CN102357356B - Preparation method of azo dye adsorbent - Google Patents
Preparation method of azo dye adsorbent Download PDFInfo
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- CN102357356B CN102357356B CN 201110269721 CN201110269721A CN102357356B CN 102357356 B CN102357356 B CN 102357356B CN 201110269721 CN201110269721 CN 201110269721 CN 201110269721 A CN201110269721 A CN 201110269721A CN 102357356 B CN102357356 B CN 102357356B
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Abstract
The invention discloses a preparation method and application of an azo dye adsorbent, which comprises following operating steps: first, pretreatment of graphite is carried out to obtain oxidation graphite capable of adsorbing azo dye through pi-pi interaction; and then polymine is used for chemical modification of the oxidation graphite, so that the oxidation graphite has good dispersion stability in aqueous solution. Modified oxidation graphite is used for waste water treatment containing azo dye. The preparation method and the application of the azo dye adsorbent is convenient in preparation, fast in absorption, high in efficient, wide in application scope, free of residues and adverse reactions and the like, and is expected to be widely used in the field of environmental engineering.
Description
Technical field
The invention belongs to field of environment engineering technology, particularly a kind of azo dye adsorbent and its preparation method and application.
Background technology
Azo dyes is to use maximum dyes in the present dyeing, and stable chemical nature, its waste water have that colourity is dark, difficult, catabolite toxicity is high and to characteristics such as environmental hazard are large, be the dyeing waste water of a quasi-representative.At present the method for processing azo dye wastewater commonly used mainly contains absorption method, chemical oxidization method, biochemical process etc., wherein absorption method relatively low owing to cost, can avoid secondary pollution and the advantage such as have no side effect becomes and studies and the most widely used a kind of method.The key that this technology is implemented is to select high-performance adsorbent.Study at present and use more adsorbent and mainly contain active carbon, natural minerals (diatomite, cinder etc.), high performance resin and CNT etc.For example, Rocher etc. are with magnetic nano-particle and activated carbon supported in the crosslinked sodium alginate micro ball of shell, use it for the absorption research of methylene blue and methyl orange, because this adsorbent can be regulated and control separating of adsorbent and adsorbing medium by magnetic field, thereby be difficult for to produce residual (Journal of Hazardous Materials 2010,178:434-439).Wang Yong etc. are take CMC, acrylic resin and bentonite etc. as raw material, make a class low-cost, can be used for the high-performance water-absorbing resin that azo dye wastewater processes (Chinese invention patent, CN100591627C).The CNT of the use chemical modifications such as Yao adsorbs research to methylene blue, because CNT has abundant nanoaperture structure and huge specific area, therefore this adsorbent show good adsorption effect (Bioresource Technology 2010,101:3040-3046).
But adsorbance and the adsorption efficiency of the adsorbents such as above-mentioned resin or active carbon are relatively low, have increased the use amount of adsorbent, easily cause secondary pollution; Although CNT relies on its special nanostructured azo dyes to show higher adsorbance, its water dispersible is poor, can not be fully contacts with azo dyes in the waste water, and its adsorption efficiency also is under some influence.Therefore, how to make up the new adsorbent with high absorption capacity and become the important topic that this field needs to be resolved hurrily.Up to now, utilizing poly-acetimide that graphite oxide is carried out chemical modification prepares the water dispersible graphite oxide and uses it for the azo dyes adsorption applications and there is not yet report.
Summary of the invention
In order to solve the shortcoming and defect that exists in the above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method with azo dye adsorbent of high absorption property; The present invention at first carries out preliminary treatment to graphite, prepares graphite oxide; This graphite oxide has good dispersion stabilization in the aqueous solution after the polymine chemical modification.
Another object of the present invention is to provide a kind of azo dye adsorbent by the said method preparation.That this sorbent material has is easy to prepare, rapidly and efficiently, applied widely, noresidue and the characteristics such as have no side effect.
A further object of the present invention is to provide the application of above-mentioned azo dye adsorbent in field of environment engineering.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of azo dye adsorbent comprises following operating procedure:
(1) preparation of pre-oxidation graphite:
With 5～10g potassium peroxydisulfate (K
2S
2O
8) and 5～10g phosphorus pentoxide (P
2O
5) join in 20～40mL concentrated sulfuric acid, fully after the dissolving, be warming up to 60～90 ℃, add again 5～10g graphite powder, stir stopped heating after 4～8 hours, naturally cool to room temperature; With products therefrom with to original volume 3～10 times of distilled water diluting, centrifugal collecting precipitation, and with the distilled water washing, obtain pre-oxidation graphite;
(2) preparation of graphite oxide:
Step (1) gained pre-oxidation graphite is scattered in 20～40mL concentrated sulfuric acid, and cryosel is bathed and is cooled to-5～0 ℃, obtains the pre-oxidation graphite dispersing solution; With potassium permanganate (KMnO
4) add in the pre-oxidation graphite dispersing solution, reacted 1～3 hour, then add distilled water and hydrogen peroxide, impurity is removed in centrifugation, again supernatant is continued centrifugation, and collecting precipitation obtains graphite oxide (GO);
(3) azo dye adsorbent (be the polyethyleneimine-modified graphite oxide, preparation PEI-GO):
At ambient temperature, 10～50mg step (2) gained graphite oxide is scattered in 20～50mL water, after the ultrasonic dispersion with polymine (PEI) blend, in gained solution, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) and N-hydroxy-succinamide (NHS) again, regulate pH value to 6～7, reacted under the room temperature condition 24～48 hours; With the product centrifugation, collecting precipitation obtains azo dye adsorbent.
The described room temperature of step (1) is 15～35 ℃; Magnetic agitation is adopted in described stirring; Described centrifugal employing rotating speed is 2000～4000r/min; Described number of times with the distilled water washing is 3～5 times.
The described concentrated sulfuric acid of step (2) is the aqueous sulfuric acid of mass fraction 70%～98%; The mass ratio of described pre-oxidation graphite and potassium permanganate is 1: 2～1: 4; The described concentrated sulfuric acid: distilled water: the volume ratio of hydrogen peroxide is (1～2): 56: 1.
It is 500r/min that impurity employing rotating speed is removed in the described centrifugation of step (2); Describedly supernatant is continued centrifugation to adopt rotating speed be 4000～6000r/min.
The time of the described ultrasonic dispersion of step (3) is 1～2 hour, and it is 30～60W that power is adopted in ultrasonic dispersion; Rotating speed 4000～10000r/min is adopted in described centrifugation.
The described room temperature of step (3) is 15～35 ℃; Described graphite oxide: polymine: 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate: the mass ratio of N-hydroxy-succinamide is 1: (5～20): 2: 2; The weight average molecular weight of described polymine is 10000 or 25000; Described adjusting pH value is to adopt the acid solution of 0.1～0.5mol/L to regulate.
Described acid solution is hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution, citric acid solution or acetic acid solution.
A kind of azo dye adsorbent according to the said method preparation.
The application of above-mentioned azo dye adsorbent in field of environment engineering.
Principle of the present invention is: graphite oxide is nontoxic, inertia, has unique nanostructured, and its two dimensional surface can interact effectively compoundly with the little molecule that contains phenyl ring by π-π, and load capacity is high, therefore can be used for the removal of azo dyes.The present invention is at first with graphite oxidation, obtain having the graphite oxide of nanostructured, then utilize PEI that graphite oxide is carried out chemical modification, the water dispersible of the graphite oxide after the modification obviously improves, and be single layer structure more, avoid the gathering between the nano oxidized graphite, relatively increased the specific area of material, be conducive to the absorption of its azo dyes.This adsorbent and azo dyes mainly interact compound by π-π.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) azo dye adsorbent of the present invention is easy to prepare, and composition is simple, and material non-toxic, inertia;
(2) main compound by π-π interaction between this adsorbent and the azo dyes, than chemical precipitation method, bioanalysis etc., can not produce secondary pollution;
(3) the graphite oxide dispersion stability after PEI modifies is good, is conducive to the absorption of its azo dyes;
(4) the graphite oxide absorption property after PEI modifies obviously improves, and shows as that the rate of adsorption is fast, adsorbance is large, but the treatment effeciency of Effective Raise azo dyes;
(5) graphite oxide of PEI modification all shows good adsorption effect at room temperature condition, pH=5-7, is fit to daily dyeing and printing sewage treatment conditions;
(6) adsorbent can separate with water body by filter membrane, is easy to collection, purifying.
Description of drawings
Fig. 1 is the absorbance curve map over time of the aqueous dispersions of graphite oxide and azo dye adsorbent.
Fig. 2 is the transmission electron microscope picture figure of azo dye adsorbent.
Fig. 3 is azo dye adsorbent of the present invention curve of adsorption kinetics figure to methyl orange under 25 ℃ of conditions.
Fig. 4 is azo dye adsorbent of the present invention curve of adsorption kinetics figure to methyl orange under condition of different temperatures, and 1 is 55 ℃, and 2 is 40 ℃, and 3 is 25 ℃.
Fig. 5 is azo dye adsorbent of the present invention curve of adsorption kinetics figure to methylene blue under 25 ℃ of conditions.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment 1
With 5g K
2S
2O
8With 5g P
2O
5Join in the 20mL concentrated sulfuric acid, after it fully dissolves, be warming up to 80 ℃, add the 5g graphite powder again, magnetic agitation is stopped heating after 4 hours, naturally cools to 15 ℃ of room temperatures; With products therefrom with to original volume 5 times of distilled water diluting, centrifugal (2000r/min) collecting precipitation, and with 3 washings of distilled water, obtain pre-oxidation graphite;
Gained pre-oxidation graphite is scattered in the concentrated sulfuric acid of 40mL mass fraction 70%, and cryosel is bathed and is cooled to 0 ℃, with 10g KMnO
4Add in the pre-oxidation graphite dispersing solution, reacted 1 hour, and then add 1120mL distilled water and 20mL hydrogen peroxide, centrifugation (500r/min) is to remove impurity, supernatant continues centrifugation (4000r/min), and collecting precipitation obtains graphite oxide (GO).
With 10g K
2S
2O
8With 10g P
2O
5Join in the 30mL concentrated sulfuric acid, after it fully dissolves, be warming up to 60 ℃, add the 10g graphite powder again, magnetic agitation is stopped heating after 6 hours, naturally cooling room temperature to 35 ℃; With products therefrom with to original volume 3 times of distilled water diluting, centrifugal (4000r/min) collecting precipitation, and with 4 washings of distilled water, obtain pre-oxidation graphite;
Gained pre-oxidation graphite is scattered in the concentrated sulfuric acid of 80mL mass fraction 98%, and cryosel is bathed and is cooled to-5 ℃, with 40g KMnO
4Add in the pre-oxidation graphite dispersing solution, reacted 2 hours, and then add a certain amount of 2240mL distilled water and 40mL hydrogen peroxide, centrifugation (500r/min) is to remove impurity, supernatant continues centrifugation (6000r/min), and collecting precipitation obtains graphite oxide A.
Embodiment 3
With 10g K
2S
2O
8With 10g P
2O
5Join in the 40mL concentrated sulfuric acid, after it fully dissolves, be warming up to 90 ℃, add the 5g graphite powder again, magnetic agitation is stopped heating after 8 hours, naturally cools to 25 ℃ of room temperatures; With products therefrom with to original volume 10 times of distilled water diluting, centrifugal (3000r/min) collecting precipitation, and with 5 washings of distilled water, obtain pre-oxidation graphite;
Gained pre-oxidation graphite is scattered in the concentrated sulfuric acid of 40mL mass fraction 85%, and cryosel is bathed and is cooled to 0 ℃, with 40g KMnO
4Add in the pre-oxidation graphite dispersing solution, reacted 3 hours, and then add 2240mL distilled water and 40mL hydrogen peroxide, centrifugation (500r/min) is to remove impurity, supernatant continues centrifugation (6000r/min), and collecting precipitation obtains graphite oxide.
Under 15 ℃ of conditions of room temperature, the graphite oxide A of 50mg is scattered in the 50mL distilled water, adopt power be the ultrasonic dispersion of 60W after 1 hour with 500mg PEI (weight average molecular weight is 10000) blend, in gained solution, add 100mg EDCHCl and 100mg NHS again, and with the hydrochloric acid of 0.1mol/L the pH value of system being adjusted to 6.0, reaction is 24 hours under the room temperature condition; With product centrifugation (10000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. azo dye adsorbent B after reaction finished.
Embodiment 5
Under 25 ℃ of conditions of room temperature, the graphite oxide A of 20mg is scattered in the 20mL distilled water, adopting power is that the ultrasonic dispersion of 30W adds 100mg PEI (weight average molecular weight is 25000) blend again after 1 hour, in gained solution, add 40mg EDCHCl and 40mg NHS again, and with the phosphoric acid of 0.1mol/L the pH value of system being adjusted to 6.0, reaction is 24 hours under the room temperature condition.With product centrifugation (6000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. azo dye adsorbent after reaction finished.
Under 35 ℃ of conditions of room temperature, the graphite oxide A of 10mg is scattered in the 20mL distilled water, adopting power is that the ultrasonic dispersion of 50W adds 200mg PEI (weight average molecular weight is 25000) blend again after 1 hour, in gained solution, add 20mg EDCHCl and 20mg NHS again, and with the sulfuric acid of 0.1mol/L the pH value of system being adjusted to 7.0, reaction is 48 hours under the room temperature condition.With product centrifugation (10000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. azo dye adsorbent after reaction finished.
Embodiment 7
Under 25 ℃ of conditions of room temperature, the graphite oxide A of 50mg is scattered in the 20mL distilled water, adopting power is that the ultrasonic dispersion of 40W adds 250mg PEI (weight average molecular weight is 10000) blend again after 2 hours, in gained solution, add 100mg EDCHCl and 100mg NHS again, and with the hydrochloric acid of 0.1mol/L the pH value of system being adjusted to 7.0, reaction is 48 hours under the room temperature condition.With product centrifugation (6000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. azo dye adsorbent after reaction finished.
Under 25 ℃ of conditions of room temperature, the graphite oxide A of 50mg is scattered in the 50mL distilled water, adopting power is that the ultrasonic dispersion of 60W adds 250mg PEI (weight average molecular weight is 25000) blend again after 2 hours, in gained solution, add 100mg EDCHCl and 100mg NHS again, and with the citric acid of 0.5mol/L the pH value of system being adjusted to 7.0, reaction is 24 hours under the room temperature condition.With product centrifugation (6000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. azo dye adsorbent after reaction finished.
Under 35 ℃ of conditions of room temperature, the graphite oxide A of 50mg is scattered in the 20mL distilled water, adopting power is that the ultrasonic dispersion of 30W adds 250mg PEI (weight average molecular weight is 10000) blend again after 2 hours, in gained solution, add 100mg EDCHCl and 100mg NHS again, and with the acetic acid of 0.2mol/L the pH value of system being adjusted to 7.0, reaction is 48 hours under the room temperature condition.With product centrifugation (4000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. azo dye adsorbent after reaction finished.
Under 15 ℃ of conditions of room temperature, the graphite oxide A of 20mg is scattered in the 20mL distilled water, adopting power is that the ultrasonic dispersion of 40W adds 400mg PEI (weight average molecular weight is 25000) blend again after 2 hours, in gained solution, add 40mg EDCHCl and 40mg NHS again, and with the hydrochloric acid of 0.2mol/L the pH value of system being adjusted to 7.0, reaction is 24 hours under the room temperature condition.With product centrifugation (10000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. azo dye adsorbent after reaction finished.
Embodiment 11
The azo dye adsorbent B that the graphite oxide A that embodiment 2 is obtained and embodiment 4 obtain is scattered in respectively in the aqueous solution, and the relative absorbance of measuring dispersion liquid by ultraviolet-uisible spectrophotometer is curve over time.Its result as shown in Figure 1, azo dye adsorbent B, namely the graphite oxide after PEI modifies shows better dispersion stability, after its aqueous dispersions left standstill for 2 week, absorbance was still without significant change.
The aqueous dispersions of the azo dye adsorbent B that embodiment 4 is obtained is added drop-wise on the copper mesh, carries out transmission electron microscope observing after air-dry, and its result as shown in Figure 2.Shown in the transmission electron microscope picture, the graphite oxide good dispersion in the aqueous solution after PEI modifies, without agglomeration, size below 1 micron and be single layer structure more.
Embodiment 13
The azo dye adsorbent B that the graphite oxide A that embodiment 2 is obtained and embodiment 4 obtain is that the methyl orange solution of 20mg/L mixes with mass concentration respectively, under 25 ℃ of conditions, carry out adsorption test, the time point of setting, get part methyl orange solution and measure it at the absorbance at 470nm wavelength place with ultraviolet specrophotometer, carry out adsorption dynamics adsorption kinetics research.The result as shown in Figure 3, azo dye adsorbent B, namely the graphite oxide after PEI modifies because the good and unique single layer structure of its water dispersible is very fast to Adsorption of Methyl Orange, namely reaches adsorption equilibrium about 100 minutes; And simple graphite oxide A is relatively relatively poor owing to the dispersiveness in the aqueous solution, and its rate of adsorption to methyl orange is slower.
Be that the methyl orange solution of 20mg/L mixes with the azo dye adsorbent B that obtains among the embodiment 4 and mass concentration, respectively at carrying out adsorption dynamics adsorption kinetics research under 25,40,55 ℃ of conditions.The result as shown in Figure 4, azo dye adsorbent B all shows the faster rate of adsorption to methyl orange under condition of different temperatures, and temperature is higher, its adsorbance is larger.
Embodiment 15
Be that the methylene blue solution of 20mg/L mixes with the azo dye adsorbent B that obtains among the embodiment 4 and mass concentration, under 25 ℃ of conditions, carry out adsorption dynamics adsorption kinetics research.The result as shown in Figure 5, azo dye adsorbent B shows good adsorption effect to methylene blue.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. the preparation method of an azo dye adsorbent is characterized in that comprising following operating procedure:
(1) preparation of pre-oxidation graphite:
5～10g potassium peroxydisulfate and 5～10g phosphorus pentoxide are joined in 20～40mL concentrated sulfuric acid, fully after the dissolving, be warming up to 60～90 ℃, add again 5～10g graphite powder, stir stopped heating after 4～8 hours, naturally cool to room temperature; With products therefrom with to original volume 3～10 times of distilled water diluting, centrifugal collecting precipitation, and with the distilled water washing, obtain pre-oxidation graphite;
(2) preparation of graphite oxide:
Step (1) gained pre-oxidation graphite is scattered in 20～40mL concentrated sulfuric acid, and cryosel is bathed and is cooled to-5～0 ℃, obtains the pre-oxidation graphite dispersing solution; Potassium permanganate is added in the pre-oxidation graphite dispersing solution, reacted 1～3 hour, then add distilled water and hydrogen peroxide, impurity is removed in centrifugation, again supernatant is continued centrifugation, and collecting precipitation obtains graphite oxide;
(3) preparation of azo dye adsorbent
At ambient temperature, 10～50mg step (2) gained graphite oxide is scattered in 20～50mL water, after the ultrasonic dispersion with the polymine blend, in gained solution, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and N-hydroxy-succinamide again, regulate pH value to 6～7, reacted under the room temperature condition 24～48 hours; With the product centrifugation, collecting precipitation obtains azo dye adsorbent.
2. the preparation method of a kind of azo dye adsorbent according to claim 1, it is characterized in that: the described room temperature of step (1) is 15～35 ℃; Magnetic agitation is adopted in described stirring; Described centrifugal employing rotating speed is 2000～4000r/min; Described number of times with the distilled water washing is 3～5 times.
3. the preparation method of a kind of azo dye adsorbent according to claim 1, it is characterized in that: the described concentrated sulfuric acid of step (2) is the aqueous sulfuric acid of mass fraction 70%～98%; The mass ratio of described pre-oxidation graphite and potassium permanganate is 1:2～1:4; The described concentrated sulfuric acid: distilled water: the volume ratio of hydrogen peroxide is (1～2): 56:1.
4. the preparation method of a kind of azo dye adsorbent according to claim 1 is characterized in that: impurity is removed in the described centrifugation of step (2), and to adopt rotating speed be 500r/min; Describedly supernatant is continued centrifugation to adopt rotating speed be 4000～6000r/min.
5. the preparation method of a kind of azo dye adsorbent according to claim 1, it is characterized in that: the time of the described ultrasonic dispersion of step (3) is 1～2 hour, it is 30～60W that power is adopted in ultrasonic dispersion; Rotating speed 4000～10000r/min is adopted in described centrifugation.
6. the preparation method of a kind of azo dye adsorbent according to claim 1, it is characterized in that: the described room temperature of step (3) is 15～35 ℃; Described graphite oxide: polymine: 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate: the mass ratio of N-hydroxy-succinamide is 1:(5～20): 2:2; The weight average molecular weight of described polymine is 10000 or 25000; Described adjusting pH value is to adopt the acid solution of 0.1～0.5mol/L to regulate.
7. the preparation method of a kind of azo dye adsorbent according to claim 6, it is characterized in that: described acid solution is hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution, citric acid solution or acetic acid solution.
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| CN103962108B (en) * | 2014-04-11 | 2016-05-18 | 陕西科技大学 | One utilizes polyethyleneimine-modified graphite oxide to remove chromic method in water |
| CN104785221B (en) * | 2015-03-23 | 2016-05-11 | 湖南大学 | A kind of preparation of heavy metal absorbent and application |
| CN108855009B (en) * | 2018-07-11 | 2021-03-23 | 河南科技大学 | Preparation method of graphene-based dual-network PEI-GO/SA composite material for dye adsorption |
| CN108620045A (en) * | 2018-07-11 | 2018-10-09 | 河南科技大学 | A kind of preparation method of graphene-based PEI-mGO/CMC/PVA three-dimensional composite materials |
| CN109174023B (en) * | 2018-09-05 | 2021-07-16 | 河南科技大学 | Nano-cellulose crosslinked graphene/chitosan aerogel and preparation method and application thereof |
| CN113070047B (en) * | 2021-03-30 | 2022-11-25 | 江西理工大学 | Functionalized mineral material and preparation method and application thereof |
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| CN101381524A (en) * | 2008-10-24 | 2009-03-11 | 南开大学 | Mono-layer graphite oxide and water-soluble high molecule reinforced compound material |
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| CN101381524A (en) * | 2008-10-24 | 2009-03-11 | 南开大学 | Mono-layer graphite oxide and water-soluble high molecule reinforced compound material |
| CN101973620A (en) * | 2010-09-21 | 2011-02-16 | 上海大学 | Method for removing heavy metal ions in water by using graphene oxide sheet |
| CN102093700A (en) * | 2010-12-30 | 2011-06-15 | 常州大学 | Method for preparing graphene/waterborne polyurethane conductive composite material |
| CN102167314A (en) * | 2011-05-23 | 2011-08-31 | 浙江大学 | Method for preparing graphene |
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