CN106630076A - Flocculating agent for removing cationic dyes as well as preparation method and application of flocculating agent - Google Patents
Flocculating agent for removing cationic dyes as well as preparation method and application of flocculating agent Download PDFInfo
- Publication number
- CN106630076A CN106630076A CN201710100128.9A CN201710100128A CN106630076A CN 106630076 A CN106630076 A CN 106630076A CN 201710100128 A CN201710100128 A CN 201710100128A CN 106630076 A CN106630076 A CN 106630076A
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- Prior art keywords
- flocculating agent
- flocculant
- dye
- beta
- positive ion
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a flocculating agent for removing cationic dyes as well as a preparation method and an application of the flocculating agent. The flocculating agent is a black suspension prepared from beta-cyclodextrin-reduced graphene oxide (beta-CD-RGO) dispersed in water. When added to a cationic dye solution, the flocculating agent can be combined with the cationic dyes and rapidly produces flocculation, the cationic dyes in the solution are removed, and the effect of decolorizing the cationic dye solution is realized. The flocculating agent has the advantages that the preparation method is simple and fast, cost is lower, flocculation speed is high and the decolorizing effect is excellent; the flocculating agent is expected to be widely applied to the field of decoloration of cationic industrial dye wastewater.
Description
Technical field
It is the present invention relates to dye of positive ion flocculant more particularly to a kind of for removing dyeing waste water cationic dyestuff
Flocculant and its preparation method and application.
Background technology
The discharge of dyeing waste water causes extreme influence to water body, it has also become the important pollution sources in each big waters of China, seriously
Injure healthy and crops the growth of the mankind.Dyeing waste water is effectively and reasonably administered, with far-reaching environment and society
Can meaning.Water-soluble dye is generally the organic compound of difficult degradation, different according to the electrically charged property of chromophoric group institute, can be by
It is divided into the dye of positive ion and the class of anionic dye two.Wherein, dye of positive ion molecular weight, with water molecules ability
By force, biodegradability is poor, therefore traditional treatment method is difficult to make colourity reach discharge standard.That what is studied both at home and abroad contaminates for cation
The discoloration method of material mainly includes：Absorption method, chemical coagulation process, biological contact oxidation process etc., though the decolorizing effect of these methods
So lifted, but can't be satisfactory, and process cycle is longer, and it is relatively costly.
Two-dimension nano materials Graphene has extra specific surface area, and (theoretical value is up to 2630m2/ g), this is inhaling Graphene
The application in subsidiary formula face possesses huge potentiality and natural advantage.But there is stronger π-π phases in high-quality graphene interlayer
Interaction, easily produces irreversible cohesion so as to which specific surface area is had a greatly reduced quality, and this inhales to the pollutant that Graphene is used in water
Incidentally come difficult, it is necessary to functional modification is carried out to graphenic surface and is scattered in water phase with just stabilizing it, so as to convenient
Adsorbed.Beta-schardinger dextrin is 7 glucose units by the bonded cyclic oligomer glycan molecule of α-Isosorbide-5-Nitrae glucosides, the molecule
With a hydrophobic cavity and hydrophilic appearance, its hydrophobic cavity can pass through hydrophobic effect with many organic molecules
Power forms Host-guest inclusion complex.When functional modification is carried out to Graphene with cyclodextrin, the functionalization graphene nanometer of gained
Composite has been provided simultaneously with Graphene and the respective peculiar property of cyclodextrin, not only increases Graphene stablizing in water
Property, and also improve the ability combined with organic compound.
In addition, the dye of positive ion is positively charged, industrial all flocculants for using are also positively charged, and both occur electrostatic
Repel, it is difficult to assemble dye molecule.And graphenic surface has elecrtonegativity, the positive charge of the dye of positive ion can be neutralized, with
The dye of positive ion attracts each other and combines.Hydrophobic forces between beta-schardinger dextrin and organic dye molecule further enhancing β-ring
Binding ability of the compound that dextrin and Graphene are formed to organic dyestuff.Dye molecule can be thus set absorption to occur and wad a quilt with cotton
Solidifying effect, is cross-linked into bulky grain and settles down.
The content of the invention
It is an object of the invention to provide a kind of flocculant and its preparation for removing dyeing waste water cationic dyestuff
Methods and applications, the flocculant flocculation rate is fast, and percent of decolourization is high, prepares simply, and cost for wastewater treatment is relatively low.
A kind of flocculant for removing the dye of positive ion that the present invention is provided, the method system by comprising the steps
：
Beta-schardinger dextrin, graphene oxide are added in secondary water, after electromagnetic agitation 3-20min, is added under stirring
Ammoniacal liquor and hydrazine hydrate, the mass ratio of described graphene oxide, beta-schardinger dextrin, ammoniacal liquor, hydrazine hydrate and secondary water is 1:1-7:20-
100:1-3:1500-3000 (preferably 1:1-5:30:2:2000), it is placed in electromagnetic agitation in 40-80 DEG C of (preferably 60 DEG C) water-bath anti-
Answer 2-4 hours (preferably 3.5 hours)；Under room temperature, 11000-13000rpm is centrifuged 15-25min, abandons supernatant, adds secondary water to obtain
To 1mg/mL beta-schardinger dextrin functionalization graphene (β-CD-RGO) black suspension (Graphene at this moment be low oxygen content graphite
Alkene).
Flocculant β-CD-RGO can be used for waste water decoloration of cation dyes.
Compared with prior art, flocculant of the invention can be used for the flocculation decoloration of cationic dyeing waste water, Er Qiexu
Solidifying speed is fast, and percent of decolourization is high.The preparation process of flocculant is carried out at normal temperatures and pressures, method simple possible.
Description of the drawings
The thermogravimetric analysis figure of flocculant β-CD-RGO prepared by Fig. 1 present invention.
Flocculant β-CD-RGO prepared by Fig. 2 present invention are to the purple before and after methylene blue and malachite green solution flocculation treatment
Outward-visible ray spectrogram.
Specific embodiment
Embodiment 1
The preparation of flocculant β-CD-RGO and the flocculation decoloration for dye of positive ion methylene blue solution (MB).
1. the preparation of flocculant β-CD-RGO：
(1) 50.0mg beta-schardinger dextrins, 1.0mg/mL graphene oxide solutions 10.0mL are added in 9.68mL secondary waters, electromagnetism
After stirring 20min, the 25% μ L of ammoniacal liquor 300 and the μ L of 80% hydrazine hydrate 20.0 is added under stirring, in being placed in 60 DEG C of water-baths
Electromagnetic agitation is reacted 3.5 hours.
(2) under room temperature, 12000rpm is centrifuged 20min, abandons supernatant, adds 10.0mL secondary waters to obtain the β-CD- of 1mg/mL
RGO, is black suspension.
2. flocculant β-CD-RGO are used for the flocculation decoloration of dye of positive ion methylene blue (MB) solution：
Under room temperature, MB original solution 0.50mL of the concentration for 0.05mg/mL is added in 4.40mL secondary waters, middling speed is stirred
Mix, β-CD-RGO black suspension 0.10mL prepared in step 1 are added under stirring, stir 15min, make flocculant
Flocculation is fully combined with MB in water, with spectrophotometer the absorbance (see Fig. 2) of solution before and after flocculation is detected, MB can be obtained molten
The percent of decolourization of liquid is 98.71%.
Embodiment 2
The preparation of flocculant β-CD-RGO and the flocculation decoloration for dye of positive ion malachite green (MG) solution.
1. the preparation of flocculant β-CD-RGO：
(1) 10.0mg beta-schardinger dextrins, 1.0mg/mL graphene oxide solutions 10.0mL are added in 9.68mL secondary waters, electromagnetism
After stirring 20min, the 25% μ L of ammoniacal liquor 300 and the μ L of 80% hydrazine hydrate 20.0 is added under stirring, in being placed in 60 DEG C of water-baths
Electromagnetic agitation is reacted 3.5 hours.
(2) under room temperature, 12000rpm is centrifuged 20min, abandons supernatant, adds 10.0mL secondary waters to obtain the β-CD- of 1mg/mL
RGO, is black suspension.
2. flocculant β-CD-RGO are used for the flocculation decoloration of dye of positive ion malachite green (MG) solution：
Under room temperature, MG original solution 0.50mL of the concentration for 0.05mg/mL is added in 4.30mL secondary waters, middling speed is stirred
Mix, β-CD-RGO black suspension 0.20mL prepared in step 1 are added under stirring, stir 15min, make flocculant
Flocculation is fully combined with MG in water, with spectrophotometer the absorbance (see Fig. 2) of solution before and after flocculation is detected, MG can be obtained molten
The percent of decolourization of liquid is 97.27%.
Flocculant β-CD-RGO of the present invention are good to the flocculating effect of water cationic dyestuff, and percent of decolourization is high, prepared by material
Method is simple, and the process for processing cationic dyes waste water is simple and convenient.Compared with other composite flocculants, its performance has
Large increase (is shown in Table 1), with extraordinary application prospect.
The various flocculant percent of decolourizations of table 1 compare
Claims (5)
1. a kind of flocculant for removing the dye of positive ion, it is characterised in that be obtained by the method for comprising the steps：
Beta-schardinger dextrin, graphene oxide are added in secondary water, after electromagnetic agitation 3-20min, under stirring ammoniacal liquor is added
And hydrazine hydrate, the mass ratio of described graphene oxide, beta-schardinger dextrin, ammoniacal liquor, hydrazine hydrate and secondary water is 1:1-7:20-100:
1-3:1500-3000, is placed in electromagnetic agitation reaction 2-4 hours in 40-80 DEG C of water-bath；Under room temperature, 11000-13000rpm, centrifugation
15-25min, abandons supernatant, adds secondary water to obtain beta-schardinger dextrin functionalization graphene black suspension.
2. a kind of flocculant for removing the dye of positive ion as claimed in claim 1, it is characterised in that the graphite oxide
The mass ratio of alkene, beta-schardinger dextrin, ammoniacal liquor, hydrazine hydrate and secondary water is 1:1-5:30:2:2000.
3. a kind of flocculant for removing the dye of positive ion as claimed in claim 1, it is characterised in that the bath temperature
For 60 DEG C.
4. a kind of flocculant for removing the dye of positive ion as claimed in claim 1, it is characterised in that the reaction time
For 3.5 hours.
5. flocculant is used for waste water decoloration of cation dyes as described in claim 1-4 any claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710100128.9A CN106630076A (en) | 2017-02-23 | 2017-02-23 | Flocculating agent for removing cationic dyes as well as preparation method and application of flocculating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710100128.9A CN106630076A (en) | 2017-02-23 | 2017-02-23 | Flocculating agent for removing cationic dyes as well as preparation method and application of flocculating agent |
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| CN106630076A true CN106630076A (en) | 2017-05-10 |
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|---|---|---|---|
| CN201710100128.9A Pending CN106630076A (en) | 2017-02-23 | 2017-02-23 | Flocculating agent for removing cationic dyes as well as preparation method and application of flocculating agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133286A (en) * | 2018-09-14 | 2019-01-04 | 清华大学 | A kind of graphene oxide composite flocculation agent and preparation method thereof for sewage treatment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211015A (en) * | 2011-06-04 | 2011-10-12 | 山西大学 | Printing and dyeing wastewater adsorbent and preparation method and application thereof |
| CN102774949A (en) * | 2012-08-10 | 2012-11-14 | 山西大学 | Method for decolorizing cationic dye waste water |
-
2017
- 2017-02-23 CN CN201710100128.9A patent/CN106630076A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211015A (en) * | 2011-06-04 | 2011-10-12 | 山西大学 | Printing and dyeing wastewater adsorbent and preparation method and application thereof |
| CN102774949A (en) * | 2012-08-10 | 2012-11-14 | 山西大学 | Method for decolorizing cationic dye waste water |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133286A (en) * | 2018-09-14 | 2019-01-04 | 清华大学 | A kind of graphene oxide composite flocculation agent and preparation method thereof for sewage treatment |
| CN109133286B (en) * | 2018-09-14 | 2021-06-08 | 清华大学 | Graphene oxide composite flocculant for sewage treatment and preparation method thereof |
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