CN108126678B - Renewable carbon nanomaterial coated fiber adsorbent and preparation method thereof - Google Patents
Renewable carbon nanomaterial coated fiber adsorbent and preparation method thereof Download PDFInfo
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- CN108126678B CN108126678B CN201711497919.6A CN201711497919A CN108126678B CN 108126678 B CN108126678 B CN 108126678B CN 201711497919 A CN201711497919 A CN 201711497919A CN 108126678 B CN108126678 B CN 108126678B
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- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a reproducible nano carbon material coated fiber adsorbent and a preparation method thereof. The material comprises a fiber base layer grafted on the surface of polydopamine and a nano carbon material layer, wherein the nano carbon material layer is one or a mixture of two of graphene oxide or acidified carbon nanotubes. After 10 times of adsorption-desorption treatment, the adsorption capacity of the nano carbon material coated fiber still reaches 80 percent of the original adsorption capacity. According to the invention, a dopamine substance surface grafting layer is formed on the surface of the fiber, the surface grafting layer enables the surface of the fiber to contain amino, the charge adsorption of the amino and the nano-carbon material containing negative charges is realized by utilizing the principle that the amino carries positive charges under an acidic condition, and finally the nano-carbon material coated fiber is obtained, and the fiber has good capability of adsorbing dye wastewater.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and the field of dye wastewater treatment, and relates to a renewable carbon nanomaterial coated fiber adsorbent and a preparation method thereof.
Background
With the development of the dye and printing industry, the wastewater discharged in the production process becomes one of the most important water pollution sources at present. The waste water belongs to organic waste water containing a certain amount of toxic substances, has the characteristics of deep chromaticity, strong toxicity, complex and variable components, large discharge amount, wide distribution range, difficult biochemical degradation and the like, and brings serious harm to the ecological environment if the waste water is directly discharged without treatment, so that the treatment of the dye waste water is the focus of attention of the chemical and environmental protection industries.
At present, the dye wastewater is treated by a physical chemical method, a biological method or a chemical method and the like at home and abroad. These include adsorption, membrane separation, extraction, coagulation, photocatalytic oxidation, electrochemical oxidation, ultrasonic degradation, biological treatment, and ozonization, but these treatment techniques generally have some disadvantages, such as secondary pollution, high cost, etc., and among these treatment techniques, adsorption is increasingly favored because of its advantages of high removal efficiency, safety, high toxicity, and simple operation.
The commonly used adsorbents mainly include carbon nanotubes, graphene, ion exchange resin, silica, diatom, and the like. The carbon nanotube and graphene, as nanomaterials, have a very large specific surface area, and contain oxygen-containing groups such as hydroxyl, carboxyl and epoxy groups after certain treatment, which is beneficial to better adsorbing harmful substances in dye wastewater, and thus are considered to have higher efficiency in dye adsorption. Chinese patent with patent publication number CN 105056899A provides a method for preparing dye wastewater adsorbent, the method prepares the graphene oxide/nano-microcrystallite cellulose composite material by blending, the dye adsorption capacity is enhanced, and especially the adsorption effect of low-concentration dye is particularly obvious; chinese patent with patent publication number CN106902762A prepares a graphene oxide/multi-walled carbon nanotube/magnetic aerobic particle composite adsorbent, and the adsorbent can effectively treat dye wastewater, especially cationic dye.
The adsorbing material obtained in the patent is often obtained by blending, is in a powder shape and has poor dispersibility; after adsorption in the wastewater is completed, the recovery difficulty is high, and secondary pollution is easy to generate; meanwhile, the adsorption material is difficult to recycle, so that the manufacturing cost is increased. Therefore, it is required to develop a nano adsorbent having high adsorption efficiency, good dispersibility, and easy recycling.
Disclosure of Invention
The first purpose of the invention is to provide a renewable nano carbon material coated fiber adsorbent aiming at the defects of the prior art.
The renewable nano carbon material coated fiber comprises a fiber base layer grafted on the surface of polydopamine and a nano carbon material layer, wherein the nano carbon material layer is one or a mixture of graphene oxide and acidified carbon nanotubes.
After 10 times of adsorption and desorption treatment, the adsorption capacity of the renewable nano carbon material coated fiber still reaches 80 percent of the original adsorption capacity.
The second purpose of the invention is to provide a preparation method of renewable nano carbon material coated fiber, which comprises the following specific steps:
step (1), preparing nano carbon material dispersion liquid:
adding the nano carbon material powder into a dispersion medium at normal temperature, wherein the pH value of the dispersion medium is 0.5-6, mechanically stirring for 10-20 min at the stirring speed of 300-1000r/min, and performing ultrasonic treatment in an ice-water bath for 20-40 min to obtain a uniform and stable nano carbon material dispersion system. Wherein the weight of the nano carbon material powder is 0.01-2% of the weight of the dispersion medium.
The nano carbon material is one or a mixture of two of graphene oxide and acidified carbon nano tubes; the carbon-oxygen atom ratio of the carbon material is 1: 1-5: 1, preferably 2: 1-4: 1;
the dispersion medium is one or a mixture of water, ethanol, glycol, N-methylpyrrolidone (NMP) and Dimethylformamide (DMF);
preferably, the nano carbon material accounts for 0.03 to 1 percent of the weight of the dispersion medium;
preferably, the pH value of the dispersion medium is 1-5;
step (2), washing and removing fiber oil agent:
and (3) immersing the fiber into an organic solvent at normal temperature, ultrasonically cleaning for 5-60 min, finally cleaning with deionized water, and drying to remove oil agents and pollutants on the surface of the fiber.
The organic solvent is one or a mixture of more of ethanol, acetone, tetrahydrofuran or glycerol;
the fiber is one of UHMWPE fiber, polyester fiber, carbon fiber, polyvinyl alcohol fiber or glass fiber.
Step (3), grafting on the surface of the fiber:
adding a dopamine substance into a buffer solution with the pH value of 8-11, then adding the fiber treated in the step (2), stirring and reacting for 8-24 h, and washing and drying to obtain a polydopamine surface grafted fiber;
the buffer solution is one of sodium dihydrogen phosphate citric acid buffer solution, disodium hydrogen phosphate sodium dihydrogen phosphate buffer solution, barbiturate sodium hydrochloric acid buffer solution, Tris (hydroxymethyl) aminomethane (namely Tris) hydrochloric acid buffer solution and sodium carbonate sodium bicarbonate buffer solution;
the dopamine substance is one or a mixture of two of catecholamine or diphenoquinone compounds, and the structural formula is shown as formula (1) or (2)
Wherein R is- (CH) with an amino group2)x-NH2Or- (CH)y)x-NH-(CHq)p-CH3Or- (CH)2)x-NH-(CHOH)x-(CH2)P-CH3Or- (CH)2)x-NH-(CHOH)x-(CH2)P-C6H5Or- (CH)x-N(CHj)h-(CHq)p-(CH3)eor-CO-NH- (CH)2)p-CH3or-CO- (CH)2)x-NH2Wherein x is a natural number of 1-199, p and h are natural numbers of 0-199, y, q and e are 1 or 2, and j is 1, 2 or 3;
preferably, R is
n is a natural number of 1-20;
preferably, the pH value of the buffer solution is 8.5-10.5;
preferably, the mass concentration of the dopamine solution is 0.05-4%;
the mass ratio of the fibers to the dopamine solution is 1-10: 100;
the surface carbon-oxygen atom ratio of the surface grafted fiber is 2: 1-12: 1, preferably 3: 1-10: 1 (the surface carbon-oxygen atom ratio refers to the carbon-oxygen atom ratio of the fiber and the polydopamine);
the surface nitrogen-oxygen atom ratio of the surface grafted fiber is 1: 2-1: 7 (the surface nitrogen-oxygen atom ratio refers to the nitrogen-oxygen atom ratio of the fiber and the polydopamine);
step (4), preparing the nano carbon material coated fiber:
and (3) immersing the surface grafted fibers obtained in the step (3) into the nano carbon material dispersion liquid obtained in the step (1), stirring at the temperature of 20-60 ℃ for 0.1-1 h at the rotating speed of 100-800 r/min, washing and drying the fibers, and repeating the dipping reduction process for 2-20 times to obtain the nano carbon material coated fibers.
The mass ratio of the nano carbon material to the fiber is 20: 1-1: 1; preferably 10: 1-4: 1;
the carbon-oxygen atom ratio of the surface of the nano carbon material coated fiber is 2: 1-6: 1, preferably 3: 1-5: 1 (the carbon-oxygen atom ratio of the surface refers to the carbon-oxygen atom ratio of the fiber, the polydopamine and the nano carbon material);
the ratio of nitrogen atoms to oxygen atoms on the surface of the carbon nano-material coated fibers is 1: 8-1: 30 (the ratio of nitrogen atoms to oxygen atoms on the surface refers to the ratio of nitrogen atoms to oxygen atoms of the fibers, the polydopamine and the carbon nano-material).
The adsorption and desorption tests were carried out on the nanocarbon material-coated fibers of the present invention:
adsorption assayTest: a dye wastewater solution having a concentration of 500mg/L was added to a 250ml flask, the conjugate fiber of the present invention in an amount of 0.1 wt% based on the mass of the solution was put into the solution, the flask was put into a constant temperature shaking chamber, shaken at 30 ℃ for 1 hour, and the absorbance of the supernatant was measured with a spectrophotometer (in 580 nm). Calculating the adsorption quantity q of the dye wastewater according to a formulae。
(1)
In the formula: ce(mg/L) is the equilibrium mass concentration of the dye in solution; c0(mg/L) is the initial concentration of dye; v (mL) is the volume of the solution; m (g) is the mass of the adsorbent;
desorption test: taking out the composite fiber, placing the composite fiber in NaOH solution with the concentration of 2mg/L, desorbing the composite fiber in a constant-temperature oscillation box for 1 hour at the temperature of 30 ℃, washing the composite fiber with deionized water for a plurality of times, and drying the composite fiber.
The dye wastewater can contain one or more of crystal violet, basic fuchsin, night blue, phenol saffron red or nai blue;
according to the invention, a polydopamine substance surface grafting layer is formed on the surface of the fiber, the surface grafting layer enables the surface of the fiber to contain amino, the charge adsorption of the amino and the nano carbon material containing negative charges is realized by utilizing the principle that the amino carries positive charges under an acidic condition, and finally the nano carbon material coated fiber is obtained, and the fiber has good capability of adsorbing dye wastewater.
The invention has the following specific beneficial effects:
1. the nano adsorbent is graphite oxide and acidified carbon tube, and their surface area is large. Various oxygen-containing functional groups on the surface enable the dye to have good hydrophilicity, and the surface of the dye has certain negative charges, so that the dye can well adsorb cationic dyes.
2. The nano material is convenient to coat and is taken out and dried after being soaked;
3. the process for adsorbing and desorbing the dye wastewater is simple, the operation is simple and convenient, and the popularization and the application are easy;
4. the dye wastewater has high adsorption rate, and the adsorption rate is kept after repeated recycling.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, which are not intended to limit the invention thereto.
Example 1
Weighing 500mL of sodium dihydrogen phosphate citric acid buffer solution with pH of 8, adding 0.25g of dopamine substance (shown in Table 1), stirring uniformly, adding UHMWPE fiber (treated by ethanol ultrasonic for 5min), and stirring for reacting for 8h to obtain surface grafted fiber; then adding 0.05g of the nano carbon material into 500mL of deionized water with the pH value of 0.5, mechanically stirring for 20min, and carrying out ultrasonic treatment for 20 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.1h, completing coating, washing, drying, and repeating the immersion reduction process for 2 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption wastewater contains crystal violet, the adsorption amount is 100mg/g, and the adsorption amount is 95mg/g after 10 times of adsorption and desorption cycles.
Example 2
Weighing 500mL of disodium hydrogen phosphate and sodium dihydrogen phosphate buffer solution with the pH value of 11, adding 20g of dopamine substances (shown in table 1), uniformly stirring, adding polyester fibers (treated by acetone ultrasonic for 60min), and stirring for reacting for 24h to obtain surface grafted fibers; then adding 10g of the nano carbon material into 500mL of ethanol with the pH value of 6, mechanically stirring for 10min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 20 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption waste water contains basic fuchsin, the adsorption amount is 300mg/g, and after 10 times of adsorption and desorption cycles, the adsorption amount is 287 mg/g.
Example 3
Weighing 500mL of barbital sodium hydrochloric acid buffer solution with the pH value of 8.5, adding 10g of dopamine substances (shown in table 1), uniformly stirring, adding carbon fibers (treated by tetrahydrofuran ultrasonic for 5min), and stirring for reacting for 8h to obtain surface grafted fibers; then adding 0.15g of the nano carbon material into 500mL of glycol with the pH value of 1, mechanically stirring for 15min, and carrying out ultrasonic treatment for 30 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.5h, completing coating, washing, drying, and repeating the immersion reduction process for 10 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption wastewater contains cymbidium, the adsorption capacity is 260mg/g, and after 10 times of adsorption and desorption cycles, the adsorption capacity is 256 mg/g.
Example 4
Weighing 500mL of Tris (hydroxymethyl) aminomethane (namely Tris) -hydrochloric acid buffer solution with pH of 10.5, adding 0.25g of dopamine substances (shown in Table 1), uniformly stirring, adding glass fibers (treated by ultrasonic treatment of twenty-oil for 60min), and stirring for reacting for 24h to obtain surface grafted fibers; then adding 5g of the nano carbon material into 500ml DMF with pH of 5, mechanically stirring for 20min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.1h, completing coating, washing, drying, and repeating the immersion reduction process for 8 times to finally obtain the nano carbon material coated fibers.
The fiber prepared by the method is shown in Table 2, wherein the adsorption wastewater contains safranine with the adsorption amount of 208mg/g, and the adsorption amount is 201mg/g after 10 times of adsorption and desorption cycle.
Example 5
Weighing 500mL of sodium carbonate and sodium bicarbonate buffer solution with pH of 9.5, adding 20g of dopamine substances (shown in table 1), uniformly stirring, adding UHMWPE fibers (ultrasonically treating with a mixed solution of ethanol and acetone for 30min), and stirring for reacting for 16h to obtain surface grafted fibers; then 2.5g of the nano carbon material is added into 500ml NMP with the pH value of 3.5, mechanically stirred for 15min and ultrasonically treated for 30 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.5h, completing coating, washing, drying, and repeating the immersion reduction process for 20 times to finally obtain the nano carbon material coated fibers.
The fiber prepared by the method is shown in Table 2, wherein the adsorption waste water contains the Narlan blue, the adsorption amount is 291mg/g, and the adsorption amount is 290mg/g after 10 times of adsorption and desorption cycles.
Example 6
Weighing 500mL of disodium hydrogen phosphate and sodium dihydrogen phosphate buffer solution with the pH value of 8, adding 10g of dopamine substances (shown in table 1), uniformly stirring, adding carbon fibers (subjected to ultrasonic treatment for 32min by using a mixed solution of ethanol and tetrahydrofuran), and stirring for reacting for 8h to obtain surface grafted fibers; then adding 5.5g of the nano carbon material into 500mL of a mixed solution of deionized water and ethanol with the pH value of 3, mechanically stirring for 20min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 15 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption waste water contains crystal violet and basic fuchsin, the adsorption amount is 270mg/g, and after 10 times of adsorption and desorption cycle, the adsorption amount is 265 mg/g.
Example 7
Weighing 500mL of sodium carbonate and sodium bicarbonate buffer solution with pH of 11, adding 15g of dopamine substances (shown in Table 1), uniformly stirring, adding UHMWPE fibers (treated by ultrasonic treatment of a mixed solution of ethanol, tetrahydrofuran and kerosene for 60min), and reacting for 24h under stirring to obtain surface grafted fibers; then adding 0.05g of the nano carbon material into 500mL of ethanol and ethylene glycol mixed solution with the pH value of 0.5, mechanically stirring for 10min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 5 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption waste water contains basic fuchsin and night blue, the adsorption amount is 200mg/g, and after 10 times of adsorption and desorption cycle, the adsorption amount is 195 mg/g.
Example 8
Weighing 500mL of sodium dihydrogen phosphate citric acid buffer solution with pH of 8.5, adding 5g of dopamine substances (shown in table 1), uniformly stirring, adding glass fiber (treated by glycerol ultrasonic for 30min), and stirring for reacting for 16h to obtain surface grafted fiber; then adding 10g of the nano carbon material into a 500ml mixed solution of DMMF and NMP with the pH value of 6, mechanically stirring for 150min, and carrying out ultrasonic treatment for 30 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.4h, completing coating, washing, drying, and repeating the immersion reduction process for 8 times to finally obtain the nano carbon material coated fibers.
The fiber prepared by the method is shown in Table 2, wherein the adsorption waste water contains safranine and Narlan blue, the adsorption capacity is 240mg/g, and after 10 times of adsorption and desorption cycle, the adsorption capacity is 231 mg/g.
Example 9
Weighing 500mL of sodium carbonate and sodium bicarbonate buffer solution with the pH value of 10, adding 2.5g of dopamine substances (shown in table 1), uniformly stirring, adding UHMWPE fibers (treated by tetrahydrofuran and ultrasonic for 60min), and stirring for reacting for 10h to obtain surface grafted fibers; then adding 0.15g of the nano carbon material into 500mL of mixed solution of deionized water, DMF and ethanol with the pH value of 3.5, mechanically stirring for 20min, and carrying out ultrasonic treatment for 20 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 20 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption waste water contains crystal violet, basic fuchsin, night blue, phenol saffron and Nalrblue, the adsorption amount is 184mg/g, and the adsorption amount is 180mg/g after 10 times of adsorption and desorption cycles.
Example 10
Weighing 500mL of disodium hydrogen phosphate and sodium dihydrogen phosphate buffer solution with the pH value of 8.5, adding 5g of dopamine substances (shown in table 1), uniformly stirring, adding polyester fibers (treated by acetone ultrasonic for 30min), and stirring for reacting for 24h to obtain surface grafted fibers; then adding 5g of the nano carbon material into 500mL of mixed solution of ethanol, ethylene glycol, DMF and NMP with the pH value of 4, mechanically stirring for 10min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.5h, completing coating, washing, drying, and repeating the immersion reduction process for 10 times to finally obtain the nano carbon material coated fibers.
The fiber prepared by the method is shown in Table 2, wherein the adsorption wastewater contains night blue and phenol saffron, the adsorption capacity is 290mg/g, and the adsorption capacity is 285mg/g after 10 times of adsorption and desorption cycles.
Example 11
Weighing 500mL of sodium dihydrogen phosphate citric acid buffer solution with pH of 8 and 5g of dopamine substances (shown in Table 1), uniformly stirring, adding glass fiber (treated by glycerol ultrasonic for 30min), and stirring for reacting for 16h to obtain surface grafted fiber; then adding 10g of the nano carbon material into a 500ml mixed solution of DMMF and NMP with the pH value of 6, mechanically stirring for 150min, and carrying out ultrasonic treatment for 30 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.4h, completing coating, washing, drying, and repeating the immersion reduction process for 8 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption wastewater contains cymbidium, the adsorption amount is 221mg/g, and the adsorption amount is 206mg/g after 10 times of adsorption and desorption cycles.
Example 12
Weighing 500mL of disodium hydrogen phosphate and sodium dihydrogen phosphate buffer solution with the pH value of 11, adding 10g of dopamine substances (shown in table 1), uniformly stirring, adding polyvinyl alcohol fibers (subjected to ultrasonic treatment for 32min by using a mixed solution of ethanol and tetrahydrofuran), and stirring for reacting for 8h to obtain surface grafted fibers; then adding 5.5g of the nano carbon material into 500mL of a mixed solution of deionized water and ethanol with the pH value of 3, mechanically stirring for 20min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 15 times to finally obtain the nano carbon material coated fibers.
The fiber prepared by the method is shown in Table 2, wherein the adsorption wastewater contains safranine with the adsorption amount of 106mg/g, and the adsorption amount is 104mg/g after 10 times of adsorption and desorption cycle.
Example 13
Weighing 500mL of barbituric sodium salt acid buffer solution with the pH value of 8.5, adding 0.25g of dopamine substances (shown in table 1), uniformly stirring, adding UHMWPE fibers (through ethanol ultrasonic treatment for 5min), and stirring for reacting for 8h to obtain surface grafted fibers; then adding 0.05g of the nano carbon material into 500mL of deionized water with the pH value of 0.5, mechanically stirring for 20min, and carrying out ultrasonic treatment for 20 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.1h, completing coating, washing, drying, and repeating the immersion reduction process for 2 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption wastewater contains crystal violet and phenol saffron, the adsorption capacity is 100mg/g, and the adsorption capacity is 98mg/g after 10 times of adsorption and desorption cycles.
Example 14
Weighing 500mL of Tris (hydroxymethyl) aminomethane (namely Tris) hydrochloric acid buffer solution with the pH value of 10.5, adding glass fiber (treated by glycerol ultrasonic for 60min), and stirring for reacting for 24h to obtain surface grafted fiber; then adding 5g of the nano carbon material into 500ml DMF with pH of 5, mechanically stirring for 20min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 0.1h, completing coating, washing, drying, and repeating the immersion reduction process for 8 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption wastewater contains crystal violet, night blue and saffron, the adsorption capacity is 200mg/g, and after 10 times of adsorption and desorption cycle, the adsorption capacity is 188 mg/g.
Example 15
Weighing 500mL of sodium dihydrogen phosphate citric acid buffer solution with pH of 9.5, adding 10g of dopamine substances (shown in table 1), uniformly stirring, adding carbon fiber (treated by ultrasonic treatment of mixed solution of ethanol and tetrahydrofuran for 32min), and stirring for reacting for 8h to obtain surface grafted fiber; then adding 5.5g of the nano carbon material into 500mL of a mixed solution of deionized water and ethanol with the pH value of 3, mechanically stirring for 20min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 15 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption wastewater contains night blue and phenol saffron, the adsorption capacity is 280mg/g, and the adsorption capacity is 273mg/g after 10 times of adsorption and desorption cycles.
Example 16
Weighing 500mL of sodium dihydrogen phosphate citric acid buffer solution with pH of 11, adding 10g of dopamine substances (shown in table 1), uniformly stirring, adding carbon fiber (subjected to ultrasonic treatment for 32min by using a mixed solution of ethanol and tetrahydrofuran), and stirring for reacting for 8h to obtain surface grafted fiber; then adding 5.5g of the nano carbon material into 500mL of a mixed solution of deionized water and ethanol with the pH value of 3, mechanically stirring for 20min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 15 times to finally obtain the nano carbon material coated fibers.
The fiber prepared by the method is shown in Table 2, wherein the adsorption wastewater contains safranine with an adsorption amount of 220mg/g, and the adsorption amount is 215mg/g after 10 times of adsorption and desorption cycle.
Example 17
Weighing 500mL of Tris (hydroxymethyl) aminomethane (namely Tris) -hydrochloric acid buffer solution with pH of 10.5, adding 20g of dopamine substances (shown in table 1), uniformly stirring, adding polyester fibers (treated by acetone ultrasonic for 60min), and stirring for 24h to obtain surface grafted fibers; then adding 10g of the nano carbon material into 500mL of ethanol with the pH value of 6, mechanically stirring for 10min, and carrying out ultrasonic treatment for 40 min; and then, immersing the surface grafted fibers into the nano carbon material dispersion liquid, stirring for 1h, completing coating, washing and drying, and repeating the immersion reduction process for 20 times to finally obtain the nano carbon material coated fibers.
The fibers prepared by the method are shown in Table 2, wherein the adsorption wastewater contains cymbidium, the adsorption amount is 180mg/g, and the adsorption amount is 170mg/g after 10 times of adsorption and desorption cycles.
Claims (9)
1. A renewable nano carbon material coated fiber adsorbent is characterized by comprising a dopamine surface grafted fiber base layer and a nano carbon material layer, wherein the nano carbon material layer is one or a mixture of graphene oxide and acidified carbon nanotubes;
the carbon-oxygen atom ratio of the surface of the nano carbon material coated fiber is 2: 1-6: 1, and the nitrogen-oxygen atom ratio is 1: 8-1: 30;
the preparation method comprises the following steps:
step (1), preparing nano carbon material dispersion liquid:
adding the nano carbon material powder into a dispersion medium with a pH value of 0.5-6 at normal temperature, mechanically stirring for 10-20 min at a stirring speed of 300-1000r/min, and performing ultrasonic treatment in an ice water bath for 20-40 min to obtain a uniform and stable nano carbon material dispersion system; the carbon-oxygen atom ratio of the nano carbon material is 1: 1-5: 1;
step (2), fiber surface grafting:
adding a dopamine substance into a buffer solution with the pH value of 8-11, then adding fibers with surface finish and pollutants removed, stirring for reacting for 8-24 h, and washing and drying to obtain a dopamine surface grafted fiber; the surface carbon-oxygen atom ratio of the surface grafted fiber is 2: 1-12: 1, and the nitrogen-oxygen atom ratio is 1: 2-1: 7;
the mass ratio of the fibers to the dopamine solution is 1-10: 100, respectively;
step (3), preparing the nano carbon material coated fiber:
and (3) immersing the surface grafted fiber obtained in the step (2) into the nano carbon material dispersion liquid obtained in the step (1), stirring at the temperature of 20-60 ℃ for 0.1-1 h at the rotating speed of 100-800 r/min, washing and drying the fiber, and repeating the immersion process for 2-20 times to obtain the nano carbon material coated fiber.
2. The regenerable nanocarbon material coated fibrous adsorbent of claim 1, wherein the dopamine is one or a mixture of two of catecholamines or diphenoquinones, and has a structural formula of formula (1) or (2):
wherein R is- (CH) with an amino groupy)x-NH-(CHq)p-CH3Or- (CH)2)x-NH-(CHOH)x-(CH2)P-CH3Or- (CH)2)x-NH-(CHOH)x-(CH2)P-C6H5Or- (CH)2)x-NH2Or- (CH)y)x-N(CHj)h-(CHq)p-(CH3)eor-CO-NH- (CH)2)p-CH3or-CO- (CH)2)x-NH2Wherein x is a natural number of 1-199, p and h are natural numbers of 0-199, y, q and e are 1 or 2, and j is 1, 2 or 3.
3. The regenerable nanocarbon material coated fibrous adsorbent of claim 1, wherein the dopamine is one or a mixture of two of catecholamines or diphenoquinones, and has a structural formula of formula (1) or (2):
wherein R is
n is a natural number of 1 to 20.
4. The regenerable nanocarbon material coated fibrous sorbent of claim 1, wherein the fibers are one of UHMWPE fibers, polyester fibers, carbon fibers, polyvinyl alcohol fibers, or glass fibers.
5. The regenerable nanocarbon material coated fiber adsorbent of claim 1, wherein the nanocarbon material coated fibers have a surface carbon to oxygen atom ratio of 3:1 to 5: 1.
6. The regenerable nanocarbon material coated fiber adsorbent of claim 1, wherein a mass ratio of the nanocarbon material to the fibers is 20:1 to 1: 1.
7. The regenerable nanocarbon material coated fiber adsorbent of claim 1, wherein the mass ratio of the nanocarbon material to the fibers is 10:1 to 4: 1.
8. A regenerable nanocarbon material coated fibrous adsorbent of claim 1, wherein the nanocarbon material of step (1) has a carbon to oxygen atomic ratio of 2:1 to 4: 1; the surface carbon-oxygen atom ratio of the surface grafted fiber in the step (2) is 3: 1-10: 1.
9. The use of a regenerable nanocarbon material coated fibrous sorbent of claim 1 for adsorbing dye waste water comprising one or more of crystal violet, basic fuchsin, night blue, safranin or nai blue.
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