CN109289781B - Preparation method of composite hydrogel fiber - Google Patents
Preparation method of composite hydrogel fiber Download PDFInfo
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- CN109289781B CN109289781B CN201811120423.1A CN201811120423A CN109289781B CN 109289781 B CN109289781 B CN 109289781B CN 201811120423 A CN201811120423 A CN 201811120423A CN 109289781 B CN109289781 B CN 109289781B
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000000017 hydrogel Substances 0.000 title claims abstract description 36
- 239000000835 fiber Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000499 gel Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims description 95
- 229960000892 attapulgite Drugs 0.000 claims description 71
- 229910052625 palygorskite Inorganic materials 0.000 claims description 71
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 53
- 235000010410 calcium alginate Nutrition 0.000 claims description 49
- 239000000648 calcium alginate Substances 0.000 claims description 49
- 229960002681 calcium alginate Drugs 0.000 claims description 49
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 49
- 238000009987 spinning Methods 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 36
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 31
- 235000010413 sodium alginate Nutrition 0.000 claims description 31
- 239000000661 sodium alginate Substances 0.000 claims description 31
- 229940005550 sodium alginate Drugs 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000002166 wet spinning Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 39
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 38
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 238000001514 detection method Methods 0.000 abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 239000011133 lead Substances 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
- B01J20/28047—Gels
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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
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Specific cations in water, e.g. heavy metals
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a preparation method of composite hydrogel fibers, and belongs to the field of high polymer materials. The product of the invention is characterized in that the product not only can effectively carry out qualitative detection on the heavy metal ions in the water, but also can absorb the heavy metal ions in the water. The adsorption removal rate of the product of the invention on low-concentration heavy metal ions such as nickel, chromium, lead, mercury and the like in wastewater reaches more than 90%. The preparation of the product of the invention does not need special equipment, is easy to realize industrialization and has low product cost. The composite gel fiber product is convenient to apply, can be used in a bundling way, and can be woven into fabrics or assembled into a separation component. After the product of the invention adsorbs heavy metal ions, the adsorbed heavy metal ions can be efficiently recovered by cleaning with a cleaning solution, more than 95% of the adsorbed heavy metal ions can be washed away at one time, and the fiber can be reused.
Description
The present application is a divisional application of the following applications: the application date is 2016, 12, and 07, the application number is 201611116739.4, and the invention discloses a heavy metal ion adsorption and detection type composite hydrogel fiber and a preparation method thereof.
Technical Field
The invention relates to the field of high polymer materials, in particular to a composite high polymer hydrogel fiber with good detection function and adsorption function on heavy metal ions such as nickel, chromium, lead, mercury and the like and a preparation method thereof. The composite hydrogel can effectively perform qualitative detection on conventional heavy metal ions in water, can adsorb the heavy metal ions in water, and can be applied to the field of sewage treatment in the electroplating industry, the chemical industry and the like.
Background
With the rapid development of chemical industry, metallurgical industry and the like, heavy metal ion pollution causes serious harm to human bodies. At present, the main methods for harmlessly treating the wastewater containing heavy metal ions include a membrane separation method, an electrochemical precipitation method, an ion exchange method, an adsorption and biological treatment method and the like. Wherein, the adsorption method has high removal rate of heavy metal ions, large adsorption capacity, high adsorption rate and simple and convenient operation. However, adsorbents that can adsorb heavy metal ions are generally expensive. Therefore, the development of a novel adsorbent with low cost and high adsorption efficiency by using a low-price material to compositely modify the existing adsorbent is an important direction for researching the adsorbent capable of adsorbing heavy metal ions.
Attapulgite (ATP) is a natural nonmetallic mineral material, is a water-containing magnesium-rich silicate clay mineral with a chain lamellar structure, and has a large specific surface area and strong physical adsorption capacity due to the special structure; on the other hand, the attapulgite has negative charges on the bedding surface, and the exchangeable cations are adsorbed between the layers to balance the charges, so that the attapulgite has strong ion adsorption and exchange capacity and can be applied to the treatment of wastewater containing heavy metal ions. However, in the field of water treatment, powdered attapulgite cannot be directly put into water for use and needs to be treated by a certain method despite its good suspensibility in water and its good adsorption capacity. At present, a better treatment method is to adopt a certain carrier to fixedly carry attapulgite and then put the attapulgite into water for use. The present inventors have disclosed a method for producing an adsorption-type polymer composite hydrogel and a product thereof (patent No. ZL201020595998.1) in the prior invention, in which the polymer hydrogel is used as a carrier to immobilize attapulgite, thereby exerting the adsorption effect of the attapulgite well. In addition, a preparation method of the chitosan composite flocculant with large heavy metal ion adsorption capacity and high adsorption efficiency and a product thereof (CN103274509A) are disclosed.
The Sodium Alginate (SA) is odorless, tasteless and faint yellow amorphous powder, has excellent performance, is widely applied to various fields of food, textile, medicine, daily chemical industry and the like, is easy to form Calcium Alginate (CA) gel in a calcium ion solution, and has good adsorption performance on heavy metal ions. Guerra D L et al modified natural ATP added to calcium alginate films to prepare hybrid composite films, studied the adsorption performance of hybrid films on Th [ Guerra D L, Viewa R, da Costa L P, et al: Retracted: Sodium alginate films modified by raw and functionalized adsorbed for use of Sodium (IV) adsorption: A theromyamic pro-ach [ J ]. Journal of Physics and Chemistry of Solids,2009,70(11):1413-1421 ]. Li Y and the like fix carbon nanotubes in calcium alginate to prepare a fibrous composite gel, and research results show that the fibrous gel can increase the specific surface area and improve the adsorption performance of copper ions [ Li Y, Liu F, Xia B, et al. Therefore, the calcium alginate gel is used as a carrier to coat and fix the attapulgite, and the characteristics of good adsorption performance and excellent formability of the calcium alginate gel can be fully utilized to coordinate with the heavy metal ion adsorption effect of the attapulgite to prepare the heavy metal ion adsorption type gel material.
However, the existing heavy metal ion adsorbing material generally only has a single heavy metal ion adsorbing function, and cannot detect heavy metal ions at the same time. Many researchers at home and abroad are dedicated to the research on heavy metal ion pollution, and it is still a challenge to design an adsorption material which has good adsorption performance and can rapidly detect the existence of heavy metals on site.
Carbon quantum dots (CD) are non-toxic or low-toxic, low in molecular weight, small in particle size, low in manufacturing cost, have very peculiar chemical and physical properties, have strong fluorescence, water solubility, biocompatibility and the like, can be applied to biological imaging, medical diagnosis, catalysts and photovoltaic devices, and simultaneously have the characteristic of being easily quenched by metal ions, so that the characteristic of being easily quenched by the metal ions attracts great attention of researchers in recent years and is used for detection application of the heavy metal ions. Gogoi N et al mixed chitosan carbon dot solution with gelatin solution, microwave formed, prepared gelatin/carbon dot hybrid flat sheet membrane, studied the separation and detection performance of heavy metals [ Gogoi N, Barooah M, Majumdar G, et al, carbon dots grafted synthetic hydrogel hybrid for optical detection and separation of heavy metals [ J ]. ACS applied materials & interfaces 2015,7(5):3058-3067 ]. However, in general, the research on materials capable of adsorbing and detecting heavy metal ions simultaneously in the field of water treatment is not much, i.e., the adsorption and fluorescence detection type composite material has a great application prospect.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problem to be solved by the invention is to provide a preparation method of a high-molecular hydrogel capable of adsorbing and monitoring heavy metal ions simultaneously. The composite hydrogel is a calcium alginate/attapulgite/carbon dot composite hydrogel fiber, can effectively perform qualitative detection on conventional heavy metal ions in water, and can adsorb the heavy metal ions in the water.
The product of the invention adopts sodium alginate and attapulgite as raw materials, adopts a wet spinning process to prepare spun fibers, and can form calcium alginate hydrogel fibers CA/ATP by crosslinking in a calcium ion solution. The product adopts a commercial carbon dot, and is modified by a coupling agent 3-glycidyloxypropyltrimethoxysilane (KH560) to prepare the KH560 modified carbon dot.
The heavy metal ion adsorption and detection type composite hydrogel fiber is prepared by the following method:
(1) and (3) preparing a CA/ATP composite gel. A certain amount of SA is dissolved in 100g of deionized water to prepare an SA solution with the concentration of 1-5%. And adding ATP with the SA content of 10-50% into the SA solution, and stirring to fully disperse the ATP in the solution to obtain the spinning solution. Pouring the spinning solution into a wet spinning machine material kettle, sealing the spinning machine material kettle, heating the spinning machine material kettle to enable the temperature of the spinning solution to be 25-50 ℃, standing for 12 hours, and then vacuumizing and defoaming for 20-60 minutes. And after the defoaming treatment of the spinning feed liquid is finished, opening a switch of an outlet of the material kettle, introducing nitrogen into the kettle for pressurization, opening a switch of a metering pump, adjusting the rotating speed to 8-20 rpm, and starting spinning. Spun yarn is injected with 1-5% CaCl rapidly2In the solution, crosslinking and solidifying for 10-15 h for molding to obtain the fibrous CA/ATP hydrogel. Washing the product with distilled water to remove Ca from the surface of the product2+. Washing the obtained hydrogel product, and freeze-drying for use。
(2) KH560 modified carbon dots are prepared. Weighing a certain mass of CD solid, and dissolving the CD solid in deionized water to prepare a CD solution with the solution concentration of 1-5 mg/mL. Adding a certain amount of KH560 into the carbon dot aqueous solution, wherein the addition amount of the KH560 is 5-20% of the volume of the CD solution. Uniformly stirring for 15-30 h at 20-50 ℃ to obtain the CD-KH560 solution.
(3) CA/ATP/CD complex gel preparation. Weighing 10mg of the CA/ATP fibrous gel prepared in the step (1), calculating and weighing a certain volume of the CD-KH560 solution prepared in the step (2) according to the mass ratio of 1-5% of the CA/ATP composite gel, immersing the fibrous gel into the CD-KH560 solution, oscillating for 6-24 h in a shaking table at the temperature of 20-40 ℃ in a dark place, washing the obtained product with distilled water for three times, and then freeze-drying to obtain the heavy metal ion adsorption and detection type CA/ATP/CD composite hydrogel fiber.
Has the advantages that:
the composite gel for monitoring and removing heavy metal ions prepared by the invention adopts a blending and surface grafting method, the composite gel fiber product can adsorb and monitor the heavy metal ions simultaneously, the heavy metal ions have excellent adsorbability and outstanding fluorescence quenching property, and the composite gel fiber product is a novel calcium alginate composite hydrogel product. The composite gel fiber product of the invention has the function of weakening or quenching fluorescence in heavy metal ion solution, and the responsiveness can achieve the purpose of monitoring water quality in real time. The adsorption removal rate of the composite gel fiber product on low-concentration heavy metal ions such as nickel, chromium, lead, mercury and the like reaches more than 90%. Therefore, the product of the invention not only has excellent effect of removing heavy metal ions, but also has real-time monitoring effect on the heavy metal ions in water quality
Compared with the prior art, the preparation method of the composite gel has the advantages of simple process, no need of special equipment and easy industrial implementation. The product technology CA has larger coating amount on ATP, thereby having low product cost and good compatibility among materials.
The attapulgite is used as a natural non-metal inorganic mineral material, and has low price and rich storage. The carbon dots of the present invention are common commercially available carbon dots. With the present technology, ATP can be easily surface grafted with CD.
The composite gel fiber product has good mechanical property and convenient application, can be used in a bundling way, and can also be woven into fabrics or assembled into a separate component. After the fiber disclosed by the invention adsorbs heavy metal ions, the adsorbed heavy metal ions can be efficiently recovered by cleaning through a cleaning solution, more than 95% of the adsorbed heavy metal ions can be washed away at one time, and the fiber can be reused.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Unless otherwise specified, technical means not described in the embodiments may be implemented in a manner well known to those skilled in the art. Various modifications, substitutions, and improvements to the conventional variables in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention, and equivalents will also fall within the scope of the invention as defined by the appended claims. In particular, the specific parameters defined in the present invention should have allowable error ranges.
Example 1
(1) And (3) preparing a CA/ATP composite gel. A certain amount of SA is dissolved in 100g of deionized water to prepare an SA solution with the concentration of 1%. ATP with 10% of SA content is added into the SA solution, and stirring is carried out to ensure that the ATP is fully dispersed in the solution, so as to obtain spinning solution. Pouring the spinning solution into a wet spinning machine material kettle, sealing the spinning machine material kettle, heating the spinning machine material kettle to enable the temperature of the spinning solution to be 25 ℃, standing for 12 hours, and then vacuumizing and defoaming for 20 minutes. And after the deaeration treatment of the spinning feed liquid is finished, opening a switch of an outlet of the material kettle, introducing nitrogen into the kettle for pressurization, opening a switch of a metering pump, adjusting the rotating speed to 8 revolutions per minute, and starting spinning. Spun yarn is injected with 1% CaCl rapidly2In the solution, crosslinking and solidifying for 10h to form the fibrous CA/ATP hydrogel. Washing the product with distilled water to remove Ca from the surface of the product2+. And washing the obtained hydrogel product, and freeze-drying for later use.
(2) KH560 modified carbon dots are prepared. Weighing a certain mass of CD solid, and dissolving the CD solid in deionized water to prepare a CD solution with the solution concentration of 1 mg/mL. Adding a certain amount of KH560 into the carbon dot aqueous solution, wherein the addition amount of the KH560 is 5 percent of the volume of the CD solution. Stirring at 20 deg.C for 15 hr to obtain CD-KH560 solution.
(3) CA/ATP/CD complex gel preparation. Weighing 10mg of CA/ATP fibrous gel prepared in the step (1), weighing a certain volume of the CD-KH560 solution prepared in the step (2) according to the mass ratio of 1% of the CA/ATP composite gel, immersing the fibrous gel into the CD-KH560 solution, vibrating for 6 hours in a shaking table at 20 ℃ in a dark place, washing the obtained product with distilled water for three times, and freeze-drying to obtain the heavy metal ion adsorption and detection type CA/ATP/CD composite hydrogel fiber.
Example 2
(1) And (3) preparing a CA/ATP composite gel. A certain amount of SA is dissolved in 100g of deionized water to prepare an SA solution with the concentration of 2%. ATP with an SA content of 20% is added to the SA solution, and stirring is carried out to fully disperse the ATP in the solution, so as to obtain the spinning solution. Pouring the spinning solution into a wet spinning machine material kettle, sealing the spinning machine material kettle, heating the spinning machine material kettle to ensure that the temperature of the spinning solution is 30 ℃, standing for 12 hours, and then vacuumizing and defoaming for 30 minutes. And after the defoaming treatment of the spinning material liquid is finished, opening a switch of an outlet of the material kettle, introducing nitrogen into the kettle for pressurization, opening a switch of a metering pump, adjusting the rotating speed to 10 revolutions per minute, and starting spinning. Spun yarn is injected with CaCl with concentration of 2%2In the solution, crosslinking and solidifying for 10h to form the fibrous CA/ATP hydrogel. Washing the product with distilled water to remove Ca from the surface of the product2+. And washing the obtained hydrogel product, and freeze-drying for later use.
(2) KH560 modified carbon dots are prepared. Weighing a certain mass of CD solid, and dissolving the CD solid in deionized water to prepare a CD solution with the solution concentration of 2 mg/mL. Adding a certain amount of KH560 into the carbon dot aqueous solution, wherein the addition amount of the KH560 is 8 percent of the volume of the CD solution. Stirring at 20 deg.C for 15 hr to obtain CD-KH560 solution.
(3) CA/ATP/CD complex gel preparation. Weighing 10mg of CA/ATP fibrous gel prepared in the step (1), weighing a certain volume of CD-KH560 solution prepared in the step (2) according to the mass ratio of 2% of the CA/ATP composite gel, immersing the fibrous gel into the CD-KH560 solution, vibrating in a shaking table at 20 ℃ in a dark place for 10h, washing the obtained product with distilled water for three times, and freeze-drying to obtain the heavy metal ion adsorption and detection type CA/ATP/CD composite hydrogel fiber.
Example 3
(1) And (3) preparing a CA/ATP composite gel. A certain amount of SA is dissolved in 100g of deionized water to prepare a 3% SA solution. ATP with the SA content of 30% is added into the SA solution, and stirring is carried out to ensure that the ATP is fully dispersed in the solution, so as to obtain the spinning solution. Pouring the spinning solution into a wet spinning machine material kettle, sealing the spinning machine material kettle, heating the spinning machine material kettle to enable the temperature of the spinning solution to be 40 ℃, standing for 12 hours, and then vacuumizing and defoaming for 40 minutes. And after the defoaming treatment of the spinning material liquid is finished, opening a switch of an outlet of the material kettle, introducing nitrogen into the kettle for pressurization, opening a switch of a metering pump, adjusting the rotating speed to 12 revolutions per minute, and starting spinning. Spun yarn is injected with 1% CaCl rapidly2In the solution, crosslinking and solidifying for 15h to form the fibrous CA/ATP hydrogel. Washing the product with distilled water to remove Ca from the surface of the product2+. And washing the obtained hydrogel product, and freeze-drying for later use.
(2) KH560 modified carbon dots are prepared. Weighing a certain mass of CD solid, and dissolving the CD solid in deionized water to prepare a CD solution with the solution concentration of 5 mg/mL. Adding a certain amount of KH560 into the carbon dot aqueous solution, wherein the addition amount of the KH560 is 20 percent of the volume of the CD solution. Stirring at 50 deg.C for 30 hr to obtain CD-KH560 solution.
(3) CA/ATP/CD complex gel preparation. Weighing 10mg of CA/ATP fibrous gel prepared in the step (1), weighing a certain volume of the CD-KH560 solution prepared in the step (2) according to the mass ratio of 3% of the CA/ATP composite gel, immersing the fibrous gel into the CD-KH560 solution, vibrating in a shaking table at 40 ℃ in a dark place for 24h, washing the obtained product with distilled water for three times, and freeze-drying to obtain the heavy metal ion adsorption and detection type CA/ATP/CD composite hydrogel fiber.
Example 4
(1) And (3) preparing a CA/ATP composite gel. A certain amount of SA is dissolved in 100g of deionized water to prepare a 3% SA solution. ATP with the SA content of 40% is added into the SA solution, and stirring is carried out to ensure that the ATP is fully dispersed in the solution, so as to obtain the spinning solution. Pouring the spinning solution into a wet spinning machine material kettle, sealing the spinning machine material kettle, heating the spinning machine material kettle to enable the temperature of the spinning solution to be 50 ℃, standing for 12 hours, and then vacuumizing and defoaming for 20 minutes. And after the defoaming treatment of the spinning material liquid is finished, opening a switch of an outlet of the material kettle, introducing nitrogen into the kettle for pressurization, opening a switch of a metering pump, adjusting the rotating speed to 20 revolutions per minute, and starting spinning. Spun yarn was injected rapidly with 4% CaCl2In the solution, crosslinking and solidifying for 12h to obtain the fibrous CA/ATP hydrogel. Washing the product with distilled water to remove Ca from the surface of the product2+. And washing the obtained hydrogel product, and freeze-drying for later use.
(2) KH560 modified carbon dots are prepared. Weighing a certain mass of CD solid, and dissolving the CD solid in deionized water to prepare a CD solution with the solution concentration of 4 mg/mL. Adding a certain amount of KH560 into the carbon dot aqueous solution, wherein the addition amount of the KH560 is 15 percent of the volume of the CD solution. Stirring at 40 deg.C for 20 hr to obtain CD-KH560 solution.
(3) CA/ATP/CD complex gel preparation. Weighing 10mg of CA/ATP fibrous gel prepared in the step (1), weighing a certain volume of CD-KH560 solution prepared in the step (2) according to the mass ratio of 3% of the CA/ATP composite gel, immersing the fibrous gel into the CD-KH560 solution, oscillating the fibrous gel in a shaking table at 30 ℃ in a dark place for 12 hours, washing the obtained product with distilled water for three times, and freeze-drying to obtain the heavy metal ion adsorption and detection type CA/ATP/CD composite hydrogel fiber.
Example 5
(1) And (3) preparing a CA/ATP composite gel. A certain amount of SA is dissolved in 100g of deionized water to prepare an SA solution with the concentration of 5%. ATP with the SA content of 50% is added into the SA solution, and stirring is carried out to ensure that the ATP is fully dispersed in the solution, so as to obtain the spinning solution. Pouring the spinning solution into a wet spinning machine material kettle, sealing the spinning machine material kettle, heating the spinning machine material kettle to enable the temperature of the spinning solution to be 35 ℃, standing for 12 hours, and then vacuumizing and defoaming for 60 minutes.And after the defoaming treatment of the spinning material liquid is finished, opening a switch of an outlet of the material kettle, introducing nitrogen into the kettle for pressurization, opening a switch of a metering pump, adjusting the rotating speed to 20 revolutions per minute, and starting spinning. Spun yarn was injected rapidly with 5% CaCl2In the solution, crosslinking and solidifying for 15h to form the fibrous CA/ATP hydrogel. Washing the product with distilled water to remove Ca from the surface of the product2+. And washing the obtained hydrogel product, and freeze-drying for later use.
(2) KH560 modified carbon dots are prepared. Weighing a certain mass of CD solid, and dissolving the CD solid in deionized water to prepare a CD solution with the solution concentration of 5 mg/mL. Adding a certain amount of KH560 into the carbon dot aqueous solution, wherein the addition amount of the KH560 is 20 percent of the volume of the CD solution. Stirring at 40 deg.C for 24 hr to obtain CD-KH560 solution.
(3) CA/ATP/CD complex gel preparation. Weighing 10mg of CA/ATP fibrous gel prepared in the step (1), weighing a certain volume of the CD-KH560 solution prepared in the step (2) according to the mass ratio of 5% of the CA/ATP composite gel, immersing the fibrous gel into the CD-KH560 solution, oscillating for 18h in a shaking table at 30 ℃ in a dark place, washing the obtained product for three times by distilled water, and freeze-drying to obtain the heavy metal ion adsorption and detection type CA/ATP/CD composite hydrogel fiber.
Claims (1)
1. The preparation method of the composite hydrogel fiber is characterized by comprising the following steps of:
(1) preparing calcium alginate/attapulgite composite gel: dissolving a certain amount of sodium alginate in 100g of deionized water to prepare a sodium alginate solution with the concentration of 1%; adding attapulgite with the sodium alginate content of 10% into a sodium alginate solution, and stirring to fully disperse the attapulgite in the solution to obtain a spinning solution; pouring the spinning solution into a wet spinning machine material kettle, sealing the spinning machine material kettle, heating the spinning machine material kettle to enable the temperature of the spinning solution to be 25 ℃, standing for 12 hours, and then vacuumizing and defoaming for 20 minutes; after the deaeration treatment of the spinning feed liquid is finished, opening a switch at the outlet of the material kettle, introducing nitrogen into the kettle for pressurization, opening a switch of a metering pump, adjusting the rotating speed to 8 revolutions per minute, and starting spinning; the spun silk has a rapid injection concentration of 1%In (C) is2In the solution, crosslinking and solidifying for 10h for forming to obtain fibrous calcium alginate/attapulgite hydrogel; washing the product with distilled water to remove Ca from the surface of the product2+(ii) a Washing the obtained hydrogel product, and then freeze-drying for later use;
(2) preparation of 3-glycidyloxypropyltrimethoxysilane KH560 modified carbon dots: weighing a certain mass of carbon quantum dot solid, dissolving the carbon quantum dot solid in deionized water to prepare a carbon quantum dot solution with the solution concentration of 1 mg/mL; adding a certain amount of 3-glycidoxypropyltrimethoxysilane KH560 into the carbon quantum dot aqueous solution, wherein the addition amount of the 3-glycidoxypropyltrimethoxysilane KH560 is 5 percent of the volume of the carbon quantum dot solution; uniformly stirring for 15h at the temperature of 20 ℃ to obtain a carbon quantum dot-3-glycidyloxypropyltrimethoxysilane KH560 solution;
(3) preparing calcium alginate/attapulgite/carbon quantum dot composite gel: weighing 10mg of the calcium alginate/attapulgite fibrous gel prepared in the step (1), weighing a certain volume of the carbon quantum dot-3-glycidyloxypropyltrimethoxysilane KH560 solution prepared in the step (2) according to the mass ratio of 1% of the calcium alginate/attapulgite composite gel, immersing the fibrous gel into the carbon quantum dot-3-glycidyloxypropyltrimethoxysilane KH560 solution, oscillating the fibrous gel in a shaking table at 20 ℃ in a dark place for 6 hours, washing the obtained product with distilled water for three times, and then freeze-drying to obtain the calcium alginate/attapulgite/carbon quantum dot composite hydrogel fiber.
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