WO2021079750A1 - Procédé de production de dispersion aqueuse de polymère - Google Patents

Procédé de production de dispersion aqueuse de polymère Download PDF

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Publication number
WO2021079750A1
WO2021079750A1 PCT/JP2020/038175 JP2020038175W WO2021079750A1 WO 2021079750 A1 WO2021079750 A1 WO 2021079750A1 JP 2020038175 W JP2020038175 W JP 2020038175W WO 2021079750 A1 WO2021079750 A1 WO 2021079750A1
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membrane
polymer
aqueous dispersion
suva
filtration
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PCT/JP2020/038175
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English (en)
Japanese (ja)
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迫郁弥
山村寛
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株式会社カネカ
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Priority to JP2021554260A priority Critical patent/JPWO2021079750A1/ja
Priority to CN202080074831.7A priority patent/CN114641342A/zh
Publication of WO2021079750A1 publication Critical patent/WO2021079750A1/fr

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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
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material

Definitions

  • the present invention relates to a method for producing a polymer aqueous dispersion having a concentration step by membrane filtration. More specifically, the present invention relates to a method for producing a polymer aqueous dispersion having a concentration step by membrane filtration with reduced fouling (membrane obstruction).
  • Patent Document 1 the suspended water is filtered by external pressure with a porous hollow fiber membrane having an outer surface opening ratio of 20% or more and a minimum porosity layer pore diameter of 0.03 ⁇ m or more and 1 ⁇ m or less. It is described that the turbid water is turbid.
  • Patent Document 2 when a flow path having a flow path diameter of 1.5 mm or less is formed inside a separation membrane for solid-liquid separation and the fluid to be treated is separated, the fluid to be treated is placed in the flow path. It is described that the fluid to be treated is separated by circulating the fluid under the condition that the linear velocity of the membrane surface is 6 m / s or more.
  • the present invention provides a method for producing a polymer aqueous dispersion by membrane filtration in which fouling is suppressed on the inner surface of the filtration membrane and inside the filtration membrane in order to solve the above problems.
  • a polymer aqueous dispersion containing a polymer and water is filtered using a filtration membrane to obtain a concentrated polymer aqueous dispersion and a polymer-free filtrate.
  • the filtration membrane has pores on the inner surface, and when the total number of pores is 100%, 50% or more of the pores have a pore diameter smaller than the minimum particle diameter of the polymer.
  • the dispersion of the surface opening diameter distribution is 0.2 or less, and in the membrane filtration step, the initial SUVA ratio represented by the following formula (1) is 0.8 or more and 1.2 or less, and the following formula (1)
  • the present invention relates to a method for producing a polymer aqueous dispersion, wherein the absolute value of the difference between the initial SUVA ratio represented by the above and the secondary SUVA ratio represented by the following formula (2) is 0.2 or less.
  • the life of the membrane can be extended by reducing the fouling on the inner surface of the filtration membrane and the inside of the filtration membrane, and the productivity of the polymer dispersion liquid can be achieved. Can be enhanced.
  • by reducing fouling it is possible to reduce the frequency of use of the chemical that cleans the filtration membrane, and it is possible to prevent membrane deterioration due to the chemical, so that the life of the membrane can be extended, and by extension, the polymer dispersion liquid.
  • Productivity can be increased.
  • the frequency of use of the chemical for cleaning the filtration membrane can be reduced, the cost of using the chemical can be reduced, and the productivity of the polymer dispersion can be increased.
  • FIG. 1 is a graph showing the ratio of the solid content concentration of the PHBH aqueous dispersion measured in Example 1 and Comparative Example 1 to the permeated flux (J) at each solid content concentration with respect to the initial permeated flux (J0). is there.
  • FIG. 2 shows the difference between the permeation flow rate per membrane area of the PHBH aqueous dispersion measured in Example 1 and Comparative Example 1 and the SUVA ratio (the difference between the initial SUVA ratio and the permeation flow rate per predetermined membrane area). It is a graph which shows (absolute value).
  • FIG. 3 is a graph showing the difference between the solid content concentration of the PHBH aqueous dispersion measured in Example 1 and Comparative Example 1 and the SUVA ratio (absolute value of the difference between the initial SUVA ratio and the SUVA ratio at each solid content concentration). is there.
  • FIG. 4A is an SEM photograph of the cross section of the membrane after concentrating the polymer dispersion of the filtration membrane used in Example 1
  • FIG. 4B shows the concentration of the polymer dispersion of the filtration membrane used in Comparative Example 1. It is an SEM photograph of the membrane cross section after this.
  • FIG. 5A is an SEM photograph of the cross section of the membrane before concentrating the polymer dispersion of the filtration membrane used in Example 1, and FIG.
  • FIG. 5B shows the concentration of the polymer dispersion of the filtration membrane used in Comparative Example 1. It is an SEM photograph of the previous membrane cross section.
  • FIG. 6 is a graph showing the ratio of the total permeation flow rate per membrane area measured in Example 2 and Comparative Example 2 to the permeation flux (J) at a predetermined permeation flow rate with respect to the initial permeation flux (J0). ..
  • FIG. 7 is a schematic view of the filtration device used for concentrating the PHBH aqueous dispersion in Example 1 and Comparative Example 1.
  • FIG. 8 is a schematic view of the filtration device used for circulating the PHBH aqueous dispersion in Example 2 and Comparative Example 2.
  • the inventors of the present invention have diligently studied the suppression of fouling on the inner surface of the filtration membrane and the inside of the filtration membrane in the filtration membrane used for solid-liquid separation during the production of the polymer dispersion.
  • the pore diameter is 50% or more smaller than the minimum particle diameter of the polymer, and the dispersion of the surface pore diameter distribution is 0.
  • a filtration membrane of .2 or less is used, and in the membrane filtration step, the initial SUVA ratio (expressed by the mathematical formula (1) described later) is 0.8 or more and 1.2 or less, and the initial SUVA ratio and the secondary.
  • the "inner surface" of the filtration membrane means the filtration surface in contact with the polymer dispersion.
  • the method for producing a polymer aqueous dispersion includes the following step (a) of concentrating the polymer aqueous dispersion as an essential step.
  • the step (a) is a membrane filtration step of filtering the polymer aqueous dispersion with a filtration membrane to obtain a concentrated polymer aqueous dispersion and a polymer-free filtrate.
  • step (a) the polymer aqueous dispersion is sent into the filter membrane to filter the polymer aqueous dispersion with the filter membrane.
  • the filtration method is not particularly limited, and is a cross-flow method (a method in which the flow directions of the liquid to be filtered and the filtered liquid are orthogonal to each other) and a dead-end method (a method in which the flow directions of the liquid to be filtered and the filtered liquid are the same). ) Etc. can be mentioned.
  • the cross flow method is preferable from the viewpoint of suppressing fouling on the surface of the filtration membrane due to the polymer particles.
  • the polymer aqueous dispersion comprises water and a polymer. Specifically, it is an aqueous dispersion in which polymer particles are dispersed in water.
  • the polymer is not particularly limited, but polyhydroxy alkanoate (PHA), polyvinyl chloride and the like can be preferably used.
  • PHA is a general term for polymers having 3-hydroxyalkanoic acid as a monomer unit.
  • the 3-hydroxyalkanoic acid is not particularly limited, and is, for example, 3-hydroxypropionate, 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate and 3-hydroxyalkanoate. Hydroxyoctanoate and the like can be mentioned.
  • the PHA may be a homopolymer having one kind of 3-hydroxyalkanoic acid as a monomer unit, or may be a copolymer having two or more kinds of 3-hydroxyalkanoic acid as a monomer unit.
  • the copolymer of 3-hydroxybutyrate (3HB) and other 3-hydroxyalkanoic acid the co-weight of 3-hydroxyalkanoic acid containing at least 3-hydroxyhexanoate (3HH) as a monomer unit. Coalescence etc. can be mentioned.
  • copolymers containing 3HH as a monomer unit for example, 3HB and 3HH two-component copolymers (PHBH) (Macromolecules, 28,4822-4828 (1995)), 3HB, 3-hydroxyvalerate (3HV) and A 3HH three-component copolymer (PHBVH) (Patent No. 27777757, Japanese Patent Application Laid-Open No.
  • the composition ratio of each monomer unit constituting the two-component copolymer PHBH of 3HB and 3HH is not particularly limited, but when the total of all the monomer units is 100 mol%, the 3HH unit is 1 mol%. It is preferably 99 mol% or more, more preferably 1 mol% or more and 50 mol% or less, and further preferably 1 mol% or more and 25 mol% or less.
  • the composition ratio of each monomer unit constituting the three-component copolymer PHBVH of 3HB, 3HV and 3HH is not particularly limited, but when the total of all the monomer units is 100 mol%, for example, 3HB.
  • a range in which the unit is 1 mol% or more and 95 mol% or less, the 3HV unit is 1 mol% or more and 96 mol% or less, and the 3HH unit is 1 mol% or more and 30 mol% or less is preferable.
  • the polymer aqueous dispersion may contain one kind of polymer or may contain two or more kinds of polymers.
  • the polymer aqueous dispersion to be concentrated in the step (a) may contain other components in addition to water and the polymer (particles).
  • other components include solvents other than water, dispersants, surfactants, preservatives and the like.
  • the content of other components can be appropriately selected according to the purpose and the like.
  • the polymer aqueous dispersion to be concentrated in the step (a) may be a PHA suspension derived from a crushed product of a PHA-containing microorganism.
  • the PHA suspension can be obtained, for example, as described in WO 2010/116681.
  • the concentration of the polymer (solid content) in the polymer aqueous dispersion before being filtered in the step (a), that is, the membrane filtration step is not particularly limited, but is, for example, 5% by weight (w / v%) or more and 40% by weight. It may be 10% by weight or more and 35% by weight or less.
  • the aqueous polymer dispersion can be effectively concentrated.
  • the concentration of the polymer (solid content) of the concentrated polymer aqueous dispersion after being filtered in the step (a), that is, the membrane filtration step is not particularly limited, but is, for example, 30% by weight (w / v%) or more. It may be 65% by weight or less, and may be 35% by weight or more and 60% by weight or less. It facilitates the removal of water from the concentrated polymer aqueous dispersion.
  • the filtration membrane has 50% or more pores whose pore diameter is smaller than the minimum particle diameter of the polymer and 50% or more pores, assuming that the total number of pores existing on the inner surface is 100%.
  • the dispersion of the pore size distribution is 0.2 or less (hereinafter, also referred to as a surface pore size requirement).
  • the filtration membrane preferably has 55% or more of pores having a pore diameter smaller than the minimum particle diameter of the polymer, preferably 60% or more, assuming that the total number of pores existing on the inner surface is 100%. More preferably, it is more preferably 65% or more.
  • the filtration membrane has a pore diameter when the total number of openings existing on the inner surface is 100%.
  • the pores smaller than the minimum particle size of the polymer are 100%, but may be 85% or less. Specifically, it may be within the range of any of the above lower limit values and upper limit values.
  • the dispersion of the surface opening diameter distribution is preferably 0.15 or less, more preferably 0.10 or less, and further preferably 0.05 or less.
  • the filtration membrane ideally has a dispersion of the surface opening diameter distribution of 0 from the viewpoint of further enhancing the effect of suppressing fouling on the surface and inside of the filtration membrane, but even if it is 0.02 or more. Good. Specifically, it may be within the range of any of the above lower limit values and upper limit values.
  • the minimum particle size of the polymer is the minimum particle size in the volume-based particle size distribution curve measured by the laser diffraction / scattering method using the polymer aqueous dispersion before concentration in step (a) as a sample. It means the diameter Dmin.
  • the particle size distribution curve can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device “Microtrack MT3300EX II” manufactured by Microtrack Bell. The polymer aqueous dispersion that has not been concentrated even once in step (a) is used as the measurement sample.
  • the surface opening diameter of the filtration membrane can be measured, for example, as follows.
  • the inner surface of the filtration membrane is observed with a scanning electron microscope (SEM), and the image is captured by a computer.
  • the scanning electron microscope is not particularly limited, but for example, "JSM-7001FA” manufactured by JEOL Ltd. can be used for observation at a magnification of 3500.
  • the type and magnification of the microscope may be appropriately changed depending on the size of the holes.
  • All the holes existing in the range of 5 ⁇ m ⁇ 5 ⁇ m arbitrarily selected from the obtained images are analyzed by image processing software (ImageJ, developer: National Institutes of Health).
  • the SEM image is binarized to obtain an image in which the pores are black and the structural part is white. If the pores and the structural part cannot be binarized cleanly due to the difference in contrast in the analysis image, the holes are painted black and then image processing is performed to obtain the ferret diameter of the holes within the analysis range. To get. At this time, holes having an area of 0.0001 ⁇ m 2 or less are excluded from the data in order to cut noise.
  • the filtration membrane is a tubular membrane, the tubular membrane is cut into a semi-cylindrical shape, and the inner surface of the filtration membrane is observed with a scanning electron microscope in a state where the inner surface is exposed.
  • the filtration membrane is a flat membrane, the surface on the side with a small pore diameter is observed with a scanning electron microscope.
  • the filtration membrane has an initial SUVA ratio (represented by the mathematical formula (1) described later) of 0.8 or more and 1.2 or less and an initial SUVA ratio in the membrane filtration step. It satisfies the requirement that the absolute value of the difference between the quadratic SUVA ratio (represented by the mathematical formula (2) described later) is 0.2 or less (hereinafter, also referred to as the SUVA ratio requirement).
  • the initial SUVA ratio is 0.8 or more and 1.2 or less, that is, the initial SUVA ratio is close to 1, and the absolute value of the difference between the initial SUVA ratio and the secondary SUVA ratio is 0.2 or less.
  • the secondary SUVA ratio is close to the initial SUVA ratio means that the water quality of the concentrated polymer dispersion is the same as that of the filtrate. In other words, it means that the concentrated polymer dispersion and the organic contaminants contained in the filtrate are equivalent labels. When the concentrated polymer dispersion liquid and the organic contaminants contained in the filtrate have the same label, the adsorption of the organic contaminants on the inner surface of the filtration membrane and the pores is reduced.
  • DOC is measured using, for example, a total organic carbon meter (TOC-L) manufactured by Shimadzu Corporation.
  • UV is measured using, for example, a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Corporation.
  • the filtration membrane may satisfy the above-mentioned requirements for surface opening diameter, and the material thereof is not particularly limited. It may be an organic material or an inorganic material.
  • the organic material include resins such as polypropylene, fluorine-based resin, cellulose ester, polysulfone-based resin, polyacrylonitrile, and polyimide.
  • the fluorine-based resin include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride / propylene hexafluoride copolymer, ethylene / ethylene tetrafluoride copolymer and the like.
  • Examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.
  • Examples of the polysulfone-based resin include polysulfone and polyethersulfone.
  • Examples of the inorganic material include porous ceramics such as alumina, mullite, zirconia, and cozilite, and porous bodies made of porous sintered metal such as stainless steel. Among them, an inorganic material is preferable from the viewpoint that the roundness of the surface pores is high and the above-mentioned SUVA ratio requirement is easily satisfied.
  • the shape of the filtration membrane is not particularly limited, and may be any of a tubular membrane, a flat membrane, a hollow fiber membrane, and the like. Of these, a tubular membrane is preferable from the viewpoint that the flow path is less likely to be blocked by the polymer and that the above-mentioned SUVA ratio requirement is easily satisfied.
  • the polymer aqueous dispersion can be produced by the filtration device shown in FIG. 7. As shown in FIG. 7, the polymer aqueous dispersion a that is agitated by the stirrer 4 in the tank 3 and supplied to the filter film 1 via the pump 2 is filtered by the filter film 1. It is divided into a concentrated polymer aqueous dispersion b and a polymer-free filtrate c, the concentrated polymer aqueous dispersion b returns to the tank 3, and the filtrate c is removed from the system to be removed from the tank 3 in the tank 3. The polymer aqueous dispersion is concentrated.
  • the polymer aqueous dispersion can be produced by the filtration device shown in FIG.
  • the concentration of the polymer aqueous dispersion can be made constant by returning the filtrate c to the tank 3.
  • a membrane filtration step of obtaining a concentrated polymer aqueous dispersion and a polymer-free filtrate by filtering the polymer aqueous dispersion containing polymer and water using a filtration membrane is included.
  • the filtration membrane has pores on the inner surface, and when the total number of pores is 100%, 50% or more of the pores have a pore diameter smaller than the minimum particle diameter of the polymer, and the surface pore diameter distribution.
  • the variance of is 0.2 or less
  • the initial SUVA ratio represented by the following formula (1) is 0.8 or more and 1.2 or less
  • the initial SUVA ratio represented by the following formula (1) and the following formula (2) are used.
  • a method for producing a polymer aqueous dispersion wherein the absolute value of the difference in the secondary SUVA ratio represented is 0.2 or less.
  • the particle size distribution curve (volume basis) was measured using a laser diffraction / scattering type particle size distribution measuring device "Microtrack MT3300EX II" manufactured by Microtrack Bell, and the minimum particle size Dmin and the median size D50 were calculated.
  • the holes are painted black and then image processing is performed to obtain the ferret diameter of the holes within the analysis range. Got At this time, holes having an area of 0.0001 ⁇ m 2 or less were excluded from the data in order to cut noise.
  • UV measurement The measurement was performed using a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science.
  • Example 1 Ralstonia utrofa KNK-005 strain is cultivated by the method described in Example 1 of WO2010 / 116681 and contains poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH).
  • a cell culture solution was prepared. Next, the cell culture solution obtained above was heated and stirred at an internal temperature of 60 to 80 ° C. for 20 minutes to perform a sterilization treatment. To the sterilized cell culture solution obtained above, 0.2% by weight of sodium dodecyl sulfate was added. Further, after adding an aqueous sodium hydroxide solution so that the pH became 11.0, the temperature was kept at 50 ° C. for 1 hour.
  • PHBH aqueous dispersion having a median diameter (D50) of PHBH particles of 2 ⁇ m and a solid content concentration of 26% by weight (PHBH particle content: 260 g / L).
  • D50 median diameter
  • Dmin minimum particle size of the polymer particles in the PHBH aqueous dispersion
  • the PHBH aqueous dispersion was circulated and supplied to the tubular membrane by the filtration apparatus shown in FIG. 7 using a tubular membrane (MEMBRALOX (registered trademark) 1T1-70, manufactured by PALL Corporation, material: alumina ceramic) as the filtration membrane. Concentration was performed. When the total number of pores of the tubular membrane is 100%, the ratio of the number of pores whose pore diameter is smaller than the minimum particle diameter of the polymer particles in the PHBH aqueous dispersion is 67%, which is the distribution of the surface pore diameter.
  • the dispersion was 0.02, the initial SUVA ratio was 0.83, and the absolute value of the difference between the initial SUVA ratio and the secondary SUVA ratio was 0.05 or more and 0.2 or less.
  • the polymer aqueous dispersion a that is agitated by the stirrer 4 in the tank 3 and supplied to the filter membrane 1 via the pump 2 is concentrated by being filtered by the filter membrane 1. It is divided into a polymer aqueous dispersion b and a polymer-free filtrate c, and the concentrated polymer aqueous dispersion b returns to the tank 3, and the filtrate c is removed from the system to disperse the PHA water in the tank 3. The liquid is concentrated.
  • Example 1 Comparative Example 1 Using the cell culture solution obtained by the same method as in Example 1, the median diameter D50 of the PHBH particles was 2 ⁇ m in the same manner as in Example 1 except that the amount of water added at the end was changed. , A PHBH aqueous dispersion having a solid content concentration of 23% by weight (PHBH particle content: 230 g / L) was obtained. The minimum particle size (Dmin) of the polymer particles in the PHBH aqueous dispersion is 0.75 ⁇ m. The PHBH aqueous dispersion was circulated and supplied to the tubular membrane by a filtration device shown in FIG.
  • the polymer aqueous dispersion a that is agitated by the stirrer 4 in the tank 3 and supplied to the filter membrane 1 via the pump 2 is concentrated by being filtered by the filter membrane 1.
  • the PHA water in the tank 3 is divided into a polymer water dispersion b and a polymer-free filter solution c, the concentrated polymer water dispersion b returns to the tank 3, and the filter solution c is removed from the system.
  • the dispersion is concentrated.
  • FIG. 1 is a graph showing the ratio of the solid content concentration of the PHBH aqueous dispersion measured in Example 1 and Comparative Example 1 to the permeated flux (J) at each solid content concentration with respect to the initial permeated flux (J0).
  • FIG. 2 shows the difference between the permeation flow rate per membrane area of the PHBH aqueous dispersion measured in Example 1 and Comparative Example 1 and the SUVA ratio (absolute value of the difference between the initial SUVA ratio and the permeation flow rate per membrane area). ) Is a graph showing.
  • FIG. 3 is a graph showing the difference between the solid content concentration of the PHBH aqueous dispersion measured in Example 1 and Comparative Example 1 and the SUVA ratio (absolute value of the difference between the initial SUVA ratio and the SUVA ratio at each solid content concentration). is there.
  • FIG. 4A is an SEM photograph of the cross section of the membrane after concentrating the polymer dispersion of the filtration membrane used in Example 1
  • FIG. 4B shows the concentration of the polymer dispersion of the filtration membrane used in Comparative Example 1. It is an SEM photograph of the membrane cross section after this.
  • Example 1 even when the concentration is completed and the solid content concentration of the aqueous dispersion of the polymer is about 40% by weight, the ratio of the permeated flux to the initial permeated flux is 0.5 or more. It was confirmed that fouling was effectively suppressed. From FIGS. 2 and 3, in Example 1, in the membrane filtration step, the initial SUVA ratio is 0.8 or more and 1.2 or less, and the absolute value of the difference between the initial SUVA ratio and the secondary SUVA ratio is 0. When it was 2 or less, it was confirmed that the adhesion of impurities to the inside of the filtration membrane was suppressed and the fouling inside the filtration membrane was reduced. FIG.
  • Example 5A is an SEM photograph of the cross section of the membrane before concentrating the polymer dispersion of the filtration membrane used in Example 1. From the comparison between FIGS. 4A and 5A, it was confirmed that in Example 1, the fouling inside the filtration membrane was reduced because the PHBH particles could be prevented from entering the inside of the filtration membrane.
  • 5B is an SEM photograph of the cross section of the membrane before concentrating the polymer dispersion of the filtration membrane used in Comparative Example 1. As can be seen from the comparison between FIGS. 4B and 5B, in Comparative Example 1, since the PHBH particles could not be prevented from entering the inside of the membrane, the fouling inside the membrane could not be suppressed.
  • Example 2 Using the cell culture solution obtained by the same method as in Example 1, the median diameter D50 of the PHBH particles was 2 ⁇ m in the same manner as in Example 1 except that the amount of water added at the end was changed. , A PHBH aqueous dispersion having a solid content concentration of 25% by weight (PHBH particle content: 250 g / L) was obtained. The minimum particle size (Dmin) of the polymer particles in the PHBH aqueous dispersion was 0.75 ⁇ m.
  • PHBH aqueous dispersion was circulated and supplied to the tubular membrane, and circulation was carried out. As shown in FIG. 8, fouling is performed by returning the filtrate c to the tank 3 to keep the concentration of the PHBH aqueous dispersion constant and to carry out circulation in a state where the permeation flux lowering factors other than fouling are eliminated.
  • Example 2 Using the same tubular membrane as in Example 1, a PHBH aqueous dispersion was circulated and supplied to the tubular membrane
  • Example 2 In the same manner as in Example 2, a PHBH aqueous dispersion having a median diameter of 2 ⁇ m and a solid content concentration of 25% by weight (PHBH particle content: 250 g / L) was obtained. The minimum particle size (Dmin) of the polymer particles in the PHBH aqueous dispersion was 0.75 ⁇ m.
  • a PHBH aqueous dispersion was circulated and supplied to the tubular membrane, and circulation was carried out in the same manner as in Example 2. As shown in FIG. 8, fouling is performed by returning the filtrate c to the tank 3 to keep the concentration of the PHBH aqueous dispersion constant and to carry out circulation in a state where the permeation flux lowering factors other than fouling are eliminated. was evaluated.
  • FIG. 6 is a graph showing the ratio of the permeation flux (J) at a predetermined permeation flow rate to the initial permeation flux (J0) to the permeation flow rate per membrane area measured in Example 2 and Comparative Example 2.
  • J permeation flux
  • J0 initial permeation flux
  • FIG. 6 shows that in Example 1, when the amount of permeated liquid with respect to the membrane area is 10000 kg / m 2 , the ratio of the permeated flux to the initial permeated flux is 0.8 or more, and fouling is suppressed. I was able to.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé de production d'une dispersion aqueuse de polymère, ledit procédé comprenant une étape de filtration sur membrane dans laquelle une dispersion aqueuse de polymère contenant un polymère et de l'eau est filtrée au moyen d'une membrane de filtration, ce qui permet d'obtenir une dispersion aqueuse de polymère concentrée et un filtrat qui ne contient pas le polymère. Par rapport à ce procédé de production d'une dispersion aqueuse de polymère, la surface interne de la membrane de filtration comprend des pores ; si le nombre total des pores est considéré comme 100 %, 50 % ou plus des pores ont un diamètre de pore qui est plus petit que le plus petit diamètre de particule du polymère ; la distribution de diamètre de pore de surface a une dispersion de 0,2 ou moins ; et dans l'étape de filtration sur membrane, le rapport SUVA initial exprimé par la formule (1) est de 0,8 à 1,2, et la valeur absolue de la différence entre le rapport SUVA initial exprimé par la formule (1) et le rapport SUVA secondaire exprimé par la formule (2) est de 0,2 ou moins. (1) : (Rapport SUVA initial) = B1/C1 (2) : (Rapport SUVA secondaire) = B2/C2 Par conséquent, la présente invention fournit un procédé de production d'une dispersion aqueuse de polymère au moyen d'une filtration sur membrane, l'encrassement sur la surface interne d'une membrane de filtration et/ou l'encrassement à l'intérieur de la membrane de filtration étant supprimés.
PCT/JP2020/038175 2019-10-25 2020-10-08 Procédé de production de dispersion aqueuse de polymère WO2021079750A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023120193A1 (fr) * 2021-12-23 2023-06-29 株式会社カネカ Procédé de fabrication de polyhydroxyalcanoate, et application associée
WO2023120310A1 (fr) * 2021-12-23 2023-06-29 株式会社カネカ Procédé de fabrication de polyhydroxyalcanoate, et application associée

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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