CN103058168A - Preparation method for nano-carbon material having graphene-like structure - Google Patents
Preparation method for nano-carbon material having graphene-like structure Download PDFInfo
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Abstract
The present invention discloses a preparation method for a nano-carbon material having a graphene-like structure. The preparation method comprises: sequentially performing drying, grinding, carbonizing, acidification washing, and drying to bentonite with dyes adsorbed therein to obtain the nano-carbon material having graphene-like structure. In the present invention, waste bentonite is used as a raw material, and a novel nano layered carbon material having a large specific surface area is prepared via a simple method; and at the same time, a new way for resource recovery and utilization of bentonite with dyes adsorbed therein is provided, thus achieving resource utilization of bentonite after being used for wastewater treatment after, and helping to promote the applications of the bentonite in dye / printing and dyeing wastewater treatment.
Description
Technical field
The present invention relates to novel nano stratiform carbon material, relate in particular to the preparation method of the nano-carbon material of a kind graphene-structured.
Background technology
Wilkinite is a kind of tonstein take montmorillonite (Montmorillonite) as essential mineral.The constitutional features of montmorillonite is a kind of layer aluminosilicate mineral with two-dimensional nanostructure, forms by aluminium of two silicon-oxy tetrahedron therebetween (magnesium) oxygen (hydrogen-oxygen) are octahedra.Because isomorphous replacement effect, montmorillonite produces permanent negative charge because the non-equivalence cation replacement easily occurs interlayer, can be by reaching charge balance at its interlamination region internal adsorption positively charged ion, and it is long-pending that montmorillonite has very large surfaces externally and internally, therefore, wilkinite can adsorb all kinds of organic and inorganic cations by ion exchange, has higher loading capacity and very strong sorptive power is.
Because the adsorptive power that the wilkinite mineral products are abundant and excellent, wilkinite is widely used in adsorbing industrial organic dye, especially is applied to dyestuff/treatment of dyeing wastewater, becomes the important sorbing material of dyestuff/dyeing waste water.Wilkinite low price, price per ton only are about 10% of gac in hundreds of units; Good to cationic dyestuff absorption property in the water, to the absorption property of Common Cations dyestuff such as methylene blue, Viola crystallina etc. all above gac.Therefore, in dyestuff/treatment of dyeing wastewater, bentonitic integrated application cost is far below gac, but will realize wilkinite applying in dyestuff/dyeing waste water, also needs to solve bentonitic recycling problem behind the absorbing dye.The present invention will discard bentonitic resource utilization novel method after a kind of absorbing dye will be provided, and also be a kind of novel method for preparing the carbon nanomaterial of class graphene-structured simultaneously.
Summary of the invention
The object of the present invention is to provide the preparation method of the nano-carbon material of a kind graphene-structured.
The technical solution used in the present invention is:
The preparation method of the nano-carbon material of one kind graphene-structured may further comprise the steps: the wilkinite that will adsorb dyestuff carries out drying, pulverizing, carbonization, acidifying washing, drying successively, gets the nano-carbon material of class graphene-structured.
Preferably, Carbonization Conditions: carry out carbonization in protective gas atmosphere, carbonization temperature is 500～800 ℃, and carbonization time is 2～5h.
Preferably, protective gas is at least a in nitrogen, the rare gas element.
Preferably, adopt hydrofluoric acid, hydrochloric acid to replace the acidifying washing after the raw material carbonization, to remove the wilkinite component.The present invention adopts the effect of hydrofluoric acid, hcl acidifying washing to be better than the effect of washing with hydrofluoric acid or hcl acidifying separately.
Preferably, described hydrofluoric acid volumetric concentration is 10～20%.
Preferably, described hydrochloric acid volumetric concentration is 6～15%.
Preferably, the wilkinite that has adsorbed dyestuff adopts the wilkinite that has adsorbed dyestuff in dyestuff/treatment of dyeing wastewater.
Preferably; this preparation method; may further comprise the steps: the wilkinite that will adsorb dyestuff carries out drying, pulverizing successively; then 500～800 ℃ of carbonization 2～5h in protective gas atmosphere; it is that 10～20% hydrofluoric acid, volumetric concentration are that 6～15% hydrochloric acid replaces the acidifying washing that wilkinite after the carbonization adopts volumetric concentration; removing the wilkinite component, final drying gets the nano-carbon material of class graphene-structured.
The nano-carbon material of one kind graphene-structured adopts above-mentioned preparation method's preparation.
The present invention utilizes the special two-dimensional nanostructure of wilkinite, with bentonite lamella as template, by being adsorbed onto the cationic dyestuff secluding air carbonization in the wilkinite interlamination region, generate the two-dimensional nano interbed matrix material of wilkinite-class Graphene carbon material, behind pickling removal bentonite lamella, the surface of carbon material exposes, become the carbon material that has bigger serface, thereby make the class Graphene carbon material with high-specific surface area, an i.e. class novel nano stratiform carbon material, the gained carbon material can be used as sorbing material, capacitor material etc.
The invention has the beneficial effects as follows:
The present invention is take discarded wilkinite as raw material, prepares by simple method a kind ofly to have class graphene nano carbon material than bigger serface (specific surface area reaches 428～510 m
2/ g), for bentonitic resource utilization recycling after solving absorbing dye provides new way, realized the bentonite resource utilization after the wastewater treatment, thereby helped to promote the application of wilkinite in dyestuff/treatment of dyeing wastewater simultaneously.
Description of drawings
Fig. 1 is the XRD spectrum figure of embodiment 1 product;
Fig. 2 is the Raman spectrogram of embodiment 1 product.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but be not limited to this.
Embodiment 1
The preparation method of the nano-carbon material of one kind graphene-structured may further comprise the steps:
1) the 2g wilkinite is put into 5 L and contained in the waste water that Viola crystallina concentration is 200 mg/L, adsorb 1 h postprecipitation 2h, it is limpid that waste water becomes;
The discarded wilkinite that 2) will precipitate is dry, pulverizing, then place retort furnace, under nitrogen protection, be warming up to 600 ℃ of carbonization 2h, then adopting volumetric concentration is that 10% hydrofluoric acid, volumetric concentration are that 10% hydrochloric acid alternately washs 4 times, and each washing time is that the consumption of 4 h, acid is 40mL; Obtain the nano-carbon material of class graphene-structured after the product drying.
The XRD characterization result shows (Fig. 1), and the wilkinite basal spacing is respectively 1.52nm and 1.32 nm before the carbonization and after the carbonization; Because bentonite lamella thickness 0.96 nm therefore theoretical is 0.36 nm between the lamella of gained nano-carbon material, can infer that the carbon atom of nano-carbon material between bentonite bed is monolayer alignment, has the class graphene-structured.Behind the wilkinite process hydrofluoric acid and salt acid elution after the carbonization, the Raman spectral characterization of product is seen Fig. 2, shows obvious D peak and G peak among the figure, shows that product has the constitutional features of Graphene.The specific surface area that records product is 423 m
2/ g.
Embodiment 2
The preparation method of the nano-carbon material of one kind graphene-structured may further comprise the steps:
1) the 2g wilkinite is put into 5 L and contained in the waste water that methylene blue concentration is 200 mg/L, adsorb 1 h postprecipitation 2h, it is limpid that waste water becomes;
2) with above wilkinite separation, drying, pulverizing of having adsorbed the cationic dyestuff methylene blue; then place retort furnace under nitrogen protection, to be warmed up to 600 ℃ of carbonization 3h; wilkinite volumetric concentration after the carbonization is that 15% hydrofluoric acid, volumetric concentration are that 12% hydrochloric acid alternately washs 4 times; each washing time is 3 h, and sour consumption is 30mL.Product is dry, gets the nano-carbon material of class graphene-structured.
The demonstration of XRD characterization result, the wilkinite basal spacing after the carbonization is 1.33 nm; Get the nano-carbon material of class graphene-structured behind the acid elution, the Raman spectral characterization shows that this material has the constitutional features of Graphene, obvious D peak and G peak occur.The specific surface area that the surface analysis instrument records product is 451 m
2/ g.
Embodiment 3
The preparation method of the nano-carbon material of one kind graphene-structured may further comprise the steps:
1) the 2g wilkinite is put into 5 L and contained in the waste water that Viola crystallina concentration is 250 mg/L, adsorb 1 h postprecipitation 2h, it is limpid that waste water becomes;
The discarded wilkinite that 2) will precipitate is dry, pulverizing; then place retort furnace; under nitrogen protection, be warming up to 500 ℃ of carbonization 5h; wilkinite volumetric concentration after the carbonization is that 20% hydrofluoric acid, volumetric concentration are that 6% hydrochloric acid alternately washs 3 times; each washing time is 4 h; the acid consumption is 30mL, and drying gets the nano carbon material of class graphene-structured.
The demonstration of XRD characterization result, the wilkinite basal spacing after the carbonization is 1.32 nm; Product behind the acid elution has the constitutional features of Graphene, the demonstration of Raman spectral characterization, and obvious D peak and G peak appear in material; The specific surface area of material is 408 m
2/ g.
Embodiment 4
The preparation method of the nano-carbon material of one kind graphene-structured may further comprise the steps:
1) the 2g wilkinite is put into 5 L and contained Viola crystallina concentration and be, in the waste water of 300 mg/L, adsorb 1 h postprecipitation 2h, it is limpid that waste water becomes;
The discarded wilkinite that 2) will precipitate is dry, pulverizing; then place retort furnace; under nitrogen protection, be warming up to 800 ℃ of carbonization 4h; wilkinite volumetric concentration after the wilkinite carbonization after the carbonization is that 15% hydrofluoric acid, volumetric concentration are that 15% hydrochloric acid alternately washs 4 times; each washing time is 4 h; the acid consumption is 50mL, and drying gets the nano-carbon material of class graphene-structured.
The demonstration of XRD characterization result, the wilkinite basal spacing after the carbonization is 1.32 nm; Product behind the acid elution has the constitutional features of Graphene, the demonstration of Raman spectral characterization, and obvious D peak and G peak appear in material; The specific surface area of material is 508 m
2/ g.
Adsorption test:
0.05 g carbon material (embodiment 1 products therefrom) is put in the ethyl naphthol aqueous solution that 20 mL contain 50 mg/L, adsorbed that the clearance of ethyl naphthol reaches 99.9% behind 1 h.Get the adsorption experiment that 0.05 g wilkinite carries out similarity condition, show that wilkinite can not adsorb ethyl naphthol.
0.05 g carbon material (embodiment 2 products therefroms) is put in the phenol solution that 20 mL contain 50 mg/L, adsorbed that the clearance of phenol reaches 98.9% behind 1 h.Get the adsorption experiment that 0.05 g wilkinite carries out similarity condition, show that wilkinite can not adsorbing phenol.
By above-mentioned experiment as can be known, the nano-carbon material of the class graphene-structured of the present invention's preparation has good absorption property to organic pollutant.
Claims (8)
1. the preparation method of the nano-carbon material of a kind graphene-structured may further comprise the steps:
The wilkinite that has adsorbed dyestuff is carried out drying, pulverizing, carbonization, acidifying washing, drying successively, get the nano-carbon material of class graphene-structured.
2. preparation method according to claim 1, it is characterized in that: Carbonization Conditions: carry out carbonization in protective gas atmosphere, carbonization temperature is 500～800 ℃, and carbonization time is 2～5h.
3. preparation method according to claim 2 is characterized in that: protective gas is at least a in nitrogen, the rare gas element.
4. preparation method according to claim 1 is characterized in that: adopt hydrofluoric acid, hydrochloric acid to replace the acidifying washing after the raw material carbonization, with eccysis wilkinite component.
5. preparation method according to claim 4, it is characterized in that: described hydrofluoric acid volumetric concentration is 10～20%.
6. preparation method according to claim 4, it is characterized in that: described hydrochloric acid volumetric concentration is 6～15%.
7. preparation method according to claim 1 is characterized in that: the wilkinite that has adsorbed dyestuff adopts the wilkinite that has adsorbed dyestuff in dyestuff/treatment of dyeing wastewater.
8. the nano-carbon material of a kind graphene-structured is characterized in that: adopt each described preparation method's preparation of claim 1～7.
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| CN103303895A (en) * | 2013-07-02 | 2013-09-18 | 西南大学 | Method for modifying carbon material by adopting ink |
| CN103638901A (en) * | 2013-11-25 | 2014-03-19 | 中国科学院广州地球化学研究所 | Method for regenerating porous template carbon material by utilizing LDH |
| CN103979529A (en) * | 2014-06-04 | 2014-08-13 | 北京化工大学 | Preparation method of porous carbon material and application of porous carbon material as electrode material |
| CN104085874A (en) * | 2014-06-05 | 2014-10-08 | 中国科学院广州地球化学研究所 | Preparation method for doped graphene-like structural nanometer carbon material |
| CN106243389A (en) * | 2016-08-03 | 2016-12-21 | 中国地质大学（武汉） | A kind of preparation method and applications of montmorillonite graphene composite powder |
| CN108264033A (en) * | 2018-01-08 | 2018-07-10 | 石河子大学 | A kind of method and carbon material that carbon material is prepared using dyeing waste water |
| CN108264032A (en) * | 2018-01-08 | 2018-07-10 | 石河子大学 | A kind of method and carbon material that the mud that flocculates is utilized to prepare carbon material with dyestuff dangerous waste |
| CN108328598A (en) * | 2018-01-08 | 2018-07-27 | 石河子大学 | A kind of method and carbon material preparing carbon material with petroleum coke using flocculation mud |
| CN108328597A (en) * | 2018-01-08 | 2018-07-27 | 石河子大学 | A kind of carbon material prepared using dyeing waste water |
| CN113422082A (en) * | 2021-07-06 | 2021-09-21 | 中国科学技术大学 | Nitrogen-doped carbon five-membered ring structure-containing graphene-like carbon material electrocatalyst and preparation method and application thereof |
| CN114433010A (en) * | 2022-02-18 | 2022-05-06 | 内蒙古大学 | Treatment method of waste rectorite, heterogeneous interlayer material, preparation method and application thereof |
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| CN103303895A (en) * | 2013-07-02 | 2013-09-18 | 西南大学 | Method for modifying carbon material by adopting ink |
| CN103303895B (en) * | 2013-07-02 | 2015-02-25 | 西南大学 | Method for modifying carbon material by adopting ink |
| CN103638901B (en) * | 2013-11-25 | 2017-01-04 | 中国科学院广州地球化学研究所 | A kind of method utilizing discarded LDH regeneration foraminous die plate material with carbon element |
| CN103638901A (en) * | 2013-11-25 | 2014-03-19 | 中国科学院广州地球化学研究所 | Method for regenerating porous template carbon material by utilizing LDH |
| CN103979529A (en) * | 2014-06-04 | 2014-08-13 | 北京化工大学 | Preparation method of porous carbon material and application of porous carbon material as electrode material |
| CN104085874A (en) * | 2014-06-05 | 2014-10-08 | 中国科学院广州地球化学研究所 | Preparation method for doped graphene-like structural nanometer carbon material |
| CN106243389A (en) * | 2016-08-03 | 2016-12-21 | 中国地质大学（武汉） | A kind of preparation method and applications of montmorillonite graphene composite powder |
| CN106243389B (en) * | 2016-08-03 | 2019-07-26 | 中国地质大学（武汉） | A kind of preparation method and applications of montmorillonite-graphene composite powder |
| CN108264033A (en) * | 2018-01-08 | 2018-07-10 | 石河子大学 | A kind of method and carbon material that carbon material is prepared using dyeing waste water |
| CN108264032A (en) * | 2018-01-08 | 2018-07-10 | 石河子大学 | A kind of method and carbon material that the mud that flocculates is utilized to prepare carbon material with dyestuff dangerous waste |
| CN108328598A (en) * | 2018-01-08 | 2018-07-27 | 石河子大学 | A kind of method and carbon material preparing carbon material with petroleum coke using flocculation mud |
| CN108328597A (en) * | 2018-01-08 | 2018-07-27 | 石河子大学 | A kind of carbon material prepared using dyeing waste water |
| CN108328597B (en) * | 2018-01-08 | 2022-12-06 | 石河子大学 | Carbon material prepared from printing and dyeing wastewater |
| CN113422082A (en) * | 2021-07-06 | 2021-09-21 | 中国科学技术大学 | Nitrogen-doped carbon five-membered ring structure-containing graphene-like carbon material electrocatalyst and preparation method and application thereof |
| CN114433010A (en) * | 2022-02-18 | 2022-05-06 | 内蒙古大学 | Treatment method of waste rectorite, heterogeneous interlayer material, preparation method and application thereof |
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