CN103143267B - The preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane - Google Patents
The preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane, comprise: polysulfones, polyurethane, polyvinyl chloride, additive and solvent add in reactor by (1), at 40-90 DEG C, dissolve and be uniformly mixed 6-48 hour, obtain casting solution; (2) casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously; (3) through the air section evaporation between spinning head and coagulating bath and drawing-off, enter in coagulating bath and realize gel solidification, obtain hollow fiber separating film; (4) hollow fiber separating film with self-supporting layer is obtained after cleaning.The advantages such as filming technology of the present invention has reliable and stable, easy to implement, and cost of manufacture is low; The hollow fiber separating film manufactured, has good resistance tocrocking, hydrophily, pliability, high water flux, high compressive strength, is applicable to the application of the industrial circles such as water treatment, wastewater treatment, concentrating and separating.
Description
Technical field
The invention belongs to the preparation field of hollow fiber separating film, particularly a kind of preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane.
Background technology
Membrane separation technique is as a kind of novel isolation technics, and owing to having environmental protection, energy-conservation, without phase transformation, the feature such as simple to operate, its application is throughout fields such as petrochemical industry, biological medicine, electricity power, municipal water treatment, waste water recyclings.Hollow fiber separating film is high owing to having packed density, back-washable, the features such as low cost of manufacture, and the service life of film is significantly enhanced, and investment cost also significantly reduces.But hollow fiber separating film great majority used at present adopt cellulose acetate, polysulfones, polyvinyl chloride, polyether sulfone, Kynoar, polyacrylonitrile, the single such as polyvinyl chloride or two kinds of high polymer materials are made, because often kind of high polymer material has the limitation of self performance, such as the cellulose acetate PH scope of application is narrow, polysulfones endurance life is poor, Kynoar hydrophily difference is expensive, polyacrylonitrile is easily aging, the shortcomings such as polyvinyl chloride fragility height easily shrinks into ridges, in use effect is bad to cause film, cost performance is not high, life-span is short, limit it to apply widely.
As everyone knows, it is blended etc. that the method changing membrane material character comprises copolymerization, grafting, membrane surface modification and membrane material.Wherein blended owing to having, membrane material range of choice is wide, compatibility is easy to adjust, be easy to the advantages such as processing and be with a wide range of applications for membrane material.By selecting the polyblend of different hydrophilic, the hydrophily of film can be changed, improving the permeability and separation performance of film.By selecting the polymeric material that mechanical property is good blended, the mechanical strength of film can be changed.By selecting the polymeric material that heat resistance is good blended, the heat resistance of film can be changed.
Summary of the invention
The advantages such as technical problem to be solved by this invention is to provide a kind of preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane, and this filming technology has reliable and stable, easy to implement, and cost of manufacture is low; The polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane manufactured, has good resistance tocrocking, hydrophily, pliability, high water flux, high compressive strength, is applicable to the application of the industrial circles such as water treatment, wastewater treatment, concentrating and separating.
The preparation method of a kind of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane of the present invention, comprising:
(1) by weight percentage, 1.5-22% polysulfones, 0.5-4% polyurethane, 1.5-16% polyvinyl chloride, 15-25% additive and 50-80% solvent are added in reactor, at 40-90 DEG C, dissolve and be uniformly mixed 6-48 hour, obtain casting solution;
(2) above-mentioned casting solution is extruded under 0.1-0.5MPa pressure the exit orifice entering diplopore spinning head, core liquid is extruded under 0.05-0.2MPa pressure the endoporus core liquid pipe entering diplopore spinning head, casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously;
(3) through the air section evaporation between spinning head and coagulating bath and drawing-off, enter in coagulating bath and realize gel solidification, obtain hollow fiber separating film;
(4) hollow fiber separating film of self-supporting layer is obtained having after being cleaned by above-mentioned hollow fiber separating film.
The inherent viscosity of the polysulfones in described step (1) is 0.45-0.7.
Polyurethane in described step (1) is thermoplastic polyurethane.
The average degree of polymerization of the polyvinyl chloride in described step (1) is 1000-3000.
Additive in described step (1) be polyvinylpyrrolidone, polyvinyl alcohol, propane diols, glycerine, lithium chloride, lithium nitrate, polyethylene glycol to isooctyl phenyl ether, polyethylene glycol, triethylene glycol one or more.
Solvent in described step (1) is dimethyl formamide, dimethylacetylamide, one or more of dimethyl sulfoxide (DMSO), triethyl phosphate, 1-METHYLPYRROLIDONE, sulfolane, glyceryl triacetate.
Core liquid component in described step (2) is deionized water.
Coagulating bath component in described step (3) is deionized water, and temperature is 10 ~ 45 DEG C.
Spinning head in described step (3) and the air section evaporation time between coagulating bath are 0.01 second-0.3 second.
Hollow fiber separating film in described step (4) is inside and outside pair of cortex construction, and the supporter of film section is double-deck finger-like pore structure therebetween, and diffusion barrier nominal pore size is 0.008-0.3 micron, porosity 65-85%, pure water flux 280-1700L/h.m
2..25 DEG C .1bar.
Different from way in the past, the present invention combines the necessary factor such as resistance tocrocking, hydrophily, physicochemical stability, mechanical strength, pliability of the required film improved of hollow fiber separating film of a manufacture function admirable, on the basis of fully experiment and industry test and even industrial applications, disclose the manufacture method of the liquid phase blending type hollow fiber separating film containing three kinds of high polymer materials.
The present invention adopts polysulfones, polyurethane, the liquid phase of polyvinyl chloride three kinds of membrane materials is blended, the intermolecular force of three kinds of components is greater than the system of one pack system, the diffusion barrier structure formed is finer and close, polysulfones, polyurethane, polychloroethylene blended membrane material have accumulated high strength toughness and the resistance to ag(e)ing of polysulfones, the hydrophily of polyurethane and elasticity, the advantages such as the rigidity of polyvinyl chloride, for the present invention adopts the manufacture of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane to create essential condition, ensure that the blended hollow fiber separating film of manufacture has good resistance to ag(e)ing, resistance tocrocking, hydrophily, pliability, high water flux, high compressive strength, overcome the deficiency in single membrane material and two kinds of blended membrane material performances.
In hollow fiber separating film film forming procedure, casting solution and core liquid are extruded from spinning nozzle, to evaporate in short-term through the carrying out of the air section of the spacing of spinning head and coagulating bath, evaporation time is 0.01 second-0.3 second, after the drawing-off same period reaches required size, in rapid immersion coagulating bath (non-solvent bath), sovent diffusion exchanges in coagulating bath and core liquid, but not sovent diffusion exchanges to inside and outside nascent hollow fiber film, the diffusion of solvent and solidification liquid (non-solvent) exchanges two surfaces inside and outside nascent doughnut and occurs simultaneously, and interact and affect the final structure of film.
Additive is intended to change the interaction in casting solution between each component, thus changes the desolvated speed of adjustment and mechanism, to realizing membrane structure and the performance of expectation.The kind of additive, molecular size range, consumption, all can affect the size of pore effect and water flux; Such as, when polyvinylpyrrolidone is additive, fiber cross sections morphosis micropore is fine and close, and such as, when polyvinyl alcohol is additive, the surface micropore of generation is more tiny.By the screening of additive types, quantity, good pore effect can be reached.
In sum, three kinds of membrane materials and the solvent liquid phase of the present invention's employing are blended, and dry-jet wet-spinning, additive stripping pore-creating, removes dried up freezing film, and the filming technology of cleaning treatment has reliable and stable, easy to implement, the advantages such as cost of manufacture is low.
beneficial effect
The advantages such as filming technology of the present invention has reliable and stable, easy to implement, and cost of manufacture is low; The polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane manufactured, has good resistance tocrocking, hydrophily, pliability, high water flux, high compressive strength, is applicable to the application of the industrial circles such as water treatment, wastewater treatment, concentrating and separating.
Accompanying drawing explanation
Fig. 1 is the spinning head structural representation with diplopore nozzle of the present invention;
Fig. 2 is the Electronic Speculum photograph in hollow fiber separating film cross section of the present invention;
Fig. 3 is the Electronic Speculum photograph of hollow fiber separating film partial cross-section of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Raw material is taken by following weight percents, the trade mark that Dalian polysulfone plastic Co., Ltd produces be P7304(inherent viscosity is 0.45) polysulfone resin 1.75%, the trade mark that Dajie Chemical Co., Ltd., Tianjin produces is the Corvic 13.5% of DG-1000, the trade mark that Yantai Wanhua Polyurethane Co., Ltd produces is the TPU 1.75% of WHT-14, the trade mark that Boai Xinkaiyuan Pharmacy stock Co., Ltd produces is the polyvinylpyrrolidone 12% of K-30, the trade mark that Anhui Wanwei New High-tech Materials Co., Ltd produces is the polyvinyl alcohol 8% of 1788, the dimethyl formamide 63% that special amine water chestnut sky (Nanjing) Fine Chemical Co., Ltd produces, above-mentioned substance is thrown in reactor in order, stir 48 hours at 90 DEG C of temperature, obtain casting solution.Natural standing and defoaming 12 hours at 80 DEG C of temperature, maintenance casting solution 80 DEG C, 0.5MPa extrude the exit orifice entering the spinning head with diplopore nozzle, core liquid extrudes the endoporus core liquid pipe entering diplopore spinning head under 0.1MPa pressure, and the component of core liquid is 100% deionized water, and water temperature is 45 DEG C; Casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously.The casting solution of ejection is after the air section evaporation of 0.15 second between spinning head and coagulating bath and drawing-off reach institute's phase size; Enter in coagulating bath, the component of coagulating bath is 100% deionized water, and water temperature is 45 DEG C; Then be wound on wire wrapping wheel and cut bunchy; Then hollow fiber separating film obtains the hollow fiber separating film with self-supporting layer after carrying out abundant washed with de-ionized water.The hollow fiber separating film obtained thus is inside and outside pair of cortex construction, and the supporter of film section is double-deck finger-like pore structure therebetween, film external diameter 1.5 millimeters, internal diameter 0.85 millimeter, 0.03 micron, diffusion barrier nominal pore size, porosity 75%, pure water flux 510L/h.m
2.25 DEG C .1bar.
Embodiment 2
By manufacture method and condition described in embodiment 1, casting solution takes raw material by following weight percents, the trade mark that Dalian polysulfone plastic Co., Ltd produces be P7304(inherent viscosity is 0.5) polysulfone resin 1.67%, the trade mark that Dajie Chemical Co., Ltd., Tianjin produces is the Corvic 11.66% of DG-1000, the trade mark that Yantai Wanhua Polyurethane Co., Ltd produces is the TPU 1.67% of WHT-14, the trade mark that Boai Xinkaiyuan Pharmacy stock Co., Ltd produces is the polyvinylpyrrolidone 15% of K-30, the trade mark that Anhui Wanwei New High-tech Materials Co., Ltd produces is the polyvinyl alcohol 5% of 1788, the dimethyl formamide 65% that special amine water chestnut sky (Nanjing) Fine Chemical Co., Ltd produces, above-mentioned substance is thrown in reactor in order, stir 6 hours at 80 DEG C of temperature, obtain casting solution.Natural standing and defoaming 12 hours at 70 DEG C of temperature, maintenance casting solution 70 DEG C, 0.1MPa extrude the exit orifice entering the spinning head with diplopore nozzle, core liquid extrudes the endoporus core liquid pipe entering diplopore spinning head under 0.2MPa pressure, and the component of core liquid is 100% deionized water, and water temperature is 10 DEG C; Casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously.The casting solution of ejection is after the air section evaporation of 0.3 second between spinning head and coagulating bath and drawing-off reach institute's phase size; Enter in coagulating bath, the component of coagulating bath is 100% deionized water, and water temperature is 10 DEG C; Then be wound on wire wrapping wheel and cut bunchy; Then hollow fiber separating film obtains the hollow fiber separating film with self-supporting layer after carrying out abundant washed with de-ionized water.The hollow fiber separating film obtained thus is inside and outside pair of cortex construction, and the supporter of film section is double-deck finger-like pore structure therebetween, film external diameter 1.5 millimeters, internal diameter 0.85 millimeter, 0.08 micron, diffusion barrier nominal pore size, porosity 80%, pure water flux 732L/h.m
2.25 DEG C .1bar.
Embodiment 3
By manufacture method and condition described in embodiment 1, casting solution takes raw material by following weight percents, the trade mark that Dalian polysulfone plastic Co., Ltd produces be P7304(inherent viscosity is 0.6) polysulfone resin 1.11%, the trade mark that Dajie Chemical Co., Ltd., Tianjin produces is the Corvic 7.78% of DG-1000, the trade mark that Yantai Wanhua Polyurethane Co., Ltd produces is the TPU 1.11% of WHT-14, the trade mark that Boai Xinkaiyuan Pharmacy stock Co., Ltd produces is the polyvinylpyrrolidone 18% of K-30, the trade mark that Anhui Wanwei New High-tech Materials Co., Ltd produces is the polyvinyl alcohol 2% of 1788, the dimethyl formamide 70% that special amine water chestnut sky (Nanjing) Fine Chemical Co., Ltd produces, above-mentioned substance is thrown in reactor in order, stir 40 hours at 40 DEG C of temperature, obtain casting solution.Natural standing and defoaming 12 hours at 40 DEG C of temperature, maintenance casting solution 40 DEG C, 0.2MPa extrude the exit orifice entering the spinning head with diplopore nozzle, core liquid extrudes the endoporus core liquid pipe entering diplopore spinning head under 0.05MPa pressure, and the component of core liquid is 100% deionized water, and water temperature is 25 DEG C; Casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously.The casting solution of ejection is after the air section evaporation of 0.01 second between spinning head and coagulating bath and drawing-off reach institute's phase size; Enter in coagulating bath, the component of coagulating bath is 100% deionized water, and water temperature is 25 DEG C; Then be wound on wire wrapping wheel and cut bunchy; Then hollow fiber separating film obtains the hollow fiber separating film with self-supporting layer after carrying out abundant washed with de-ionized water.The hollow fiber separating film obtained thus is inside and outside pair of cortex construction, and the supporter of film section is double-deck finger-like pore structure therebetween, film external diameter 1.5 millimeters, internal diameter 0.85 millimeter, 0.3 micron, diffusion barrier nominal pore size, porosity 85%, pure water flux 1700L/h.m
2.25 DEG C .1bar.
Embodiment 4
By manufacture method and condition described in embodiment 1, casting solution takes raw material by following weight percents, the trade mark that Dalian polysulfone plastic Co., Ltd produces be P7304(inherent viscosity is 0.6) polysulfone resin 2.06%, the trade mark that Dajie Chemical Co., Ltd., Tianjin produces is the Corvic 15.88% of DG-1000, the trade mark that Yantai Wanhua Polyurethane Co., Ltd produces is the TPU 2.06% of WHT-14, the trade mark that Boai Xinkaiyuan Pharmacy stock Co., Ltd produces is the polyvinylpyrrolidone 18% of K-30, the trade mark that Anhui Wanwei New High-tech Materials Co., Ltd produces is the polyvinyl alcohol 2% of 1788, the dimethylacetylamide 60% that special amine water chestnut sky (Nanjing) Fine Chemical Co., Ltd produces, above-mentioned substance is thrown in reactor in order, stir 24 hours at 85 DEG C of temperature, obtain casting solution.Natural standing and defoaming 20 hours at 80 DEG C of temperature, maintenance casting solution 80 DEG C, 0.45MPa extrude the exit orifice entering the spinning head with diplopore nozzle, core liquid extrudes the endoporus core liquid pipe entering diplopore spinning head under 0.2MPa pressure, and the component of core liquid is 100% deionized water, and water temperature is 15 DEG C; Casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously.The casting solution of ejection is after the air section evaporation of 0.05 second between spinning head and coagulating bath and drawing-off reach institute's phase size; Enter in coagulating bath, the component of coagulating bath is 100% deionized water, and water temperature is 15 DEG C; Then be wound on wire wrapping wheel and cut bunchy; Then hollow fiber separating film obtains the hollow fiber separating film with self-supporting layer after carrying out abundant washed with de-ionized water.The hollow fiber separating film obtained thus is inside and outside pair of cortex construction, and the supporter of film section is double-deck finger-like pore structure therebetween, film external diameter 1.5 millimeters, internal diameter 0.85 millimeter, 0.008 micron, diffusion barrier nominal pore size, porosity 65%, pure water flux 282L/h.m
2.25 DEG C of .1bar.
Embodiment 5
By manufacture method and condition described in embodiment 1, casting solution takes raw material by following weight percents, the trade mark that Dalian polysulfone plastic Co., Ltd produces be P7304(inherent viscosity is 0.5) polysulfone resin 1%, the trade mark that Dajie Chemical Co., Ltd., Tianjin produces is the Corvic 15% of DG-1000, the trade mark that Yantai Wanhua Polyurethane Co., Ltd produces is the TPU 2% of WHT-14, the trade mark that Boai Xinkaiyuan Pharmacy stock Co., Ltd produces is the polyvinylpyrrolidone 19% of K-30, the trade mark that Anhui Wanwei New High-tech Materials Co., Ltd produces is the polyvinyl alcohol 1% of 1788, the dimethyl formamide 62% that special amine water chestnut sky (Nanjing) Fine Chemical Co., Ltd produces, above-mentioned substance is thrown in reactor in order, stir 30 hours at 75 DEG C of temperature, obtain casting solution.Natural standing and defoaming 24 hours at 75 DEG C of temperature, maintenance casting solution 70 DEG C, 0.35MPa extrude the exit orifice entering the spinning head with diplopore nozzle, core liquid extrudes the endoporus core liquid pipe entering diplopore spinning head under 0.1MPa pressure, and the component of core liquid is 100% deionized water, and water temperature is 20 DEG C; Casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously.The casting solution of ejection is after the air section evaporation of 0.25 second between spinning head and coagulating bath and drawing-off reach institute's phase size; Enter in coagulating bath, the component of coagulating bath is 100% deionized water, and water temperature is 20 DEG C; Then be wound on wire wrapping wheel and cut bunchy; Then hollow fiber separating film obtains the hollow fiber separating film with self-supporting layer after carrying out abundant washed with de-ionized water.The hollow fiber separating film obtained thus is inside and outside pair of cortex construction, and the supporter of film section is double-deck finger-like pore structure therebetween, film external diameter 1.5 millimeters, internal diameter 0.85 millimeter, 0.01 micron, diffusion barrier nominal pore size, porosity 65%, pure water flux 320L/h.m
2.25 DEG C .1bar.
Embodiment 6
Raw material is taken by following weight percents, the trade mark that Dalian polysulfone plastic Co., Ltd produces be P7304(inherent viscosity is 0.6) polysulfone resin 16.5%, the trade mark that Dajie Chemical Co., Ltd., Tianjin produces is the Corvic 1.75% of DG-1000, the trade mark that Yantai Wanhua Polyurethane Co., Ltd produces is the TPU 1.75% of WHT-41, the trade mark that Dow Chemical company produces is the polyethylene glycol 2% of PEG-300, the trade mark that Germany's BASF is produced is the polyvinylpyrrolidone 16% of K30, the pure level lithium chloride 1% of analysis that Shanghai Chemical Reagent Co., Ltd., Sinopharm Group produces, the dimethyl formamide 61% that special amine water chestnut sky (Nanjing) Fine Chemical Co., Ltd produces, above-mentioned substance is thrown in reactor in order, stir 8 hours at 80 DEG C of temperature, obtain casting solution.Natural standing and defoaming 12 hours at 80 DEG C of temperature, maintenance casting solution 75 DEG C, 0.2MPa extrude the exit orifice entering the spinning head with diplopore nozzle, core liquid extrudes the endoporus core liquid pipe entering diplopore spinning head under 0.1MPa pressure, and the component of core liquid is 100% deionized water, and water temperature is 25 DEG C; Casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously.The casting solution of ejection is after the air section evaporation of 0.1 second between spinning head and coagulating bath and drawing-off reach institute's phase size; Enter in coagulating bath, the component of coagulating bath is 100% deionized water, and water temperature is 25 DEG C; Then be wound on wire wrapping wheel and cut bunchy; Then hollow fiber separating film obtains the hollow fiber separating film with self-supporting layer after carrying out abundant washed with de-ionized water.The hollow fiber separating film obtained thus is inside and outside pair of cortex construction, and the supporter of film section is double-deck finger-like pore structure therebetween, film external diameter 1.5 millimeters, internal diameter 0.85 millimeter, 0.01 micron, diffusion barrier nominal pore size, porosity 75%, pure water flux 800L/h.m
2.25 DEG C .1bar.
Claims (1)
1. a preparation method for polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane, comprising:
Casting solution takes raw material by following weight percents, polysulfone resin 1.11%, Corvic 7.78%, TPU 1.11%, polyvinylpyrrolidone 18%, polyvinyl alcohol 2%, dimethyl formamide 70%, above-mentioned substance is thrown in reactor in order, stirs 40 hours at 40 DEG C of temperature, obtain casting solution; Natural standing and defoaming 12 hours at 40 DEG C of temperature, maintenance casting solution 40 DEG C, 0.2MPa extrude the exit orifice entering the spinning head with diplopore nozzle, core liquid extrudes the endoporus core liquid pipe entering diplopore spinning head under 0.05MPa pressure, and the component of core liquid is 100% deionized water, and water temperature is 25 DEG C; Casting solution, core liquid carry out common ejection by the outer endoporus of diplopore spinning head respectively simultaneously; The casting solution of ejection is after the air section evaporation of 0.01 second between spinning head and coagulating bath and drawing-off reach institute's phase size; Enter in coagulating bath, the component of coagulating bath is 100% deionized water, and water temperature is 25 DEG C; Then be wound on wire wrapping wheel and cut bunchy; Then hollow fiber separating film obtains the hollow fiber separating film with self-supporting layer after carrying out abundant washed with de-ionized water.
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| CN101406812A (en) * | 2008-11-04 | 2009-04-15 | 东华大学 | Method for producing thermoplastic polyurethane elastomer/polyvinylidene fluoride blended hollow fiber film |
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| CN102151491A (en) * | 2011-05-23 | 2011-08-17 | 刘镇江 | Modified polyvinyl chloride alloy ultra-filtration membrane and preparation method of hollow fiber ultra-filtration membrane |
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| CN101406812A (en) * | 2008-11-04 | 2009-04-15 | 东华大学 | Method for producing thermoplastic polyurethane elastomer/polyvinylidene fluoride blended hollow fiber film |
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Address after: 315191, 123, 1, 124, 134 East Ring North Road, Jiangbei District, Zhejiang, Ningbo Applicant after: Zhejiang Jing Yuanmo Science and Technology Ltd. Address before: 315191, Zhejiang, Ningbo province Yinzhou District Jiang Shan town wall, Yu Village Applicant before: Ningbo Jingyuan Membrane Technology Co., Ltd. |
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Free format text: CORRECT: APPLICANT; FROM: NINGBO JINGYUAN MEMBRANE TECHNOLOGY CO., LTD. TO: ZHEJIANG JINGYUAN MEMBRANE TECHNOLOGY CO., LTD. |
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Address after: 315191, 123, 1, 124, 134 East Ring North Road, Jiangbei District, Zhejiang, Ningbo Patentee after: ZHEJIANG JINGYUAN MEMBRANE TECHNOLOGY CO., LTD. Address before: 315191, 123, 1, 124, 134 East Ring North Road, Jiangbei District, Zhejiang, Ningbo Patentee before: Zhejiang Jing Yuanmo Science and Technology Ltd. |