WO2021153486A1 - 油をろ過する方法 - Google Patents

油をろ過する方法 Download PDF

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Publication number
WO2021153486A1
WO2021153486A1 PCT/JP2021/002396 JP2021002396W WO2021153486A1 WO 2021153486 A1 WO2021153486 A1 WO 2021153486A1 JP 2021002396 W JP2021002396 W JP 2021002396W WO 2021153486 A1 WO2021153486 A1 WO 2021153486A1
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WIPO (PCT)
Prior art keywords
porous membrane
oil
porous
hydrophobic
filtering
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Ceased
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PCT/JP2021/002396
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English (en)
French (fr)
Japanese (ja)
Inventor
志村俊
花川正行
岩井健太
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Toray Industries Inc
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Toray Industries Inc
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Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to CN202180011567.7A priority Critical patent/CN114981001B/zh
Priority to EP21748365.0A priority patent/EP4098350A4/en
Priority to JP2021518011A priority patent/JP6996662B2/ja
Priority to US17/791,991 priority patent/US11806673B2/en
Publication of WO2021153486A1 publication Critical patent/WO2021153486A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B01D65/06—Membrane cleaning or sterilisation ; Membrane regeneration with special washing compositions
    • 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
    • B01D61/10—Accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/033—Specific distribution of fibres within one potting or tube-sheet
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/02—Specific process operations before starting the membrane separation process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/02—Forward flushing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/04—Backflushing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/18—Use of gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/281—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by applying a special coating to the membrane or to any module element
    • 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

Definitions

  • the present invention relates to a method for filtering oil.
  • porous membranes such as microfiltration membranes and ultrafiltration membranes have been used in various fields such as water treatment fields such as water purification or wastewater treatment, medical fields such as blood purification, food industry fields, and oil and fat industry fields.
  • Porous membranes in such fields are usually required to have high permeation performance in order to realize high processing efficiency. Further, in order to maintain high processing efficiency for a long period of time, it is required to restore the permeability that gradually decreases due to the filtration operation by washing.
  • Patent Document 1 discloses a technique for removing gums accumulated in a porous membrane by washing the porous membrane with a dilute oil during a filtration operation using a porous membrane made of polyimide.
  • Patent Document 2 discloses a technique for removing gums accumulated in a porous membrane by washing the porous membrane with an organic solvent during a filtration operation using a porous membrane made of polyimide.
  • Patent Document 3 discloses a technique for removing gums accumulated in a porous membrane by washing the porous membrane with a surfactant during a filtration operation using a porous membrane made of polyimide. There is.
  • the present invention can provide a technique for maintaining excellent permeability by recovering it by a simple method and continuing the filtration operation with high processing capacity for a long period of time.
  • a hydrophobic gas is permeated through a porous membrane containing a hydrophobic polymer as a main component, and the relative humidity of the hydrophobic gas that has permeated the porous membrane is 0 to 60.
  • a method for filtering the oil which is shifted to the step of permeating the oil through the porous membrane, is provided.
  • the present invention by permeating a hydrophobic gas through a porous membrane containing a hydrophobic polymer as a main component, it is possible to suppress deterioration of permeation performance due to accumulation of water in the porous membrane, and the porous membrane is porous. It is possible to provide a method for filtering an oil that maintains a high permeation performance of a quality film.
  • the method for filtering oil of the present invention comprises the following steps (A) and (B), and after confirming that the relative humidity of the hydrophobic gas that has permeated the porous membrane is 0 to 60%, ( B) It is necessary to move to the process.
  • a hydrophobic gas is permeated through a porous membrane containing a hydrophobic polymer as a main component
  • B Permeate oil through the porous membrane
  • the pores in the porous membrane through which oil can permeate decrease, and the permeation performance of the porous membrane deteriorates.
  • the main component of the porous membrane is a hydrophobic polymer, it has a low affinity for water, so that it is difficult for water to accumulate in the porous membrane, and high permeation performance can be maintained for a long period of time.
  • the affinity with water can be indexed by the contact angle of the porous membrane with water.
  • the contact angle of the porous membrane with water is preferably 65 to 130 °, more preferably 70 to 120 °, and 70 to 100 °. It is more preferable to have.
  • the contact angle can be measured by the static sessile drop method using a commercially available contact angle meter.
  • the hydrophobic gas refers to an inert gas such as air, nitrogen, and carbon dioxide. What is not a hydrophobic gas is a hydrophilic gas, such as water vapor having a relative humidity of 100%. Relative humidity can be measured using a commercially available hygrometer.
  • the relative humidity of the hydrophobic gas before it permeates the porous membrane is preferably 0 to 60%, more preferably 0 to 40%, and even more preferably 0 to 30%. Relative humidity can be measured using a commercially available hygrometer.
  • the relative humidity of the hydrophobic gas after permeating the porous membrane was 0 to 60%. Later, it is necessary to shift to the step (B).
  • the relative humidity of the hydrophobic gas after passing through the porous membrane can be measured and confirmed using a commercially available hygrometer.
  • the relative humidity of the hydrophobic gas after permeating through the porous membrane is more preferably 0 to 40%, still more preferably 0 to 30%.
  • the filtration method may be a total amount filtration method in which the entire amount of oil supplied to the porous membrane is permeated, or a part of the oil supplied to the porous membrane is permeated and the oil that is not permeated is used as oil.
  • a cross-flow filtration method may be used in which the oil is circulated in a direction orthogonal to the permeation direction. If the total amount filtration method is used, the energy for flowing the oil can be suppressed to a small level.
  • oil is permeated while cleaning the porous membrane with the shearing force of the cross-flow, so that it is easy to maintain the high permeation ability of the porous membrane.
  • step (A-1) By including the following step (A-1) in the step (A), it is easy to easily reduce the water content of the porous membrane in a short time, which is preferable.
  • step (A-1) the hydrophobic gas is permeated through the porous film at a rate of 5 to 80 m 3 / m 2 / h in terms of 50 kPa in the direction in which the oil is permeated into the porous film.
  • the permeation flux of the hydrophobic gas is extremely small, but by continuing to supply the hydrophobic gas, the water content in the porous film is reduced, and the permeation flux of the hydrophobic gas gradually increases. ..
  • the permeation flux of the hydrophobic gas in the step (A-1) is preferably 5 to 80 m 3 / m 2 / h in terms of 50 kPa because it is easy to confirm that the water content can be reduced because the oil permeates. , 10 to 70 m 3 / m 2 / h in terms of 50 kPa, and even more preferably 38 to 60 m 3 / m 2 / h in terms of 50 kPa.
  • the permeation flux of the hydrophobic gas can be obtained by dividing the flow rate at which the hydrophobic gas permeates the porous membrane from the primary side to the secondary side by the area of the porous membrane on the primary side.
  • the permeation flow rate is assumed to be proportional to the pressure, and can be appropriately converted based on the measured pressure of the permeation flow rate.
  • the hydrophobic gas is permeated through the porous membrane with a permeation flux of 5 to 80 m 3 / m 2 / h in terms of 50 kPa. Since a large amount of impurities such as water and gums that have been collected tend to accumulate on the primary side of the porous film, the hydrophobic gas is generated from the secondary side to the primary side in the opposite direction to the permeation of oil through the porous film. Permeation makes it easy to remove impurities such as water and gums from the porous film, which is preferable.
  • the permeation flux of the hydrophobic gas in the step (A-2) increases as the water content in the porous film decreases, and the fact that it is 5 to 80 m 3 / m 2 / h in terms of 50 kPa permeates the oil. Therefore, it is easy to confirm that the water content has been reduced, so it is preferably 10 to 70 m 3 / m 2 / h in terms of 50 kPa, and 30 to 60 m 3 / m 2 / h in terms of 50 kPa. Is even more preferable.
  • the permeation flux of the hydrophobic gas can be obtained by dividing the flow rate at which the hydrophobic gas permeates the porous membrane from the secondary side to the primary side by the area of the porous membrane on the secondary side.
  • the step (A) includes the following steps (A-3) because it is easy to easily reduce the water content of the porous membrane in a short time.
  • the flow rate of the hydrophobic gas in the step (A-3) is preferably 0.1 to 10 m 3 / m 2 / s, more preferably 1 to 10 m 3 / m 2 / s, and 3 to 10 m. It is more preferably 3 / m 2 / s.
  • the flow rate of the hydrophobic gas is the flow rate area of the gas perpendicular to the porous film in the space on the primary side of the porous film, and divides the flow rate of the hydrophobic gas flowing in the direction parallel to the porous film. It can be obtained by.
  • a mixed phase flow of a hydrophobic gas and a cleaning liquid is flowed at 0.1 to 10 m 3 / m 2 / s in a direction parallel to the porous film on the primary side through which the oil of the porous film is permeated. Since a large amount of impurities such as water and gum contained in the oil circulated at a high rate tend to accumulate on the primary side of the porous film, it is hydrophobic on the primary side of the porous film in a direction parallel to the porous film. By circulating a mixed phase flow of a sex gas and a cleaning liquid, it is easy to effectively remove impurities such as water and gum from the porous film by the shearing force of the mixed phase flow, which is preferable.
  • the flow rate of the mixed phase flow in the step (A-4) is preferably 0.1 to 10 m 3 / m 2 / s, more preferably 1 to 10 m 3 / m 2 / s, and 3 to 10 m 3 It is more preferably / m 2 / s.
  • the flow rate of the multiphase flow is the flow rate of the multiphase flow in the direction perpendicular to the porous membrane in the space on the primary side of the porous membrane, which divides the flow rate of the multiphase flow flowing in the direction parallel to the porous membrane.
  • the cleaning liquid used here may be any liquid that is incompatible with water, and oil, an organic solvent, or the like is preferable.
  • the organic solvent alcohol and ketone are preferable because they can be easily removed from the porous membrane after washing.
  • hydrocarbons such as hexane are preferable because they can easily remove gum.
  • no special equipment is required, which is preferable.
  • the steps (A) or (A)'and (B) are repeated a plurality of times to continue the filtration while appropriately recovering the deterioration of the permeation performance of the porous membrane.
  • a plurality of steps (A-1) to (A-4) may be included in the steps (A) or (A)'in any order, and steps other than (A-1) to (A-4) may be included.
  • the process may be included.
  • by performing the steps (A) or (A)'even after assembling the porous membrane as a module or element water may be present for a long period of time during storage of the porous membrane, making it difficult to remove the water. Can be prevented.
  • the moisture content of the porous membrane is increased by further including the step (A-5) in addition to the steps (A-1) to (A-4). Is preferable because it can be easily and easily reduced in a short time.
  • the cleaning liquid is permeated through the porous film with a permeation flux of 0.05 to 5.0 m 3 / m 2 / h in terms of 50 kPa (A-). 5)
  • the permeated flow flux of the cleaning liquid in the step is preferably 0.05 to 5.0 m 3 / m 2 / h in terms of 50 kPa, and 0.1 to 3.0 m 3 / m 2 / h in terms of 50 kPa. It is more preferable that it is 0.2 to 2.0 m 3 / m 2 / h in terms of 50 kPa.
  • the porous membrane is formed. It is preferable because it is easy to easily reduce the water content in a short time.
  • the cleaning liquid is permeated through the porous film with a permeation flux of 0.05 to 5.0 m 3 / m 2 / h in terms of 50 kPa. Since a large amount of impurities such as water and gum contained in the oil tend to accumulate on the primary side of the porous film, it is in the opposite direction to the permeation of the oil through the porous film, that is, from the secondary side to the primary side. By allowing the cleaning liquid to permeate, impurities such as water and gum can be easily removed from the porous film, which is preferable.
  • the permeation flux of the cleaning liquid in the step (A-6) is preferably 0.05 to 5.0 m 3 / m 2 / h in terms of 50 kPa, and 0.1 to 3.0 m 3 / m in terms of 50 kPa. more preferably 2 / h, it is further preferred 50kPa terms is 0.2 ⁇ 2.0m 3 / m 2 / h.
  • the moisture content of the porous membrane is increased by further including the step (A-7) in addition to the steps (A-1) to (A-4). Is preferable because it can be easily and easily reduced in a short time.
  • the flow rate of the cleaning liquid in the step (A-7) is preferably 0.1 to 10 m 3 / m 2 / s, more preferably 1 to 10 m 3 / m 2 / s, and 3 to 10 m. It is more preferably 3 / m 2 / s.
  • the flow rate of the cleaning liquid is the flow rate area for cleaning in the direction perpendicular to the porous membrane in the space on the primary side of the porous membrane, and the flow rate of the cleaning liquid flowing in the direction parallel to the porous membrane. It can be calculated by dividing.
  • the porous membrane has an ⁇ -plane and a ⁇ -plane, and the contact angle of the porous membrane with water satisfies the following formula 1, and a hydrophobic gas is released from the ⁇ -plane of the porous membrane in the step (A) or (A)'. It is preferable to permeate through the porous membrane and allow oil to permeate through the porous membrane from the ⁇ surface of the porous membrane in the step (B).
  • the value obtained by subtracting the contact angle of the ⁇ -plane with water from the ⁇ -plane from the contact angle of the ⁇ -plane with water is preferably 10 ° or more, preferably 15 ° or more. Is even more preferable, 20 ° or more is even more preferable, and 25 ° or more is most preferable. It is preferable that the relationship between the ⁇ -plane and ⁇ -plane contact angles of the porous membrane with respect to water is satisfied after the step (B) because it is particularly easy to maintain high permeation performance.
  • the porous membrane may be composed of a single layer, or may be a composite porous membrane in which layers having different contact angles with water are laminated.
  • the contact angle with water is likely to differ between the ⁇ -plane and ⁇ -plane, and by allowing oil to permeate through the porous membrane from the ⁇ -plane with a small contact angle, it is in the oil. It is easy to retain the water contained in the porous film near the ⁇ surface, and it is easy to effectively remove the water by permeating the hydrophobic gas from the ⁇ surface having a large contact angle, and to maintain high permeation performance.
  • the method for filtering oil of the present invention needs to include the following steps (A)'and (B).
  • the water content of the porous membrane containing the hydrophobic polymer as the main component is 0 to 35%.
  • the main component of the porous membrane that allows oil to permeate the porous membrane is the hydrophobic polymer.
  • the affinity with water can be indexed by the contact angle of the porous membrane with water.
  • the contact angle of the porous membrane with water is preferably 65 to 130 °, more preferably 70 to 120 °, and 70 to 100 °. It is more preferable to have.
  • the contact angle can be measured by the static sessile drop method using a commercially available contact angle meter.
  • the main component of the porous membrane is a hydrophobic polymer, it has a high affinity with oil and can exhibit high permeation performance.
  • the water content of the porous membrane is 0 to 35%, a sufficiently large number of pores through which oil can permeate can be present in the porous membrane, and high permeation performance can be exhibited.
  • the water content needs to be 0 to 35%, preferably 0 to 15%, and even more preferably 0 to 7%.
  • the Karl Fischer titration method or the dry weight loss method is generally used as the water content of the porous membrane. In the case of a porous film that does not contain volatile components other than water and does not thermally decompose during measurement, the water content measured by the Karl Fischer titration method and the dry weight loss method can be regarded as the same. ..
  • the step (A)'in which the water content of the porous membrane is 0 to 35% is achieved by a plurality of means such as opening the porous membrane to the atmosphere, and particularly after the porous membrane is brought into contact with a volatile solvent. It is easy to achieve by opening to the atmosphere, but it is preferable because the water content of the porous membrane can be easily set to 0 to 35% in a short time by allowing the hydrophobic gas to permeate through the porous membrane.
  • Steps (A), (A)'and (B) can be carried out at any temperature.
  • the higher the temperature the larger the saturated vapor amount and the easier it is to remove water from the porous membrane, which is preferable.
  • the higher the temperature the lower the viscosity of the oil, and it is easy to reduce the resistance permeating through the porous membrane and the resistance flowing through the primary side and the secondary side, which is preferable.
  • the hydrophobic polymer which is the main component of the porous membrane, is preferably a polyvinylidene fluoride (PVDF) resin.
  • PVDF polyvinylidene fluoride
  • the polyvinylidene fluoride-based resin refers to a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride.
  • the copolymer of vinylidene fluoride refers to a polymer having a vinylidene fluoride residue structure.
  • the polymer having a vinylidene fluoride residue structure is typically a copolymer of a vinylidene fluoride monomer and another fluorine-based monomer or the like.
  • Examples of such a fluorine-based monomer include vinyl fluoride, ethylene tetrafluoride, propylene hexafluoride, and ethylene trifluoride.
  • vinyl fluoride ethylene tetrafluoride
  • propylene hexafluoride propylene hexafluoride
  • ethylene trifluoride examples of such a fluorine-based monomer.
  • ethylene or the like other than the above-mentioned fluorine-based monomer may be copolymerized to the extent that the effect of the present invention is not impaired.
  • the weight average molecular weight of the polyvinylidene fluoride-based resin is preferably 50,000 to 1,000,000 Da because the permeation performance of the porous membrane deteriorates when it becomes large, and the separation performance of the porous membrane deteriorates when it becomes small.
  • the weight average molecular weight is preferably 100,000 to 900,000 Da, more preferably 150,000 to 800,000 Da.
  • the porous membrane may contain components other than the polymer as long as the effects of the present invention are not impaired.
  • components other than the polymer include surfactants and inorganic particles.
  • the porous membrane is mainly composed of a polymer containing a polyvinylidene fluoride resin as a main component.
  • the content of the porous membrane other than the polymer is preferably less than 50% by mass.
  • the porous membrane may contain a hydrophilic resin in addition to the hydrophobic polymer. By containing the hydrophilic resin, the contact angle of the porous membrane with water can be controlled, and the affinity with the water contained in the oil can be easily controlled.
  • the "hydrophilic resin” refers to a resin having a high affinity for water and being soluble in water, or a resin having a contact angle with water smaller than that of a polyvinylidene fluoride resin.
  • the hydrophilic resin include cellulose esters such as cellulose acetate or cellulose acetate propionate, fatty acid vinyl esters, polyvinyl acetate, polyvinylpyrrolidone, ethylene oxide, propylene oxide or acrylic acid esters such as polymethyl methacrylate, or methacrylic acid. Examples thereof include ester polymers and copolymers of these polymers.
  • Oil has a higher viscosity than water, so it has a large flow resistance, and therefore requires a large amount of energy for filtration operation.
  • it is preferable not only to exhibit the high permeation performance of the porous membrane but also to reduce the resistance to flow on the primary side and the secondary side of the porous membrane.
  • the shape of the porous membrane of the present invention is not particularly limited, but in order to reduce the flow resistance on the secondary side of the porous membrane, a hollow fiber membrane having a larger secondary side flow path than the flat membrane is preferable.
  • the external pressure type hollow fiber membrane that allows oil to permeate from the outside to the inside of the hollow fiber is more preferable because the flow path on the primary side having a high viscosity can be expanded.
  • the pore size of the porous membrane may be uniform from the primary side to the secondary side, or may be non-uniform.
  • the pore size on the primary side of the porous membrane is smaller than the pore diameter on the secondary side, it is difficult for water and gum to be taken into the porous membrane, and because the pore diameter on the secondary side is large, high permeation performance is achieved. Easy to develop.
  • the average surface pore diameter on the primary side of the porous membrane is 1 to 50 nm, and the average surface pore diameter on the secondary side is 100 to 1000 nm, so that high permeation performance can be easily exhibited over a long period of time.
  • the average surface pore size on the primary side of the porous film is 1 to 50 nm, it is difficult for water and gum to be taken into the porous film.
  • the average surface pore diameter on the primary side of the porous film is preferably 1 to 50 nm, more preferably 2 to 30 nm, still more preferably 3 to 20 nm. Further, since the average surface pore diameter on the secondary side is 100 to 1000 nm, high permeation performance is likely to be exhibited, and when the water content is reduced to 0 to 35%, deterioration of physical properties due to shrinkage or the like is likely to be suppressed.
  • the average surface pore size of the porous membrane can be calculated by observing the surface of the porous membrane with an electron microscope (hereinafter, “SEM”).
  • the surface of the porous membrane is observed using SEM at a magnification of 1,000 to 100,000 times, and the areas of 300 randomly selected pores are measured respectively. From the area of each hole, the diameter when it is assumed that the hole is a circle is calculated as the hole diameter, and the average value thereof can be used as the surface average hole diameter.
  • the porous film is a composite porous film because it is easy to individually control the average surface pore size on the primary side and the secondary side. At this time, since the average surface pore diameter on the secondary side is larger than the average surface pore diameter on the primary side, not only is it easy to exhibit high permeation performance, but also the porous layer on the secondary side also acts as a support to reduce the physical properties. It is preferable because it is easy to suppress.
  • the present invention relates to a method for filtering oil, and a method for filtering vegetable oil made from a plant is particularly preferable.
  • Vegetable oil which is a raw material for cooking oil, contains a large amount of glyceride, and also contains lecithin and vitamin E, which are called gums.
  • Phospholipids such as lecithin and vitamin E are impurities that should be removed in order to obtain refined edible oils, and are also useful nutrient sources.
  • the method for filtering oil of the present invention can be suitably used for a step of separating phospholipids from vegetable oil.
  • the surface pore size of the porous membrane is preferably 1 to 50 nm, more preferably 2 to 20 nm, and even more preferably 3 to 9 nm.
  • the absolute humidity of the hydrophobic gas before passing through the porous membrane 0 is preferable to confirm that the ⁇ 20.0g / m 3, 0 ⁇ 10.0g / m 3 and more It is preferably 0 to 5.0 g / m 3 , and more preferably 0 to 5.0 g / m 3.
  • Absolute humidity can be measured using a commercially available hygrometer.
  • the absolute humidity of the hydrophobic gas after passing through the porous membrane can be measured and confirmed using a commercially available hygrometer.
  • the absolute humidity of the hydrophobic gas after permeating through the porous membrane was 0 to 20.0 g / m 3 , so that the water content accumulated in the porous membrane was sufficiently reduced.
  • Absolute humidity of the hydrophobic gas after passing through the porous film is preferably 0 ⁇ 10.0g / m 3, more preferably 0 ⁇ 5.0g / m 3.
  • Example 1 Preparation of Porous Membrane 38% by mass of PVDF1 (manufactured by Kureha; KF1300) and 62% by mass of ⁇ -butyrolactone were mixed and dissolved at 160 ° C. to prepare a membrane-forming stock solution.
  • This film-forming stock solution is discharged from the double tube mouthpiece with an 85% by mass ⁇ -butyrolactone aqueous solution accompanied as a hollow portion forming liquid, and an 85% by mass ⁇ -butyrolactone aqueous solution at a temperature of 20 ° C. installed 30 mm below the mouthpiece is contained.
  • a porous layer serving as a hollow filament-like support having a spherical structure was prepared.
  • the coating polymer solution was uniformly applied at 10 m / min to the outer surface of the hollow thread-like support (thickness 50 ⁇ m).
  • the support coated with the polymer solution was immersed in distilled water at 15 ° C. for 10 seconds to solidify it to form a porous layer having a three-dimensional network structure, and a composite porous film was prepared.
  • (Ii) Average Surface Pore Diameter of Porous Membrane The hollow fiber-shaped porous membrane prepared as described in (i) above was immersed in ethanol for 2 hours, then immersed in water overnight, and taken out of the water. The removed porous membrane was dried under reduced pressure overnight at room temperature.
  • the surface of the porous membrane was observed using SEM (manufactured by HITACHI; S-5500) at a magnification of 30,000 to 100,000 times, and the areas of 300 randomly selected holes were measured. From the area of each hole, the diameter when the hole was assumed to be a circle was calculated as the hole diameter, and the average value was taken as the surface average hole diameter. The average of the primary side (outer surface) having a three-dimensional network structure was used. The pore diameter was 8 nm, and the average surface pore diameter on the secondary side (inner surface) was 200 nm.
  • Example 2 (I) Preparation of Porous Membrane The porous membrane prepared in Example 1 (i) was immersed in a 30% by mass aqueous glycerin solution for 1 hour and air-dried. (Iii) Contact angle of porous membrane As shown in (iv) below, a miniature module that has permeated a hydrophobic gas is disassembled, and 1 ⁇ l of water droplets are brought into contact with the outer surface of the removed porous membrane by the static sessile drop method. When the measurement was performed 5 times and the average value was calculated, it was 66 °. (Iv) Permeation of hydrophobic gas through the porous membrane A miniature module was prepared in the same manner as in Example 1. As shown in FIG.
  • Example 3 (Iii) Contact angle of porous membrane As shown in (iv) below, a miniature module that has permeated a hydrophobic gas is disassembled, and 1 ⁇ l of water droplets are brought into contact with the outer surface of the removed porous membrane by the static sessile drop method. When the measurement was performed 5 times and the average value was calculated, it was 74 °. (Iv) Permeation of Hydrophobic Gas into Porous Membrane Using the porous membrane prepared in Example 1 (i), a miniature module was prepared in the same manner as in Example 1. As shown in FIG.
  • Example 4 (I) Preparation of Porous Membrane A polymer solution for coating was prepared by mixing 20% by mass of PVDF3 (manufactured by Alchema; Kynar710) and 80% by mass of NMP and dissolving at 120 ° C. to prepare a polymer solution for coating. A porous membrane was prepared in the same manner as in Example 1. (Ii) Average surface pore size of the porous film The average surface pore size of the outer surface was determined in the same manner as in Example 1 and found to be 32 nm.
  • Example 5 (I) Preparation of Porous Film A porous film was prepared in the same manner as in Example 1 except that PVDF4 (manufactured by Arkema; Kynar710) was used instead of PVDF2 (manufactured by Solvay Specialty Chemicals; Solef9007) of the polymer solution for coating. did. (Ii) Average surface pore size of the porous film The average surface pore size of the outer surface was determined in the same manner as in Example 1 and found to be 20 nm.
  • Example 6 When the oil filtration was continued in Example 3, the oil permeation flux gradually decreased. When the permeated flux of oil reached 1.0 L / m 2 / h (initial ratio: 0.5), filtration was stopped and the following operation was performed. (Iii) Contact angle of the porous membrane As shown in (iv) below, the miniature module that has permeated the hydrophobic gas is disassembled, and 1 ⁇ l of water droplets are brought into contact with the outer surface ( ⁇ surface) of the removed porous membrane to be static. It was measured 5 times by the sessile drop method and the average value was calculated to be 74 °.
  • Example 7 When the oil filtration was continued in Example 3, the oil permeation flux gradually decreased. When the permeated flux of oil reached 1.0 L / m 2 / h (initial ratio: 0.5), filtration was stopped and the following operation was performed. (Iii) Contact angle of the porous membrane As shown in (iv) below, the miniature module that has permeated the hydrophobic gas is disassembled, and 1 ⁇ l of water droplets are brought into contact with the outer surface ( ⁇ surface) of the removed porous membrane to be static. It was measured 5 times by the sessile drop method and the average value was calculated to be 64 °.
  • Example 8 When the oil filtration was continued in Example 4, the oil permeation flux gradually decreased. When the permeated flux of oil reached 0.7 L / m 2 / h (initial ratio: 0.5), filtration was stopped and the following operation was performed. (Iii) Contact angle of the porous membrane As shown in (iv) below, the miniature module that has permeated the hydrophobic gas is disassembled, and 1 ⁇ l of water droplets are brought into contact with the outer surface ( ⁇ surface) of the removed porous membrane to be static. When the measurement was performed 5 times by the sessile drop method and the average value was calculated, it was 90 °.
  • This film-forming stock solution is discharged from the double tube mouthpiece with an 85% by mass ⁇ -butyrolactone aqueous solution accompanied as a hollow portion forming liquid, and an 85% by mass ⁇ -butyrolactone aqueous solution at a temperature of 20 ° C. installed 30 mm below the mouthpiece is contained.
  • a hollow filamentous support having a spherical structure was prepared by solidifying in a cooling bath.
  • the coating polymer solution was uniformly applied at 10 m / min to the outer surface of the hollow thread-like support (thickness 50 ⁇ m).
  • the support coated with the polymer solution was immersed in distilled water at 15 ° C. for 10 seconds to solidify, and a porous film having a three-dimensional network structure was formed.
  • (Ii) Average Surface Pore Diameter of Porous Membrane The hollow fiber-shaped porous membrane prepared as described in (i) above was immersed in ethanol for 2 hours, then immersed in water overnight, and taken out of the water. The removed porous membrane was dried under reduced pressure overnight at room temperature.
  • the surface of the porous membrane was observed using SEM (manufactured by HITACHI; S-5500) at a magnification of 30,000 to 100,000 times, and the areas of 300 randomly selected holes were measured. From the area of each hole, the diameter when the hole was assumed to be a circle was calculated as the hole diameter, and the average value was taken as the surface average hole diameter. The average of the primary side (outer surface) having a three-dimensional network structure was used. The pore diameter was 8 nm, and the average surface pore diameter on the secondary side (inner surface) was 200 nm.
  • Example 10 (I) Preparation of Porous Membrane The porous membrane prepared in Example 9 (i) was immersed in a 30% by mass aqueous glycerin solution for 1 hour and air-dried. (Iii) Contact angle of the porous membrane As shown in (iv) below, the miniature module that has permeated the hydrophobic gas is disassembled, and 1 ⁇ l of water droplets are brought into contact with the outer surface of the removed porous membrane, and the static liquid method is 5 When the measurement was performed several times and the average value was calculated, it was 66 °. (Iv) Permeation of hydrophobic gas through the porous membrane A miniature module was prepared in the same manner as in Example 9. As shown in FIG.
  • Example 11 (Iii) Contact angle of the porous membrane As shown in (iv) below, the miniature module that has permeated the hydrophobic gas is disassembled, and 1 ⁇ l of water droplets are brought into contact with the outer surface of the removed porous membrane, and the static liquid method is 5 When the measurement was performed several times and the average value was calculated, it was 74 °. (Iv) Permeation of Hydrophobic Gas into Porous Membrane Using the porous membrane prepared in Example 9 (i), a miniature module was prepared in the same manner as in Example 9. As shown in FIG.
  • Example 12 (I) Preparation of Porous Membrane A polymer solution for coating was prepared by mixing 20% by mass of PVDF3 (manufactured by Alchema; Kynar710) and 80% by mass of NMP and dissolving at 120 ° C. to prepare a polymer solution for coating. A porous membrane was prepared in the same manner as in Example 9. (Ii) Average surface pore size of the porous film The average surface pore size of the outer surface was determined in the same manner as in Example 9 and found to be 32 nm.
  • Example 13 (I) Preparation of Porous Film A porous film was prepared in the same manner as in Example 9 except that PVDF4 (manufactured by Arkema; Kynar710) was used instead of PVDF2 (manufactured by Solvay Specialty Chemicals; Solef9007) of the polymer solution for coating. did. (Ii) Average surface pore size of the porous film The average surface pore size of the outer surface was determined in the same manner as in Example 9 and found to be 20 nm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Microbiology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
PCT/JP2021/002396 2020-01-28 2021-01-25 油をろ過する方法 Ceased WO2021153486A1 (ja)

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CN202180011567.7A CN114981001B (zh) 2020-01-28 2021-01-25 过滤油的方法
EP21748365.0A EP4098350A4 (en) 2020-01-28 2021-01-25 OIL FILTERING PROCESS
JP2021518011A JP6996662B2 (ja) 2020-01-28 2021-01-25 油をろ過する方法
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JPS5494167A (en) * 1978-01-10 1979-07-25 Asahi Chem Ind Co Ltd Oil separation method
JPS58194995A (ja) 1982-05-10 1983-11-14 リノ−ル油脂株式会社 粗製グリセリド油組成物の精製方法
JPS58194996A (ja) 1982-05-10 1983-11-14 リノ−ル油脂株式会社 粗製グリセリド油組成物の精製方法
JPS5920394A (ja) 1982-07-26 1984-02-02 リノ−ル油脂株式会社 粗製グリセリド油組成物の精製方法
JPS6017478B2 (ja) * 1982-04-09 1985-05-02 旭化成株式会社 植物油の処理法
JP2007260671A (ja) * 2006-03-03 2007-10-11 Mitsubishi Electric Engineering Co Ltd フィルタ再生処理方法及びフィルタ再生処理装置

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JPS6017478A (ja) * 1983-07-11 1985-01-29 株式会社小糸製作所 表示装置
JPH0947641A (ja) * 1995-08-04 1997-02-18 Asahi Chem Ind Co Ltd 多孔質膜の洗浄方法
JPH10244103A (ja) 1997-03-06 1998-09-14 Mitsubishi Rayon Co Ltd 油水分離方法
PT1005390E (pt) * 1997-08-12 2002-10-31 Unilever Nv Processo de limpeza de membranas
CN105722585A (zh) 2013-09-18 2016-06-29 三菱丽阳株式会社 多孔质中空纤维膜及其制造方法
JP6017478B2 (ja) 2014-02-27 2016-11-02 富士フイルム株式会社 蛍光撮影装置及び蛍光撮影装置用の光源ユニット

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JPS5494167A (en) * 1978-01-10 1979-07-25 Asahi Chem Ind Co Ltd Oil separation method
JPS6017478B2 (ja) * 1982-04-09 1985-05-02 旭化成株式会社 植物油の処理法
JPS58194995A (ja) 1982-05-10 1983-11-14 リノ−ル油脂株式会社 粗製グリセリド油組成物の精製方法
JPS58194996A (ja) 1982-05-10 1983-11-14 リノ−ル油脂株式会社 粗製グリセリド油組成物の精製方法
JPS5920394A (ja) 1982-07-26 1984-02-02 リノ−ル油脂株式会社 粗製グリセリド油組成物の精製方法
JP2007260671A (ja) * 2006-03-03 2007-10-11 Mitsubishi Electric Engineering Co Ltd フィルタ再生処理方法及びフィルタ再生処理装置

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CN114981001A (zh) 2022-08-30
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