CN107308909A - The preparation method of sulfonated graphene and its application for handling antibiotic water body - Google Patents
The preparation method of sulfonated graphene and its application for handling antibiotic water body Download PDFInfo
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- CN107308909A CN107308909A CN201710342009.4A CN201710342009A CN107308909A CN 107308909 A CN107308909 A CN 107308909A CN 201710342009 A CN201710342009 A CN 201710342009A CN 107308909 A CN107308909 A CN 107308909A
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- graphene
- sulfonated graphene
- antibiotic
- sulfonated
- water body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/005—Black water originating from toilets
Abstract
The invention belongs to water-treatment technology field, a kind of preparation method of sulfonated graphene, step is as follows：(1) add graphene oxide into deionized water, carry out ultrasonic disperse processing while opening stirring, obtain graphene oxide dispersion；(2) chlorosulfonic acid is added in the graphene oxide dispersion obtained to step (1), backflow cooling is dried to obtain sulfoxidation graphene；(3) the sulfoxidation graphene obtained to step (2) carries out radiation treatment, obtains sulfonated graphene.Wherein, the mass concentration of the graphene oxide dispersion described in step (1) is 0.05~0.1%, and the ultrasonic disperse time is：10~20 minutes.Degradation effect of the ozone to antibiotic can be significantly improved by making catalyst using sulfonated graphene, the good absorption property of sulfonated graphene is utilized simultaneously, antibiotic in water body and Degradation of Antibiotics product are further adsorbed so that preferable clean-up effect has been reached by the water body that antibiotic pollutes.
Description
Technical field
The invention belongs to water-treatment technology field, the preparation method and its processing antibiosis of more particularly to a kind of sulfonated graphene
The application of plain water body.
Background technology
Antibiotic is indispensable medicine in people's life, and people has been widely used in as antibacterial or sterilization class medicine
The multiple fields such as disease treatment, livestock and poultry and the aquaculture of class, mainly including Tetracyclines, sulfamido, beta-lactam, fluorine quinoline
Promise ketone and macrolides etc..China is antibiotics production and uses big country, and annual antibiotics production amount is used up to 210,000 tons
Amount is up to 18.9 ten thousand tons.Research finds, organism is taken in after a large amount of antibiotics in addition to part is by organism metabolism, have 40%~
90% is excreted in the form of active compound or metabolite with excrement and urine, enters soil eventually through modes such as fertilisings
Environment enters water body environment by seepage and sewage discharge, because it is made up of organic chemicals, it is impossible in water
Self-purification capacity under purify, cause antibiotic contamination to be detected in water body, deposit and soil, or even in vegetables, milk
The residual of antibiotic is have also discovered in the product such as class and meat.
Research is found, is chronically exposed under antibiotic environment, and not only the illness of humans and animals and the incidence of disease can be raised, and
All have an impact to the Chlorophyll synthesis, enzyme secretion and root growth of plant.In addition microorganism also can gradually adapt to antibiotic environment,
And produce antibiotic resistance and resistant gene.Meanwhile, Antibiotics of Low Concentration can also rise to microbial population in ecological environment
To screening effect, the microbial population with antibiotic resistance is set to retain and gradually grow, and the population sensitive to its
Constantly dead to disappear, direct result is exactly to make microbiological paper method unbalance, and ecological environment and human health are caused greatly
Harm, therefore it is extremely urgent to solve pollution problem of the antibiotic to water body.
The content of the invention
The purpose of the present invention：For solution antibiotic polluted-water, the high risks caused to ecological environment and human health,
The problem of for antibiotic treatment hardly possible, the present invention provides a kind of preparation method of sulfonated graphene and its handles antibiotic water body
Using.
To realize this purpose, the invention provides a kind of preparation method of sulfonated graphene, step is as follows：
(1) add graphene oxide into deionized water, carry out ultrasonic disperse processing while opening stirring, aoxidized
Graphene dispersing solution；
(2) chlorosulfonic acid is added in the graphene oxide dispersion obtained to step (1), backflow cooling is dried to obtain sulfonation oxygen
Graphite alkene；
(3) the sulfoxidation graphene obtained to step (2) carries out radiation treatment, obtains sulfonated graphene.
Wherein, the mass concentration of the graphene oxide dispersion described in step (1) is 0.05~0.1%, during ultrasonic disperse
Between be：10~20 minutes.
Mass ratio between the chlorosulfonic acid and graphene oxide of step (2) described addition is 10~15：1.
Present invention also offers a kind of processing procedure of sulfonated graphene to the antibiotic in water body, step is as follows：
(1) measure the antibiotic that 20 milliliters of concentration are 200ppm to be placed in 250ml glass beaker, add sulfonated graphite
Alkene, obtains mixed solution；
(2) ozone is passed through into the mixed solution of step (2), and is stirred, obtains stirring mixed liquor；
(3) the stirring mixed liquor of step (2) is filtered by diatomite, uses ultraviolet-visible spectrophotometer pair
Antibiotic water body after filtering is detected.
Wherein.The concentration of sulfonated graphene is 0.5~2mg/ml in mixed solution described in step (1).
Mixing speed described in step (2) is 300~500r/min, 2~3h of mixing time.
Beneficial effect：When handling the water body polluted by antibiotic using the inventive method, one side sulfonated graphene by with
Make catalyst, degradation speed of the ozone to antibiotic can be significantly improved, on the other hand using sulfonated graphene in Adsorption
During antibiotic, its sp2With the phenyl ring of antibiotic pi-pi bond effect can occur for the six-membered ring structure of hydridization, antibiosis be have very high
Removal efficiency, with extraordinary adsorption effect.Therefore, using sulfonated graphene to being handled by the water body that antibiotic pollutes
When, the antibiotic in the water body that can degrade can produce suction-operated, the two association to the antibiotic in water body and its catabolite again
With carrying out, while to Degradation of Antibiotics in water body, moreover it is possible to promote sulfonated graphene to the adsorption effect of antibiotic, finally lead to
Crossing diatomite and filter enables the antibiotic in water body to obtain more thoroughly removing, therefore, using the inventive method
Processing has extraordinary effect by the water body that antibiotic pollutes.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of sulfonated graphene sample of the present invention；
Fig. 2 (a) is the infrared spectrogram of sulfonated graphene sample；
(b) it is the Raman spectrogram of sulfonated graphene sample；
Adsorption efficiency of the sulfonated graphene to various antibiotic in each embodiments of Fig. 3.
Embodiment
Embodiment 1
The preparation of sulfonated graphene：
(1) add graphene oxide into deionized water, open stirring, while carrying out ultrasonic disperse 10 minutes, obtain dense
Spend the graphene oxide dispersion for 0.05%；
(2) it is 15 according to the mass ratio of chlorosulfonic acid and graphene oxide:The graphite oxide that 1 ratio is obtained to step (1)
Chlorosulfonic acid is added in alkene dispersion liquid, backflow cooling is dried to obtain sulfoxidation graphene；
(3) the sulfoxidation graphene obtained to step (2) carries out radiation treatment, obtains sulfonated graphene.
Sulfonated graphene prepared by this method is used for the process and performance evaluation for handling the Enrofloxacin in water：
Measure 20 milliliters of concentration be 200ppm Enrofloxacin solution in 250 milliliters of glass beaker, add sulfonation stone
Black alkene, obtains the mixed solution that graphene concentration is 1.5mg/ml, ozone is then passed through into mixed solution, and with 300r/min
Mixing speed stirring 2h, obtain stir mixed liquor, will stirring mixed liquor filtered by diatomite, use ultraviolet-visible
Spectrophotometer carries out result sign.
Ultraviolet-visible spectrophotometer test result shows：Sulfonated graphene is to Enrofloxacin adsorption rate in 2h
98.5%, adsorbance is 351mg/g.
Embodiment 2
The preparation of sulfonated graphene
(1) add graphene oxide into deionized water, open stirring, while carrying out ultrasonic disperse 20 minutes, obtain dense
Spend the graphene oxide dispersion for 0.1%；
(2) it is 10 according to the mass ratio of chlorosulfonic acid and graphene oxide:The graphite oxide that 1 ratio is obtained to step (1)
Chlorosulfonic acid is added in alkene dispersion liquid, backflow cooling is dried to obtain sulfoxidation graphene；
(3) the sulfoxidation graphene obtained to step (2) carries out radiation treatment, obtains sulfonated graphene.
Sulfonated graphene prepared by this method is used for the process and performance evaluation for handling the quadracycline in water：
Measure 20 milliliters of concentration be 200ppm quadracycline solution in 250 milliliters of glass beaker, add sulfonation
Graphene, obtains the mixed solution that graphene concentration is 0.8mg/ml, ozone is then passed through into mixed solution, and with 400r/
Min mixing speed stirring 3h, obtain stir mixed liquor, will stirring mixed liquor filtered by diatomite, using it is ultraviolet-can
See that spectrophotometer carries out result sign.
Ultraviolet-visible spectrophotometer test result shows：Adsorption rate of the sulfonated graphene in 2h to quadracycline
For 98%, adsorbance is 326mg/g.
Embodiment 3
The preparation be the same as Example 1 of sulfonated graphene
Sulfonated graphene prepared by this method is used for the process and performance evaluation for handling the terramycin in water：
Measure 20 milliliters of concentration be 200ppm terramycin solution in 250 milliliters of glass beaker, add sulfonated graphite
Alkene, obtains the mixed solution that graphene concentration is 1mg/ml, ozone, and stirring with 300r/min is then passed through into mixed solution
Speed stirring 2h is mixed, obtains stirring mixed liquor, stirring mixed liquor is filtered by diatomite, UV-vis spectroscopy is used
Photometer carries out result sign.
Ultraviolet-visible spectrophotometer test result shows：Sulfonated graphene is to the adsorption rate of terramycin in 2h
96.7%, adsorbance is 309mg/g.
Comparative example 1
The preparation be the same as Example 1 of sulfonated graphene
The process and performance evaluation of terramycin in sulfonated graphene absorption water：
Measure 20 milliliters of concentration be 200ppm terramycin solution in 250 milliliters of glass beaker, add sulfonated graphite
Alkene, obtains the mixed solution that graphene concentration is 1mg/ml, the liquid mixed is kept under 300r/min mixing speed
2h, is obtained stirring mixed liquor, and stirring mixed liquor is filtered by diatomite, carried out using ultraviolet-visible spectrophotometer
As a result characterize.
Ultraviolet-visible spectrophotometer test result shows：Sulfonated graphene is to terramycin adsorption rate in 2h
82.7%, adsorbance is 169mg/g.
Claims (8)
1. a kind of preparation method of sulfonated graphene, it is characterised in that：The preparation method comprises the following steps：
(1) add graphene oxide into deionized water, open stirring and carry out ultrasonic disperse processing simultaneously, obtain graphene oxide
Dispersion liquid；
(2) chlorosulfonic acid is added in the graphene oxide dispersion obtained to step (1), backflow cooling is dried to obtain sulfoxidation stone
Black alkene；
(3) the sulfoxidation graphene obtained to step (2) carries out radiation treatment, obtains sulfonated graphene.
2. the preparation method of sulfonated graphene as claimed in claim 1, it is characterised in that：Graphite oxide described in step (1)
The mass concentration of alkene dispersion liquid is 0.05~0.1%, and the ultrasonic disperse time is：10~20 minutes.
3. the preparation method of sulfonated graphene as claimed in claim 1, it is characterised in that：Chlorosulfonic acid described in step (2) with
The mass ratio of graphene oxide is 10~15：1.
4. the application of sulfonated graphene as claimed in claim 1, it is characterised in that：The sulfonated graphene is used in water body
The processing of antibiotic.
5. the processing antibiotic water body of sulfonated graphene prepared by preparation method as described in any one of Claims 1 to 4 should
With, it is characterised in that：The sulfonated graphene is used for the processing to Enrofloxacin, quadracycline or terramycin in water body.
6. the application as described in claim 4 or 5, it is characterised in that：Comprise the following steps：
(1) measure the antibiotic that 20 milliliters of concentration are 200ppm to be placed in 250ml glass beaker, add sulfonated graphene, obtain
To mixed solution；
(2) ozone is passed through into the mixed solution of step (1), and is stirred, obtains stirring mixed liquor；
(3) the stirring mixed liquor of step (2) is filtered by diatomite, using ultraviolet-visible spectrophotometer to filtering
Antibiotic water body afterwards is detected.
7. application as claimed in claim 6, it is characterised in that：Sulfonated graphene is dense in mixed solution described in step (1)
Spend for 0.5~2mg/ml.
8. application as claimed in claim 6, it is characterised in that：Mixing speed described in step (2) is 300~500r/min,
2~3h of mixing time.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619570A (en) * | 2017-10-26 | 2018-01-23 | 佛山慧创正元新材料科技有限公司 | A kind of preparation method of sulfonated graphene flame-retardant polymeric material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619570A (en) * | 2017-10-26 | 2018-01-23 | 佛山慧创正元新材料科技有限公司 | A kind of preparation method of sulfonated graphene flame-retardant polymeric material |
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Effective date of registration: 20180321 Address after: No. 303, Wuyi Road, Jiangsu, Changzhou, Jiangsu Applicant after: Changzhou city industry new Mstar Technology Ltd Address before: No. 303, Wuyi Road, Qishuyan, Changzhou, Jiangsu Applicant before: City, Jiangsu work builds Science and Technology Ltd. |
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Application publication date: 20171103 |