CN102357356A - Preparation method and application of azo dye adsorbent - Google Patents
Preparation method and application of azo dye adsorbent Download PDFInfo
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- CN102357356A CN102357356A CN2011102697219A CN201110269721A CN102357356A CN 102357356 A CN102357356 A CN 102357356A CN 2011102697219 A CN2011102697219 A CN 2011102697219A CN 201110269721 A CN201110269721 A CN 201110269721A CN 102357356 A CN102357356 A CN 102357356A
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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 dyes adsorbent.
Background technology
Azo dyes is to use maximum dyes in the present dyeing, and chemical property is stable, and its waste water has that colourity is dark, hard to manage, catabolite toxicity high and to characteristics such as environmental hazard are big, is 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 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 and use more adsorbent at present 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 through magnetic field, thus be difficult for producing residual (Journal of Hazardous Materials 2010,178:434-439).Wang Yong etc. are raw material with CMC, acrylic resin and bentonite etc., make one type of low cost, can be used for the high-performance water-absorbing resin that azo dye wastewater handles (Chinese invention patent, CN100591627C).The CNT of 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 the good adsorption effect (Bioresource Technology 2010,101:3040-3046).
But the adsorbance and the adsorption efficiency of adsorbents such as above-mentioned resin or active carbon are relatively low, have increased the use amount of adsorbent, are prone to cause secondary pollution; Though CNT relies on its special nanostructured that the azo dye sheet is revealed higher adsorbance, its water dispersible is poor, can not be fully with waste water in azo dyes contact, its adsorption efficiency also is under some influence.Therefore, how to make up new adsorbent and become the important topic that this field needs to be resolved hurrily with high absorption capacity.Up to now, utilize and to gather acetimide and graphite oxide is carried out chemical modification prepare the water dispersible graphite oxide and use it for the azo dyes adsorption applications and do not appear in the newspapers as yet.
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 azo dyes preparation of adsorbent method with 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 dyes adsorbent by method for preparing.This sorbent material has that preparation is efficient easily and fast, applied widely, noresidue and characteristics such as have no side effect.
A purpose more of the present invention is to provide the application of above-mentioned azo dyes adsorbent in field of environment engineering.
The object of the invention is realized through following technical proposals: a kind of azo dyes preparation of adsorbent method 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 5～10g graphite powder again, stirs and stop after 4～8 hours heating, naturally cool to room temperature; With products therefrom 3～10 times with distilled water diluting to original volume, centrifugal collecting precipitation, and, obtain pre-oxidation graphite with the distilled water washing;
(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 pre-oxidation graphite dispersion liquid; With potassium permanganate (KMnO
4) add in the pre-oxidation graphite dispersion liquid, reacted 1～3 hour, add distilled water and hydrogen peroxide solution then, impurity is removed in centrifugation, again supernatant is continued centrifugation, and collecting precipitation obtains graphite oxide (GO);
(3) the azo dyes adsorbent (be the modified oxidized graphite of polymine, preparation PEI-GO):
At ambient temperature; 10～50mg step (2) gained graphite oxide is scattered in 20～50mL water; Ultrasonic dispersion back and 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, room temperature condition reacted 24～48 hours down; With the product centrifugation, collecting precipitation obtains the azo dyes adsorbent.
The said room temperature of step (1) is 15～35 ℃; Magnetic agitation is adopted in said stirring; Said centrifugal employing rotating speed is 2000～4000r/min; The number of times of said use distilled water washing is 3～5 times.
The said concentrated sulfuric acid of step (2) is the aqueous sulfuric acid of mass fraction 70%～98%; The mass ratio of said pre-oxidation graphite and potassium permanganate is 1: 2～1: 4; The said concentrated sulfuric acid: distilled water: the volume ratio of hydrogen peroxide solution is (1～2): 56: 1.
It is 500r/min that impurity employing rotating speed is removed in the said centrifugation of step (2); Said is 4000～6000r/min with supernatant continuation centrifugation employing rotating speed.
The time of the said 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 said centrifugation.
The said room temperature of step (3) is 15～35 ℃; Said 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 said polymine is 10000 or 25000; Said adjusting pH value is to adopt the acid solution of 0.1～0.5mol/L to regulate.
Said acid solution is hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution, citric acid solution or acetic acid solution.
A kind of azo dyes adsorbent according to method for preparing.
The above-mentioned application of azo dyes adsorbent in field of environment engineering.
Principle of the present invention is: nontoxic, the inertia of graphite oxide, have unique nanostructured, and its two dimensional surface can be effectively compound through π-π interaction with the little molecule that contains phenyl ring, 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, utilize PEI that graphite oxide is carried out chemical modification then, the water dispersible of the graphite oxide after the modification obviously improves; And be single layer structure more; Avoided the gathering between the nano oxidized graphite, increased the specific area of material relatively, helped its absorption azo dyes.This adsorbent and azo dyes mainly interact compound through π-π.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) azo dyes adsorbent of the present invention preparation is convenient, and composition is simple, and material non-toxic, inertia;
(2) main compound between this adsorbent and the azo dyes through π-π interaction, than chemical precipitation method, bioanalysis etc., can not produce secondary pollution;
(3) the graphite oxide aqueous dispersion good stability after PEI modifies helps its absorption to 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 big, can effectively improve the treatment effeciency of azo dyes;
(5) graphite oxide of PEI modification all shows the 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 through 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 dyes adsorbent.
Fig. 2 is the transmission electron microscope picture figure of azo dyes adsorbent.
Fig. 3 is azo dyes adsorbent of the present invention curve of adsorption kinetics figure to methyl orange under 25 ℃ of conditions.
Fig. 4 for azo dyes adsorbent of the present invention under condition of different temperatures to the curve of adsorption kinetics figure of methyl orange, 1 is 55 ℃, 2 is 40 ℃, 3 is 25 ℃.
Fig. 5 is azo dyes adsorbent of the present invention curve of adsorption kinetics figure to methylene blue under 25 ℃ of conditions.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
With 5g K
2S
2O
8With 5g P
2O
5Join in the 20mL concentrated sulfuric acid, treat that it fully dissolves after, be warming up to 80 ℃, add the 5g graphite powder again, magnetic agitation stops heating after 4 hours, naturally cool to 15 ℃ of room temperatures; With products therefrom 5 times with distilled water diluting to original volume, centrifugal (2000r/min) collecting precipitation, and, obtain pre-oxidation graphite with 3 washings of distilled water;
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 dispersion liquid, reacted 1 hour, and then add 1120mL distilled water and 20mL hydrogen peroxide solution, centrifugation (500r/min) is to remove impurity, and 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, treat that it fully dissolves after, be warming up to 60 ℃, add the 10g graphite powder again, magnetic agitation stops heating after 6 hours, cool off room temperature to 35 ℃ naturally; With products therefrom 3 times with distilled water diluting to original volume, centrifugal (4000r/min) collecting precipitation, and, obtain pre-oxidation graphite with 4 washings of distilled water;
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 dispersion liquid, reacted 2 hours, and then add a certain amount of 2240mL distilled water and 40mL hydrogen peroxide solution, centrifugation (500r/min) is to remove impurity, and supernatant continues centrifugation (6000r/min), and collecting precipitation obtains graphite oxide A.
With 10g K
2S
2O
8With 10g P
2O
5Join in the 40mL concentrated sulfuric acid, treat that it fully dissolves after, be warming up to 90 ℃, add the 5g graphite powder again, magnetic agitation stops heating after 8 hours, naturally cool to 25 ℃ of room temperatures; With products therefrom 10 times with distilled water diluting to original volume, centrifugal (3000r/min) collecting precipitation, and, obtain pre-oxidation graphite with 5 washings of distilled water;
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 dispersion liquid, reacted 3 hours, and then add 2240mL distilled water and 40mL hydrogen peroxide solution, centrifugation (500r/min) is to remove impurity, and 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 is adjusted to 6.0, room temperature condition time reacted 24 hours; With product centrifugation (10000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. the azo dyes 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 is adjusted to 6.0, room temperature condition time reacted 24 hours.With product centrifugation (6000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. the azo dyes 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 is adjusted to 7.0, room temperature condition time reacted 48 hours.With product centrifugation (10000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. the azo dyes 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 is adjusted to 7.0, room temperature condition time reacted 48 hours.With product centrifugation (6000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. the azo dyes 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 is adjusted to 7.0, room temperature condition time reacted 24 hours.With product centrifugation (6000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. the azo dyes adsorbent after reaction finished.
Embodiment 9
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 acetate of 0.2mol/L the pH value of system is adjusted to 7.0, room temperature condition time reacted 48 hours.With product centrifugation (4000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. the azo dyes 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 is adjusted to 7.0, room temperature condition time reacted 24 hours.With product centrifugation (10000r/min), collecting precipitation obtained the graphite oxide (PEI-GO) of PEI modification, i.e. the azo dyes adsorbent after reaction finished.
Embodiment 11
The azo dyes adsorbent B that 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 through ultraviolet-uisible spectrophotometer is curve over time.Its result is as shown in Figure 1, the azo dyes adsorbent B, and promptly the graphite oxide after PEI modifies shows better aqueous dispersion stability, and after its aqueous dispersions left standstill for 2 week, absorbance did not still have significant change.
The aqueous dispersions of the azo dyes 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 is as shown in Figure 2.Shown in the transmission electron microscope picture, the graphite oxide good dispersion in the aqueous solution after PEI modifies, no agglomeration, size below 1 micron and be single layer structure more.
Embodiment 13
The azo dyes adsorbent B that 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 its absorbance, carry out adsorption dynamics adsorption kinetics research in the 470nm wavelength with ultraviolet specrophotometer.The result is as shown in Figure 3, the azo dyes adsorbent B, and promptly the graphite oxide after PEI modifies because the good and unique single layer structure of its water dispersible is very fast to methyl orange absorption, promptly reaches adsorption equilibrium about 100 minutes; And simple graphite oxide A is relatively poor relatively owing to the dispersiveness in the aqueous solution, and its rate of adsorption to methyl orange is slower.
With azo dyes adsorbent B that obtains among the embodiment 4 and mass concentration is that the methyl orange solution of 20mg/L mixes, respectively at carrying out adsorption dynamics adsorption kinetics research under 25,40,55 ℃ of conditions.The result is as shown in Figure 4, and the azo dyes adsorbent B all shows the rate of adsorption faster to methyl orange under condition of different temperatures, and temperature is high more, and its adsorbance is big more.
Embodiment 15
With azo dyes adsorbent B that obtains among the embodiment 4 and mass concentration is that the methylene blue solution of 20mg/L mixes, and under 25 ℃ of conditions, carries out adsorption dynamics adsorption kinetics research.The result is as shown in Figure 5, and the azo dyes adsorbent B shows the good adsorption effect to methylene blue.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit 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 (9)
1. azo dyes preparation of adsorbent method 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 5～10g graphite powder again, stirs and stop after 4～8 hours heating, naturally cool to room temperature; With products therefrom 3～10 times with distilled water diluting to original volume, centrifugal collecting precipitation, and, obtain pre-oxidation graphite with the distilled water washing;
(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 pre-oxidation graphite dispersion liquid; Potassium permanganate is added in the pre-oxidation graphite dispersion liquid, reacted 1～3 hour, add distilled water and hydrogen peroxide solution then, impurity is removed in centrifugation, again supernatant is continued centrifugation, and collecting precipitation obtains graphite oxide;
(3) azo dyes preparation of adsorbent
At ambient temperature; 10～50mg step (2) gained graphite oxide is scattered in 20～50mL water; Ultrasonic dispersion back and 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, room temperature condition reacted 24～48 hours down; With the product centrifugation, collecting precipitation obtains the azo dyes adsorbent.
2. a kind of azo dyes preparation of adsorbent method according to claim 1 is characterized in that: the said room temperature of step (1) is 15～35 ℃; Magnetic agitation is adopted in said stirring; Said centrifugal employing rotating speed is 2000～4000r/min; The number of times of said use distilled water washing is 3～5 times.
3. a kind of azo dyes preparation of adsorbent method according to claim 1 is characterized in that: the said concentrated sulfuric acid of step (2) is the aqueous sulfuric acid of mass fraction 70%～98%; The mass ratio of said pre-oxidation graphite and potassium permanganate is 1: 2～1: 4; The said concentrated sulfuric acid: distilled water: the volume ratio of hydrogen peroxide solution is (1～2): 56: 1.
4. a kind of azo dyes preparation of adsorbent method according to claim 1 is characterized in that: it is 500r/min that impurity employing rotating speed is removed in the said centrifugation of step (2); Said is 4000～6000r/min with supernatant continuation centrifugation employing rotating speed.
5. a kind of azo dyes preparation of adsorbent method according to claim 1 is characterized in that: the time of the said 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 said centrifugation.
6. a kind of azo dyes preparation of adsorbent method according to claim 1 is characterized in that: the said room temperature of step (3) is 15～35 ℃; Said 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 said polymine is 10000 or 25000; Said adjusting pH value is to adopt the acid solution of 0.1～0.5mol/L to regulate.
7. a kind of azo dyes preparation of adsorbent method according to claim 6, it is characterized in that: said acid solution is hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution, citric acid solution or acetic acid solution.
8. azo dyes adsorbent according to each said method preparation of claim 1～7.
9. the application of azo dyes adsorbent according to claim 8 in field of environment engineering.
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| CN103962108A (en) * | 2014-04-11 | 2014-08-06 | 陕西科技大学 | Method for removing hexavalent chromium in water by utilizing polyethyleneimine modified graphite oxide |
| CN104785221A (en) * | 2015-03-23 | 2015-07-22 | 湖南大学 | Preparation and application of heavy metal adsorbent |
| 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 |
| CN108855009A (en) * | 2018-07-11 | 2018-11-23 | 河南科技大学 | A kind of preparation method of the graphene-based dual network PEI-GO/SA composite material of Dye Adsorption |
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| CN103962108A (en) * | 2014-04-11 | 2014-08-06 | 陕西科技大学 | Method for removing hexavalent chromium in water by utilizing polyethyleneimine modified graphite oxide |
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| CN108855009A (en) * | 2018-07-11 | 2018-11-23 | 河南科技大学 | A kind of preparation method of the graphene-based dual network PEI-GO/SA composite material of Dye Adsorption |
| 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 |
| CN109174023A (en) * | 2018-09-05 | 2019-01-11 | 河南科技大学 | A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application |
| CN113070047A (en) * | 2021-03-30 | 2021-07-06 | 江西理工大学 | Functionalized mineral material and preparation method and application thereof |
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