CN102587133A - Preparation method of functional fiber capable of adsorbing heavy metal ions and organic pollutants at same time - Google Patents
Preparation method of functional fiber capable of adsorbing heavy metal ions and organic pollutants at same time Download PDFInfo
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Abstract
The invention provides a preparation method of a functional fiber capable of adsorbing heavy metal ions and organic pollutants at the same time. The method comprises the following steps: dissolving acrylic acid with the volume percentage of 0.5-40 percent and acrylic ester with the volume percentage of 0.5-30 percent into an organic solvent to prepare a uniform mixed solution; adding a polymerization inhibitor; then putting a fiber into the mixed solution, and standing and soaking the fiber for 0.5-12 hours; inflating nitrogen to exhaust oxygen; performing co-irradiation grafting reaction for 0.5-48 hours at room temperature; taking out the fiber after the irradiation grafting reaction; soaking the fiber with anhydrous ethanol; washing away unreacted monomers and homopolymers; and drying the fiber to obtain the functional fiber capable of adsorbing the heavy metal ions and the organic pollutants at the same time. The preparation method of the functional fiber is simple, and is convenient for large-scale production; and the functional fiber has a good adsorption performance for the heavy metal ions and organic pollutants in water.
Description
Technical field:
The invention belongs to filed of functional, be specifically related to the preparation method of the functional fiber of Adsorption of Heavy Metal Ions and organic pollution simultaneously.
Background technology:
The mankind had also paid heavy cost for it when science and technology was advanced by leaps and bounds since 20th century.Soil, water quality and atmosphere have seriously been polluted in the use of discharging, sewage irrigation and the agricultural chemicals of industry " three wastes ", motor-vehicle tail-gas, herbicide, chemical fertilizer etc.It is reported that China's colored metallurgical industrial in 1989 discharges heavy metal Hg in environment be 56t, Cd is 88t, and As is 173t, and Pb is 226t.U.S. scientist carries out chemical analysis to the soil in some highways and city, finds that wherein the content of Pb is out of sight, and reaches tens times of maximum magnitude, even hundred times.Most heavy metals are to human body, crops, the toxic effect of animal.Poisoning manifestations like arsenic is cutaneous lesions, shank gangrene and suffers from cutaneum carcinoma, lung cancer, carcinoma of urinary bladder, kidney etc.Heavy metal ion can be brought serious pollution to water quality; It not only directly jeopardizes the existence of zooplankter in the water; The gill and the body surface that can pass through aquatic animal gets in its body or sticks to body surface; Through the continuous enrichment of biological chain vegeto-animal vital movement is caused very major injury, also can get into human body, the direct or indirect human beings'health that jeopardizes through food chain.The mankind drink the fish of this water or edible enriching heavy metal ion etc., can give rise to diseases, and can cause death when serious.Minamata disease (mercury poisoning) and the bone aching (cadmium poisoning) of Japan is exactly that heavy metal ion water is not effectively addressed and the tragedy that brings.Heavy metal pollution is quite serious, and it is very harmful to environment and biology, has caused countries in the world scientists' great attention, addresses this problem extremely urgent.
China does not also have good removal way for the heavy metal pollution in water body and the soil at present; The heavy metal ion processing method of using in the industry comprises: chemical precipitation method, electrochemical process, microbial method and absorption method [Joumal of Environmental Management; 2011,92:407-418].Chemical precipitation method is used the most extensive in the removal heavy metal ions in wastewater; Its principle is to make the heavy metal ion that is dissolved state in the waste water change water-fast heavy metal compound into through chemical reaction, and then through steps such as filtration and depositions sediment is removed from the aqueous solution.Because processing procedure will add chemical reagent, mud stripping once again under the situation that the pH value changes causes secondary pollution, and operating condition is complicated, and the water concentration that goes out after the processing does not often reach requirement, is unfavorable for the recycling of heavy metal yet.Electrochemical process is utilized the electrochemical properties of metal, is reduced at the electronics of negative electrode, and heavy metal ion is separated from the solution of relative high concentration, has overcome the secondary pollution problem of the precipitation method.But this method power consumption is big, and wastewater treatment capacity is little, and effluent quality is poor.Utilize the biochemical metabolism effect of bacterium, fungi; Also can heavy metal element be separated with water body or reduces its toxicity; But this method receives the influence of external conditions such as ion concentration, pH, temperature bigger, is difficult for separating with water body, is only applicable to the aid in treatment of the higher sewage of content of beary metal.
Absorption method is big with adsorbance, the rate of adsorption is fast, the high method of handling heavy metal wastewater thereby that extensively adopts at present that becomes of efficient.Adsorb employed material and comprise activated carbon and bentonite, mineral material, pectin etc.They have high specific area or the surface has highly developed gap structure, high adsorption capacity, and clearance is high, but expensive, and service life is short, its large-scale application that heavy metal ion has reclaimed drawbacks limit such as difficulty.Amino-contained (NH
2), hydroxyl (OH) and sulfydryl (SH) etc. the chelating resin of dissimilar functional groups is widely used in the removal research of heavy metal ions in wastewater; The subject matter that exists at present is that the resin regeneration cost is high and is prone to cause second environmental pollution; In addition; Resin adsorption speed is slower, and organic absorption often causes the obstruction in aperture in the resin and had a strong impact on its adsorption efficiency to heavy metal ion.
Fibrous material is compared with resin, has that specific surface is big, adsorbance is high, exchange and an advantage such as elution speed is fast, regeneration easily, can be prepared into various shape, and easy to use, application form is various.Professor Wei Junfu has prepared the acid ion exchange fiber with the gamma ray radiation grafting, can adsorb Pb fast
2+, Cu
2+, Cr
3+Etc. heavy metal ion, for example to Pb
2+Adsorbance can reach 400mg/g, adsorption rate is very fast, and can be filled in the post, the modes such as nonwoven fabric, net of processing are filtered; Perhaps directly drop in the water body and use, just can regenerate with acid or NaCl in the absorption back that reaches capacity, reuse [Jun Fu Wei; Zhi Peng Wang, Jing Zhang, Yue Ying Wu; Zheng Pu Zhang.Reactive & Functional Polymers, 2005,65 (1): 127-134].This technology is simple, and cost is low, and is easy to use.
In recent years, environment incretion interferent more and more receives global concern to human health and ecological harm, and becomes the third-largest environmental problem after ozone layer, terrestrial climate warm.Environment incretion interferent extensively is present in our daily life; Like synthetic detergent, cosmetics, agricultural chemicals and degradation product thereof; Use polyvinyl chloride as the articles for use of raw material, contain cinnamic polyvinyl chloride and make things convenient for the anti-corrosion of metal film in box, the metal can; These materials such as the pollutant that waste incineration produces advance in people's aquatic environment through water and atmosphere through physical-chemical reaction; Can have a negative impact to hydrobiological growth, growth, breeding and existence, finally on ecosystem level, cause effect.
If can design synthetic a kind of functional fiber material, Adsorption of Heavy Metal Ions and organic pollution then can solve the great environmental problem that heavy metal ion and organic matter pollute preferably simultaneously.Wei Junfu etc. are base material with the polypropylene of grafted polyacrylic acid; Through esterification with part carboxyl and long chain alkanol esterification; Prepare and contain hydrophilic simultaneously and esterify cellobiose lipophilic group, studied this esterify cellobiose the micro-dibutyl phthalate in the water and the adsorption capacity of heavy metal ion.The result shows, this fiber can be simultaneously micro-dibutyl phthalate and the heavy metal ion in the adsorbed water effectively, clearance reaches 70% and 95% respectively.But this method is time consumption and energy consumption relatively, and reactions step is many and wayward, is difficult to large-scale production.Han Zhaoxiang utilizes the special microcellular structure of bamboo charcoal and the good absorption property of shitosan; With the sodium alginate is crosslinking agent; Developing a kind of is the matrix loading chitosan with the bamboo charcoal; Can simultaneously efficiently remove heavy metal ion and the adsorbent [a kind of adsorbent that adsorbs heavy metal ions in wastewater and dyestuff, CN200910205648.1] of dyestuff in the dyeing waste water.But this adsorbent needs to pulverize, and sieves, and uses inconveniently, and sodium alginate is natural polymer with shitosan, and easy biodegradation has had a strong impact on its service life.
This patent provides the preparation method of the functional fiber of a kind of Adsorption of Heavy Metal Ions simultaneously and organic pollution.At first acrylic acid and acrylic acid ester are dissolved in the mixed solution that is mixed with homogeneous in the organic solvent; Add polymerization inhibitor; Fiber is put into above-mentioned mixed solution and is left standstill and soak a period of time then, feeds nitrogen and gets rid of oxygen, at room temperature carries out the mutual radiation graft reaction 0.5 hour-48 hours.Fiber behind the irradiation grafting is taken out the back with soaked in absolute ethyl alcohol flush away unreacted monomer and homopolymers, obtain the functional fiber of while Adsorption of Heavy Metal Ions and organic pollution after the drying.
Summary of the invention:
The objective of the invention is to propose a kind of simple to operate, be produced on a large scale, simultaneously the preparation method of the functional fiber of Adsorption of Heavy Metal Ions and organic pollution.Concrete steps of the present invention are following:
1) be that the acrylic acid of 0.5%-40% and acrylic acid ester that percentage by volume is 0.5%-30% are dissolved in the mixed solution that is mixed with homogeneous in the organic solvent with percentage by volume; Adding mass percent is the polymerization inhibitor of 0.1%-3%, then fiber is put into above-mentioned mixed solution and leaves standstill immersion 0.5-12 hour;
2) soaked fiber is transferred in the sealable plastic bag together with the organic matter mixed solution; Feed nitrogen and get rid of oxygen; Then with plastic bag sealing; Fiber is dispersed in plastic bag is no more than the thick thin layer of 5mm, at room temperature the irradiation dose by 5kGy-60kGy carried out the mutual radiation graft reaction 1 minute-48 hours under irradiation bomb;
3) fiber behind the irradiation grafting is taken out the back with soaked in absolute ethyl alcohol flush away unreacted monomer and homopolymers, obtain the functional fiber of while Adsorption of Heavy Metal Ions and organic pollution after the drying.
The fibrous matrix that is adopted among the present invention comprises polyamide, polypropylene, polyethylene, polytetrafluoroethylene (PTFE), polyacrylonitrile and polysulfones, and form comprises monfil, nonwoven fabric, tow and doughnut.Described organic solvent comprises a kind of or its mixture in absolute ethyl alcohol, isopropyl alcohol, acetone, benzene, toluene, the chloroform.The polymerization inhibitor that adds is a kind of or its mixture in hydroquinones, 1,4-benzoquinone, the MEHQ.Described acrylic acid ester comprises a kind of or its mixture in methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, dodecyl acrylate, the octadecyl acrylate.
Irradiation bomb described in the present invention comprises high-power electron beam, gamma ray, high energy ultraviolet ray.
Used monomer is active higher among the present invention, has the acrylic acid and the acrylic ester monomer of hydroxy-acid group.In the process of preparation,, can obtain the functional fiber of different percent graftings through the factors such as concentration, polymerization inhibitor consumption, radiation source type and dosage of radiation of control monomer.The percent grafting of the functional fiber of the present invention's preparation is 0.1-80%, and the carboxyl Adsorption of Heavy Metal Ions on this functional fiber capable of using is utilized the polyacrylate adsorb organic compound on this functional fiber.
The specific embodiment
Introduce specific embodiment of the present invention below, but the present invention does not receive the restriction of embodiment.
Embodiment 1: the preparation method of the polypropylene tows of a kind of Adsorption of Heavy Metal Ions simultaneously and organic pollution
1) be that 0.5% acrylic acid and percentage by volume are that 30% methyl acrylate is dissolved in the mixed solution that is mixed with homogeneous in the absolute ethyl alcohol with percentage by volume; The adding mass percent is 0.5% hydroquinone of polymerization retarder, then fiber is put into above-mentioned mixed solution and leaves standstill immersion 0.5 hour;
2) soaked polypropylene tows is transferred in the sealable plastic bag together with the organic matter mixed solution; Feed nitrogen and get rid of oxygen; Then with plastic bag sealing; Fiber is dispersed in plastic bag is no more than the thick thin layer of 5mm, under the high energy ultraviolet ray, carried out the mutual radiation graft reaction 0.5 hour under the room temperature;
3) polypropylene tows behind the irradiation grafting is taken out the back with soaked in absolute ethyl alcohol flush away unreacted monomer and homopolymers, obtaining after the drying can the while Adsorption of Heavy Metal Ions and the polypropylene tows of organic pollution.
The percent grafting of this functional fiber is 28.6%, to Pb
2+Adsorbance be 3.4mg/g, to heavy metal ion Cr
2+Adsorbance be 12.1mg/g, the clearance rate of dibutyl phthalate is reached 75.93%.
Embodiment 2: the preparation method of the polypropylene non-woven fabric of a kind of Adsorption of Heavy Metal Ions simultaneously and organic pollution
1) be that 40% acrylic acid and percentage by volume are that 0.5% methyl acrylate is dissolved in the mixed solution that is mixed with homogeneous in the absolute ethyl alcohol with percentage by volume; The adding mass percent is 3% hydroquinone of polymerization retarder, then fiber is put into above-mentioned mixed solution and leaves standstill immersion 2 hours;
2) soaked polypropylene non-woven fabric is transferred in the sealable plastic bag together with the organic matter mixed solution; Feed nitrogen and get rid of oxygen; Then with plastic bag sealing; Fiber is dispersed in plastic bag is no more than the thick thin layer of 5mm, at room temperature the irradiation dose by 5kGy carried out the mutual radiation graft reaction 1 minute under high-power electron beam;
3) polypropylene non-woven fabric behind the irradiation grafting is taken out the back with soaked in absolute ethyl alcohol flush away unreacted monomer and homopolymers, obtaining after the drying can the while Adsorption of Heavy Metal Ions and the polypropylene non-woven fabric of organic pollution.
The percent grafting of this functional fiber is 13.8%, to Pb
2+Adsorbance be 54.1mg/g, to heavy metal ion Cr
2+Adsorbance be 67.2mg/g, the clearance rate of dibutyl phthalate is reached 54.9%.
Embodiment 3: the preparation method of the polyamide nonwoven fabric of a kind of Adsorption of Heavy Metal Ions simultaneously and organic pollution
1) be that 10% acrylic acid and percentage by volume are that 10% methyl acrylate is dissolved in the mixed solution that is mixed with homogeneous in the absolute ethyl alcohol with percentage by volume; The adding mass percent is 0.5% polymerization inhibitor, then fiber is put into above-mentioned mixed solution and leaves standstill immersion 12 hours;
2) soaked polyamide nonwoven fabric is transferred in the sealable plastic bag together with the organic matter mixed solution; Feed nitrogen and get rid of oxygen; Then with plastic bag sealing; Fiber is dispersed in plastic bag is no more than the thick thin layer of 5mm, at room temperature the irradiation dose by 20kGy carried out the mutual radiation graft reaction 24 hours under gamma ray;
3) the polyamide nonwoven fabric behind the irradiation grafting is taken out the back with soaked in absolute ethyl alcohol flush away unreacted monomer and homopolymers, obtaining after the drying can the while Adsorption of Heavy Metal Ions and the polyamide nonwoven fabric of organic pollution.
The percent grafting of this functional fiber is 58.9%, to Pb
2+Adsorbance be 61.2mg/g, to heavy metal ion Cr
2+Adsorbance be 71.0mg/g, the clearance rate of dibutyl phthalate is reached 68.9%.
Embodiment 4: the preparation method of the ps hollow fiber uf membrane of a kind of Adsorption of Heavy Metal Ions simultaneously and organic pollution
1) be that 5% acrylic acid and percentage by volume are that 5% methyl acrylate is dissolved in the mixed solution that is mixed with homogeneous in the absolute ethyl alcohol with percentage by volume; The adding mass percent is 1% hydroquinone of polymerization retarder, then fiber is put into above-mentioned mixed solution and leaves standstill immersion 12 hours;
2) soaked ps hollow fiber uf membrane is transferred in the sealable plastic bag together with the organic matter mixed solution; Feed nitrogen and get rid of oxygen; Then with plastic bag sealing; Fiber is dispersed in plastic bag is no more than the thick thin layer of 5mm, at room temperature the irradiation dose by 10kGy carried out the mutual radiation graft reaction 10 minutes under high-power electron beam;
3) ps hollow fiber uf membrane behind the irradiation grafting is taken out the back with soaked in absolute ethyl alcohol flush away unreacted monomer and homopolymers, obtaining after the drying can the while Adsorption of Heavy Metal Ions and the ps hollow fiber uf membrane of organic pollution.
The percent grafting of this functional fiber is 11.2%, to Pb
2+Adsorbance be 24.3mg/g, to heavy metal ion Cr
2+Adsorbance be 36.2mg/g, the clearance rate of dibutyl phthalate is reached 68.2%.
Claims (7)
1. preparation method of the functional fiber of Adsorption of Heavy Metal Ions and organic pollution simultaneously, its key step is following:
1) be that the acrylic acid of 0.5%--40% and acrylic acid ester that percentage by volume is 0.5%-30% are dissolved in the mixed solution that is mixed with homogeneous in the organic solvent with percentage by volume; Adding mass percent is the polymerization inhibitor of 0.1%--3%, then fiber is put into above-mentioned mixed solution and leaves standstill immersion 0.5-12 hour;
2) soaked fiber is transferred in the sealable plastic bag together with the organic matter mixed solution; Feed nitrogen and get rid of oxygen; Then with plastic bag sealing; Fiber is dispersed in plastic bag is no more than the thick thin layer of 5mm, at room temperature the irradiation dose by 5kGy--60kGy carried out the mutual radiation graft reaction 1 minute under irradiation bomb--and 48 hours;
3) fiber behind the irradiation grafting is taken out the back with soaked in absolute ethyl alcohol flush away unreacted monomer and homopolymers, obtain the functional fiber of while Adsorption of Heavy Metal Ions and organic pollution after the drying.
2. according to the preparation method of the functional fiber of described a kind of Adsorption of Heavy Metal Ions simultaneously of claims 1 and organic pollution; It is characterized in that; The fibrous matrix that is adopted comprises polyamide, polypropylene, polyethylene, polytetrafluoroethylene (PTFE), polyacrylonitrile and polysulfones, and form comprises monfil, nonwoven fabric, tow and doughnut.
3. according to the preparation method of the functional fiber of described a kind of Adsorption of Heavy Metal Ions simultaneously of claims 1 and organic pollution, it is characterized in that the polymerization inhibitor of adding is a kind of or its mixture in hydroquinones, 1,4-benzoquinone, the MEHQ.
4. according to the preparation method of the functional fiber of described a kind of Adsorption of Heavy Metal Ions simultaneously of claims 1 and organic pollution; It is characterized in that described acrylic acid ester comprises a kind of or its mixture in methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, dodecyl acrylate, the octadecyl acrylate.
5. according to the preparation method of the functional fiber of described a kind of Adsorption of Heavy Metal Ions simultaneously of claims 1 and organic pollution, it is characterized in that described irradiation bomb comprises that high-power electron beam, gamma ray, high energy are ultraviolet.
6. according to the preparation method of the functional fiber of described a kind of Adsorption of Heavy Metal Ions simultaneously of claims 1 and organic pollution; It is characterized in that described organic solvent comprises a kind of or its mixture in absolute ethyl alcohol, isopropyl alcohol, acetone, benzene, toluene, the chloroform.
7. according to the preparation method of the functional fiber of described a kind of Adsorption of Heavy Metal Ions simultaneously of claims 1 and organic pollution; It is characterized in that; The percent grafting that this fiber is removed material is 0.1-80%; Carboxyl Adsorption of Heavy Metal Ions on this functional fiber capable of using is utilized the polyacrylate adsorb organic compound on this functional fiber.
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| CN102941070A (en) * | 2012-11-30 | 2013-02-27 | 南京大学 | Polyethylene-methacrylic acid-polyethylene polyamine fiber and method for preparing same |
| CN103091429A (en) * | 2012-12-27 | 2013-05-08 | 天津工业大学 | Preparation method and application of solid phase extraction membrane comprising amphipathicity functional group |
| CN103614911A (en) * | 2013-11-07 | 2014-03-05 | 中国石油天然气集团公司 | Functionalized non-woven oil-absorbing material and preparation method thereof |
| CN103911862A (en) * | 2014-03-24 | 2014-07-09 | 福建鑫华股份有限公司 | Floating oil removing material and preparation method thereof |
| CN104492286A (en) * | 2014-12-19 | 2015-04-08 | 天津工业大学 | Preparation and application of support layer functionalized adsorption-enhanced type composite ultrafiltration membrane |
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| CN104611926A (en) * | 2014-12-30 | 2015-05-13 | 中国地质大学（武汉） | Method for preparing ion exchange fiber by ultraviolet grafting |
| CN106268699A (en) * | 2016-09-24 | 2017-01-04 | 北京益净环保设备科技有限公司 | For granule adsorbent adsorbing furan and preparation method thereof |
| CN108061716A (en) * | 2017-12-15 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of carboxy-functionalized modified acrylic fibre is to the selective absorbing detection method of heavy metal cadmium ion |
| CN109235032A (en) * | 2018-07-28 | 2019-01-18 | 安徽省义顺渔网渔具有限公司 | A kind of freeze proof wear-resisting high-strength degree fishing lines |
| CN109403033A (en) * | 2018-11-28 | 2019-03-01 | 天津工业大学 | A kind of functionalization non-woven cloth, preparation method and its usage loading graphene |
| CN109440459A (en) * | 2018-11-28 | 2019-03-08 | 天津工业大学 | It is a kind of to load the functionalization non-woven cloth of graphene oxide, preparation method and applications |
| CN109537302A (en) * | 2018-12-28 | 2019-03-29 | 宁波三同编织有限公司 | A kind of multi-function health-care linen-cotton fabric and preparation method thereof |
| CN110860277A (en) * | 2019-12-09 | 2020-03-06 | 天津工业大学 | Method for extracting rare earth metal from aminodiacetic acid modified fiber |
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| CN102941070A (en) * | 2012-11-30 | 2013-02-27 | 南京大学 | Polyethylene-methacrylic acid-polyethylene polyamine fiber and method for preparing same |
| CN103091429A (en) * | 2012-12-27 | 2013-05-08 | 天津工业大学 | Preparation method and application of solid phase extraction membrane comprising amphipathicity functional group |
| CN103614911A (en) * | 2013-11-07 | 2014-03-05 | 中国石油天然气集团公司 | Functionalized non-woven oil-absorbing material and preparation method thereof |
| CN103911862B (en) * | 2014-03-24 | 2016-03-23 | 福建鑫华股份有限公司 | A kind of clean-up of oil spill material and preparation method thereof |
| CN103911862A (en) * | 2014-03-24 | 2014-07-09 | 福建鑫华股份有限公司 | Floating oil removing material and preparation method thereof |
| CN104492286A (en) * | 2014-12-19 | 2015-04-08 | 天津工业大学 | Preparation and application of support layer functionalized adsorption-enhanced type composite ultrafiltration membrane |
| CN104492286B (en) * | 2014-12-19 | 2016-10-05 | 天津工业大学 | The preparation of the absorption enhancement mode composite hyperfiltration membrane of a kind of supporting layer functionalization and application |
| CN104525115A (en) * | 2014-12-25 | 2015-04-22 | 东华大学 | Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and WO3 |
| CN104525115B (en) * | 2014-12-25 | 2016-08-17 | 东华大学 | A kind of CNT is combined WO3the preparation method of green deep water treatment agent |
| CN104611926A (en) * | 2014-12-30 | 2015-05-13 | 中国地质大学（武汉） | Method for preparing ion exchange fiber by ultraviolet grafting |
| CN106268699A (en) * | 2016-09-24 | 2017-01-04 | 北京益净环保设备科技有限公司 | For granule adsorbent adsorbing furan and preparation method thereof |
| CN108061716A (en) * | 2017-12-15 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of carboxy-functionalized modified acrylic fibre is to the selective absorbing detection method of heavy metal cadmium ion |
| CN109235032A (en) * | 2018-07-28 | 2019-01-18 | 安徽省义顺渔网渔具有限公司 | A kind of freeze proof wear-resisting high-strength degree fishing lines |
| CN109403033A (en) * | 2018-11-28 | 2019-03-01 | 天津工业大学 | A kind of functionalization non-woven cloth, preparation method and its usage loading graphene |
| CN109440459A (en) * | 2018-11-28 | 2019-03-08 | 天津工业大学 | It is a kind of to load the functionalization non-woven cloth of graphene oxide, preparation method and applications |
| CN109537302A (en) * | 2018-12-28 | 2019-03-29 | 宁波三同编织有限公司 | A kind of multi-function health-care linen-cotton fabric and preparation method thereof |
| CN110860277A (en) * | 2019-12-09 | 2020-03-06 | 天津工业大学 | Method for extracting rare earth metal from aminodiacetic acid modified fiber |
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