CN104028222A - Composite nano-material, preparation method and application thereof to remove tetrabromobisphenol-A - Google Patents
Composite nano-material, preparation method and application thereof to remove tetrabromobisphenol-A Download PDFInfo
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- CN104028222A CN104028222A CN201410201055.9A CN201410201055A CN104028222A CN 104028222 A CN104028222 A CN 104028222A CN 201410201055 A CN201410201055 A CN 201410201055A CN 104028222 A CN104028222 A CN 104028222A
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Abstract
The invention relates to a composite nano-material, a preparation method and application thereof to remove tetrabromobisphenol-A. The preparation method comprises: (1) firstly performing ultrasonic processing on graphene oxide in ethylene glycol for 3-4 h; (2) dissolving sodium citrate in ethylene glycol, heating to 60-65 DEG C and reacting for 20-30 min; (3) at room temperature, under the assistant effect of strong magnetic stirring, dissolving FeCl3.6H2O and urea in the mixed solution of sodium citrate and ethylene glycol obtained in the step (2), so as to obtain a ferric-salt precursor/ethylene glycol mixed solution; (4) with stirring, mixing the graphene oxide/ethylene glycol mixed solution obtained in the step (1) and the ferric-salt precursor/ethylene glycol mixed solution obtained in the step (3), and reacting for 2-3 h, then transferring the reaction solution to a reaction kettle, reacting at 200-250 DEG C for 12-14 h, and then naturally cooling along the room temperature; and (5) centrifuging with a speed of 6000-7000 rpm to obtain a black precipitate, repeatedly washing with ethanol and deionized water, and performing freeze drying, so as to obtain the product. Compared with the prior art, the preparation method has the advantages of high efficiency, low cost and the like.
Description
Technical field
The invention belongs to nano composite material technical field, the nano material of relate to a kind of preparation method of magnetic nanometer composite material, being prepared by the method and the application of removing tetrabromobisphenol-A (TBBPA) thereof.
Background technology
Tetrabromobisphenol-A is a kind of very representative brominated flame-retardant, be mainly used in plastics, textile, electronics, electrical equipment, transportation and packing, building materials and other fire proofing materials, owing to thering is good chemical stability, heat endurance, inertia and dielectricity, produced widely and used in many countries and regions, therefore also having been caused the severe contamination of the surrounding mediums such as atmosphere, water body, deposit and soil and relevant ecological system.About the TBBPA especially physiology toxicity research of its derivative draws attention gradually, comprise immunotoxicity, liver renal toxicity, neurotoxicity and endocrine interference.In traditional water treatment technology, the clearance of TBBPA is very low, mainly concentrates on two class methods for the removal of TBBPA, physical absorption and chemical degradation, and chemical degradation research mainly concentrates on biodegradation and two aspects of photocatalytic degradation.Emphasis is physical absorption, and research material is mainly depended in physical absorption, and existing sorbing material comprises: CNT, clay, molecular modification particle, magnetic composite nano material etc.
Along with the development of nanometer technology, nano material is extensively used in water treatment.Because graphene oxide has good suction-operated to organic pollution, therefore utilize stannic oxide/graphene nano material to remove TBBPA and become possibility, in water treatment procedure, GO separates conventionally to be needed centrifugal or filters, the introducing of magnetic material is made to magnetic oxygenated reduced graphene (RGO-MSP) and there is good magnetic response performance, can make RGO effectively separate rapidly from solution.
Summary of the invention
Object of the present invention is exactly the application that a kind of composite nano materials and preparation method thereof is provided and removes tetrabromobisphenol-A in order to overcome the defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions: a kind of composite nano materials, it is characterized in that, and the raw material of this material comprises following component and weight portion formula:
A preparation method for composite nano materials, is characterized in that, the method comprises the following steps:
(1) first by graphene oxide ultrasonic 3-4 hour in ethylene glycol;
(2) natrium citricum is dissolved in ethylene glycol, is heated to 60-65 DEG C, make its reaction 20-30min;
(3) at room temperature, by FeCl
36H
2o and urea are dissolved in the natrium citricum and ethylene glycol mixed solution of step (2) acquisition under strong magnetic agitation is auxiliary, obtain molysite predecessor/ethylene glycol mixed solution;
(4) molysite predecessor/ethylene glycol mixed solution that graphene oxide/ethylene glycol mixed solution step (1) being obtained and step (3) obtain is uniformly mixed, and the reaction time is 2-3h; Then moved in reactor, at 200-250 DEG C, reacted 12-14h, at room temperature naturally cooling subsequently;
(5) centrifugal acquisition black precipitate under 6000-7000rpm, washs repeatedly by ethanol and deionized water, and then freeze drying obtains product.
The graphene oxide that step (1) is described and the mass volume ratio of ethylene glycol are (0.025-0.05): (8-15) g/mL.
The natrium citricum that step (2) is described and the mass volume ratio of ethylene glycol are (0.4-0.8): (7-14) g/mL.
The described reactor of step (4) is polytetrafluoroethylene (PTFE) lining stainless steel cauldron.
A kind of composite nano materials is being removed the application of tetrabromobisphenol-A, it is characterized in that, in pending water, add described composite nano materials, making its concentration is 10-20mg/L, is 25-35 DEG C in temperature, and pH is 6.0-6.5, vibration 24-30h, frequency of oscillation is 150-180 time per minute, and under outside magnetic field effect, magnetic separates after 30-40min, measures and remains TBBPA concentration with high performance liquid chromatography and corresponding detector.
Compared with prior art, the present invention has the following advantages:
1, composite magnetic responsiveness of the present invention is good, and superparamagnetism is convenient to carry out magnetic separation and recovery, and the structure of material makes it have larger specific area, is conducive to improve adsorption efficiency.
2, the preparation method of composite of the present invention is easy, and cost is low, and controllability is strong; TBBPA in water is had to good suction-operated; at pH while being neutral, adsorption capacity is up to 100-120mg/g, far away higher than the adsorption capacity of the 20-40mg/g of granular activated carbon; as shown in Figure 4, the method is easy to TBBPA Adsorption in the aqueous solution fitting result of different models.
Brief description of the drawings
Fig. 1 is scanning electron and the transmission electron microscope schematic diagram of composite nano materials of the present invention;
Fig. 2 is the thermogravimetric analysis figure of composite nano materials of the present invention;
Fig. 3 is the magnetic property curve synoptic diagram of composite nano materials of the present invention;
Fig. 4 is the adsorption capacity of composite nano materials of the present invention to variable concentrations TBBPA and the fitting result of different models;
Fig. 5 magnetic composite nano material of the present invention is to variable concentrations TBBPA time of equilibrium adsorption and adsorption capacity figure.
Detailed description of the invention
Embodiment 1
(1) first by 0.025g graphene oxide in the ethylene glycol of 8mL ultrasonic 3 hours.
(2) 0.408g natrium citricum is dissolved in 7mL ethylene glycol, is heated to 60 DEG C, make its reaction 20min.
(3) at room temperature, by 0.12g FeCl
36H
2o and 0.186g urea are dissolved in the natrium citricum and ethylene glycol mixed solution of (2) acquisition under strong magnetic agitation is auxiliary.
(4) molysite predecessor/ethylene glycol mixed solution that the graphene oxide/ethylene glycol mixed solution (1) being obtained and (3) obtain is uniformly mixed, and the reaction time is 2h.Then moved in the polytetrafluoroethylene (PTFE) lining stainless steel cauldron of 50mL, at 200 DEG C, reacted 12h, at room temperature naturally cooling subsequently.
(5) centrifugal acquisition black precipitate under 6500rpm, washs repeatedly by ethanol and deionized water, and then freeze drying obtains product, and its scanning electron and transmission electron microscope schematic diagram are as shown in Figure 1.The product obtaining is because graphene oxide is partial reduction in the ethylene glycol solution that ferriferous oxide microballoon forms at 200 DEG C, so product is magnetic composite nano material.
As shown in Figure 2, can find out that this material list reveals splendid heat endurance;
As shown in Figure 3, can find out that this material list reveals splendid magnetic responsiveness, obtains 7.85emu/g by magnetism testing hysteresis curve;
As shown in Figure 4, can find out that this material shows good adsorptivity to TBBPA, this adsorption process has well met Lang Gemiaoer adsorption isotherm model.
Containing in the 30mL aqueous solution that TBBPA concentration is 2.76mg/L, add redox graphene (RGO-M) 0.60mg preparing, making its concentration is 20mg/L.Temperature is 25 DEG C, and pH is 6.0, vibration 24h, and vibration is to carry out in oscillator, frequency of oscillation is 150 times per minute.Under outside magnetic field effect, magnetic separates after 30min, with high performance liquid chromatography (HPLC)---ultraviolet-visible detector is measured TBBPA concentration in surplus solution, at this moment magnetic composite nano material reaches 106.56mg/g to the adsorption capacity of TBBPA, if Fig. 5 time of equilibrium adsorption is 300min left and right.
Embodiment 2
(1) first by 0.035g graphene oxide in the ethylene glycol of 12mL ultrasonic 3.5 hours.
(2) 0.616g natrium citricum is dissolved in 11mL ethylene glycol, is heated to 60 DEG C, make its reaction 25min.
(3) at room temperature, by 0.15g FeCl
36H
2o and 0.24g urea are dissolved in the natrium citricum and ethylene glycol mixed solution of (2) acquisition under strong magnetic agitation is auxiliary.
(4) molysite predecessor/ethylene glycol mixed solution that the graphene oxide/ethylene glycol mixed solution (1) being obtained and (3) obtain is uniformly mixed, and the reaction time is 2.5h.Then moved in the polytetrafluoroethylene (PTFE) lining stainless steel cauldron of 50mL, at 220 DEG C, reacted 14h, at room temperature naturally cooling subsequently.
(5) centrifugal acquisition black precipitate under 6500rpm, washs repeatedly by ethanol and deionized water, and then freeze drying obtains product.The product obtaining is because graphene oxide is partial reduction in the ethylene glycol solution that ferriferous oxide microballoon forms at 200 DEG C, so product is magnetic composite nano material.
Containing in the 30mL aqueous solution that TBBPA concentration is 2.85mg/L, add the magnetic composite nano material 0.60mg preparing, making its concentration is 20mg/L.Temperature is 25 DEG C, and pH is 6.3, vibration 24h, and vibration is to carry out in oscillator, frequency of oscillation is 160 times per minute.Under outside magnetic field effect, magnetic separates after 30min, with high performance liquid chromatography (HPLC)---ultraviolet-visible detector is measured the concentration of TBBPA in surplus solution, at this moment magnetic composite nano material reaches 112.31mg/g to the adsorption capacity of TBBPA, if Fig. 5 time of equilibrium adsorption is 300min left and right.
Embodiment 3
(1) first by 0.05g graphene oxide in the ethylene glycol of 14mL ultrasonic 4 hours.
(2) 0.752g natrium citricum is dissolved in 14mL ethylene glycol, is heated to 60 DEG C, make its reaction 30min.
(3) at room temperature, by 0.15gFeCl
36H
2o and 0.286g urea are dissolved in the natrium citricum and ethylene glycol mixed solution of (2) acquisition under strong magnetic agitation is auxiliary.
(4) molysite predecessor/ethylene glycol mixed solution that the graphene oxide/ethylene glycol mixed solution (1) being obtained and (3) obtain is uniformly mixed, and the reaction time is 2h.Then moved in the polytetrafluoroethylene (PTFE) lining stainless steel cauldron of 50mL, at 220 DEG C, reacted 14h, at room temperature naturally cooling subsequently.
(5) centrifugal acquisition black precipitate under 6500rpm, washs repeatedly by ethanol and deionized water, and then freeze drying obtains product.The product obtaining is because graphene oxide is partial reduction in the ethylene glycol solution that ferriferous oxide microballoon forms at 200 DEG C, so product is magnetic composite nano material.
Containing in the 30mL aqueous solution that TBBPA concentration is 2.97mg/L, add the magnetic composite nano material 0.6mg preparing, making its concentration is 20mg/L.Temperature is 25 DEG C, and pH is 6.5, vibration 24h, and vibration is to carry out in oscillator, frequency of oscillation is 150 times per minute.Under outside magnetic field effect, magnetic separates after 40min, with high performance liquid chromatography (HPLC)---ultraviolet-visible detector is measured the concentration of TBBPA in surplus solution, at this moment magnetic composite nano material reaches 117.36mg/g to the adsorption capacity of TBBPA, if Fig. 5 time of equilibrium adsorption is 300min left and right.
Embodiment 4
(1) first by 0.035g graphene oxide in the ethylene glycol of 12mL ultrasonic 3.5 hours.
(2) 0.8g natrium citricum is dissolved in 14mL ethylene glycol, is heated to 60 DEG C, make its reaction 25min.
(3) at room temperature, by 0.2g FeCl
36H
2o and 0.3g urea are dissolved in the natrium citricum and ethylene glycol mixed solution of (2) acquisition under strong magnetic agitation is auxiliary.
(4) molysite predecessor/ethylene glycol mixed solution that the graphene oxide/ethylene glycol mixed solution (1) being obtained and (3) obtain is uniformly mixed, and the reaction time is 3h.Then moved in the polytetrafluoroethylene (PTFE) lining stainless steel cauldron of 50mL, at 250 DEG C, reacted 12h, at room temperature naturally cooling subsequently.
(5) centrifugal acquisition black precipitate under 7000rpm, washs repeatedly by ethanol and deionized water, and then freeze drying obtains product.The product obtaining is because graphene oxide is partial reduction in the ethylene glycol solution that ferriferous oxide microballoon forms at 250 DEG C, so product is magnetic composite nano material.
Containing in the 30mL aqueous solution that TBBPA concentration is 3mg/L, add the magnetic composite nano material 0.6mg preparing, making its concentration is 20mg/L.Temperature is 25 DEG C, and pH is 6.5, vibration 30h, and vibration is to carry out in oscillator, frequency of oscillation is 180 times per minute.Under outside magnetic field effect, magnetic separates after 40min, with high performance liquid chromatography (HPLC)---ultraviolet-visible detector is measured the concentration of TBBPA in surplus solution, at this moment magnetic composite nano material reaches 112.31mg/g to the adsorption capacity of TBBPA, and time of equilibrium adsorption is 300min left and right.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various amendments to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from improvement and the amendment that category of the present invention makes all should be within protection scope of the present invention.
Claims (6)
1. a composite nano materials, is characterized in that, the raw material of this material comprises following component and weight portion formula:
2. a preparation method for composite nano materials as claimed in claim 1, is characterized in that, the method comprises the following steps:
(1) first by graphene oxide ultrasonic 3-4 hour in ethylene glycol;
(2) natrium citricum is dissolved in ethylene glycol, is heated to 60-65 DEG C, make its reaction 20-30min;
(3) at room temperature, by FeCl
36H
2o and urea are dissolved in the natrium citricum and ethylene glycol mixed solution of step (2) acquisition under strong magnetic agitation is auxiliary, obtain molysite predecessor/ethylene glycol mixed solution;
(4) molysite predecessor/ethylene glycol mixed solution that graphene oxide/ethylene glycol mixed solution step (1) being obtained and step (3) obtain is uniformly mixed, and the reaction time is 2-3h; Then moved in reactor, at 200-250 DEG C, reacted 12-14h, at room temperature naturally cooling subsequently;
(5) centrifugal acquisition black precipitate under 6000-7000rpm, washs repeatedly by ethanol and deionized water, and then freeze drying obtains product.
3. the preparation method of a kind of composite nano materials according to claim 2, is characterized in that, the graphene oxide that step (1) is described and the mass volume ratio of ethylene glycol are (0.025-0.05): (8-15) g/mL.
4. the preparation method of a kind of composite nano materials according to claim 2, is characterized in that, the natrium citricum that step (2) is described and the mass volume ratio of ethylene glycol are (0.4-0.8): (7-14) g/mL.
5. the preparation method of a kind of composite nano materials according to claim 2, is characterized in that, the described reactor of step (4) is polytetrafluoroethylene (PTFE) lining stainless steel cauldron.
6. a composite nano materials as claimed in claim 1 is in the application of removing tetrabromobisphenol-A, it is characterized in that, in pending water, add described composite nano materials, making its concentration is 10-20mg/L, be 25-35 DEG C in temperature, pH is 6.0-6.5, vibration 24-30h, frequency of oscillation is 150-180 time per minute, and under outside magnetic field effect, magnetic separates 30-40min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104698052A (en) * | 2015-03-26 | 2015-06-10 | 盐城工学院 | Preparation method of graphene/Fe3O4/gold nanocomposite and application thereof |
| CN107045949A (en) * | 2017-04-07 | 2017-08-15 | 江苏大学 | A kind of N Fe2O3/ nitrogen sulphur codope graphene combination electrode material and preparation method |
| CN112473624A (en) * | 2020-12-15 | 2021-03-12 | 安徽省灵磁新材料科技股份有限公司 | Preparation process of magnetic carbon nano composite material |
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| CN102989420A (en) * | 2012-12-11 | 2013-03-27 | 湖南大学 | Sulfonylation graphene oxide magnetic adsorbent, and preparation method and application thereof |
| CN103301812A (en) * | 2013-06-14 | 2013-09-18 | 湖北大学 | Magnetic core-shell microspheres, and preparation method and use thereof |
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| CN102989420A (en) * | 2012-12-11 | 2013-03-27 | 湖南大学 | Sulfonylation graphene oxide magnetic adsorbent, and preparation method and application thereof |
| CN103301812A (en) * | 2013-06-14 | 2013-09-18 | 湖北大学 | Magnetic core-shell microspheres, and preparation method and use thereof |
Non-Patent Citations (2)
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|---|
| YULIN TANG等: "Synthesis of reduced grapheme oxide/magnetite composites and investigation of their adsorption performance of fluoroquinolone antibiotics", 《JORUNAL OF COLLOIDS AND SURFACES A:PHYSICOCHEMICAL AND ENGINEERING ASPECTS》, vol. 424, 5 May 2013 (2013-05-05) * |
| YUNHAI ZHANG 等: "Sorption and removal of tetrabromobisphenol A from solution by grapheme oxide", 《CHEMICAL ENGINEERING JOURNAL》, vol. 222, 15 April 2013 (2013-04-15) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104698052A (en) * | 2015-03-26 | 2015-06-10 | 盐城工学院 | Preparation method of graphene/Fe3O4/gold nanocomposite and application thereof |
| CN107045949A (en) * | 2017-04-07 | 2017-08-15 | 江苏大学 | A kind of N Fe2O3/ nitrogen sulphur codope graphene combination electrode material and preparation method |
| CN107045949B (en) * | 2017-04-07 | 2018-12-14 | 江苏大学 | A kind of N-Fe2O3/ nitrogen sulphur codope graphene combination electrode material and preparation method |
| CN112473624A (en) * | 2020-12-15 | 2021-03-12 | 安徽省灵磁新材料科技股份有限公司 | Preparation process of magnetic carbon nano composite material |
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Inventor after: Tang Yulin Inventor after: Li Shuyan Inventor after: Wang Dailong Inventor before: Tang Yulin Inventor before: Li Shuyan Inventor before: Wang Yilong |
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Application publication date: 20140910 |