CN107930607A - A kind of method that tetracycline and Ciprofloxacin single and binary-combined contamination water body are handled using modified graphene oxide - Google Patents
A kind of method that tetracycline and Ciprofloxacin single and binary-combined contamination water body are handled using modified graphene oxide Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- 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
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
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- C02F2101/36—Organic compounds containing halogen
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- 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
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Abstract
The present invention provides the method that the magnetic oxygenated graphene composite material that a kind of DTPA is modified is applied to Adsorption TC and CIP single and binary-combined contamination water body, the magnetic oxygenated graphene being specifically modified using DTPA is then added into TC and CIP single and binary-combined contamination water bodys as adsorbent.Test result indicates that, in single antibiotic water body, the quality that every gram of adsorbent exchanges TC in text is hundreds of milligrams all nearly, the quality for exchanging CIP has reached more than 100 milligrams, the magnetic oxygenated graphene that DTPA is modified is all very good to the adsorption effect of TC and CIP, while solid-liquid can be separated well after absorption.In combined pollution water body, influence of the competitive Adsorption to Ciprofloxacin is weaker, and the removal for Ciprofloxacin in combined pollution water body provides a kind of new approaches.Compared with prior art, processing method of the present invention is simple, material prepares and operating cost is low, and the improvement polluted for antibiotic in waste water provides new approach, can be promoted as a kind of new adsorbent in antibiotic pollution control.
Description
Technical field
The invention belongs to environment functional material and water process new technical field, and in particular to a kind of diethylene triamine pentacetic acid (DTPA)
Modified graphene oxide processing tetracycline and the method for Ciprofloxacin single and binary-combined contamination water body.
Background technology
Antibiotic is as one of most common organic matter in sewage, it is considered to be persistent pollutant, can cause animal
With the change of mankind's drug resistance gene, so as to suppress activity of the antibiotic to disease, the life of plant, animal and microorganism is disturbed
It is long.Degradation capability is very weak under field conditions (factors) for remaining antibiotic in environment.Therefore, effective treatment technology needs studied next
Handle contaminated antibiotic water source.Tetracycline (TC) and Ciprofloxacin (CIP) are two kinds and are widely used in human and animal
Antibiotic, is continually detected in water environment.In the past few decades, a variety of chemically and physically methods handle
These antibiotic waste waters, such as photocatalytic method, chemical oxidization method, biological degradation method, liquid extraction, absorption and membrane separation technique
Deng.Wherein, absorption method has the advantages that efficient, easy to operate, cost is low, toxic intermediate is few, is controlled in actual pollutant effluents
Applied in reason.And graphene oxide is as a kind of emerging sorbing material in absorption method, have derive from a wealth of sources, dispersion performance
Well, the advantages that stability is strong, specific surface area is big, oxygen-containing functional group enriches and can produce in batches.But graphene oxide adsorption potential
Point is limited and extremely difficult is separated from aqueous solution.Therefore, research and develop it is new using graphene oxide as matrix, at a low price simultaneously
And efficient composite material, have become graphene oxide and further develop and handle one of antibiotic waste water using absorption method
Key matter of science and technology.
Diethylene triamine pentacetic acid (DTPA) (DTPA) is a kind of well-known complexones, has three amino and five carboxylics
Base, can form stable chelate with most metals.In addition, nitrogenous and oxygen-containing functional group has higher reactivity, easily
With a variety of chemical reactions.Therefore, DTPA is considered as the ideal chose of GO surfaces modification application.In addition, by magnetism
Nanometer particle load can assign graphene oxide magnetism, can divide well from solid liquid phase to surface of graphene oxide
From.By the present invention in that being chemically crosslinked with crosslinking agents such as diethylenetriamines to DTPA and graphene oxide, its stabilization is improved
Property.
The content of the invention
The technical problems to be solved by the invention are:For technical problem existing in the prior art, it is low to develop a kind of cost
Honest and clean, the efficient and segregative magnetic oxygenated graphene composite material available for Adsorption TC and CIP;And provide a kind of work
Skill is simple, prepares the method that quickly magnetic oxygenated graphene composite material is applied to Adsorption TC and CIP.
In order to solve the above technical problems, the present invention uses following technical scheme:The present invention relates to a kind of diethylenetriamine five
The method that the magnetic oxygenated graphene composite material of acetic acid (DTPA) modification removes TC and CIP single and binary-combined contamination water bodys, its
It is characterized in that, the graphene oxide uniform load is magnetic nano-particle, then it is coupled with DTPA again, the magnetic
It is crosslinked between property graphene oxide and DTPA by diethylenetriamine.The composite material of preparation applied to TC and CIP it is single and
In combined pollution water body, its removal effect to two kinds of pollutants is observed.Comprise the following steps that:
(1) by 5~7g graphite powders, 4~6gK2S2O8, 4~6gP2O5With the 98% of 20~30mL H2SO4It is added to 1L tri-
In the flask of angle, 4~6h is stirred in 70~100 DEG C of water-baths.It is cooled to room temperature, then adds 0.5~2L ultra-pure waters and dilute and put
Put overnight.Supernatant is outwelled, mixture is filtered and washed with deionized water rinsing to neutrality.Oven drying obtains pre- at 50~60 DEG C
Graphite oxide.Obtained pre-oxidation graphite is added to conical flask, adds 200~260mL98%H2SO4In solution, while stirring
Mix side and add 4~6gNaNO3, 25~35gKMnO4(potassium permanganate medication spoon is slowly added in mixed solution), stirs in ice bath anti-
Answer 3~6 it is small when.Then it will heat up to when reaction 1~2.5 is small at 30~40 DEG C, it is ultrapure to be slowly added to 400~700mL with drop bottle
Water reacted at 90~100 DEG C 1~2 it is small when, after mixed liquor is cooled to room temperature, with 1~2L deionized waters dilute, add 30~
50mL30%H2O2The reaction was continued 1.5~2.5 it is small when.Obtained mixture is washed with 5~20% HCl, then with a large amount of water
Washing is to neutrality and adds water constant volume, and graphene oxide aqueous suspensions are obtained when ultrasonic disperse 2~4 is small at 25~60 DEG C;
(2) the ferrous sulfate mixed solution of the iron chloride of 180~220mL 0.1mol/L and 0.05mol/L are added to
In 180~220mL, 3~10mg/mL graphene oxides, heating stirring 1~5 minute, adds 100 in 80~90 DEG C of water-baths
~200mL ammonium hydroxide, stirs 30~60min, and Magnetic Isolation is washed to neutrality;
(3) 0.1~0.5g 1- (3- are added in the aqueous solution of 0.2~0.6g diethylene triamine pentacetic acid (DTPA)s (ammonium hydroxide hydrotropy)
Dimethylamino-propyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and 0.1~0.5g n-hydroxysuccinimides (NHS), room temperature
When persistently stirring 1~3 is small down, magnetic oxygenated graphene made from 10~30mL diethylenetriamines and above-mentioned steps is then added,
Mixed solution persistently stirs 4~8h in 60~90 DEG C of water-bath.Obtained product is cooled to room temperature, and is washed with deionized
The diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material is obtained after to neutrality.
(4) above-mentioned material is added in TC and CIP single and binary-combined contamination water bodys, be mixed reaction after with magnet into
Row separation of solid and liquid, with ultraviolet specrophotometer (UV-2550, SHIMADZU, Japan) the remaining adsorption liquid concentration of measure, studies it
To the mechanism of both removal ability and absorption.
In above-mentioned preparation method, the order of preparation is that first magnetic nano-particle is supported on graphene oxide, then with two
Ethene triamine to the magnetic oxygenated graphene of preparation and is crosslinked for crosslinking agent.
It is mono- applied to Adsorption TC and CIP that the present invention provides the magnetic oxygenated graphene composite material that a kind of DTPA is modified
One and the method for combined pollution water body, comprise the following steps:Institute is added into the solution of the single and binary-combined contamination thing containing TC and CIP
The magnetic oxygenated graphene of DTPA modifications is stated, at room temperature oscillating reactions Adsorption TC and CIP, externally-applied magnetic field divides solid-liquid
From completing the Adsorption to TC and CIP.
In above application, magnetic oxygenated graphene composite material that the DTPA is modified in waste water dosage preferably 0.1~
10g/L。
In above application, the condition of the adsorption reaction is preferably:PH value is 2.0~10.0, and the reaction time is small for 1~36
When, reaction temperature is 10~50 DEG C.
Compared with prior art, the advantage of the invention is that:
1st, the magnetic oxygenated graphene composite material that DTPA of the invention is modified, the raw material sources used are extensive, main former
Work stone ink powder, FeCl3·6H2O and FeSO4·4H2O and diethylenetriamine etc. are common chemical products.
2nd, product toxicity is low, and modified magnetic oxygenated graphene is easy to separate again from the solution after processing
Utilize, it is environmentally friendly.
3rd, the sorbing material preparation process used in the present invention is fairly simple, nonhazardous effect, husky to tetracycline and ring third
Star has good adsorption effect, and in combined pollution water body, influence of the competitive Adsorption to Ciprofloxacin is weaker, is compound dirt
The removal of Ciprofloxacin provides a kind of new approaches in dye water body, and the improvement polluted for antibiotic in waste water provides new way
Footpath, can promote as a kind of new adsorbent in antibiotic pollution control.
Brief description of the drawings
Fig. 1 is the SEM signals before and after the magnetic oxygenated graphene composite material absorption that the DTPA of the embodiment of the present invention 1 is modified
Figure;
Fig. 2 is the XRD schematic diagrames for the magnetic oxygenated graphene composite material that the DTPA of the embodiment of the present invention 1 is modified;
Embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Embodiment 1:
By 5~6g graphite powders, 4~6gK2S2O8, 4~6gP2O5With the 98% of 20~30mL H2SO4It is added to 1L triangles
In flask, 4~6h is stirred in 70~100 DEG C of water-baths.It is cooled to room temperature, then adds 0.5~2L ultra-pure waters and dilute and place
Overnight.Supernatant is outwelled, mixture is filtered and washed with deionized water rinsing to neutrality.Oven drying obtains pre- oxygen at 50~60 DEG C
Graphite.Obtained pre-oxidation graphite is added to conical flask, adds 200~260mL98%H2SO4In solution, side stirring
Side adds 4~6gNaNO3, 25~35gKMnO4(potassium permanganate medication spoon is slowly added in mixed solution), reaction is stirred in ice bath
3~6 it is small when.Then it will heat up to when reaction 1~2.5 is small at 30~40 DEG C, 400~700mL ultra-pure waters be slowly added to drop bottle
When reaction 1~2 is small at 90~100 DEG C, after mixed liquor is cooled to room temperature, diluted with 1~2L deionized waters, addition 30~
50mL30%H2O2The reaction was continued 1.5~2.5 it is small when.Obtained mixture is washed with 5~20% HCl, then with a large amount of water
Washing is to neutrality and adds water constant volume, and graphene oxide aqueous suspensions are obtained when ultrasonic disperse 2~4 is small at 25~60 DEG C;By 180~
The iron chloride of 220mL 0.1mol/L and the ferrous sulfate mixed solution of 0.05mol/L are added to 180~220mL3~10mg/mL
In graphene oxide, heating stirring 1~5 minute in 80~90 DEG C of water-baths adds 100~200mL ammonium hydroxide, and stirring 30~
60min, Magnetic Isolation are washed to neutrality;Added in the aqueous solution of 0.2~0.6g diethylene triamine pentacetic acid (DTPA)s (ammonium hydroxide hydrotropy)
0.1~0.5g 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) and 0.1~0.5g N- hydroxysuccinimidyls
Acid imide (NHS), when persistently stirring 1~3 is small at room temperature, then adds made from 10~30mL diethylenetriamines and above-mentioned steps
Magnetic oxygenated graphene, mixed solution persistently stir 4~8h in 60~90 DEG C of water-bath.Obtained product is cooled to room
Temperature, it is compound to obtain the diethylene triamine pentacetic acid modified magnetic oxygenated graphene after being washed with deionized to neutrality
Material.Under conditions of pH is 3 and temperature is 30 DEG C, above-mentioned material is added to 50mg/L TC and CIP single and binary-combined contaminations
In water body, it is mixed after 24h and carries out separation of solid and liquid with magnet, obtained solid is dry in freeze drying box.It is obtained above
Diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material appearance is in black, is adsorbed front and rear material and is placed in
Observed under scanning electron microscope, shown in its surface texture such as Fig. 1 (a), it can be seen that surface of graphene oxide uniform load largely changes
Property particle.In after TC and CIP single adsorptions, its surface wrinkle grain is reduced, and is become smooth (such as Fig. 1 (b) and (c)), is especially existed
After TC and CIP composite adsorptions, its surface compared with former three all it is smooth very much, illustrate TC and CIP be adsorbed onto DTPA modification
Magnetic oxygenated grapheme material surface.The DTPA magnetic oxygenated graphenes being modified are observed under X-ray diffractometer, such as Fig. 2 institutes
Show, it can be seen that obvious Fe3O4Diffraction maximum, it was demonstrated that the material is already provided with magnetism.
Embodiment 2:
In the different TC and CIP solution of pH value, the magnetic oxygenated graphene composite material that above-mentioned DTPA is modified is added, bag
Include following steps:
The 2.30mgDTPA magnetic oxygenated graphene composite materials being modified are separately added into 25mL 50mg/L TC and 50mg/
In L CIP solution, adjust pH be 2.0~10.0, carry out vibration adsorption reaction in 30 DEG C of water-bath constant temperature oscillators, 24 it is small when after lead to
Cross magnet to separate the adsorbent from waste water, measured with ultraviolet specrophotometer at 357 and 276nm not to be adsorbed in waste water
TC and CIP content, the results are shown in Table 1 for the adsorbance of calculating:
Table 1:Adsorbance data of the adsorbent to TC and CIP under condition of different pH
As shown in Table 1, with the increase of pH, which is all after first increasing to tetracycline and Ciprofloxacin adsorption capacity
Reduce, illustrate that pH plays an important role during the adsorbent removes tetracycline and Ciprofloxacin.
Embodiment 3:
0-20mg/L CIP are added in 50mg/L TC solution, add 0-20mg/L TC in 50mg/L CIP, then distinguish
The magnetic oxygenated graphene composite material that above-mentioned DTPA is modified is added, is comprised the following steps:
0-20mg/L CIP are added in the TC solution that initial concentration is 50mg/L, and the CIP that initial concentration is 50mg/L
0-20mg/L TC are added in solution, respectively toward the magnetic oxygenated graphene that addition 2.30mgDTPA is modified in both mixed liquors
Composite material.Carry out vibration adsorption reaction in 30 DEG C of water-bath constant temperature oscillators, 24 it is small when after by magnet by the adsorbent from useless
Separated in water, measure the content of TC not to be adsorbed in waste water and CIP at 357 and 276nm with ultraviolet specrophotometer, calculate
Adsorbance the results are shown in Table 2:
Table 2:Adsorbance data of the adsorbent to tetracycline under different CIP concentration
CIP concentration (mg/L) | 0 | 1 | 2 | 4 | 6 | 10 | 15 | 20 |
TC adsorbances (mg/g) | 301.55 | 271.01 | 251.46 | 218.98 | 189.52 | 160.55 | 122.61 | 116.74 |
Table 3:Adsorbance data of the adsorbent to Ciprofloxacin under different TC concentration
TC concentration (mg/L) | 0 | 1 | 2 | 4 | 6 | 10 | 15 | 20 |
CIP adsorbances (mg/g) | 110.27 | 107.57 | 110.34 | 109.22 | 106.95 | 110.32 | 108.21 | 106.95 |
From table 2 and table 3, with the increase of CIP concentration, the trend gradually weakened is presented to TC adsorbances in adsorbent.
This is probably that, with the increase of TC concentration, adsorbent is to CIP adsorbances because existing CIP can be with TC competitive Adsorptions site
Influence it is little, this be probably CIP the rate of adsorption it is stronger than TC caused by.
Embodiment 4:
Study recycling situation of the magnetic oxygenated graphene of DTPA modifications in TC and CIP water bodys, including following step
Suddenly:
In the single solution of 250mL TC and CIP (50mg/L) and mixed solution (A:50mg/L TC and 10mg/L CIP;B:
50mg/L CIP and 10mg/L TC) in, the magnetic oxygenated graphene composite material that 23.0mgDTPA is modified is added, in 30 DEG C of water
Bath constant temperature oscillator carries out vibration adsorption reaction 24h, is separated the adsorbent from waste water by magnet., will be above-mentioned after separation
Resulting materials are separately added into 250mL 0.01mol/L sodium hydroxide solutions and are parsed, and repeat aforesaid operations 4 times, and use is ultraviolet
Spectrophotometer measures the content of TC not to be adsorbed in waste water and CIP at 357 and 276nm, and the adsorbance result of calculating is such as
Shown in table 4:
Table 4:Sorbent circulation is used influences data to the adsorbance of TC and CIP
As shown in Table 4, as material reuses the increase of number, the TC and CIP in single and binary-combined contamination water body
Adsorbance slight decrease, shows that the adsorbent all has good repeat performance in single and binary-combined contamination water body.
It the above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation case
Example, with various process programs of the present inventive concept without substantial differences in protection scope of the present invention.
Claims (5)
- A kind of 1. diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material, it is characterised in that the composite wood Material is using graphene oxide as matrix, uniform load magnetic nano-particle and diethylene triamine pentacetic acid (DTPA) on matrix.The preparation order of the diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material is first by magnetic Nano Particle is supported on graphene oxide, is then activated the surface functional group of diethylene triamine pentacetic acid (DTPA) with EDC and NHS, The magnetic oxygenated graphene of preparation is crosslinked using diethylenetriamine as crosslinking agent again.Comprise the following steps that:(1) by 5~6g graphite powders, 4~6gK2S2O8, 4~6gP2O5With the 98% of 20~30mL H2SO4It is added to 1L triangles burning In bottle, 4~6h is stirred in 70~100 DEG C of water-baths.It is cooled to room temperature, then adds 0.5~2L ultra-pure waters and dilute and placed Night.Supernatant is outwelled, mixture is filtered and washed with deionized water rinsing to neutrality.Oven drying is pre-oxidized at 50~60 DEG C Graphite.Obtained pre-oxidation graphite is added to conical flask, adds 200~260mL98%H2SO4In solution, while stirring Add 4~6gNaNO3, 25~35gKMnO4(potassium permanganate medication spoon is slowly added in mixed solution), stirring reaction 3 in ice bath ~6 it is small when.Then it will heat up to when reaction 1~2.5 is small at 30~40 DEG C, be slowly added to 400~700mL ultra-pure waters with drop bottle and exist When reaction 1~2 is small at 90~100 DEG C, after mixed liquor is cooled to room temperature, diluted with 1~2L deionized waters, addition 30~ 50mL30%H2O2The reaction was continued 1.5~2.5 it is small when.Obtained mixture is washed with 5~20% HCl, then with a large amount of water Washing is to neutrality and adds water constant volume, and graphene oxide aqueous suspensions are obtained when ultrasonic disperse 2~4 is small at 25~60 DEG C;(2) the ferrous sulfate mixed solution of the iron chloride of 180~220mL 0.1mol/L and 0.05mol/L is added to 180~ In 220mL 3~10mg/mL graphene oxides, heating stirring 1~5 minute in 80~90 DEG C of water-baths, add 100~ 200mL ammonium hydroxide, stirs 30~60min, and Magnetic Isolation is washed to neutrality;(3) 0.1~0.5g 1- (3- diformazans are added in the aqueous solution of 0.2~0.6g diethylene triamine pentacetic acid (DTPA)s (ammonium hydroxide hydrotropy) Aminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and 0.1~0.5g n-hydroxysuccinimides (NHS), hold at room temperature When continuous stirring 1~3 is small, magnetic oxygenated graphene made from 10~30mL diethylenetriamines and above-mentioned steps, mixing are then added Solution persistently stirs 4~8h in 60~90 DEG C of water-bath.Obtained product is cooled to room temperature, and is washed with deionized into Property after obtain the diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material.
- A kind of 2. use of diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material as claimed in claim 1 On the way, it is characterised in that handle tetracycline and Ciprofloxacin single and binary-combined contamination waste water with the composite material.
- 3. purposes according to claim 2, it is characterised in that composite material dosage in waste water is 0.1~10g/ L。
- 4. application according to claim 2, it is characterised in that:The pH value of the adsorption reaction is 2.0~10.0, during reaction Between for 1~36 it is small when, the reaction temperature be 10~50 DEG C.
- 5. application according to claim 2, it is characterised in that:The concentration of single antibiotic polluted-water is 50mg/L, multiple It is respectively 50mg/L and 0-20mg/L to close two kinds of antibiotic concentrations in pollution.
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CN112076759A (en) * | 2020-09-08 | 2020-12-15 | 湖南农业大学 | Graphite felt cathode, preparation method and application thereof |
CN112547016A (en) * | 2020-11-06 | 2021-03-26 | 惠州学院 | Graphene oxide composite material and preparation method and application thereof |
CN113070041A (en) * | 2021-04-29 | 2021-07-06 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Graphene oxide-organic composite adsorption material and preparation method and application thereof |
CN114053229A (en) * | 2022-01-17 | 2022-02-18 | 山东国邦药业有限公司 | Sarafloxacin hydrochloride water-soluble granules and preparation method thereof |
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CN106111064A (en) * | 2016-06-24 | 2016-11-16 | 湖南大学 | The preparation method of a kind of diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material and purposes |
CN106423088A (en) * | 2016-05-29 | 2017-02-22 | 湖南大学 | Preparation and application of novel functional magnetic graphene oxide composite material |
CN106512952A (en) * | 2016-11-24 | 2017-03-22 | 湖南大学 | Method for treating antibiotic and heavy metal combined pollution water by using modified graphene oxide |
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CN105617995A (en) * | 2016-01-21 | 2016-06-01 | 湖南大学 | Preparation method and application of nitrilotriacetic acid modified magnetic graphene oxide composite material |
CN106423088A (en) * | 2016-05-29 | 2017-02-22 | 湖南大学 | Preparation and application of novel functional magnetic graphene oxide composite material |
CN106111064A (en) * | 2016-06-24 | 2016-11-16 | 湖南大学 | The preparation method of a kind of diethylene triamine pentacetic acid modified magnetic oxygenated graphene composite material and purposes |
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Cited By (7)
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CN112076759A (en) * | 2020-09-08 | 2020-12-15 | 湖南农业大学 | Graphite felt cathode, preparation method and application thereof |
CN112076759B (en) * | 2020-09-08 | 2023-07-25 | 湖南农业大学 | Graphite felt cathode, preparation method and application thereof |
CN112547016A (en) * | 2020-11-06 | 2021-03-26 | 惠州学院 | Graphene oxide composite material and preparation method and application thereof |
CN113070041A (en) * | 2021-04-29 | 2021-07-06 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Graphene oxide-organic composite adsorption material and preparation method and application thereof |
CN113070041B (en) * | 2021-04-29 | 2023-06-30 | 中科南京绿色制造产业创新研究院 | Graphene oxide-organic composite adsorption material and preparation method and application thereof |
CN114053229A (en) * | 2022-01-17 | 2022-02-18 | 山东国邦药业有限公司 | Sarafloxacin hydrochloride water-soluble granules and preparation method thereof |
CN114053229B (en) * | 2022-01-17 | 2022-04-22 | 山东国邦药业有限公司 | Sarafloxacin hydrochloride water-soluble granules and preparation method thereof |
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