CN103480333A - Compound grapheme absorption agent, method for preparing compound grapheme absorption agent and application of compound grapheme absorption agent - Google Patents
Compound grapheme absorption agent, method for preparing compound grapheme absorption agent and application of compound grapheme absorption agent Download PDFInfo
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Abstract
The invention discloses a compound grapheme absorption agent which comprises grapheme, nanometer zero-valent iron and cetyl trimethyl ammonium bromide. The invention further discloses a method for preparing the compound grapheme absorption agent. The method for preparing the compound grapheme absorption agent includes the following steps that firstly, oxidized grapheme is dispersed in water with ultrasonic waves and oxidized grapheme suspension liquid is obtained; secondly, the nanometer zero-valent iron and the cetyl trimethyl ammonium bromide are added into the oxidized grapheme suspension liquid obtained in the first step, fully stirred and fully reacted and a reaction solution is obtained; thirdly, the reaction solution obtained in the second step is added with reductive agents and fully reacted and black flocks are obtained; fourthly, the black flocks obtained in the third step are filtered, washed and dried to obtain the compound grapheme absorption agent. The compound grapheme absorption agent is efficient, green, economic, friendly to environment, and suitable for large-scale production. The preparing method is simple and conditions are easy to control.
Description
Technical field
The present invention relates to Adsorption of Organic agent field, particularly a kind of compound Graphene adsorbent and preparation method thereof, application.
Background technology
Due to improving constantly of industrial fast development and people's living standard, organic pollution shared proportion in polluted water body is increasing, paranitrochlorobenzene is large as a kind of harmfulness, the organic pollution of difficult for biological degradation, obtain already people's extensive concern, it is widely used in the production process of agricultural chemicals, medicine, dyestuff and rubber chemicals, and, along with the discharge of industrial wastewater enters into various water bodys, cause all detecting the existence of paranitrochlorobenzene in some main water bodys of China.It is except causing people and other mammiferous methemoglobinemias, or a kind of mutagens and carcinogen, and in environment hard degradation.Therefore, in the research water body removal of paranitrochlorobenzene to the protection health with prevent that the environment tool that is damaged is of great significance.
In the aqueous solution of current own Application and Development, the processing method of organic pollution mainly contains Physical, chemical reduction method, advanced oxidation processes and bioanalysis etc., wherein more than 90%, use chemical method, main chemical method comprises again: chemical precipitation method, membrane separation process, ion-exchange, electrolysis, electroosmose process, active carbon adsorption etc.In these methods, absorption method is that a kind of equipment investment is few, simple to operate, efficient and be easy to the method for organic pollution in the removal aqueous solution of extensive use, and the key of improving absorption method is that exploitation is more efficient, environmental protection, inexpensive novel absorption material.
Current, a large amount of sorbing materials is in the news with removing the organic pollution in water body, such as active carbon, flyash, biomass adsorbent etc.Owing to having great specific area, nano material is regarded as a kind of more high efficiency sorbing material, is conducive to remove the organic pollution in the aqueous solution.For example, CNT is proved to be a kind of very effective organic pollution new adsorbent, and its efficiency exceeds 5～7 times than common acticarbon.Yet cost is high, easily produced secondary pollution and be difficult for the drawbacks limit such as removal the use of CNT.For this problem, develop the focus that more efficient, economic and nontoxic nano adsorber becomes current concern.
After Graphene is developed first, due to its excellent physicochemical properties, mechanical strength, high conductivity and thermal conductivity etc. as great specific area, excellence, obtained in fields such as electrochmical power source, opto-electronic device and heterogeneous catalysis widely and paid close attention to.Yet the application of grapheme material in environment is less.Existing research shows that Graphene can remove the pollutants such as organic pollution, but the agglomeration of Graphene has not only reduced the specific area of Graphene, also is unfavorable for being dispersed in solution, and this has limited its removal application to pollutant in the aqueous solution.
Summary of the invention
For the above-mentioned shortcoming that overcomes prior art, with not enough, one of purpose of the present invention is to provide the compound Graphene adsorbent of a kind of efficient, green, economy, environmental protection.
Two of purpose of the present invention is to provide the preparation method of above-mentioned compound Graphene adsorbent, and technique is simple, condition is easily controlled, be suitable for large-scale production.
Three of purpose of the present invention is to provide the application of above-mentioned compound Graphene adsorbent.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of compound Graphene adsorbent comprises the following steps:
(1) graphene oxide is dispersed in water, by making graphene oxide suspension after ultrasonic dispersion;
(2) in the graphene oxide suspension obtained in step (1), add nano zero valence iron and softex kw; Wherein, the mass ratio of nano zero valence iron, graphene oxide and softex kw is 1: 2: (7～9), fully stir, obtain reaction solution after complete reaction;
(3) reaction solution step (2) obtained is heated to 80 ℃～85 ℃, adds reducing agent, fully after reaction, obtains the black flocculent deposit; Described reducing agent is at least one in sodium borohydride, potassium borohydride; The quality of described reducing agent is 9～11 times of graphene oxide quality;
(4) suction filtration, washing and drying are carried out in black flocculent deposit step (3) obtained, and obtain compound Graphene adsorbent.
The time of described ultrasonic dispersion is 30min～60min.
The concentration of described graphene oxide suspension is 4mg/mL～6mg/mL.
The preparation method of described nano zero valence iron is as follows:
Under nitrogen protection, churned mechanically condition, solution of potassium borohydride is added drop-wise to FeSO
4in solution, continue to stir, react completely rear standing, then through vacuum filtration, washing, vacuum drying to constant weight, obtain nano zero valence iron.
Obtain reaction solution after the described complete reaction of step (2), be specially:
React 3h～5h under 50 ℃～55 ℃ conditions, obtain reaction solution.
The compound Graphene adsorbent that above-mentioned preparation method prepares, comprise Graphene, nano zero valence iron and cationic surfactant softex kw.
Described nano zero valence iron inserts edge or the top layer of stratiform Graphene by chemical b `.
Described nano zero valence iron is embedded in edge or the top layer of lamellar graphite alkene by chemical b `.
The application of above-mentioned compound Graphene adsorbent, for removing the paranitrochlorobenzene of the aqueous solution.
Paranitrochlorobenzene in the described removal aqueous solution, detailed process is as follows:
Every premium on currency solution adds the compound Graphene adsorbent of 1g～2g; In adsorption process, the temperature of controlling the aqueous solution is 20 ℃～50 ℃, fully adsorbs and vibrate to after reacting completely, and utilizes filter membrane to be filtered the remaining liquid after adsorbing, and completes the removal to paranitrochlorobenzene in the aqueous solution.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention takes full advantage of the physicochemical characteristics of Graphene and nano zero valence iron uniqueness, by the softex kw modified method, significantly reduce the effect of the reunion of compound Graphene, significantly improved the specific area of compound Graphene, improve its dispersiveness and hydrophily in solution, and then improved its absorption property to Organic Pollutants In Water;
(2) do not produce the accessory substance that environment is had to pollution in preparation process of the present invention, and only adopt conventional surfactants, raw material is simple and easy to get, and preparation cost is lower;
(3) preparation technology of the present invention is simple, and condition is easily controlled, and is suitable for the batch production of continuous large-scale; And planar structure and intrinsic propesties to Graphene in processing procedure can not produce destruction;
(4) the compound Graphene adsorbent that prepared by the present invention, when removing the paranitrochlorobenzene of the aqueous solution, can directly add containing in the paranitrochlorobenzene aqueous solution, and whole treatment process cost is lower, and operating condition is relatively simple and easily implement.
The accompanying drawing explanation
The stereoscan photograph of the Graphene that Fig. 1 is embodiments of the invention 1 preparation.
The stereoscan photograph of the nano zero valence iron that Fig. 2 is embodiments of the invention 1 preparation.
The stereoscan photograph of the compound Graphene adsorbent that Fig. 3 is embodiments of the invention 1 preparation.
The fourier-transform infrared contrast schematic diagram of the compound Graphene adsorbent that Fig. 4 is Graphene and embodiments of the invention 1 preparation.
The thermogravimetric curve figure of the compound Graphene adsorbent that Fig. 5 is Graphene and embodiments of the invention 1 preparation.
Fig. 6 is that Graphene contrasts schematic diagram from compound Graphene adsorbent clearance to the organic pollution paranitrochlorobenzene under different pH values of embodiments of the invention 1 preparation.
The compound Graphene adsorbent that Fig. 7 is 1 preparation of Graphene and embodiments of the invention is at different disposal adsorption capacity contrast schematic diagram to the organic pollution paranitrochlorobenzene under the time.
The adsorption isotherm contrast schematic diagram of the compound Graphene adsorbent that Fig. 8 is Graphene and embodiments of the invention 1 preparation to the organic pollution paranitrochlorobenzene.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The preparation method of the compound Graphene adsorbent of the present embodiment comprises the following steps:
(1) graphene oxide is dispersed in water, by after ultrasonic dispersion 30min, making the graphene oxide suspension that concentration is 4mg/mL;
The graphene oxide of the present embodiment adopts the Hummers method of revising synthetic, concrete steps are as follows: 10g graphite and 5g sodium nitrate are slowly added in the flask that contains the 230ml concentrated sulfuric acid, and be placed in mixture of ice and water and stir, after 30min, slowly add 30g potassium permanganate, control reaction temperature and be less than all the time 15 ℃ in whipping process, and keep 90min; Reaction system is transferred in the water bath with thermostatic control of 35 ℃, keeping reaction temperature is 35 ℃, stirs 30min; To the deionized water that adds 460mL in reaction system, reaction temperature is controlled at 80 ℃～95 ℃, and mixing time is 30min; Then add 100mL, 30% hydrogenperoxide steam generator, filter while hot after solution becomes glassy yellow, and the hydrochloric acid solution that is 5% with 500mL concentration washing washs three times with the 1400mL deionized water, until solution sulfate radical-free ion (detecting with barium chloride solution).Gained sample 50 ℃ of oven dry 48h in vacuum freeze dryer, to constant weight, are obtained to graphene oxide, and its microstructure is shown in Fig. 1.
(2) in the graphene oxide suspension obtained in step (1), add nano zero valence iron and softex kw; Wherein, the mass ratio of nano zero valence iron, graphene oxide and softex kw is 1: 2: 7, fully stirs, and under 55 ℃ of conditions, reacts 3h, obtains reaction solution after complete reaction;
The synthetic method of the nano zero valence iron of the present embodiment is as follows:
Under room temperature by 11.12g FeSO
47H
2o is dissolved in the 200mL ethanol water, and (ethanol: water=3:7), in the there-necked flask as for 1000mL, under nitrogen protection, mechanical agitation condition, the solution of potassium borohydride that is 0.12mol/L by 200mL concentration is added drop-wise to FeSO fast
4in solution, continue stirring reaction 30min.Standing 5min final vacuum suction filtration, use respectively ultra-pure water and absolute ethanol washing for several times, and vacuum drying, to constant weight, obtains nano zero valence iron, and its microstructure is shown in Fig. 2.
(3) reaction solution step (2) obtained is heated to 80 ℃, adds the borane reducing agent sodium hydride, fully after reaction, obtains the black flocculent deposit; The quality of described reducing agent is 10 times of graphene oxide quality;
(4) suction filtration, washing and drying are carried out in black flocculent deposit step (3) obtained, and obtain compound Graphene adsorbent.
The microstructure of the compound Graphene adsorbent that the present embodiment obtains as shown in Figure 3, with a large amount of Graphenes of reuniting in Fig. 1, compare, Graphene in Fig. 3 becomes thinner, present laminar structured, and sheet interlayer spacing increases, this may be owing to the introducing of softex kw, and can see clearly from Fig. 3 that nano zero valence iron is evengranular to be attached to Graphene surface or lamella.
The fourier-transform infrared contrast schematic diagram that Fig. 4 is the compound Graphene adsorbent for preparing of Graphene and the present embodiment.Compound Graphene adsorbent prepared by the present embodiment is at 2918cm
-1and2849cm
-1wave band methylene and methyl C-H stretching vibration have appearred, this proves that compound Graphene adsorbent contains softex kw; Compound Graphene adsorbent is at 1643cm
-1wave band carbonylic stretching vibration has appearred, at 3201cm
-1wave band the stretching vibration of intermolecular O-H key has appearred, this proves that compound Graphene adsorbent contains nano zero valence iron.The functional group on Graphene surface mainly is distributed in edge or top layer, and the functional groups on the functional group in nano zero valence iron and Graphene surface makes nano zero valence iron insert or be embedded in edge or the top layer of lamellar graphite alkene by chemical b `.
The thermogravimetric curve figure of the compound Graphene adsorbent that Fig. 5 is Graphene and the present embodiment 1 preparation.As seen from the figure, the compound Graphene adsorbent that prepared by the present embodiment is by mass percentage containing 56% the Graphene of having an appointment, approximately 10% nano zero valence iron, approximately 14% cationic surfactant softex kw and about 20% impurity.
The preparation method of the compound Graphene adsorbent of the present embodiment comprises the following steps:
(1) graphene oxide is dispersed in water, by after ultrasonic dispersion 60min, making the graphene oxide suspension that concentration is 6mg/mL;
(2) in the graphene oxide suspension obtained in step (1), add nano zero valence iron and softex kw; Wherein, the mass ratio of nano zero valence iron, graphene oxide and softex kw is 1: 2: 9, fully stirs, and under 50 ℃ of conditions, reacts 5h, obtains reaction solution after complete reaction;
(3) reaction solution step (2) obtained is heated to 85 ℃, adds the borane reducing agent hydrofining, fully after reaction, obtains the black flocculent deposit; The quality of described reducing agent is 9 times of graphene oxide quality;
(4) the black flocculent deposit obtained after step (3) is carried out to suction filtration, washing and drying, obtain compound Graphene adsorbent.
Microstructure and the results of IR of compound Graphene adsorbent prepared by the present embodiment are similar to Example 1.
Embodiment 3
The preparation method of the compound Graphene adsorbent of the present embodiment comprises the following steps:
(1) graphene oxide is dispersed in water, by after ultrasonic dispersion 40min, making the graphene oxide suspension that concentration is 5mg/mL;
(2) in the graphene oxide suspension obtained in step (1), add nano zero valence iron and softex kw; Wherein, the mass ratio of nano zero valence iron, graphene oxide and softex kw is 1: 2: 8, fully stirs, and under 52 ℃ of conditions, reacts 4h,, obtain reaction solution after complete reaction;
(3) reaction solution step (2) obtained is heated to 82 ℃, adds the borane reducing agent sodium hydride, fully after reaction, obtains the black flocculent deposit; The gross mass of described reducing agent is 11 times of graphene oxide quality;
(4) the black flocculent deposit obtained after step (3) is carried out to suction filtration, washing and drying, obtain compound Graphene adsorbent.
Microstructure and the results of IR of compound Graphene adsorbent prepared by the present embodiment are similar to Example 1.
Application examples
Test 1:
(1) the compound Graphene adsorbent of embodiment 1 is divided into to 6 groups, then be added into respectively the paranitrochlorobenzene initial concentration and be 200ppm containing in the paranitrochlorobenzene aqueous solution, the consumption of adsorbent is 2mg/mL;
(2) the above-mentioned aqueous solution of respectively organizing is carried out to oscillating reactions, each pH value of organizing the aqueous solution is respectively 2,4,6,8,10 and 12, and each reaction temperature of organizing the aqueous solution is 25 ℃, and the oscillating reactions rotating speed is 150rpm, and the oscillating reactions time is 120min;
(3) respectively the organize aqueous solution of the filter membrane that utilizes 0.45 μ m after to oscillating reactions is filtered, and completes the removal to paranitrochlorobenzene in the aqueous solution.
Measure the residual volume of respectively organizing organic pollution paranitrochlorobenzene in aqueous sample, result as shown in Figure 6.As seen from Figure 6, the original ph of solution does not have a significant impact the removal of paranitrochlorobenzene.Graphene (not utilizing surfactant to carry out modification) sample as a comparison with preparation in embodiment 1, operating procedure during application is identical with above-mentioned applying step, the clearance effect of its organic pollution paranitrochlorobenzene as shown in Figure 6, as seen from Figure 6, it removes efficiency clearly lower than the removal efficiency of compound Graphene adsorbent.
Utilize the compound Graphene adsorbent made in embodiment 1 to remove the paranitrochlorobenzene in the aqueous solution, concrete steps comprise:
(1) above-mentioned compound Graphene adsorbent is divided into to 10 groups, then be added into respectively the paranitrochlorobenzene initial concentration and be 200ppm containing in the paranitrochlorobenzene aqueous solution, the consumption of adsorbent is 2mg/mL;
(2) the above-mentioned aqueous solution of respectively organizing is carried out to oscillating reactions, each temperature of organizing the aqueous solution is 25 ℃, and the rotating speed of oscillating reactions is 150rpm, and the oscillating reactions time is respectively 0.1h, 0.2h, 0.5h, 1h, 1.5h, 2h, 4h, 6h, 12h and 24h;
(3) respectively the organize aqueous solution of the filter membrane that utilizes 0.45m after to oscillating reactions is filtered, and completes the removal to paranitrochlorobenzene in the aqueous solution.
Measure the residual volume of respectively organizing organic pollution paranitrochlorobenzene in aqueous sample, result as shown in Figure 7.As seen from Figure 7, adsorption reaction reaches balance after 2h, rising subsequently, and absorption finally reaches capacity.Therefore, in actual application, generally can not be less than 2h the time of contact of adsorption reaction.The same Graphene (not utilizing surfactant to carry out modification) with preparation in embodiment 1 is sample as a comparison, operating procedure during application is identical with above-mentioned applying step, the clearance effect of its organic pollution paranitrochlorobenzene as shown in Figure 7, as seen from Figure 7, the rate of adsorption of compound Graphene adsorbent is apparently higher than the rate of adsorption of Graphene.
Test 3
Utilize the compound Graphene adsorbent made in embodiment 1 to remove the paranitrochlorobenzene in the aqueous solution, concrete steps comprise:
(1) above-mentioned compound Graphene adsorbent is divided into to 5 groups, be added into respectively the paranitrochlorobenzene initial concentration and be 60ppm, 120ppm, 180ppm, 240ppm and 300ppm containing in the paranitrochlorobenzene aqueous solution, the consumption of adsorbent is 1mg/mL;
(2) the above-mentioned aqueous solution of respectively organizing is carried out to oscillating reactions, each temperature of organizing the aqueous solution is respectively 20 ℃, 35 ℃ and 50 ℃, and the vibration rotating speed is 150rpm, and the reaction time is 120min;
(3) respectively the organize aqueous solution of the filter membrane that utilizes 0.45 μ m after to oscillating reactions is filtered, and completes the removal to paranitrochlorobenzene in the aqueous solution.
Measure the concentration of paranitrochlorobenzene in the aqueous sample of absorption front and back as shown in Figure 8.As seen from Figure 8, adsorbance raises and reduces with reaction temperature, and low temperature is conducive to absorption, and the quantity of sorbent of unit mass, along with the paranitrochlorobenzene initial concentration increases and increases.Then according to the organic pollution paranitrochlorobenzene equilibrium concentration (C obtained
e) and equilibrium adsorption ability (q
e) data are known, this adsorption reaction process meets the Langmuir adsorption isotherm model.The result of Fig. 8 shows: compound Graphene adsorbent is 105mg/g to the maximum adsorption capacity of paranitrochlorobenzene.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. the preparation method of a compound Graphene adsorbent, is characterized in that, comprises the following steps:
(1) graphene oxide is dispersed in water, by making graphene oxide suspension after ultrasonic dispersion;
(2) add nano zero valence iron and softex kw in the graphene oxide suspension obtained in step (1), fully stir, obtain reaction solution after complete reaction; Wherein, the mass ratio of nano zero valence iron, graphene oxide and softex kw is 1: 2: (7～9);
(3) reaction solution step (2) obtained is heated to 80 ℃～85 ℃, adds reducing agent, fully after reaction, obtains the black flocculent deposit; Described reducing agent is at least one in sodium borohydride, potassium borohydride; The quality of described reducing agent is 9～11 times of graphene oxide quality;
(4) suction filtration, washing and drying are carried out in black flocculent deposit step (3) obtained, and obtain compound Graphene adsorbent.
2. the preparation method of compound Graphene adsorbent according to claim 1, is characterized in that, the time of described ultrasonic dispersion is 30min～60min.
3. the preparation method of compound Graphene adsorbent according to claim 1, is characterized in that, the concentration of described graphene oxide suspension is 4mg/mL～6mg/mL.
4. the preparation method of compound Graphene adsorbent according to claim 1, is characterized in that, the preparation method of described nano zero valence iron is as follows:
Under nitrogen protection, churned mechanically condition, solution of potassium borohydride is added drop-wise to FeSO
4in solution, continue to stir, react completely rear standing, then through vacuum filtration, washing, vacuum drying to constant weight, obtain nano zero valence iron.
5. the preparation method of compound Graphene adsorbent according to claim 1, is characterized in that, after the described complete reaction of step (2), obtains reaction solution, is specially:
React 3h～5h under 50 ℃～55 ℃ conditions, obtain reaction solution.
6. the compound Graphene adsorbent that the described preparation method of claim 1～5 any one prepares, comprise Graphene, nano zero valence iron and cationic surfactant softex kw.
7. compound Graphene adsorbent according to claim 6, is characterized in that, described nano zero valence iron inserts edge or the top layer of stratiform Graphene by chemical b `.
8. compound Graphene adsorbent according to claim 6, is characterized in that, described nano zero valence iron is embedded in edge or the top layer of lamellar graphite alkene by chemical b `.
9. the application of compound Graphene adsorbent claimed in claim 6, is characterized in that, for removing the paranitrochlorobenzene of the aqueous solution.
10. the application of compound Graphene adsorbent according to claim 9, is characterized in that, the paranitrochlorobenzene in the described removal aqueous solution, and detailed process is as follows:
Every premium on currency solution adds the compound Graphene adsorbent of 1g～2g; In adsorption process, the temperature of controlling the aqueous solution is 20 ℃～50 ℃, fully adsorbs and vibrate to after reacting completely, and utilizes filter membrane to be filtered the remaining liquid after adsorbing, and completes the removal to paranitrochlorobenzene in the aqueous solution.
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