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  • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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  • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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  • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
  • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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  • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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  • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
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  • C12P7/00—Preparation of oxygen-containing organic compounds
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  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/62—Carboxylic acid esters
  • C12P7/625—Polyesters of hydroxy carboxylic acids

Definitions

• the present invention relates to a method for producing recycled water and a method for producing polyhydroxyalkanoic acid (hereinafter also referred to as "PHA").
• PHA polyhydroxyalkanoic acid
• Biodegradable plastics are completely biodegraded by microorganisms in the soil or water, and are incorporated into the carbon cycle process of the natural world. use is desired.
• Plant-derived biodegradable plastics such as PHA have attracted attention as typical biodegradable plastics.
• PHA is an aliphatic polyester (thermoplastic polyester) that is produced by microorganisms using plant-derived natural organic acids and fats and oils as a carbon source and accumulates in cells as an energy storage substance.
• an object of the present invention is to provide a method for producing recycled water, which can greatly reduce chemical cleaning of the membrane when producing recycled water from waste water, and can substantially eliminate fouling of the membrane only by cleaning with water. That's what it is.
• one aspect of the present invention provides a method for producing recycled water, comprising the following steps (A) to (D): (A) anaerobic treatment and aerobic (B) a pretreatment filtration step in which the treated water obtained in the step (A) is pretreated and filtered by a membrane separation activated sludge method; (C) the obtained in the step (B) (D) a filtering step of filtering the treated water obtained in the step (C) with an ion removal membrane;
• a method for producing recycled water that can eliminate membrane fouling substantially only by cleaning without chemically cleaning the membrane when producing recycled water from waste water. can be done.
• a method for producing recycled water according to an embodiment of the present invention includes the following steps (A) to (D): (A) waste water discharged in the PHA production process; , (B) a pretreatment filtration step in which the treated water obtained in the step (A) is pretreated and filtered by a membrane separation activated sludge method, (C ) an alkali treatment step in which the treated water obtained in the step (B) is treated with an alkali; and (D) a filtering step in which the treated water obtained in the step (C) is filtered through an ion removal membrane.
• Membrane filtration is a typical wastewater recycling method.
• the membrane filtration method can cause fouling (clogging) due to fine and sticky suspensions in the waste water. Therefore, the membrane must be operated with repeated washings.
• there are two known methods for cleaning membranes (1) physical cleaning, typically back pressure cleaning in which filtered water flows from the permeation side (secondary side), and (2) chemical cleaning using chemicals. ing.
• the present inventors conducted extensive studies with the aim of providing a method for producing recycled water that does not require chemical cleaning in order to extend the usable period of the membrane, and as a result, found the following findings.
• Certain metal ions cause irreversible fouling of membranes.
• the treated water is subjected to an alkali treatment step to precipitate the specific fouling substances contained in the treated water as solids in advance, thereby removing the ions.
• an alkali treatment step to precipitate the specific fouling substances contained in the treated water as solids in advance, thereby removing the ions.
• To be able to suppress irreversible fouling on the removal film. ⁇ By carrying out the alkali treatment process for the treated water before performing the filtration process using the ion removal membrane, fouling of the membrane can be eliminated only by washing with water.
• the method of manufacturing recycled water which includes the characteristic steps described above, has never existed before and is an extremely superior technology.
• the present inventor produced PHA using the recycled water obtained by the above production method, and surprisingly succeeded in obtaining PHA with high thermal stability.
• the present invention will be described in detail below.
• substantially only water washing may be used as long as water washing is the main washing mode, and does not preclude including other washing modes in addition to water washing.
• substantially only water cleaning may include chemical cleaning in addition to water cleaning, using a smaller amount than usual.
• only water washing is intended.
• Anaerobic treatment and aerobic treatment by microorganisms are not particularly limited, and can be performed by general methods used in water treatment.
• Anaerobic treatment for example, decomposes high-molecular-weight carbohydrates, lipids, etc. into organic acids, lower alcohols, etc. by the action of acid-producing bacteria, and then converts them into organic acids, lower alcohols, etc. by the action of granular methanogens. etc. may be decomposed into methane gas and carbon dioxide gas.
• the anaerobic treatment apparatus can be composed of, for example, an acidification tank in which the acidogenic bacteria react and an EGSB-type methanogenic reaction tank in which the methanogenic bacteria react.
• Step (B) The step (B) in the present production method is a pretreatment filtration step in which the treated water obtained in the step (A) is pretreated and filtered by a membrane separation activated sludge method.
• the step (B) it is possible to remove the large particle size substances contained in the waste water which are not decomposed in the step (A).
• the pretreatment filtration process by the membrane separation activated sludge method is not particularly limited, and can be performed by a general method used in water treatment.
• a UF membrane or MF membrane bioreactor membrane separation activated sludge method osmosis membrane (MBR) is installed in an aeration tank (activated sludge treatment tank) or a reaeration tank (activated sludge treatment tank). This can be done in a well-equipped device.
• the membrane pores of the MF membrane are not particularly limited, but may be, for example, about 0.4 ⁇ m. Also, the membrane pores of the UF membrane are not particularly limited, but may be, for example, about 0.05 ⁇ m.
• step (C) when the alkali treatment in step (C) is not performed, the salt concentration of the water that does not permeate the membrane increases in the filtration step using the membrane in step (D), and as a result, crystals form on the surface of the ion removal membrane. Precipitate. If the filtration is continued, the precipitation of crystals is repeated, so that the crystals grow and adhere firmly to the ion removal membrane, clogging the membrane. Therefore, in the conventional technique, it is necessary to remove crystals adhering to the film surface by chemical cleaning. However, by carrying out the alkali treatment in step (C), crystals are precipitated before filtration through the membrane, so that the crystals do not adhere firmly to the membrane.
• the method of carrying out the alkali treatment in step (C) is not particularly limited as long as it is a method capable of adjusting each parameter of the treated water to a desired value. From the viewpoint of facilitating adjustment of each parameter, the alkali treatment is preferably carried out by adding an alkaline aqueous solution.
• the pH of the treated water is preferably adjusted to 7.0 to 11.0, more preferably 8.0 to 11.0, and adjusted to 8.5 to 11.0. is more preferred. If the pH is 7.0 or higher, metal salts will precipitate in the treated water. Also, if the pH is 11.0 or less, deterioration of the ion removal membrane can be prevented.
• the turbidity of the treated water is preferably 0.1 or higher, more preferably 0.2 or higher, and even more preferably 0.3 or higher. If the turbidity is 0.1 or more, the solid content is sufficiently precipitated. Moreover, the upper limit of the turbidity of the treated water is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less. If the turbidity is 30 or less, it does not interfere with the filtration of treated water. The turbidity of the treated water is measured by the method described in Examples below.
• the FI value of the treated water is preferably 4.5 or more, more preferably 5.0 or more, even more preferably 5.5 or more, and 6.0 or more. It is particularly preferred that it is at least 6.5, and more preferably at least 6.5. If the FI value is within the above range, the solid content is sufficiently precipitated in the treated water.
• the upper limit of the FI value is not particularly limited.
• the "FI value" is derived by the following formula (1).
• PF indicates the blockage factor
• T1 indicates the time required for 500 mL of treated water to permeate the ion removal membrane
• T2 indicates that after T1 is measured, another 500 mL of treated water is treated with the same ion. The time required to permeate the removal membrane is shown. Also, T indicates the time from the time when the measurement of T1 is started to the time when the measurement of T2 is started.
• the method for precipitating the solid is not particularly limited, but it can be carried out, for example, by pH adjustment, concentration, temperature control, and the like.
• said multiply charged ions are Si 2+ , Ca 2+ , PO 4 2 ⁇ , SO 4 2 ⁇ , Mg 2+ , Mn 2+ , Zn 2+ , Fe 2+ , Fe 3+ , Sr 2+ , Cu 2+ , Al 3+ , and Sn 3+ .
• monovalent ions such as Na + , K + , and NH 4+
• anions such as Cl ⁇ and NO 3 ⁇
• the polyvalent ions have low solubility in water and tend to precipitate as solids, which can cause fouling of the ion removal membrane.
• the present production method preferably further includes the following step (C'').
• the method for sedimentation and removal of precipitated solids is not particularly limited, but it can be carried out, for example, by using a centrifugal sedimentation machine, a thickener, or the like.
• a scale inhibitor may be added when performing step (C). Addition of the scale inhibitor makes it more difficult for crystals to grow on the surface of the ion removal film.
• Usable scale inhibitors are not particularly limited, but examples thereof include Genesys LF (manufactured by Genesys), PC-191T (manufactured by Katayama Nalco), Kuriverta N series (manufactured by Kurita Water Industries) and the like.
• the amount of the scale inhibitor to be added is not particularly limited, but may be, for example, 1 to 50 ppm.
• Step (D) The step (D) in this production method is a filtration step of filtering the treated water obtained in the step (C) with an ion removal membrane.
• the step (D) can remove the solid matter deposited in the step (C).
• the treated water that has passed through the step (D) becomes recycled water.
• recycled water means water that can be used for PHA production, which is obtained by performing the steps (A) to (D) on the wastewater discharged in the PHA production process. intended to
• the ion-removing membrane in step (D) preferably has a MgSO 4 blocking rate of 60 to 100%, more preferably 70 to 100%, and 90 to 100% at 20° C. under a pressure of 3000 kPa. is more preferred. If the MgSO4 rejection is 60% or more, the ion permeability of the ion removal membrane will not be high. Further, when the obtained recycled water is used for refining PHA, the decrease in molecular weight at high temperatures is likely to be suppressed.
• the transmembrane pressure difference of the ion removal membrane in step (D) is not particularly limited, it is preferably 0.4 MPa to 4.14 MPa, more preferably 0.5 MPa to 2.5 MPa, from the viewpoint of ion removal rate. , 0.6 MPa to 2.0 MPa. If the transmembrane pressure difference is 0.4 MPa or more, the permeation water amount and the ion removal rate do not decrease, and if it is 4.14 MPa or less, the membrane is less likely to break.
• the transmembrane pressure difference of the ion removal membrane is measured by the method described in Examples below.
• the timing of cleaning the ion removal membrane is not particularly limited, but for example, it is preferably performed when the transmembrane pressure difference of the ion removal membrane reaches 4.14 MPa or more, and is performed when it reaches 2.5 MPa or more. is more preferable, and it is even more preferable to carry out when the pressure reaches 2.0 MPa or more.
• the transmembrane pressure difference of the ion removal membrane reaches 4.14 MPa or more, the ion removal membrane is washed to maintain the transmembrane pressure difference within the preferred range.
• the time for cleaning the ion removal membrane is not particularly limited as long as the transmembrane pressure difference of the ion removal membrane can be sufficiently reduced, but may be, for example, 30 minutes or longer.
• the permeation rate of the ion removal membrane in step (D) is preferably 0.01 to 2000 L/min, more preferably 0.5 to 1500 L/min. Productivity improves as permeation rate is 0.01 L/min or more. Also, if the permeation rate is 2000 L/min or less, the ion removal membrane is less likely to be damaged.
• the water temperature of the treated water during filtration in step (D) is not particularly limited, but is preferably 50°C or lower, more preferably 45°C or lower. If the water temperature of the treated water is 50° C. or less, the membrane is less likely to deteriorate. Although the lower limit of the water temperature of the treated water is not particularly limited, it is preferably 1° C. or higher from the viewpoint of smooth filtration.
• step (D) it is preferable to wash the ion removal membrane periodically in order to remove the precipitated metal salt.
• Flushing cleaning is physical cleaning in which low-pressure, high-flow water is run for the purpose of removing initial contamination of the ion removal membrane.
• the water used for flushing cleaning may be simple tap water, but from the viewpoint of efficiency and cost, it is preferable to use recycled water that has passed through an ion removal membrane.
• the pressure during flushing cleaning may be such that the primary pressure of the ion removal membrane is 0.29 MPa or less.
• the flow rate of the recycled water may be set to 6 m/min or more.
• the ion removal membrane it is preferable to use one or more selected from the group consisting of an NF membrane and an RO membrane because of its high ion (e.g., calcium ion) removal performance, and it is more preferable to use an RO membrane. .
• a method for producing a PHA according to an embodiment of the present invention comprises a step (a) of crushing or solubilizing microbial cells containing a PHA, and and a step (b) of separating PHA in the resulting composition, wherein recycled water produced by the present production method is used in said step (a) and said step (b). is a manufacturing method.
• the thermal stability of the PHA can be improved by using the recycled water produced by the production method of the present invention.
• 3-hydroxyalkanoic acids include, for example, 3-hydroxyhexanoic acid (hereinafter also referred to as "3HH"), 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxy decanoic acid, 3-hydroxyundecanoic acid, 3-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 3-hydroxytetradecanoic acid, 3-hydroxypentadecanoic acid, 3-hydroxyhexadecanoic acid and the like.
• 3HH 3-hydroxyhexanoic acid
• 3-HH 3-hydroxyheptanoic acid
• 3-hydroxyoctanoic acid 3-hydroxynonanoic acid
• decanoic acid 3-hydroxyundecanoic acid
• 3-hydroxydodecanoic acid 3-hydroxytridecanoic acid
• 3-hydroxytetradecanoic acid 3-hydroxypentadecanoic acid
• 3-hydroxyhexadecanoic acid and the like 3-hydroxyhexadecano
• poly(3-hydroxybutyric acid), poly(3-hydroxybutyric acid-co-3-hydroxyhexanoic acid), poly(3-hydroxybutyric acid-co-3 -3-hydroxyoctanoic acid) and the like are preferred, and poly(3-hydroxybutyric acid-co-3-hydroxyhexanoic acid) is particularly preferred.
• the composition ratio of each monomer unit constituting the binary copolymer PHBH of 3HB and 3HH is not particularly limited. It may be mol %, it may be 1 to 25 mol %, or it may be 1 to 15 mol %.
• the microorganism having the ability to produce PHA is not particularly limited, and is a microorganism isolated from nature or a microorganism deposited with a strain depository (e.g., IFO, ATCC, etc.), or Mutants, transformants, etc. that can be prepared from can be used.
• a strain depository e.g., IFO, ATCC, etc.
• Mutants, transformants, etc. that can be prepared from can be used.
• the genus Cupriavidus the genus Alcaligenes, the genus Ralstonia, the genus Pseudomonas, the genus Bacillus, the genus Azotobacter, the genus Nocardia, the genus Aeromonas and the like.
• strains such as A. lipolytica, A. latus, A.
• a transformant obtained by introducing a desired PHA synthase gene and/or a mutant thereof into the microorganism. can also be used.
• the PHA synthase gene used for the preparation of such a transformant is not particularly limited, but a PHA synthase gene derived from Aeromonas caviae is preferable.
• the culture method is not particularly limited, but methods such as those described in Japanese Patent Application Laid-Open No. 05-93049, International Publication No. 2008/010296, etc. can be used.
• the PHA-containing microbial cells the bacterial cell culture medium containing the PHA-containing microbial cells is used as it is after the completion of the cultivation, or the sterilized bacteria after killing the bacterial cells by heating the bacterial cell culture medium.
• Body culture fluid can be used.
• the sterilization may be performed, for example, by heat treatment at a temperature of 50-80° C. for 5-120 minutes.
• the alkaline compound is not particularly limited as long as it can destroy the cell walls of the PHA-containing microbial cells and allow the PHA in the cells to flow out of the cells.
• Examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like.
• alkali metal hydroxides alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal salts of organic acids such as sodium acetate and potassium acetate , alkali metal borates such as borax, alkali metal phosphates such as trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate and dipotassium hydrogen phosphate, alkaline earths such as barium hydroxide Metal hydroxides, aqueous ammonia and the like can be mentioned.
• sodium hydroxide, sodium carbonate, potassium hydroxide, and lithium hydroxide are preferable from the viewpoint of being suitable for industrial production and reducing costs.
• proteolytic enzymes include, but are not limited to, alcalase, pepsin, trypsin, papain, chymotrypsin, aminopeptidase, carboxypeptidase, and the like.
• Specific proteolytic enzymes include, for example, "Protease A”, “Protease P”, “Protease N” (manufactured by Amano Enzyme), “Alcalase”, “Esperase”, “Zavinase”, and “Evalase” (manufactured by Novozymes, Inc.) can be industrially used, and can be suitably used from the viewpoint of decomposition activity.
• cell wall-degrading enzymes include, but are not limited to, lysozyme, amylase, cellulase, maltase, saccharase, ⁇ -glycosinase, ⁇ -glycosinase, and the like.
• lysozyme is preferably used from the viewpoint of the bacteriolytic effect.
• Specific cell wall degrading enzymes include, for example, “Lysozyme” (manufactured by Huayuan Jingmao, Shandong province), “Biozyme A”, “Cellulase A “Amano” 3", “Cellulase T “Amano” 4", and “ ⁇ -Glucosidase.”
• “Amano” manufactured by Amano Enzymes
• “Termamil” “Cellsoft” (manufactured by Novozymes) and the like can be used industrially.
• the above-mentioned enzyme treatment is preferably carried out in the presence of a surfactant in order to obtain a high separation and purification effect.
• a surfactant for example, an enzyme composition containing an enzyme and one or more additives selected from the group consisting of an enzyme stabilizer, a surfactant, an anti-soil redeposition agent, and the like may be used. .
• Surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
• Anionic surfactants and/or nonionic surfactants are preferred from the standpoint of a high effect of removing residues due to destruction of cell membranes.
• An anionic surfactant is preferably used for the purpose of removing proteins and the like, and a nonionic surfactant is preferably used for the purpose of removing fatty acids and fats and oils.
• both anionic and nonionic surfactants can be used. When both are used, the weight ratio of the anionic surfactant/nonionic surfactant is preferably 1/100 to 100/10, more preferably 5/100 to 100/20, more preferably 5/100 to 100/100. 5/100 to 50/100 is particularly preferred.
• anionic surfactants include alkyl sulfates, alkylbenzenesulfonates, alkyl sulfates, alkenyl sulfates, alkyl ether sulfates, alkenyl ether sulfates, ⁇ -olefinsulfonates, ⁇ - Examples include sulfo fatty acid salts, esters of ⁇ -sulfo fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid type surfactants, N-acylamino acid type surfactants, and the like.
• alkyl sulfates having 12 to 14 carbon atoms in the alkyl group linear alkylbenzene sulfonates having 12 to 16 carbon atoms in the alkyl group, alkyl sulfate salts or alkyl ether sulfates having 10 to 18 carbon atoms in the alkyl group
• Ester salts are preferred, and the counterions are preferably alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, and alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
• nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyalkylene alkyl ethers, fatty acid sorbitan esters, alkyl polyglucosides, fatty acid diethanolamides, and alkyl monoglyceryl ethers.
• Polyoxyethylene alkyl ethers and polyoxyalkylene alkyl ethers are preferred because of their high hydrophilicity and relatively good biodegradability.
• amphoteric surfactants examples include carbobetaine type and sulfobetaine type.
• the amount of the surfactant to be added is not particularly limited, but is preferably 0.001 to 10 parts by weight, and more preferably 0.001 to 5 parts by weight based on 100 parts by weight of the cell culture solution. .
• One type of surfactant may be used alone, or two or more types may be used in combination.
• Enzymatic treatment is preferably carried out, for example, by adding an alkaline compound and/or a surfactant to the cell culture solution and stirring the mixture. Enzyme treatment conditions are preferably controlled under the optimum value of the enzyme used. The required amount of enzyme depends on the type and activity of the enzyme. Although not particularly limited, it is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, based on 100 parts by weight of PHA.
• the physical crushing treatment is preferably carried out after adding an alkaline compound, or an alkaline compound and a surfactant, from the viewpoint of enhancing the crushing effect and facilitating recovery of PHA.
• an alkaline compound, or an alkaline compound and a surfactant those described above can be appropriately used.
• the alkaline compounds described above sodium hydroxide, sodium carbonate, potassium hydroxide, and lithium hydroxide are preferable as the alkaline compound from the viewpoint of suitability for industrial production and cost reduction.
• the amount of the surfactant to be added is not particularly limited, but is preferably 0.001 to 10 parts by weight, and more preferably 0.001 to 5 parts by weight based on 100 parts by weight of the cell culture solution. .
• One type of surfactant may be used alone, or two or more types may be used in combination.
• the device for physical crushing is not particularly limited, but examples include a high-pressure homogenizer, an ultrasonic crusher, an emulsifying disperser, a bead mill, and the like.
• a high-pressure homogenizer is preferable from the point of crushing efficiency, and the type in which the suspension is introduced into a pressure-resistant container having a fine opening and is extruded from the opening by applying high pressure is more preferable.
• this type of crusher include a high-pressure homogenizer model "PA2K type" manufactured by Nirosoavi.
• step (a) the chemical treatment and the physical crushing treatment may be used together.
• step (a) may be performed only by physical crushing.
• Recycled water produced by this production method can be used as water in step (a).
• Recycled water can be used, for example, during the addition of surfactants, alkaline compounds, and the like.
• the recycled water it is possible to reduce the amount of water consumed, thereby reducing the cost. Also, the use of recycled water improves the thermal stability of the obtained PHA.
• the recycled water preferably has a calcium ion concentration of 4.5 mg/L or less, more preferably 3.0 mg/L or less, and even more preferably 2.0 mg/L or less.
• concentration of calcium ions in the recycled water is 4.5 mg/L or less, the effect of suppressing thermal decomposition of PHA is exhibited.
• sodium ion concentration of the recycled water is preferably 450 mg/L or less, more preferably 250 mg/L or less, and even more preferably 220 mg/L or less.
• concentration of sodium ions in the recycled water is 450 mg/L or less, the effect of suppressing thermal decomposition of PHA is exhibited.
• step (b) the PHA in the composition obtained in step (a), such as the lysate, is separated. Separation is not particularly limited, and solid-liquid separation can be performed using a method such as filtration, sedimentation, centrifugation, etc., and the PHA can be recovered from the water-insoluble components. Centrifugation is preferred from the viewpoint of industrial mass processing and continuous use.
• the centrifuge is not particularly limited, it is preferably a centrifugal sedimentator having a rotating container without holes, and examples thereof include a separating plate type, a cylindrical type, and a decanter type.
• PHA particles have a small specific gravity difference with water, so the separation plate type (intermittent discharge type, nozzle discharge type), which has a large separation sedimentation area and can obtain high acceleration, is preferable. , especially the nozzle discharge type is preferred.
• the decanter type a model having a separation plate and having a large separation sedimentation area is preferable.
• the aqueous medium may be recycled water produced by this production method, or a mixed solvent of the recycled water and a water-miscible organic solvent.
• the content of recycled water in the aqueous medium is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 85% by weight or more.
• the recycled water preferably has a calcium ion concentration of 4.5 mg/L or less, more preferably 3.0 mg/L or less, and preferably 2.0 mg/L or less. More preferred.
• concentration of calcium ions in the recycled water is 4.5 mg/L or less, the effect of suppressing thermal decomposition of PHA is exhibited.
• the sodium ion concentration of the recycled water is preferably 450 mg/L or less, more preferably 250 mg/L or less, and even more preferably 220 mg/L or less.
• the concentration of sodium ions in the recycled water is 450 mg/L or less, the effect of suppressing thermal decomposition of PHA is exhibited.
• water-miscible organic solvents include, but are not limited to, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, pentanol, hexanol, and heptanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide and acetamide; Among them, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, acetonitrile, propionitrile and the like are preferable because they are easy to remove.
• the PHA may be purified by washing the separated PHA (water-insoluble component containing PHA) with the aqueous medium described above at least once.
• the aqueous medium for example, 500 to 1000 parts by weight of the aqueous medium may be added to 100 parts by weight of the water-insoluble component containing PHA.
• alkaline compounds, surfactants, proteolytic enzymes, and the like may be added to the aqueous medium in order to effectively remove impurities derived from microbial cells and enhance the purification effect.
• the present method for producing PHA may include step (c) of drying the PHA separated in step (b).
• the PHA (dehydrated resin) washed with an aqueous medium and dehydrated can be dried as it is to obtain a powdery PHA.
• the drying method can be selected as appropriate, and is not particularly limited. For example, general drying methods such as spray drying, airflow drying, fluidized drying, and band drying can be preferably used.
• a PHA dispersion liquid washed with an aqueous medium and concentrated is added with a dispersant to adjust the pH to 7 or less, and then dried to obtain powdered PHA.
• Dispersants include, for example, polyvinyl alcohol (PVA), methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, sodium polymethacrylate and the like.
• PVA polyvinyl alcohol
• Nonionic surfactants such as polyethylene glycol/polypropylene glycol/block ether type (polyoxyethylene/polyoxypropylene/block polymer type).
• a method of adjusting the pH to 7 or less includes, for example, a method of adding an acid.
• the acid is not particularly limited, and may be either an organic acid or an inorganic acid.
• sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and the like can be used as appropriate.
• PHA has high thermal stability, and the weight average molecular weight retention rate when heat-treated at 160° C. for 20 minutes is preferably 70% or more, more preferably 73% or more, and preferably 75% or more. It is more preferably 78% or more, and particularly preferably 80% or more.
• the thermal stability of PHA is measured by the method described in Examples below.
• PHA can be molded into various molded bodies such as various fibers, threads, ropes, woven fabrics, knitted fabrics, non-woven fabrics, paper, films, sheets, tubes, plates, rods, containers, bags, parts, and foams.
• the molded article can be suitably used in agriculture, fishery, forestry, gardening, medicine, sanitary goods, clothing, non-clothing, packaging and other fields.

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