CN113828162B - Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane - Google Patents
Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/36—Hydrophilic membranes
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Abstract
The invention discloses a preparation method of a sustainable hydrophilic modified polyvinylidene fluoride hollow membrane, which comprises the following steps: (1) Co-extruding a core solution and a polyvinylidene fluoride membrane casting solution from an annular spinning nozzle of hollow fiber spinning equipment to obtain a nascent state membrane filament, wherein the core solution is formed by reacting ammonium persulfate, polyvinylpyrrolidone and RO water; (2) Spinning the nascent-state membrane filaments prepared in the step (1) by a dry-wet spinning process at 40-50 ℃ to form hollow fiber membranes, wherein the coagulating bath is water or a mixture of water and a solvent, and the hollow fiber membranes with different internal and external structures are obtained by controlling the flow rate of the core liquid, the temperature of the coagulating bath and the components of the coagulating bath; and (3) membrane silk moisturizing treatment: and (3) soaking the hollow fiber membrane obtained in the step (2) in pure water at 15-40 ℃ for at least 48h, then soaking the hollow fiber membrane in a mixed solution of water and glycerol for at least 12h, and then airing to obtain the sustainable hydrophilic modified polyvinylidene fluoride hollow membrane.
Description
Technical Field
The invention belongs to the technical field of membrane preparation, and particularly relates to a preparation method of a sustainable hydrophilic modified polyvinylidene fluoride hollow membrane.
Background
When the hollow membrane is used for water treatment, the chemical stability and hydrophilicity of the material are two most important properties. Chemical stability determines the lifetime of the material under the action of acids and bases, oxidants, microbes, etc., and it is also directly related to the method that can be taken for cleaning; the hydrophilicity determines the adsorption degree of the membrane material on organic pollutants in water, and influences the flux of the membrane. The hydrophilic substance is added in the production process of the hollow membrane, so that the surface of the membrane presents hydrophilicity in water, but once the membrane is used, the hydrophilic substance can be lost along with the use process, the hydrophilicity can be lost and become impermeable after the membrane is dried, and the hollow membrane wires become brittle and are easy to break and damage. In the research of the last years, substances such as glycerin, a surfactant, a preservative, a hydrophilic agent, RO water and the like are often added into a post-treatment liquid to keep membrane filaments moist so as to maintain the wettability of the membrane filaments to keep the flux, and the treatment process is complex but cannot keep the hydrophilicity of the membrane filaments permanently.
The polyvinylpyrrolidone can be used as a pore-forming agent and a hydrophilic additive to play an important role in a membrane formula, but the polyvinylpyrrolidone is very easy to dissolve in water, and the polyvinylpyrrolidone can slowly run off in the use process of the membrane, so that the membrane has poor hydrophilicity and low pollution resistance, and the research on an effective retention method of the polyvinylpyrrolidone is particularly important.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a sustainable hydrophilic modified polyvinylidene fluoride hollow membrane.
The technical scheme of the invention is as follows:
a preparation method of a sustainable hydrophilic modified polyvinylidene fluoride hollow membrane comprises the following steps:
(1) Co-extruding a core solution and a polyvinylidene fluoride membrane casting solution from an annular spinning nozzle of hollow fiber spinning equipment, and obtaining a nascent state membrane filament after a dry process of 5-15cm, wherein the core solution is formed by the reaction of ammonium persulfate, polyvinylpyrrolidone and RO water;
(2) Spinning the nascent state membrane filaments prepared in the step (1) by a dry-wet spinning process at 40-50 ℃ to form a hollow fiber membrane, wherein a coagulating bath is water or a mixture of water and a solvent, and the hollow fiber membranes with different internal and external structures are obtained by controlling the flow rate of a core solution, the temperature of the coagulating bath and the components of the coagulating bath;
(3) Membrane silk moisturizing treatment: and (3) soaking the hollow fiber membrane obtained in the step (2) in pure water at 15-40 ℃ for at least 48h, then soaking the hollow fiber membrane in a mixed solution of water and glycerol for at least 12h, and then airing to obtain the sustainable hydrophilic modified polyvinylidene fluoride hollow membrane.
In a preferred embodiment of the invention, the mass percentages of the components in the bore fluid are as follows: 10-30% of ammonium persulfate, 9-11% of polyvinylpyrrolidone and RO water to 100%.
Further preferably, the preparation method of the bore fluid comprises the following steps: mixing ammonium persulfate, polyvinylpyrrolidone and RO water, heating to 85-95 ℃ for crosslinking reaction for 6-10h, and cooling to 40-50 ℃ to obtain the catalyst.
In a preferred embodiment of the invention, the polyvinylidene fluoride casting solution consists of the following components in percentage by weight:
further preferably, the inorganic nanoparticles are at least one of nano-silica, nano-titania, nano-alumina and nano-silver antibacterial master batches.
Further preferably, the organic hydrophilic pore-forming agent is at least one of polyethylene oxide, polyethylene glycol and polyvinylpyrrolidone.
Further preferably, the surfactant is at least one of tween, OP phosphate, alkylphenol ethoxylate, nonylphenol ethoxylate and ammonium salt of polyoxyethylene alkylbenzene sulfonate.
Further preferably, the organic solvent is at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone and triethyl phosphate.
In a preferred embodiment of the present invention, the content of glycerin in the mixed solution of water and glycerin is 10 to 35% by mass.
In a preferred embodiment of the invention, the polyvinylpyrrolidone is of type K-30 or K90.
The invention has the beneficial effects that: according to the invention, the hydrophilic cross-linking liquid formed by the reaction of ammonium persulfate and polyvinylpyrrolidone is used as the core liquid, so that a hydrophilic layer which is not easy to fall off is formed inside the membrane filament, the loss of the hydrophilic additive caused by the washing of water flow in the use process of the membrane filament is avoided, and the polyvinylidene fluoride membrane hollow membrane with sustainable hydrophilicity is formed, thus the purpose of sustainable recovery of flux is achieved, the flux and pollution resistance of the membrane filament are improved, and the application field of the membrane is greatly widened.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Comparative example 1
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core liquid and the external coagulating bath are both RO water with the temperature of 45 ℃, the casting film liquid passes through a filter screen, is extruded out by a spinning nozzle together with the core liquid, runs for 12cm in air, enters the external coagulating bath for forming, and is wound by a winding wheel. Soaking the polyvinylidene fluoride hollow fiber membrane in pure water (room temperature 15-35 ℃) for 48 hours, then continuing soaking in glycerol water (the mass percentage of glycerol is 20%) for 12 hours, measuring the initial flux of the pure water of the hollow fiber membrane at 25 ℃ to be 350L/m < 2 >. H (0.1 MPa), and continuously repeating the water drying for 10 times to obtain the flux of 68L/m < 2 >. H (0.1 MPa) 2 H (0.1 MPa), flux recovery: 19.4 percent.
Comparative example 2
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core liquid is a 30% glycerol water mixed solution at 45 ℃, the outer coagulation bath is RO water at 45 ℃, the casting film liquid passes through a filter screen, is extruded out by a spinning nozzle together with the core liquid, travels for 12cm in air, enters the outer coagulation bath for forming, and is wound by a winding wheel. The polyvinylidene fluoride hollow fiber membrane obtained by the method is soaked in pure water (room temperature 15-35 ℃) for 48 hours, and then is soaked in glycerol water(the mass percentage of the glycerol is 25%) for 12h, the outer diameter of the obtained polyvinylidene fluoride hollow fiber membrane is 1.3mm, the inner diameter is 0.8mm, the porosity is 36%, the initial flux of pure water of the hollow fiber membrane is measured to be 420L/m < 2 >. H (0.1 MPa) at 25 ℃, and the flux is 85L/m < 2 >. H (0.1 MPa) after 10 times of repeated water drying 2 H (0.1 MPa), flux recovery: 20.2 percent.
Comparative example 3
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core liquid is a mixed solution of 40% dimethylacetamide at the temperature of 45 ℃, the outer coagulation bath is RO water at the temperature of 45 ℃, the casting film liquid passes through a filter screen, is extruded out together with the core liquid by a spinning nozzle, runs for 12cm in air, enters the outer coagulation bath for forming, and is wound by a winding wheel. Soaking the polyvinylidene fluoride hollow fiber membrane in pure water (room temperature 15-35 ℃) for 48 hours, then continuing soaking in glycerol water (the mass percentage of glycerol is 30%) for 12 hours, measuring the initial flux of the pure water of the hollow fiber membrane at 25 ℃ to be 460L/m < 2 >. H (0.1 MPa), and continuously repeating the water drying for 10 times to obtain the flux of 92L/m < 2 >. H (0.1 MPa) 2 H (0.1 MPa), flux recovery: 20.0 percent.
Comparative example 4
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core liquid is a cross-linking liquid prepared by reacting 30 mass percent of ammonium persulfate with 10 mass percent of polyvinylpyrrolidone K30 at 80 ℃ for 6 hours, and the temperature of the core liquid is 45 ℃ when the core liquid is used. And after passing through a filter screen, the membrane casting solution and core solution are extruded together by a spinning nozzle, and after the membrane casting solution and the core solution travel for 12cm in the air, the membrane casting solution enters an external coagulating bath for forming and is wound by a winding wheel. The polyvinylidene fluoride hollow fiber membrane obtained by the method is soaked in pure water (room temperature is 15-35 ℃) for 48 hours, and then is relayed in glycerol water (the mass percentage of the glycerol is 20 percent)Soaking for 12h, wherein the outer diameter of the obtained polyvinylidene fluoride hollow fiber membrane is 1.3mm, the inner diameter is 0.8mm, the porosity is 76%, the initial flux of pure water of the hollow fiber membrane is 880L/m < 2 >. H (0.1 MPa) at 25 ℃, and the flux is 669L/m after continuous 10-time repeated water drying 2 H (0.1 MPa), flux recovery: 76.0 percent.
Comparative example 5
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the temperature at 70 ℃, standing and defoaming for 24 hours; the core liquid is a cross-linking liquid prepared by reacting 8 mass percent of ammonium persulfate and 10 mass percent of polyvinylpyrrolidone K30 at 90 ℃ for 6 hours, and the temperature of the core liquid is 45 ℃ when the core liquid is used. And after passing through a filter screen, the membrane casting solution and core solution are extruded together by a spinning nozzle, and after the membrane casting solution and the core solution travel for 12cm in the air, the membrane casting solution enters an external coagulating bath for forming and is wound by a winding wheel. Soaking the polyvinylidene fluoride hollow fiber membrane in pure water (room temperature 15-35 ℃) for 48 hours, then continuously soaking in glycerol water (the mass percentage of glycerol is 20%) for 12 hours, measuring the initial flux of the pure water of the polyvinylidene fluoride hollow fiber membrane at 25 ℃ to be 520L/m < 2 >. H (0.1 MPa), and measuring the initial flux of the pure water of the hollow fiber membrane to be 257L/m < 2 >. H (0.1 MPa) after 10 times of repeated water drying continuously 2 H (0.1 MPa), flux recovery: 46.0 percent.
Comparative example 6
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core liquid is a cross-linking liquid prepared by reacting 31 mass percent of ammonium persulfate and 10 mass percent of polyvinylpyrrolidone K30 at 90 ℃ for 6 hours, and the temperature of the core liquid is 45 ℃ when the core liquid is used. And after passing through a filter screen, the membrane casting solution and core solution are extruded together by a spinning nozzle, and after the membrane casting solution and the core solution travel for 12cm in the air, the membrane casting solution enters an external coagulating bath for forming and is wound by a winding wheel. The polyvinylidene fluoride hollow fiber membrane obtained by the method is soaked in pure water (room temperature 15-35 ℃) for 48 hours and then is soaked in glycerolSoaking in water (20 wt% of glycerol) for 12 hr to obtain polyvinylidene fluoride hollow fiber membrane with outer diameter of 1.3mm, inner diameter of 0.8mm and porosity of 86%, and measuring pure water initial flux of 1109L/m 2. H (0.1 MPa) at 25 deg.C, and flux of 998/m after water drying for 10 times 2 H (0.1 MPa), flux recovery: 90.0 percent.
Comparative example 5
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core liquid is a cross-linking liquid which is prepared by reacting 30 mass percent of ammonium persulfate with 10 mass percent of polyvinylpyrrolidone K30 at 100 ℃ for 6 hours, the temperature of the core liquid is 45 ℃ when the spinning solution is used, the casting film liquid passes through a filter screen, is extruded out from a spinning nozzle together with the core liquid, travels 12cm in air, enters an external coagulation bath for molding, and is wound by a winding wheel. Soaking the polyvinylidene fluoride hollow fiber membrane in pure water (room temperature 15-35 ℃) for 48 hours, then continuing soaking in glycerol water (the mass percentage of glycerol is 20%) for 12 hours, measuring the initial flux of the pure water of the hollow fiber membrane at 25 ℃ to be 960L/m < 2 >. H (0.1 MPa), and continuously repeating the water drying for 10 times to obtain the flux of 768L/m < 2 >. H (0.1 MPa) 2 H (0.1 MPa), flux recovery: 80.0 percent.
Example 1
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core solution is a cross-linking solution which is prepared by reacting 10 mass percent of ammonium persulfate with 10 mass percent of polyvinylpyrrolidone K30 at 85 ℃ for 6 hours, when the spinning solution is used, the temperature of the core solution is 45 ℃, the external coagulation bath is RO water at 45 ℃, the casting film solution is extruded out from a spinning nozzle together with the core solution after passing through a filter screen, and after the spinning solution travels 12cm in the air, the spinning solution enters the external coagulation bath for molding and is wound by a winding wheel. Thus obtained polyvinylidene fluorideSoaking an olefin hollow fiber membrane in pure water (room temperature 15-35 ℃) for 48 hours, then continuing soaking in glycerol water (the mass percentage of glycerol is 10-35%) for 12 hours, measuring the initial flux of the pure water of the hollow fiber membrane at 25 ℃ to be 1169L/m < 2 >. H (0.1 MPa), and measuring the flux after 10 times of repeated water drying to be 1052L/m < 2 >. H (0.1 MPa) 2 H (0.1 MPa), flux recovery: 90.0 percent.
Example 2
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the stirring temperature at 70 ℃, standing and defoaming for 24 hours; the core solution is a cross-linking solution which is prepared by reacting 30 mass percent of ammonium persulfate and 10 mass percent of polyvinylpyrrolidone K30 at 85 ℃ for 6 hours, when the spinning solution is used, the temperature of the core solution is 45 ℃, the external coagulation bath is RO water at 45 ℃, the casting film solution is extruded out from a spinning nozzle together with the core solution after passing through a filter screen, and after the spinning solution travels 12cm in the air, the spinning solution enters the external coagulation bath for molding and is wound by a winding wheel. Soaking the obtained polyvinylidene fluoride hollow fiber membrane in pure water (room temperature 15-35 ℃) for 48 hours, then continuing soaking in glycerol water (the mass percentage of glycerol is 10-35%) for 12 hours, measuring the initial flux of the pure water of the hollow fiber membrane at 25 ℃ to be 1698L/m 2. H (0.1 MPa), and the flux after 10 times of continuous repeated water drying is 1630L/m 2 H (0.1 MPa), flux recovery: 96.0 percent.
Example 3
Under high-speed stirring, dissolving 100g of silicon dioxide and 80g of Tween-20 in 7220g of dimethylacetamide, uniformly stirring, adding 1800g of polyvinylidene fluoride powder and 800g of polyvinylpyrrolidone K-30, uniformly stirring and dissolving, keeping the temperature at 70 ℃, standing and defoaming for 24 hours; the core solution is a cross-linking solution prepared by reacting 15 mass percent of ammonium persulfate and 10 mass percent of polyvinylpyrrolidone K30 at 90 ℃ for 6 hours, when the composite material is used, the temperature of the core solution is 45 ℃, the external coagulation bath is RO water at 45 ℃, and after the membrane casting solution passes through a filter screen, the membrane casting solution and the core solution are processed by a spinning jet together through the filter screenExtruding, traveling in air for 12cm, entering an outer coagulating bath for forming, and winding by a winding wheel. Soaking the polyvinylidene fluoride hollow fiber membrane in pure water (room temperature 15-35 ℃) for 48 hours, then continuing soaking in glycerol water (the mass percentage of glycerol is 25%) for 12 hours, measuring the initial flux of the pure water of the hollow fiber membrane at 25 ℃ to be 1230L/m 2.h (0.1 MPa), and continuously repeating the water drying for 10 times to obtain the flux of 1252L/m 2 H (0.1 MPa), flux recovery: 93..6 percent.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, and all equivalent variations and modifications made within the scope of the present invention and the content of the description should be included in the scope of the present invention.
Claims (7)
1. A preparation method of a sustainable hydrophilic modified polyvinylidene fluoride hollow membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) Co-extruding a core solution and a polyvinylidene fluoride membrane casting solution from an annular spinning nozzle of hollow fiber spinning equipment, and obtaining a nascent state membrane filament after a dry process of 5-15cm, wherein the core solution is formed by reacting ammonium persulfate, polyvinylpyrrolidone and RO water, and the core solution comprises the following components in percentage by mass: 10-30% of ammonium persulfate, 9-11% of polyvinylpyrrolidone and 100% of RO water; the preparation method of the core liquid comprises the following steps: mixing ammonium persulfate, polyvinylpyrrolidone and RO water, heating to 85-95 ℃ for crosslinking reaction for 6-10h, and cooling to 40-50 ℃ to obtain the composite material; the polyvinylidene fluoride casting solution comprises the following components in percentage by weight:
polyvinylidene fluoride 15-30%
0.5 to 5 percent of inorganic nano particles
1 to 12 percent of organic hydrophilic pore-forming agent
0.05 to 3 percent of surfactant
Supplementing organic solvent to 100%;
(2) Spinning the nascent-state membrane filaments prepared in the step (1) by a dry-wet spinning process at 40-50 ℃ to form hollow fiber membranes, wherein the coagulating bath is water or a mixture of water and a solvent, and the hollow fiber membranes with different internal and external structures are obtained by controlling the flow rate of the core liquid, the temperature of the coagulating bath and the components of the coagulating bath;
(3) Membrane silk moisturizing treatment: and (3) soaking the hollow fiber membrane obtained in the step (2) in pure water at 15-40 ℃ for at least 48h, then soaking the hollow fiber membrane in a mixed solution of water and glycerol for at least 12h, and then airing to obtain the sustainable hydrophilic modified polyvinylidene fluoride hollow membrane.
2. The method of claim 1, wherein: the inorganic nano particles are at least one of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide and nano silver series antibacterial master batches.
3. The method of claim 1, wherein: the organic hydrophilic pore-forming agent is at least one of polyethylene oxide, polyethylene glycol and polyvinylpyrrolidone.
4. The method of claim 1, wherein: the surfactant is at least one of tween, OP phosphate, alkylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether and polyoxyethylene alkyl benzene sulfonic acid ammonium salt.
5. The method of claim 1, wherein: the organic solvent is at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone and triethyl phosphate.
6. The method of claim 1, wherein: the mass content of the glycerol in the mixed liquid of the water and the glycerol is 10-35%.
7. The production method according to any one of claims 1 to 6, characterized in that: the polyvinyl pyrrolidone is K-30 or K90.
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