CN108677261B - Integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate and use method thereof - Google Patents
Integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate and use method thereof Download PDFInfo
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- CN108677261B CN108677261B CN201810616355.1A CN201810616355A CN108677261B CN 108677261 B CN108677261 B CN 108677261B CN 201810616355 A CN201810616355 A CN 201810616355A CN 108677261 B CN108677261 B CN 108677261B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D11/00—Other features of manufacture
- D01D11/06—Coating with spinning solutions or melts
Abstract
The invention discloses an integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate and a using method thereof, relates to the technical field of hollow fiber membranes, and aims to solve the technical problems that in the prior art, the wall thickness uniformity is poor, equipment is complex, the cost is high, and the operation difficulty is high, and the wall thickness uniformity is caused by the fact that the material seepage and the wall thickness of the hollow fiber membrane cannot be well controlled. The invention discloses an integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate, which comprises: the pretreatment region, the cover plate, the first-stage distributing plate, the second-stage distributing plate and the bottom plate are sequentially communicated through the rope threading hole; wherein, one side of the pretreatment area far away from the cover plate is provided with a pretreatment liquid inlet, and one side close to the cover plate is provided with a pretreatment liquid outlet; specifically, a feed inlet is arranged on the first-stage distributing plate, a material cavity is arranged on the bottom plate, and a needle tube is arranged at the material cavity.
Description
Technical Field
The invention relates to the technical field of hollow fiber membranes, in particular to an integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate and a using method thereof.
Background
Along with the increasingly serious water environment pollution in China, the membrane filtration technology is more and more applied to the field of water treatment, in order to prolong the service life of a membrane product, the strength of a hollow fiber membrane needs to be improved so as to ensure that the problems of filament breakage, water leakage and the like do not occur in the use process, and the conventional reinforced hollow fiber membrane is mainly a fiber tube reinforced hollow fiber membrane.
In order to improve the strength of the hollow fiber membrane and reduce the occurrence of broken filaments in the operation process, many companies develop a high-woven fiber tube reinforced hollow fiber membrane, the breaking force of the high-woven fiber tube reinforced hollow fiber membrane can reach more than 50N according to different materials, the seepage of the membrane filaments, an inner surface layer mechanism and the like in the production process of the fiber tube reinforced hollow fiber membrane are difficult to control, the existing method is more technically controlled, but the control difficulty is higher.
At present, fiber tubes are mainly used as a supporting layer, and due to the fact that the pores of the crocheted fiber tubes are different and the inner layer does not contain core liquid during production, the amount of seepage of the hollow fiber membranes is difficult to control during production, the wall thickness, the inner surface layer and the like of the hollow fiber membranes are difficult to control, and in order to solve the problem, a spinneret plate capable of preprocessing the fiber tubes is arranged.
For example: the hollow fiber membrane with more uniform wall thickness and higher bonding force can be produced by adding the pre-soaking holes of the casting solution in the middle of the spinneret plate, but the hollow fiber membrane is only suitable for the fiber tube with smaller pores because of the pre-soaking holes added in the middle, and the produced hollow fiber membrane can be solid when the pores of the fiber tube are larger.
Or further: the hollow fiber membranes with uniform wall thickness can be produced by ensuring the concentricity of the needle tube and the filament outlet, and the like, and a plurality of hollow fiber membranes can be produced at one time, but the wall thickness of the hollow fiber membranes can not be controlled when the pore space of the fiber tube is larger, and the flow channel can not ensure the uniform distribution of the casting solution, thereby influencing the final wall thickness of the hollow fiber membranes.
In summary, the inventors of the present application found that in the prior art, the material permeability and the wall thickness of the hollow fiber membrane cannot be well controlled, and generally the uniformity of the wall thickness is poor; moreover, the equipment is complex, the cost is high, and the operation difficulty is large.
Therefore, how to provide an integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret and a use method thereof, which can well control the wall thickness uniformity of the hollow fiber membrane and effectively reduce the equipment cost and the operation difficulty, has become a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide an integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate and a using method thereof, and aims to solve the technical problems of poor wall thickness uniformity, complex equipment, high cost and high operation difficulty caused by the fact that the prior art cannot well control seepage and wall thickness of a hollow fiber membrane.
The invention provides an integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate, which comprises: the pretreatment region, the cover plate, the first-stage distributing plate, the second-stage distributing plate and the bottom plate are sequentially communicated through the rope threading hole; one side of the pretreatment region, which is far away from the cover plate, is provided with a pretreatment liquid inlet, and one side of the pretreatment region, which is close to the cover plate, is provided with a pretreatment liquid outlet; the first-stage distributing plate is provided with a feeding hole, the bottom plate is provided with a material cavity, and the material cavity is provided with a needle tube.
In practical application, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate, the pretreatment region, the cover plate, the primary distribution plate, the secondary distribution plate and the bottom plate are of an integrated structure.
In the integrated fiber pipe pretreatment reinforced hollow fiber membrane spinneret plate, the integrated fiber pipe pretreatment reinforced hollow fiber membrane spinneret plate is fixed on a membrane casting solution metering pump.
Specifically, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate, a fiber tube sequentially passes through the pretreatment region, the cover plate, the primary distribution plate, the secondary distribution plate and the stringing hole in the middle of the bottom plate.
Furthermore, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate, a casting solution enters through the feed inlet and is divided into two symmetrical strands by one strand through the arc-shaped flow channel on the primary distribution plate, and the two strands of casting solution are divided into four cross-shaped vertical strands through the arc-shaped flow channel on the secondary distribution plate and enter the material cavity.
Furthermore, in the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate, pretreatment liquid enters the pretreatment region from the pretreatment liquid inlet and is discharged from the pretreatment liquid outlet; the adhesion amount on the fiber tube is controlled by controlling the entering amount and time of the pretreatment liquid.
In practical application, in the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate, the pretreatment liquid is liquid.
In the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate, the pretreatment liquid is any one of a gel, a membrane casting liquid, a solvent, a non-solvent and a mixed liquid of the solvent and the non-solvent.
Alternatively, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate, the pretreatment liquid is in a gaseous state.
Compared with the prior art, the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate has the following advantages:
the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate comprises: the pretreatment region, the cover plate, the first-stage distributing plate, the second-stage distributing plate and the bottom plate are sequentially communicated through the rope threading hole; wherein, one side of the pretreatment area far away from the cover plate is provided with a pretreatment liquid inlet, and one side close to the cover plate is provided with a pretreatment liquid outlet; specifically, a feed inlet is arranged on the first-stage distributing plate, a material cavity is arranged on the bottom plate, and a needle tube is arranged at the material cavity. From the analysis, the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate disclosed by the invention has the advantages that the pretreatment area, the primary distribution plate and the secondary distribution plate are additionally arranged, so that the controllability of the seeping material can be realized, the wall thickness and the uniformity of the hollow fiber membrane can be well controlled, the structure is simple, the equipment cost and the operation difficulty can be effectively reduced, and the problems of large occupied area, complex process and the like of the traditional secondary coating equipment are solved.
The invention also provides a use method of the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate, which comprises the following steps: fixing a spinneret plate on a metering pump of the casting solution; sequentially penetrating the fiber pipe through the pretreatment area, the cover plate, the first-stage distribution plate, the second-stage distribution plate and the rope threading hole in the middle of the bottom plate; starting the filament collecting equipment to enable the fiber tube to be in a moving state; connecting the pretreatment liquid storage region with a pretreatment liquid inlet, starting the conveying device, filling the pretreatment region with the pretreatment liquid, and returning the pretreatment liquid to the pretreatment liquid storage region through a pretreatment liquid outlet; and starting the metering pump to enable the casting film liquid to enter from the feed inlet, sequentially pass through the first-stage distributing plate, the bottom plate and the material cavity, and be extruded from the outlet of the material cavity to be coated on the fiber tube.
The using method of the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate is the same as the advantages of the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate compared with the prior art, and the details are not repeated herein.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of a spinneret plate of an integrated fiber tube pretreatment reinforced hollow fiber membrane provided by an embodiment of the invention;
fig. 2 is a schematic flow chart of a method for using a spinneret plate of an integrated fiber tube pretreatment enhanced hollow fiber membrane according to an embodiment of the present invention.
In the figure: 1-a pre-treatment region; 2-pretreatment liquid inlet; 3-pretreatment liquid outlet; 4-cover plate; 5-a first-stage distribution plate; 6-a feed inlet; 7-a secondary distribution plate; 8-a bottom plate; 9-a material cavity; 10-needle tube.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; the connection can be mechanical connection or electrical connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Fig. 1 is a schematic structural diagram of an integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to an embodiment of the present invention.
As shown in fig. 1, an embodiment of the present invention provides an integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate, including: the pretreatment area 1, the cover plate 4, the first-stage distributing plate 5, the second-stage distributing plate 7 and the bottom plate 8 are sequentially communicated through the rope threading hole; one side of the pretreatment region 1, which is far away from the cover plate 4, is provided with a pretreatment liquid inlet 2, and one side of the pretreatment region, which is close to the cover plate 4, is provided with a pretreatment liquid outlet 3; the first-stage distributing plate 5 is provided with a feeding hole 6, the bottom plate 8 is provided with a material cavity 9, and the material cavity 9 is provided with a needle tube 10.
Compared with the prior art, the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate provided by the embodiment of the invention has the following advantages:
the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate provided by the embodiment of the invention, as shown in fig. 1, comprises: the pretreatment area 1, the cover plate 4, the first-stage distributing plate 5, the second-stage distributing plate 7 and the bottom plate 8 are sequentially communicated through the rope threading hole; wherein, one side of the pretreatment region 1 far away from the cover plate 4 is provided with a pretreatment liquid inlet 2, and one side near the cover plate 4 is provided with a pretreatment liquid outlet 3; specifically, a feed inlet 6 is arranged on the first-stage distributing plate 5, a material cavity 9 is arranged on the bottom plate 8, and a needle tube 10 is arranged at the material cavity 9. From the analysis, the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate disclosed by the embodiment of the invention has the advantages that the pretreatment region 1, the primary distribution plate 5 and the secondary distribution plate 7 are additionally arranged, so that the controllability of the seepage material can be realized, the wall thickness and the uniformity of the hollow fiber membrane can be well controlled, the structure is simple, the equipment cost and the operation difficulty can be effectively reduced, and the problems of more occupied land, complex process and the like of the traditional secondary coating equipment are solved.
In practical application, as shown in fig. 1, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret according to the embodiment of the present invention, the pretreatment region 1, the cover plate 4, the primary distribution plate 5, the secondary distribution plate 7 and the bottom plate 8 are preferably an integrated structure.
In the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate provided by the embodiment of the invention, the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate is fixed on a membrane casting solution metering pump.
Specifically, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate provided by the embodiment of the invention, the fiber tube passes through the pretreatment region 1, the cover plate 4, the primary distribution plate 5, the secondary distribution plate 7 and the stringing hole in the middle of the bottom plate 8 in sequence.
Further, as shown in fig. 1, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate provided in the embodiment of the present invention, the casting solution enters through the feed port 6, and is divided into two symmetrical strands by one strand through the arc-shaped flow channel on the primary distribution plate 5, and the two strands of casting solution are divided into four cross-vertical strands through the arc-shaped flow channel on the secondary distribution plate 7 and enter the material cavity 9, so that the casting solution can be uniformly dispersed in the material cavity 9 and uniformly coated on the fiber tube through the outlet of the bottom plate 8.
It should be added that, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate provided in the embodiment of the present invention, one end of the arc-shaped flow channel on the primary distribution plate 5 is an inlet, the other end is an outlet, and both ends of the arc-shaped flow channel on the secondary distribution plate 7 are outlets.
Further, as shown in fig. 1, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate provided by the embodiment of the present invention, a pretreatment liquid enters a pretreatment region 1 through a pretreatment liquid inlet 2 and is discharged through a pretreatment liquid outlet 3; further, the amount of adhesion to the fiber tube can be controlled by controlling the amount and time of the pretreatment liquid.
In practical application, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate provided by the embodiment of the invention, the pretreatment liquid can be in a liquid state.
In the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate provided by the embodiment of the invention, when the pretreatment liquid is in a liquid state, the pretreatment liquid can be any one of a gel, a membrane casting liquid, a solvent, a non-solvent and a mixed liquid of the solvent and the non-solvent.
It should be noted that the gelling agents (gels) are liquids that can form a thin film on the surface of the fiber tube to increase the adhesion of the casting solution to the fiber tube or accelerate the phase separation of the casting solution.
The membrane casting solution is a high molecular solution formed by dissolving a membrane material-high molecular compound in a good solvent and adding a pore-forming agent. The membrane casting solution has different components in different proportions, and the prepared membranes have different separation performance and geometric shapes.
Alternatively, in the integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate provided by the embodiment of the invention, the pretreatment liquid may also be in a gaseous state.
Fig. 2 is a schematic flow chart of a method for using a spinneret plate of an integrated fiber tube pretreatment enhanced hollow fiber membrane according to an embodiment of the present invention.
As shown in fig. 2 in combination with fig. 1, an embodiment of the present invention further provides a method for using an integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret, including the following steps: step S1, fixing a spinneret plate on the casting solution metering pump; step S2, the fiber tube sequentially passes through the pretreatment area 1, the cover plate 4, the first-stage distribution plate 5, the second-stage distribution plate 7 and the stringing hole in the middle of the bottom plate 8; step S3, starting the filament collecting equipment to enable the fiber tube to be in a moving state; step S4, connecting the pretreatment liquid storage region with a pretreatment liquid inlet, starting a conveying device, filling the pretreatment region 1 with the pretreatment liquid, and returning the pretreatment liquid to the pretreatment liquid storage region through a pretreatment liquid outlet 3; and step S5, starting a metering pump, enabling the casting film liquid to enter from a feed inlet 6, sequentially pass through a primary distributing plate 5, a bottom plate 8 and a material cavity 9, and be extruded from an outlet of the material cavity 9 to be coated on the fiber tube.
The integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate and the use method thereof provided by the embodiment of the invention have the following advantages:
firstly, integrated design of pretreatment and membrane yarn forming;
secondly, designing an arc-shaped flow passage of a spinneret plate, and uniformly feeding the casting solution into a material cavity through dividing into two and dividing into four;
thirdly, the needle tube is designed, the length of the needle tube is shortened by adjusting the spinneret plate, and the processing is convenient;
fourthly, the cover plate is designed, and the casting solution can enter without dead angles through the double-layer effect with the flow channel;
and fifthly, selecting a pretreatment agent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The utility model provides an integration fiber tube preliminary treatment enhancement mode hollow fiber membrane spinneret which characterized in that includes: the pretreatment region, the cover plate, the first-stage distributing plate, the second-stage distributing plate and the bottom plate are sequentially communicated through the rope threading hole;
one side of the pretreatment region, which is far away from the cover plate, is provided with a pretreatment liquid inlet, and one side of the pretreatment region, which is close to the cover plate, is provided with a pretreatment liquid outlet;
the first-stage distributing plate is provided with a feeding hole, the bottom plate is provided with a material cavity, and the material cavity is provided with a needle tube.
2. The integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to claim 1, wherein said pretreatment region, said cover plate, said primary distribution plate, said secondary distribution plate, and said base plate are an integrated structure.
3. The integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to claim 1, wherein said integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate is fixed to a membrane casting solution metering pump.
4. The integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to claim 3, wherein a fiber tube passes through said stringing hole in the middle of said pretreatment region, said cover plate, said primary distributor plate, said secondary distributor plate and said base plate in this order.
5. The integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to claim 4, wherein a casting solution enters through the feed inlet and is divided into two symmetrical strands by one strand through the arc-shaped flow channel on the primary distribution plate, and the two strands of casting solution are divided into four cross-shaped vertical strands through the arc-shaped flow channel on the secondary distribution plate and enter the material cavity.
6. The integrated fiber tube pretreatment-enhanced hollow fiber membrane spinneret plate according to claim 4 or 5, wherein a pretreatment liquid enters said pretreatment region from said pretreatment liquid inlet and is discharged from said pretreatment liquid outlet;
the adhesion amount on the fiber tube is controlled by controlling the entering amount and time of the pretreatment liquid.
7. The integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to claim 6, wherein said pretreatment liquid is in liquid state.
8. The integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to claim 7, wherein the pretreatment liquid is any one of a gel, a membrane casting liquid, a solvent, a non-solvent, and a mixed liquid of a solvent and a non-solvent.
9. The integrated fiber tube pretreatment reinforced hollow fiber membrane spinneret plate according to claim 6, wherein said pretreatment liquid is in a gaseous state.
10. The use method of the integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate is characterized by comprising the following steps of:
fixing a spinneret plate on a metering pump of the casting solution;
sequentially penetrating the fiber pipe through the pretreatment area, the cover plate, the first-stage distribution plate, the second-stage distribution plate and the rope threading hole in the middle of the bottom plate;
starting the filament collecting equipment to enable the fiber tube to be in a moving state;
connecting the pretreatment liquid storage region with a pretreatment liquid inlet, starting the conveying device, filling the pretreatment region with the pretreatment liquid, and returning the pretreatment liquid to the pretreatment liquid storage region through a pretreatment liquid outlet;
and starting the metering pump to enable the casting film liquid to enter from the feed inlet, sequentially pass through the first-stage distributing plate, the bottom plate and the material cavity, and be extruded from the outlet of the material cavity to be coated on the fiber tube.
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| CN110681269B (en) * | 2019-11-20 | 2022-04-22 | 宁波建嵘科技有限公司 | Two-stage coating heterogeneous synchronous composite film preparation device |
| CN111020715B (en) * | 2019-11-26 | 2021-03-23 | 江苏凯米膜科技股份有限公司 | Spinneret for preparing enhanced hollow fiber membrane, membrane preparation method and hollow fiber membrane |
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| SG154369A1 (en) * | 2008-02-05 | 2009-08-28 | Inst Of Environmental Science | Method for the production of an asymmetric hollow fiber membrane |
| CN202595365U (en) * | 2012-05-02 | 2012-12-12 | 北京碧水源膜科技有限公司 | Spinneret plate for producing long fibers and enhancing hollow fiber films |
| CN103007778B (en) * | 2012-12-20 | 2015-12-23 | 北京碧水源膜科技有限公司 | A kind of preparation method of enhancement type hollow fiber compound film and device |
| CN103031612B (en) * | 2013-01-21 | 2015-11-25 | 深圳市诚德来实业有限公司 | A kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane and a kind of spinning head |
| KR101321362B1 (en) * | 2013-07-16 | 2013-10-23 | 주식회사 시노펙스 | High strength membrane and method of manufacturing the same |
| CN206215055U (en) * | 2016-11-10 | 2017-06-06 | 浙江省化工研究院有限公司 | A kind of membrane equipment of improved woven tube inner support film silk |
| CN107456871B (en) * | 2017-08-02 | 2020-10-30 | 同济大学 | Preparation method of hollow fiber composite loose nanofiltration membrane |
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Address after: 301800 No.10, Fuli Road, Baodi plastic products industrial zone, Baodi District, Tianjin Patentee after: Oseco membrane technology (Tianjin) Co.,Ltd. Address before: 301800 No.10, Fuli Road, Baodi plastic products industrial zone, Baodi District, Tianjin Patentee before: TIANJIN BISHUIYUAN MEMBRANE MATERIAL Co.,Ltd. |
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