CN106049047A - Method for preparing sodium alginate-polypropylene functional heavy metal adsorption fiber - Google Patents
Method for preparing sodium alginate-polypropylene functional heavy metal adsorption fiber Download PDFInfo
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- CN106049047A CN106049047A CN201610369137.3A CN201610369137A CN106049047A CN 106049047 A CN106049047 A CN 106049047A CN 201610369137 A CN201610369137 A CN 201610369137A CN 106049047 A CN106049047 A CN 106049047A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
Abstract
The invention discloses a method for preparing a sodium alginate-polypropylene functional heavy metal adsorption fiber. The method comprises the steps of causing a polymer matrix material to undergo ultrasonic blending in an appropriate solvent to form a polymer solution; making the well prepared polymer solution into a nanometer heavy metal fiber adsorption material; functionalizing the nanometer heavy metal fiber adsorption material, wherein the functionalizing operations steps comprise adding NaOH solution in a round-bottom flask, dissolving NaOH with stirring, and cooling to room temperature; using ice-water bath to control system temperature, adding the well prepared nanometer heavy metal fiber adsorption material, adding carbon disulfide dropwise with stirring; gradually performing warming after the dropwise adding is performed, and then using distilled water to repeatedly wash the fiber material. The method is simple and convenient to operate and safe, and the prepared fiber material has the advantages of being small in diameter, large in porosity and specific surface area and high in heavy metal ion adsorption capacity and has very good application prospect in the aspects of environmental management and water quality purification.
Description
Technical field
The present invention relates to the preparation method of a kind of fibrous material, particularly to a kind of adsorbing heavy metal in water functional fiber
Preparation method, the preparation method of a kind of sodium alginate-polypropylene functionalization heavy metal adsorption fiber.
Background technology
Environmental pollution mainly includes atmospheric pollution, water pollution, noxious waste pollution, noise pollution.And heavy metal both may be used
To be directly entered air, water body and soil, cause the direct pollution of all kinds of environmental key-element；Can also be at air, water body and soil
In mutually migrate, cause the indirect pollution of all kinds of environmental key-element.Owing to heavy metal can not be degraded by microorganisms, in the environment can only
There is the mutual conversion between various form, so, the elimination of heavy metal pollution is the most difficult, the impact causing biology
Also it is the problem that people more pay close attention to harm.Along with the development of China's process of industrialization, the environment negative effect of generation
Can not be ignored.
At present, heavy metal processes and processes mainly by adsorption method, and traditional adsorbing material is at disposal ability, desorption etc.
Aspect has the biggest deficiency.Ion-exchange fibre is a kind of fibrous ion exchange material, itself containing fixed ion and and
The movable ion that fixed ion symbol is contrary, when contacting with the solution of the compound that can dissociate, movable ion gets final product and solution
The ion of middle same-sign swaps, typically with various chemical synthetic materials as matrix, through macromolecular chemistry conversion or grafting
A kind of novel functional fiber material reacted and obtain.Ion-exchange fibre is to open on the basis of amberlite fat prod
The function new material with certain characteristic sent out.The mechanism of action of the two is the same, is all to rise by the zwitterion on group
Exchange interaction, resin is usually spherical, the particle diameter of resin of industry typically between 0.3～1.5mm, fiber be unbodied more
Smaller, it may be said that the adaptable field of ion exchange resin, ion-exchange fibre just can preferably substitutional ion exchange
Resin.
The specific surface area having due to ion-exchange fibre is big and also can be in different forms (such as non-woven fabrics, film etc.)
Applying in practice, use the field of difficulty at some ion exchange resin, ion-exchange fibre has the advantage of uniqueness.Cause
This, develop novel functionalization ion-exchange fibre and be of great significance for environmental improvement aspect tool.
Summary of the invention
The present invention is directed to problems and shortcomings present in existing heavy metal treatment technology, it is provided that a kind of sodium alginate-poly-third
The preparation method of olefinic functionality heavy metal adsorption fiber, the sodium alginate that the present invention prepares-polypropylene fiber material diameter exists
10～800ppm, specific surface area reaches 2000m2/ g, then carries out activating and graft reaction on the top layer of fibrous material, is not related to
The inside of fibrous material；This preparation method is simple to operation, and the exchange of the functionalization adsorbing fiber heavy metal ion obtained is held
Amount is big.
The purpose of the present invention can be achieved through the following technical solutions:
The preparation method of a kind of sodium alginate-polypropylene functionalization heavy metal adsorption fiber, this preparation method comprises following
Step:
(1) by the most ultrasonic for matrix material blended formation polymer solution；
(2) by method of electrostatic spinning, the polymer solution prepared is made nanometer heavy metal fiber adsorbing material；
(3) this nanometer heavy metal fiber adsorbing material is carried out functionalization.
Matrix material described in step (1) is sodium alginate, polypropylene, polyvinylpyrrolidone.
In solvent selected from methanol described in step (1), formic acid, ethanol, acetic acid, oxolane, propanol, isopropanol one
Plant or the mixed solvent of above-mentioned solution.
Sodium alginate quality described in step (1) is the 15.21%～28.50% of polymer blend solution quality, poly-
Vinylpyrrolidone quality is the 5.16%～15.35% of polymer blend solution quality, and polypropylene is polymer blend solution
The 20.65%～35.25% of quality.
It is as follows that nanometer heavy metal fiber adsorbing material described in step (3) carries out functionalization operation step:
(1) in round-bottomed flask, add NaOH solution, make sodium hydroxide dissolve under stirring, be cooled to room temperature；
(2) control system temperature with ice-water bath, add the nanometer heavy metal fiber adsorbing material prepared, under agitation by
It is added dropwise to Carbon bisulfide；
(3) gradually heat up after completion of dropwise addition, insulation reaction 2h, the most available with distilled water cyclic washing fibrous material afterwards
Functionalization heavy metal adsorption fibrous material.
The mass fraction of above-mentioned NaOH solution is 5.0%～16.5%；The quality of nanometer heavy metal fiber adsorbing material is
The 0.2%～1.0% of NaOH solution quality, the Carbon bisulfide quality of dropping is the 8%～16% of NaOH solution quality；Insulation temperature
Degree is 30～45 DEG C.
Above-mentioned functions heavy metal adsorption fibrous material diameter is little, and porosity and specific surface area are relatively big, fibre diameter 10～
800ppm；Functionalization heavy metal adsorption fibrous material has good absorption property for heavy metal ion.
Beneficial effects of the present invention: sodium alginate and polypropylene mixed solution are had by the present invention by method of electrostatic spinning preparation
There is the sodium alginate-polypropylene composite materials fiber of heavy metal ion adsorbed function, then this composite fibre carried out functional modification,
This fiber has good adsorption effect for heavy metal ion in water.
Detailed description of the invention
Below by way of specific embodiment, the present invention is described, but the present invention is not only limited to these embodiments, all at this
Within bright spirit and principle, any modification, equivalent substitution and improvement made etc. should be included in protection scope of the present invention it
In.
Embodiment 1
Take sodium alginate 4.0g, polypropylene 3.0g, polyvinylpyrrolidone 0.5g, join the acetic acid water of 100ml 30%
In solution, it is ultrasonically formed and formation homogeneous polymer solution is blended, be electrostatic spinning solution；
Electrostatic spinning apparatus is utilized to be made by above-mentioned sodium alginate-Polypropylene copolymer solution (i.e. polymer solution, lower same)
Nanofiber (i.e. nanometer heavy metal fiber adsorbing material, lower same)；
Method of electrostatic spinning concrete steps and parameter be: when electrostatic spinning, the polymer solution of above-mentioned preparation is placed in note
In emitter, the positive pole connecting needle of HV generator, negative pole be connected to cleaning bare electrode on, voltage is 15V, syringe needle with
Electrode distance 15cm, uses micro-injection pump feed flow, HV generator the high-pressure electrostatic produced is applied directly to injection
On device syringe needle, collecting nanofibers is on bare electrode；Ambient temperature is 20～25 DEG C, and humid control is 30～40% (Static Spinning
Knit under step and parameter same)；
This nanometer heavy metal fiber adsorbing material is carried out functionalization: first in 100mL round-bottomed flask, add 2.4g
NaOH and 20mL distilled water, makes sodium hydroxide dissolve under stirring, is cooled to room temperature, with ice-water bath control system temperature at 0 DEG C, adds
Enter 0.1g cross filament film (i.e. nanometer heavy metal fiber adsorbing material, lower same), then be added dropwise over 2.4mL Carbon bisulfide, dropping
35 DEG C it are gradually heating to after end, insulation reaction 2h, with distilled water cyclic washing fibrous membrane, it is dried under vacuum to constant weight at 45 DEG C,
I.e. obtain sodium alginate-polypropylene functionalization heavy metal adsorption fiber.
Embodiment 2
Take sodium alginate 4.0g, polypropylene 2.0g, polyvinylpyrrolidone 0.5g, join the acetic acid water of 100ml 30%
In solution, it is ultrasonically formed and formation homogeneous polymer solution is blended, be electrostatic spinning solution；Utilize electrostatic spinning apparatus by Sargassum
Acid sodium-Polypropylene copolymer solution makes nanofiber；In 100mL round-bottomed flask, add 2.4g NaOH and 20mL distilled water,
Make sodium hydroxide dissolve under stirring, be cooled to room temperature, control system temperature with ice-water bath, add 0.1g cross filament film, then by
Being added dropwise to 2.4mL Carbon bisulfide, be gradually heating to 35 DEG C after completion of dropwise addition, insulation reaction 2h, with distilled water cyclic washing fiber
Film, is dried under vacuum to constant weight at 45 DEG C, i.e. obtains sodium alginate-polypropylene functionalization heavy metal adsorption fiber.
Embodiment 3
Take sodium alginate 4.0g, polypropylene 3.0g, polyvinylpyrrolidone 0.6g, join the acetic acid water of 100ml 30%
In solution, it is ultrasonically formed and formation homogeneous polymer solution is blended, be electrostatic spinning solution；Utilize electrostatic spinning apparatus by Sargassum
Acid sodium-Polypropylene copolymer solution makes nanofiber；In 100mL round-bottomed flask, add 2.0g NaOH and 20mL distilled water,
Make sodium hydroxide dissolve under stirring, be cooled to room temperature, control system temperature with ice-water bath, add 0.1g cross filament film, then by
Being added dropwise to 2.4mL Carbon bisulfide, be gradually heating to 35 DEG C after completion of dropwise addition, insulation reaction 2h, with distilled water cyclic washing fiber
Film, is dried under vacuum to constant weight at 45 DEG C, i.e. obtains sodium alginate-polypropylene functionalization heavy metal adsorption fiber.
Embodiment 4
Take sodium alginate 4.0g, polypropylene 3.0g, polyvinylpyrrolidone 0.5g, join the acetic acid water of 100ml 30%
In solution, it is ultrasonically formed and formation homogeneous polymer solution is blended, be electrostatic spinning solution；Utilize electrostatic spinning apparatus by Sargassum
Acid sodium-Polypropylene copolymer solution makes nanofiber；In 100mL round-bottomed flask, add 2.4g NaOH and 20mL distilled water,
Make sodium hydroxide dissolve under stirring, be cooled to room temperature, control system temperature with ice-water bath, add 0.1g cross filament film, then by
Being added dropwise to 2.4mL Carbon bisulfide, be gradually heating to 30 DEG C after completion of dropwise addition, insulation reaction 2h, with distilled water cyclic washing fiber
Film, is dried under vacuum to constant weight at 45 DEG C, i.e. obtains sodium alginate-polypropylene functionalization heavy metal adsorption fiber.
Embodiment 5
Take sodium alginate 4.0g, polypropylene 3.0g, polyvinylpyrrolidone 0.5g, join the acetic acid water of 100ml 30%
In solution, it is ultrasonically formed and formation homogeneous polymer solution is blended, be electrostatic spinning solution；Utilize electrostatic spinning apparatus by Sargassum
Acid sodium-Polypropylene copolymer solution makes nanofiber；In 100mL round-bottomed flask, add 2.4g NaOH and 20mL distilled water,
Make sodium hydroxide dissolve under stirring, be cooled to room temperature, control system temperature with ice-water bath, add 0.1g cross filament film, then by
Being added dropwise to 3.0mL Carbon bisulfide, be gradually heating to 40 DEG C after completion of dropwise addition, insulation reaction 2h, with distilled water cyclic washing fiber
Film, is dried under vacuum to constant weight at 45 DEG C, i.e. obtains sodium alginate-polypropylene functionalization heavy metal adsorption fiber.
Embodiment 6
Take sodium alginate 4.0g, polypropylene 3.0g, polyvinylpyrrolidone 0.8g, join the ethanol water of 100ml 30%
In solution, it is ultrasonically formed and formation homogeneous polymer solution is blended, be electrostatic spinning solution；Utilize electrostatic spinning apparatus by Sargassum
Acid sodium-Polypropylene copolymer solution makes nanofiber；In 100mL round-bottomed flask, add 2.4g NaOH and 20mL distilled water,
Make sodium hydroxide dissolve under stirring, be cooled to room temperature, control system temperature with ice-water bath, add 0.1g cross filament film, then by
Being added dropwise to 2.4mL Carbon bisulfide, be gradually heating to 35 DEG C after completion of dropwise addition, insulation reaction 2h, with distilled water cyclic washing fiber
Film, is dried under vacuum to constant weight at 45 DEG C, i.e. obtains sodium alginate-polypropylene functionalization heavy metal adsorption fiber.
The present invention is easy and simple to handle, safety, and prepared fibrous material to have diameter little, porosity and specific surface area
Greatly, the advantage that heavy metal ion adsorption capacity is strong, there is in terms of environmental improvement, purification of water quality good application prospect.
Above content is only citing made for the present invention and explanation, and affiliated those skilled in the art are to being retouched
The specific embodiment stated makes various amendment or supplements or use similar mode to substitute, without departing from inventing or super
More scope defined in the claims, all should belong to protection scope of the present invention.
Claims (8)
1. the preparation method of sodium alginate-polypropylene functionalization heavy metal adsorption fiber, it is characterised in that this preparation method
Comprise the steps of
(1) by the most ultrasonic for matrix material blended formation polymer solution；
(2) by method of electrostatic spinning, the polymer solution prepared is made nanometer heavy metal fiber adsorbing material；
(3) this nanometer heavy metal fiber adsorbing material is carried out functionalization.
The preparation method of a kind of sodium alginate the most according to claim 1-polypropylene functionalization heavy metal adsorption fiber, its
Being characterised by, the matrix material described in step (1) is sodium alginate, polypropylene, polyvinylpyrrolidone.
The preparation method of a kind of sodium alginate the most according to claim 1-polypropylene functionalization heavy metal adsorption fiber, its
It is characterised by, in the solvent selected from methanol described in step (1), formic acid, ethanol, acetic acid, oxolane, propanol, isopropanol
A kind of or the mixed solvent of above-mentioned solution.
The preparation method of a kind of sodium alginate the most according to claim 2-polypropylene functionalization heavy metal adsorption fiber, its
Being characterised by, the sodium alginate quality described in step (1) is the 15.21%～28.50% of polymer blend solution quality, poly-
Vinylpyrrolidone quality is the 5.16%～15.35% of polymer blend solution quality, and polypropylene is polymer blend solution
The 20.65%～35.25% of quality.
The preparation method of a kind of sodium alginate the most according to claim 1-polypropylene functionalization heavy metal adsorption fiber, its
Being characterised by, it is as follows that the nanometer heavy metal fiber adsorbing material described in step (3) carries out functionalization operation step:
(1) in round-bottomed flask, add NaOH solution, make sodium hydroxide dissolve under stirring, be cooled to room temperature；
(2) control system temperature with ice-water bath, add the nanometer heavy metal fiber adsorbing material prepared, the most dropwise add
Enter Carbon bisulfide；
(3) gradually heat up after completion of dropwise addition, insulation reaction 2h, i.e. can get function with distilled water cyclic washing fibrous material afterwards
Change heavy metal adsorption fibrous material.
The preparation method of a kind of sodium alginate the most according to claim 5-polypropylene functionalization heavy metal adsorption fiber, its
Being characterised by, the mass fraction of described NaOH solution is 5.0%～16.5%.
The preparation method of a kind of sodium alginate the most according to claim 5-polypropylene functionalization heavy metal adsorption fiber, its
Being characterised by, the quality of described nanometer heavy metal fiber adsorbing material is the 0.2%～1.0% of NaOH solution quality, dropping
Carbon bisulfide quality be the 8%～16% of NaOH solution quality.
The preparation method of a kind of sodium alginate the most according to claim 5-polypropylene functionalization heavy metal adsorption fiber, its
Being characterised by, described holding temperature is 30～45 DEG C.
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| CN109351350A (en) * | 2018-12-27 | 2019-02-19 | 安徽工业大学 | A kind of method that emulsion polymerization prepares sodium alginate micro ball adsorbent |
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| CN109289810B (en) * | 2018-11-02 | 2021-05-28 | 山东海岱园林集团有限公司 | Heavy metal ion adsorption blanket, preparation method and application in removing soil heavy metal |
| CN109351350A (en) * | 2018-12-27 | 2019-02-19 | 安徽工业大学 | A kind of method that emulsion polymerization prepares sodium alginate micro ball adsorbent |
| CN110124636A (en) * | 2019-05-29 | 2019-08-16 | 张慧 | A kind of magnetic Nano fibrous material for textile waste processing |
| CN110124636B (en) * | 2019-05-29 | 2022-07-26 | 太仓市洪宇新材料科技有限公司 | Magnetic nanofiber material for textile industry wastewater treatment |
| US11453960B2 (en) * | 2019-09-02 | 2022-09-27 | Sinotech Academy Of Textile (Qingdao) Co., Ltd. | Algae modified pp spunbond non-woven fabric |
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