CN102774949A - Method for decolorizing cationic dye waste water - Google Patents
Method for decolorizing cationic dye waste water Download PDFInfo
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- CN102774949A CN102774949A CN2012102855560A CN201210285556A CN102774949A CN 102774949 A CN102774949 A CN 102774949A CN 2012102855560 A CN2012102855560 A CN 2012102855560A CN 201210285556 A CN201210285556 A CN 201210285556A CN 102774949 A CN102774949 A CN 102774949A
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Abstract
The invention relates to a method for cationic dye waste water, which is characterized by comprising the following steps: adding 1mg/ml graphite oxide or graphene solution to 50mmol/l cationic dye solution with the same volume, stirring at room temperature until a floc appears at the bottom of the mixed solution and the mixed solution fades and becomes colorless, and filtering to remove the floc. The graphite oxide or graphene serving as the adsorbent has the two-dimensional structure of a single atomic layer and a huge surface area. Various oxygen-containing functional groups on the surface of the graphite oxide ensure that the graphite oxide is a hydrophilic substance. The surface of the graphite oxide is provided with a certain amount of the negative charges, so that the graphite oxide can effectively adsorb the cationic dye to achieve the purpose of decolorizing.
Description
Technical field
The present invention relates to method of wastewater treatment, specifically belong to a kind of method of utilizing graphite oxide or Graphene to the cationic dyestuff waste water decoloring.
Background technology
Cationic dye printing-dyeing wastewater is one of main noxious industry waste water, complicated component, COD
CrConcentration is high, saltiness is high, and PH is low, colourity up to several ten thousand times to hundreds of thousands of doubly, the poor (BOD of biodegradability
5/ COD
CrBe 0.2～0.4), water quality and quantity changes greatly, belongs to more unmanageable trade effluent, and cationic dye printing-dyeing wastewater is discharged into and has a strong impact on urban look in the water body.Simultaneously, the dyestuff in the waste water can absorb light to be reduced water transparency, the hydrobiont growth is impacted, and destroys water surrounding greatly.Therefore, the processing of research cationic dye printing-dyeing wastewater is to alleviating China's water resources serious lack, preserves the ecological environment and human health has very important significance.Because cationic dyestuff generally all has bio-toxicity, physics commonly used or chemical method are handled in the engineering, as: absorption method, membrane separation process, flocculent precipitation, electrochemical process, electrolytic process and oxidation style etc.Wherein absorption method is one of effective means, but the most important thing is to seek suitable sorbent material efficiently, improves the adsorption bleaching efficient of cationic dyestuff.
At present, there are many materials to be in the news and are used for adsorbing the cationic dyestuff of removing in the water body, for example gac, biomaterial and expanded graphite etc.Nano material has great specific surface area, thereby is considered to that higher efficient is being arranged aspect the cationic dyestuff absorption.For example, carbon nanotube is having very high efficient aspect the dyestuffs such as absorption tropeolin-D and sodium alizarinsulfonate, and specific activity charcoal and expanded graphite exceed 7-10 doubly.But carbon nanotube costs an arm and a leg, has certain toxicity, can work the mischief to HUMAN HEALTH; And it is difficult for removing in water body, thereby easy generation of secondary pollution.Therefore, need efficient more, the economic and nontoxic nano adsorber of exploitation.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, environmental protection, the method for cationic dyestuff waste water decoloring efficiently.
The present invention relates to a kind of method of cationic dyestuff waste water decoloring, comprise the steps:
With concentration is the graphite oxide solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter cationic dyestuff solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.
Described graphite oxide can replace with Graphene, and the two available Hummers method makes (specifically seeing embodiment).
Described cationic dyestuff can be that Viola crystallina, magenta, night are blue, in Safranin B Extra and the Nile blue one or more.
The present invention compared with prior art has following characteristics:
(1) used nano adsorber is graphite oxide and Graphene, and they have the two-dirnentional structure of monoatomic layer, and surface-area is huge.The various oxygen-containing functional groups on graphite oxide surface make that graphite oxide is a hydroaropic substance, and its surface has certain negative charge, guarantee that it can well adsorb cationic dyestuff.Simultaneously, graphite oxide and Graphene good biocompatibility can not cause intensive toxicity even be discharged in the environment yet.
(2) to prepare process simple, with low cost, pollution-free for used graphite oxide and Graphene.
(3) graphite oxide and Graphene are higher than other carbon materials to the adsorption efficiency of cationic dyestuff, are more than 10 times of Graphite Powder 99.
Description of drawings
Fig. 1 is adsorptive capacity and the time chart of this graphite oxide to Viola crystallina.
Fig. 2 is adsorptive capacity and the time chart of this graphite oxide to magenta.
Fig. 3 is that this graphite oxide is to night blue adsorptive capacity and time chart.
Fig. 4 is adsorptive capacity and the time chart of this graphite oxide to Safranin B Extra.
Fig. 5 is adsorptive capacity and the time chart of this graphite oxide to Nile blue.
Fig. 6 is adsorptive capacity and the time chart of this Graphene to Viola crystallina.
Fig. 7 is adsorptive capacity and the time chart of this Graphene to magenta.
Fig. 8 is that this Graphene is to night blue adsorptive capacity and time chart.
Fig. 9 is adsorptive capacity and the time chart of this Graphene to Safranin B Extra.
Figure 10 is adsorptive capacity and the time chart of this Graphene to Nile blue.
Embodiment
(1) graphite oxide solution preparation: take by weighing Graphite Powder 99 6g and join and contain 5g P
2O
5With 5g K
2S
2O
8The 25mL concentrated sulfuric acid solution in, in down heating 6 hours of 80 ° of C.Then this mixture is cooled to room temperature,, places the after scouring that spends the night and remove remaining acid, obtain the graphite of preoxidation after the drying with the dilution of 1000mL deionized water.The graphite of preoxidation is joined the 240mLH of 0 ° of C
2SO
4In, add 30g KMnO again
4Stir, maintain the temperature at 20 ° below the C, under 35 ° of C, stirred 2 hours afterwards,, stir after 2 hours, add the 1400mL deionized water again with the dilution of 500mL deionized water.With 40mL 30%H
2O
2Join in the above-mentioned mixed solution, this moment, the color of solution became glassy yellow.The mixed solution that filtration obtains is removed unreacted metal ion and excessive acid with 610mL 10% aqueous hydrochloric acid and 2500mL deionized water wash.After centrifugal, vacuum-drying is 3 days under 50 ° of C, gets graphite oxide.Graphite oxide is configured to the aqueous solution of 1mg/mL, subsequent use.
(2) graphite oxide solution is used for the decolorization experiment to various cationic dyestuff
With concentration is the graphite oxide solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter crystal violet solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphite oxide is seen Fig. 1 to the adsorptive capacity and the timing relationship of Viola crystallina.
With concentration is the graphite oxide solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter Basic Fuchsin in Aqueous Solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphite oxide is seen Fig. 2 to the adsorptive capacity and the timing relationship of magenta.
With concentration is the graphite oxide solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter night in the blue solution, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphite oxide is seen Fig. 3 to the adsorptive capacity and the timing relationship of indigo plant at night.
With concentration is the graphite oxide solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter Safranin B Extra solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphite oxide is seen Fig. 4 to the adsorptive capacity and the timing relationship of Safranin B Extra.
With concentration is the graphite oxide solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter Nile blue solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphite oxide is seen Fig. 5 to the adsorptive capacity and the timing relationship of Nile blue.
With concentration is the graphite oxide solution of 1mg/mL; Join isopyknic concentration be 50 mmoles/liter night blue and Nile blue mixing solutions (the two mixes with arbitrary proportion) in; At room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.
With concentration is the graphite oxide solution of 1mg/mL; Join isopyknic concentration and be 50 mmoles/liter the mixing solutions (three mixes with arbitrary proportion) of Viola crystallina, magenta and Safranin B Extra in; At room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.
Embodiment 2
(1) Graphene formulations prepared from solutions: with the graphite oxide aqueous solution of 30mL 1mg/mL, (20% intensity 1000W) is peeled off 30 minutes, adds the PVP aqueous solution of 30mL 5mg/mL, adds 60mL secondary water then, and 50 ° of C stir 10h down under ultrasonication.After the cooling, add 900 μ L strong aquas, 120 μ L hydrazines (80wt%) are heated to 90 ℃, stir reduction down 1.5 hours, obtain the Graphene sample behind the centrifuge washing.Gained Graphene sample ligand is changed to the graphene aqueous solution of 1mg/mL, subsequent use.
(2) Graphene solution is used for the decolorization experiment to various cationic dyestuff
With concentration is the Graphene solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter crystal violet solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphene is seen Fig. 6 to the adsorptive capacity and the timing relationship of Viola crystallina.
With concentration is the Graphene solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter Basic Fuchsin in Aqueous Solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphene is seen Fig. 7 to the adsorptive capacity and the timing relationship of magenta.
With concentration is the Graphene solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter night in the blue solution, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphene is seen Fig. 8 to the adsorptive capacity and the timing relationship of indigo plant at night.
With concentration is the Graphene solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter Safranin B Extra solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphene is seen Fig. 9 to the adsorptive capacity and the timing relationship of Safranin B Extra.
With concentration is the Graphene solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter Nile blue solution in, at room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.Graphene is seen Figure 10 to the adsorptive capacity and the timing relationship of Nile blue.
With concentration is the Graphene solution of 1mg/mL; Join isopyknic concentration be 50 mmoles/liter night blue and magenta mixing solutions (the two mixes with arbitrary proportion) in; At room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.
With concentration is the Graphene solution of 1mg/mL; Join isopyknic concentration be 50 mmoles/liter the mixing solutions (three mixes with arbitrary proportion) of Viola crystallina, magenta and Nile blue in; At room temperature stir, floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.
Claims (3)
1. the method for a cationic dyestuff waste water decoloring; It is characterized in that; Comprise the steps: with concentration to be the graphite oxide solution of 1mg/mL, join isopyknic concentration and be 50 mmoles/liter cationic dyestuff solution in, at room temperature stir; Floss occurs to the solution bottom, and solution takes off for colourless; Filter, remove floss and get final product.
2. the method for a kind of cationic dyestuff waste water decoloring as claimed in claim 1 is characterized in that, described graphite oxide can replace with Graphene.
3. the method for a kind of cationic dyestuff waste water decoloring as claimed in claim 1 is characterized in that, described cationic dyestuff can be that Viola crystallina, magenta, night are blue, in Safranin B Extra and the Nile blue one or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241796A (en) * | 2013-05-31 | 2013-08-14 | 邓杰帆 | Process and device for performing continuous filtration and adsorption treatment on sewage by using graphene |
| CN106630076A (en) * | 2017-02-23 | 2017-05-10 | 山西大学 | Flocculating agent for removing cationic dyes as well as preparation method and application of flocculating agent |
| CN107140711A (en) * | 2017-06-16 | 2017-09-08 | 扬州大学 | A kind of method for removing the dye of positive ion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009032910A1 (en) * | 2007-09-04 | 2009-03-12 | The Trustees Of Princeton University | Bridged graphite oxide materials |
| CN102211015A (en) * | 2011-06-04 | 2011-10-12 | 山西大学 | Printing and dyeing wastewater adsorbent and preparation method and application thereof |
-
2012
- 2012-08-10 CN CN2012102855560A patent/CN102774949A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009032910A1 (en) * | 2007-09-04 | 2009-03-12 | The Trustees Of Princeton University | Bridged graphite oxide materials |
| CN102211015A (en) * | 2011-06-04 | 2011-10-12 | 山西大学 | Printing and dyeing wastewater adsorbent and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王亚玲 等: "氧化石墨：制备及去除阳离子燃料的性能", 《无机化学学报》, vol. 28, no. 2, 29 February 2012 (2012-02-29) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241796A (en) * | 2013-05-31 | 2013-08-14 | 邓杰帆 | Process and device for performing continuous filtration and adsorption treatment on sewage by using graphene |
| CN103241796B (en) * | 2013-05-31 | 2015-01-14 | 邓杰帆 | Process and device for performing continuous filtration and adsorption treatment on sewage by using graphene |
| CN106630076A (en) * | 2017-02-23 | 2017-05-10 | 山西大学 | Flocculating agent for removing cationic dyes as well as preparation method and application of flocculating agent |
| CN107140711A (en) * | 2017-06-16 | 2017-09-08 | 扬州大学 | A kind of method for removing the dye of positive ion |
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Application publication date: 20121114 |