
多孔質中空糸膜の空隙率は、下記に記載の方法に準拠して、中空糸膜の重量と中空糸膜を構成する材料の密度とから算出した。
中空糸膜を一定長さに切り、その重量を測定し、空隙率を下記式(5):
疎水性ポリマーの付着量の比較はIRスペクトル解析、ATR法(全反射法,内部反射法)で、プリズムとしてZnSe結晶を用いて行った。測定装置はPerkinElmer社製 Spectrumlを用い、結晶の押し付け圧は圧力コンター30前後で行った。疎水性ポリマー由来のピーク強度と膜素材由来のピーク強度との比を求めることで、膜表面に付着した疎水性ポリマー量を求めることができる。実施例においては、側鎖がパーフルオロ基を有するアクリレートのため、1734Hz-1のνC=Oと1180Hz-1付近の(νC-F+νC-O)のピーク強度比、νC=O/(νC-F+νC-O)を算出した。付着量を測定する膜はモジュールから切り出し、中空糸膜を長手方向に対して1cm間隔で切断した。膜の外側表面を分析する際はそのサンプルを使い、内側表面を分析する際には長手方向に膜を切断し、内側表面を分析した。
このピーク強度比を膜の部位ごとに測定し、最小値を1.0倍としたときに1.2倍よりも大きな場合、付着量が多いと判断した。
図8は、実施例1で使用した膜蒸留装置300の構成を示す模式図である。内径0.7mm、外径1.3mm、ASTM-F316-86から求めた平均孔径0.21μm、最大孔径0.29μm、空隙率72%のPVDF製の多孔質中空糸膜12を長さ15cmに切出した。この多孔質中空糸膜12を、疎水性ポリマーとしてのフロロテクノロジー社製のフッ素樹脂系撥水剤FG-1610-F130(0.5)に一度完全に浸漬したのちに、引き上げ、乾燥を行った。その後15cm長の膜の両端の各々から長手方向中央に向かって約4cmまでの部位に、疎水性ポリマーを再塗布して乾燥し、長手方向中央部位の7cm分には再塗布を行わなかった。再塗布用の疎水性ポリマーとして、AGCセイミケミカル社製のフッ素樹脂系撥水剤SFE-DP02Hを用いた。
原水 3.5質量%の塩水
膜内の循環流量 600ml/分
原水の温度(モジュール入口側) 条件1 70℃ 条件2 90℃
冷却水の温度 15℃
冷却水の循環流量 1000ml/分
生成水側真空度 -90kPaG
膜蒸留装置を1000時間運転した時の生成水の導電率を表1に示す。
条件1の原水温度70℃では1000時間経過後の生成水の導電率は5μS/cm、条件2の原水温度90℃では1000時間経過後の生成水の導電率は10μS/cmと良好な水質を示し、ウェッティングが発生していないことがわかった。
実施例1と同じ多孔質中空糸膜を15cm長に切出した。この多孔質中空糸膜を、疎水性ポリマーとしてのフロロテクノロジー社製のフッ素樹脂系撥水剤FG-1610-F130(0.5)に一度完全に浸漬したのちに、引き上げ、乾燥を行った。その後15cm長の膜の両端の各々から長手方向中央に向かって約4cmまでの部位に、疎水性ポリマーを再塗布して乾燥し、長手方向中央部位の7cm分には再塗布を行わなかった。再塗布用の疎水性ポリマーとして、同じくFG-1610-F130(0.5)を用いた。
実施例1と同様に膜蒸留装置の構築及び1000時間運転を行った時の生成水の導電率は、条件1の原水温度70℃では1000時間経過後の生成水の導電率は8μS/cm、条件2の原水温度90℃では1000時間経過後の生成水の導電率は12μS/cmと良好な水質を示し、ウェッティングが発生していないことがわかった。
実施例1と同じ多孔質中空糸膜を15cm長に切出した。この多孔質中空糸膜を、疎水性ポリマーとしてのフロロテクノロジー社製のフッ素樹脂系撥水剤FS-392Bに一度完全に浸漬したのちに、引き上げ、乾燥を行った。その後15cm長の膜の両端の各々から長手方向中央に向かって約4cmまでの部位に、疎水性ポリマーを再塗布して乾燥し、長手方向中央部位の7cm分には再塗布を行わなかった。再塗布用の疎水性ポリマーとして、AGCセイミケミカル社製のフッ素樹脂系撥水剤SFE-DP02Hを用いた。
実施例1と同様に膜蒸留装置の構築及び1000時間運転を行った時の生成水の導電率は、条件1の原水温度70℃では1000時間経過後の生成水の導電率は2μS/cm、条件2の原水温度90℃では1000時間経過後の生成水の導電率は2μS/cmと良好な水質を示し、ウェッティングが発生していないことがわかった。
実施例1と同じ多孔質中空糸膜を15cm長に切出した。この多孔質中空糸膜を、疎水性ポリマーとしてのフロロテクノロジー社製のフッ素樹脂系撥水剤FS-392Bに一度完全に浸漬したのちに、引き上げ、乾燥を行った。その後15cm長の膜の両端の各々から長手方向中央に向かって約4cmまでの部位に、疎水性ポリマーを再塗布して乾燥し、長手方向中央部位の7cm分には再塗布を行わなかった。再塗布用の疎水性ポリマーとして、AGCセイミケミカル社製のフッ素樹脂系撥水剤SFE-DP02Hを用いた。
実施例1と同様に膜蒸留装置の構築及び1000時間運転を行った時の生成水の導電率は、条件1の原水温度70℃では1000時間経過後の生成水の導電率は1μS/cm、条件2の原水温度90℃では1000時間経過後の生成水の導電率は1μS/cmと良好な水質を示し、ウェッティングが発生していないことがわかった。
実施例1の膜蒸留用モジュールに、いずれの疎水性ポリマーも塗布しない以外は実施例1と同様にしてモジュールを作製した。
また、実施例1と同様に測定したIRのATR法によるピーク強度比は、いずれの部位も0であった。
実施例1と同様に膜蒸留装置の構築及び1000時間運転を行い、生成水の導電率を測定した。
実施例1と同じく、内径0.7mm、外径1.3mm、平均孔径0.21μm、最大孔径0.29μm、空隙率72%のPVDF製の多孔質中空糸膜を15cm長に切出した。この多孔質中空糸膜を、疎水性ポリマーとしてのフロロテクノロジー社製のフッ素樹脂系撥水剤FG-1610-F-130(0.5)に一度浸漬して、塗布、乾燥を行った。
実施例1の膜蒸留用モジュールを用いて、実施例1と同様に膜蒸留装置を構築し、原水として随伴水の模擬液(重質油と塩の混合液)を用いた。模擬液の組成は以下のものを用いた。
原水 随伴水模擬液
膜内の循環流量 600ml/分
原水の温度(モジュール入口側) 条件1 70℃ 条件2 90℃
冷却水の温度 15℃
冷却水の循環流量 1000ml/分
生成水側真空度 -90kPaG
膜蒸留装置を1000時間運転した時の生成水の導電率を表3に示す。
条件1の原水温度70℃では1000時間経過後の生成水の導電率は4μS/cm、条件2の原水温度90℃では1000時間経過後の生成水の導電率は8μS/cmと良好な水質を示し、ウェッティングが発生していないことがわかった。
比較例1の膜蒸留用モジュールを用いて、実施例1と同様に膜蒸留装置を構築し、原水として実施例5と同様の随伴水の模擬液(重質油と塩の混合液)を用いて、実施例5と同様に評価を行った。
膜蒸留装置を1000時間運転した時の生成水の導電率を表3に示す。
条件1の原水温度70℃では36時間で導電率が500μS/cmを超えウェッティング、条件2の原水温度90℃では4時間経過後に導電率が500μS/cmを超え、ウェッティングが発生していることがわかった。
11 ハウジング
12 多孔質中空糸膜
13 接着樹脂
13A せり上がり部
14 疎水性ポリマー
20 冷却装置
22 冷却管
30 ドレインタンク
100,200,300 膜蒸留装置
A 接着固定部位
NA 非接着固定部位
C 連結部
D 排出口
I 原水導入部
Claims (7)
- ハウジングと、前記ハウジングに両端部が接着固定されている複数本の多孔質中空糸膜とを有する膜蒸留用膜モジュールであって、
多孔質中空糸膜の外側表面の水接触角が90°以上であり、
多孔質中空糸膜の非接着固定部位の少なくとも一部の部位に疎水性ポリマーが付着しており、
多孔質中空糸膜の内側表面及び外側表面の各々について、非接着固定部位の長手方向における一端から他端までの部位を0%から100%と表したときに、前記一端から0~5%の部位に付着している膜面積当たりの疎水性ポリマーの量と、前記一端から95~100%の部位に付着している膜面積当たりの疎水性ポリマーの量との少なくとも一方が、前記一端から40~60%の部位に存在する膜面積当たりの疎水性ポリマーの量よりも多い、膜蒸留用モジュール。 - ハウジングと、前記ハウジングに両端部が接着固定されている複数本の多孔質中空糸膜とを有する膜蒸留用膜モジュールであって、
多孔質中空糸膜の非接着固定部位の少なくとも一部の部位に疎水性ポリマーが付着しており、
多孔質中空糸膜の内側表面及び外側表面の各々について、非接着固定部位の長手方向における一端から他端までの部位を0%から100%と表したときに、前記一端から0~5%の部位に付着している膜面積当たりの疎水性ポリマーの量と、前記一端から95~100%の部位に付着している膜面積当たりの疎水性ポリマーの量との両方が、前記一端から40~60%の部位に存在する膜面積当たりの疎水性ポリマーの量よりも多い、膜蒸留用モジュール。 - 多孔質中空糸膜の非接着固定部位が前記一端から50%未満の部位で原水導入部と最も近接するように原水導入部が配置されており、多孔質中空糸膜の、膜面積当たりの前記疎水性ポリマーの量が、以下の関係:
[前記一端から0~20%の部位の疎水性ポリマーの量]>[前記一端から95~100%の部位の疎水性ポリマーの量]>[前記一端から40~60%の部位の疎水性ポリマーの量]
を満たす、請求項1又は2に記載の膜蒸留用モジュール。 - 前記一端から0~20%の部位において、前記多孔質中空糸膜の原水導入面の膜面積当たりの疎水性ポリマー量が、前記多孔質中空糸膜の蒸気送出面の膜面積当たりの疎水性ポリマー量よりも多い、請求項1~3のいずれか一項に記載の膜蒸留用モジュール。
- 水生成用の膜蒸留装置であって、
請求項1~4のいずれか一項に記載の膜蒸留用モジュールを備える、膜蒸留装置。 - 膜蒸留装置は、膜蒸留用モジュールと連結された冷却装置を更に備え、
膜蒸留用モジュールは、多孔質中空糸膜が前記一端を下にして略垂直方向に固定され、かつ原水が前記一端から多孔質中空糸膜内側に導入されるように構成されており、
膜蒸留用モジュールと冷却装置との連結部の下端は、多孔質中空糸膜の非接着固定部位全高の1/2よりも高い位置にある、請求項5に記載の膜蒸留用装置。 - 膜蒸留用モジュールは、多孔質中空糸膜が前記一端を下にして略垂直方向に固定され、かつ原水が前記一端から多孔質中空糸膜内側に導入されるように構成されており、
膜蒸留用モジュールは、多孔質中空糸膜の非接着固定部位全高の1/2よりも低い位置に対応する垂直方向位置に排出口を有する、請求項5又は6に記載の膜蒸留装置。
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AU2020206280A1 (en) | 2021-07-29 |
JP7159353B2 (ja) | 2022-10-24 |
CN113286648A (zh) | 2021-08-20 |
CA3125734C (en) | 2023-06-20 |
AU2020206280B2 (en) | 2022-07-21 |
CN113286648B (zh) | 2023-03-10 |
JPWO2020145401A1 (ja) | 2021-09-27 |
EP3909665A1 (en) | 2021-11-17 |
EP3909665A4 (en) | 2022-03-02 |
CA3125734A1 (en) | 2020-07-16 |
US20220080358A1 (en) | 2022-03-17 |
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