CN107857328A - A kind of method that tetracycline in water removal is removed using two-dimensional nano lamella composite selective absorption - Google Patents
A kind of method that tetracycline in water removal is removed using two-dimensional nano lamella composite selective absorption Download PDFInfo
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- CN107857328A CN107857328A CN201711070367.0A CN201711070367A CN107857328A CN 107857328 A CN107857328 A CN 107857328A CN 201711070367 A CN201711070367 A CN 201711070367A CN 107857328 A CN107857328 A CN 107857328A
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- zif
- dimensional nano
- tetracycline
- nano lamella
- water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
Abstract
The present invention relates to a kind of method that tetracycline in water removal is removed using composite selective absorption, more particularly, to a kind of method that tetracycline in water removal is removed using the two-dimensional nano lamella composite selective absorption with " sandwich " structure, this method for first by the growth in situ of ZIF 8 two-dimensional nano lamellar structure GO upper and lower surfaces, there is the composites of two-dimensional nano lamella ZIF 8/GO/ZIF 8 of " sandwich " structure, then the composite powders of 10~100g ZIF 8/GO/ZIF 8 prepared are added in 20~50L water that tetracycline concentration is 200~600mg/L, in room temperature, 24h is adsorbed under rotating speed 110~130r/min stirring conditions；This method is up to 98.0%~99.6% to the clearance of tetracycline in water.The present invention is simple with preparation and operating process, cheap and easy to get using raw material, and material is novel, and the prepared composites of two-dimensional nano lamella ZIF 8/GO/ZIF 8 are to the advantages that tetracycline removal effect is good in water.
Description
Technical field
The present invention relates to a kind of method that tetracycline in water removal is removed using composite selective absorption, more particularly, to one
The method that kind removes tetracycline in water removal using the two-dimensional nano lamella composite selective absorption with " sandwich " structure.
Background technology
Antibiotic is one kind in numerous antibacterials, and from birth, the disease for being just widely used in human and animal is controlled
Treat.In recent years, antibiotic was widely used in animal husbandry as feed addictive, was mainly used in preventing and treating livestock and poultry disease
Disease.It is anti-without metabolism but in animal digestion absorption process, most antibiotics can not be metabolized completely in the enteron aisle of animal
Raw element excretes with animal wastes and urine, and enters environment.Antibiotic can trigger microorganism to produce resistant gene, indirectly
Or human health is directly threatened, it has been confirmed as emerging persistence organic pollutant.
Tetracycline is the most widely used one kind in numerous antibiotic, has the characteristics that low cost and high bacteriostatic activity,
Domestic animals disease treatment is widely used in, is also largely used by agricultural sector as feed addictive.The tetracycline master remained in environment
To derive from the discharge and animal husbandry of pharmacy sewage and enter the part of environment by animal wastes, urine without metabolism.
At present, it detected residual tetracycline in municipal wastewater, underground water, soil even drinking water.Tetracycline is in aquatic and soil
Can persistently exist in environment, potential toxic action, such as to biology toxicity and tetracycline resistance gene diffusion, it is necessary to
Cause extensive concern, developing low-cost and efficient minimizing technology is extremely urgent.
Due to the antibacterial characteristics of tetracycline, it is difficult to realize going completely for tetracycline residue by traditional biological treatment technology
Remove.Therefore, there is an urgent need to develop a kind of method of convenient and reliable processing tetracycline residue problem.Removing tetracycline in recent years
Some effort, including traditional flocculation sediment, advanced oxidation and membrane separation technique etc. have been done in terms of pollutant.On but
The defects of method exposes itself in practice is stated, as running cost is too high, removal efficiency is low, introduces other pollutants
Deng, it is difficult to large-scale promotion application.Unlike this, adsorption technology is simple to operate, efficiency high, cost are low, is removing tetracycline
In numerous technologies, it is considered to be one of most widely used technology.
The key of adsorption technology is to develop the high-efficiency adsorbent with Selective adsorption.Due to two-dimensional nano lamella
The material of structure possesses the incomparable peculiar property of other materials, is widely used in sensor, carrier and adsorbent.In recent years
Come, synthesis has two-dimensional nano lamellar structure composite of different nature, to provide multiple adsorption sites, the table of reinforcing material
Area and adsorption capacity turn into study hotspot.The graphene oxide of two-dimensional nano lamellar structure, there is excellent hydrophily, high
Specific surface area, easily prepare, surface includes substantial amounts of hydroxyl, carboxyl and epoxide group, and these characteristics can be used as absorption
Agent is used for the removal of antibiotic.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of method is unique, preparation and operating process are simple,
Cheap and easy to get using raw material, material is novel, and drastically increase has " three to a kind of utilize of the absorption property of tetracycline in water
The method that tetracycline in water removal is removed in the two-dimensional nano lamella composite selective absorption of Mingzhi " structure.
To achieve the above object, the present invention takes following technical scheme：
A kind of method that tetracycline in water removal is removed using two-dimensional nano lamella composite selective absorption, its feature are existed
In：This method is in the GO upper and lower surfaces of two-dimensional nano lamellar structure, is had " sandwich " first by ZIF-8 growth in situ
The two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of structure, the 10~100g ZIF-8/GO/ZIF- that then will be prepared
8 composite powders be added to tetracycline concentration be 200~600mg/L 20~50L water in, room temperature, rotating speed 110~
24h is adsorbed under 130r/min stirring conditions；
The preparation method of the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites with " sandwich " structure is
Respectively by 1~3kg Zn (NO3)2·6H2O powder is dissolved in 10~40L methanol, and 1~3kg 2-methylimidazole powder is dissolved in
In 20~60L methanol, 10~30L water alcohol volume ratio is rapidly added while two kinds of solution are mixed as 1:4 GO solution, stirring
3~5h, 5~10min is centrifuged under 5000~10000rpm, collect product, repeat above-mentioned centrifugation step and with methanol by product
Washing 3~5 times, there is the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of " sandwich " structure after drying；
The water alcohol volume ratio is 1:The preparation method of 4 GO solution be by GO through ultrasonic disperse into concentration be 4~6g/L
The aqueous solution, it is 0.8~1.2g/L that again with methanol, which is further diluted to GO concentration, subsequent 4~6h of ultrasound, ultimately forms water alcohol body
Product is than being 1:4 GO concentration is 0.8~1.2g/L solution；
The granularity of the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composite powders with " sandwich " structure is
40 mesh；
The concentration of the methanol is 98%.
The present invention has following beneficial effect：
1) method is unique：Method provided by the invention is in two-dimensional nano lamellar structure first by ZIF-8 growth in situ
GO upper and lower surfaces, there is the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of " sandwich " structure, then will system
10~100g ZIF-8/GO/ZIF-8 the composite powders got ready be added to tetracycline concentration be 200~600mg/L 20~
In 50L water, 24h is adsorbed under room temperature, rotating speed 110~130r/min stirring conditions.
2) prepare and operating process is simple：The present invention prepares water alcohol volume ratio as 1:The method of 4 GO solution is：GO is passed through
Ultrasonic disperse is into the GO aqueous solution that concentration is 4~6g/L, and then, the GO that again with methanol is further diluted to 0.8~1.2g/L is molten
Liquid, 4~6h of ultrasound, water alcohol volume ratio is ultimately formed as 1:4 GO concentration is 0.8~1.2g/L solution；The present invention prepares tool
The method for having the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of " sandwich " structure is：Respectively by 1~3kg Zn
(NO3) 26H2O powder is dissolved in 10~40L methanol, and 1~3kg 2-methylimidazole powder is dissolved in 20~60L methanol,
10~30L water alcohol volume ratio is rapidly added while two kinds of solution are mixed as 1:4 GO solution, 3~5h is stirred, 5000~
5~10min is centrifuged under 10000rpm, collects product, above-mentioned centrifugation step is repeated and is washed product 3~5 times with methanol, through dry
There is the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of " sandwich " structure after dry.
3) cost of material is relatively low：Method provided by the invention chooses zinc nitrate, 2-methylimidazole, GO and methanol as main original
Material, these raw materials are cheap and easy to get.ZIF-8 is one kind in MOF materials, has good heat endurance and chemical stability, can
Synthesize at room temperature, method is easy.
4) eliminating rate of absorption of tetracycline is high：In method provided by the invention, Zn is contained in ZIF-82+, and Zn2+Can be with
N element in tetracycline molecule on dimethylamino forms coordinate bond so that ZIF-8 has Selective adsorption to tetracycline.Zn2+From
Son is ZIF-8 nucleation and the key of growth, and the oxy radical on GO surfaces can fix Zn2+Ion.Therefore, GO fixes as carrier
Zn2+Platform is provided for ZIF-8 nucleation and growth so that ZIF-8 nano particles can be supported on GO surfaces after ion.Two dimension
The advantages of nanoscale twins ZIF-8/GO/ZIF-8 composites combine the two, there is big specific surface area, hydrophily and adsorption potential
Point it is more, easily preparation, containing a large amount of functional groups, there is Selective adsorption.Method provided by the invention is to tetracycline in water
Clearance is up to 98.0%~99.6%.
Embodiment
The present invention is described in further details with reference to specific embodiment, to be better understood from the present invention.Should
Work as understanding, specific embodiment described herein only to explain the present invention, is not intended to limit the present invention.
Embodiment 1：One kind is gone in water removal using two-dimensional nano lamella ZIF-8/GO/ZIF-8 composite selective absorptions
The method of tetracycline, this method are：GO is further diluted through ultrasonic disperse into the GO aqueous solution that concentration is 4g/L, again with methanol
To 0.8g/L GO solution, subsequent ultrasonic 4h, water alcohol volume ratio is ultimately formed as 1:4 GO concentration is 0.8g/L solution.Will
1.1kg Zn(NO3)2·6H2O and 1.4kg 2-methylimidazoles are dissolved in 20L and 30L methanol respectively, then in two kinds of mixing
15L water alcohol volume ratio is rapidly added while solution as 1:4 GO concentration is 0.8g/L solution, after stirring 3h, 6000rpm centrifugations
6min, product is collected, repeat above-mentioned centrifugation step and washed product 3 times with methanol, there is " Sanming City after 80 DEG C are dried
Control " the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of structure.By the two-dimensional nano lamella ZIF-8/ of the above-mentioned preparations of 30g
GO/ZIF-8 composite powders are added in the water that 30L tetracycline concentrations are 250mg/L, are stirred in room temperature, rotating speed 110r/min
24h is adsorbed under the conditions of mixing, is detected through high performance liquid chromatography, the material is 99.5% to the clearance of tetracycline in water.
Embodiment 2：One kind is gone in water removal using two-dimensional nano lamella ZIF-8/GO/ZIF-8 composite selective absorptions
The method of tetracycline, this method are：GO is further diluted through ultrasonic disperse into the GO aqueous solution that concentration is 5g/L, again with methanol
To 1.1g/L GO solution, subsequent ultrasonic 5h, water alcohol volume ratio is ultimately formed as 1:4 GO concentration is 1.1g/L solution.Will
1.8kg Zn(NO3)2·6H2O and 2.1kg 2-methylimidazoles are dissolved in 25L and 40L methanol respectively, then in two kinds of mixing
20L water alcohol volume ratio is rapidly added while solution as 1:4 GO concentration is 1.1g/L solution, after stirring 4h, 7000rpm centrifugations
8min, product is collected, repeat above-mentioned centrifugation step and washed product 4 times with methanol, there is " Sanming City after 80 DEG C are dried
Control " the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of structure.By the two-dimensional nano lamella ZIF-8/ of the above-mentioned preparations of 40g
GO/ZIF-8 composite powders are added in the water that 40L tetracycline concentrations are 300mg/L, are stirred in room temperature, rotating speed 120r/min
24h is adsorbed under the conditions of mixing, is detected through high performance liquid chromatography, the material is 99.0% to the clearance of tetracycline in water.
Embodiment 3：One kind is gone in water removal using two-dimensional nano lamella ZIF-8/GO/ZIF-8 composite selective absorptions
The method of tetracycline, this method are：GO is further diluted through ultrasonic disperse into the GO aqueous solution that concentration is 6g/L, again with methanol
To 1.2g/L GO solution, subsequent ultrasonic 6h, water alcohol volume ratio is ultimately formed as 1:4 GO concentration is 1.2g/L solution.Will
2.2kg Zn(NO3)2·6H2O and 2.4kg 2-methylimidazoles are dissolved in 36L and 60L methanol respectively, then in two kinds of mixing
30L water alcohol volume ratio is rapidly added while solution as 1:4 GO concentration is 1.2g/L solution, after stirring 5h, 8000rpm centrifugations
10min, product is collected, repeat above-mentioned centrifugation step and washed product 4 times with methanol.Had " three after 80 DEG C are dried
The two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of Mingzhi " structure.By the two-dimensional nano lamella ZIF- of the above-mentioned preparations of 50g
8/GO/ZIF-8 composite powders are added in the water that 50L tetracycline concentrations are 500mg/L, in room temperature, rotating speed 130r/min
24h is adsorbed under stirring condition, is detected through high performance liquid chromatography, the material is 98.5% to the clearance of tetracycline in water.
The granularity of the above-mentioned two-dimensional nano lamella ZIF-8/GO/ZIF-8 composite powders with " sandwich " structure is
40 mesh.
The concentration of above-mentioned methanol is 98%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Tetracycline clearance is measured using high performance liquid chromatography described in this method.According to test philosophy, absorption is measured
Before and after the processing in water tetracycline concentration, with the difference of the concentration when initial concentration and adsorption equilibrium of tetracycline than upper tetracycline
Initial concentration tries to achieve the clearance of tetracycline.
Claims (5)
- A kind of 1. method that tetracycline in water removal is removed using two-dimensional nano lamella composite selective absorption, it is characterised in that： This method for first by ZIF-8 growth in situ two-dimensional nano lamellar structure GO upper and lower surfaces, had " sandwich " tie The two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites of structure, the 10~100g ZIF-8/GO/ZIF-8 that then will be prepared Composite powder is added in 20~50L water that tetracycline concentration is 200~600mg/L, in room temperature, 110~130r/ of rotating speed 24h is adsorbed under min stirring conditions.
- 2. a kind of as claimed in claim 1 remove tetracycline in water removal using two-dimensional nano lamella composite selective absorption Method, it is characterised in that：The system of the two-dimensional nano lamella ZIF-8/GO/ZIF-8 composites with " sandwich " structure 1~3kg Zn (NO3) 26H2O powder is is dissolved in 10~40L methanol by Preparation Method respectively, 1~3kg 2-methylimidazoles Powder is dissolved in 20~60L methanol, and 10~30L water alcohol volume ratio is rapidly added while two kinds of solution are mixed as 1:4 GO solution, 3~5h is stirred, 5~10min is centrifuged under 5000~10000rpm, collect product, repeated above-mentioned centrifugation step and be used in combination Methanol washs product 3~5 times, is had the two-dimensional nano lamella ZIF-8/GO/ZIF-8 of " sandwich " structure after drying Composite.
- 3. a kind of as claimed in claim 2 remove tetracycline in water removal using two-dimensional nano lamella composite selective absorption Method, it is characterised in that：The water alcohol volume ratio is 1:The preparation method of 4 GO solution is to be into concentration through ultrasonic disperse by GO 4~6g/L the aqueous solution, it is 0.8~1.2g/L that again with methanol, which is further diluted to GO concentration, subsequent ultrasound 4~6h, most end form It is 1 into water alcohol volume ratio:4 GO concentration is 0.8~1.2g/L solution.
- 4. a kind of as claimed in claim 1 remove tetracycline in water removal using two-dimensional nano lamella composite selective absorption Method, it is characterised in that：The two-dimensional nano lamella ZIF-8/GO/ZIF-8 composite powders with " sandwich " structure Granularity be 40 mesh.
- 5. a kind of as claimed in claim 2 remove tetracycline in water removal using two-dimensional nano lamella composite selective absorption Method, it is characterised in that：The concentration of the methanol is 98%.
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| CN109577005A (en) * | 2018-11-28 | 2019-04-05 | 吉林大学 | A kind of preparation method and applications of the ZIF-8 functionalized nano-fiber film of poly-dopamine modification |
| CN111167412A (en) * | 2020-01-20 | 2020-05-19 | 天津城建大学 | Preparation method and application of Cu-ZIF-8 composite nano material |
| CN111744550A (en) * | 2019-03-27 | 2020-10-09 | 南京工业大学 | Preparation method of two-dimensional nanosheet layer hydrogenation catalyst |
| CN112619616A (en) * | 2020-12-31 | 2021-04-09 | 陕西科技大学 | High-load SA/GO/ZIFs composite adsorbent and preparation method and application thereof |
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| CN109577005A (en) * | 2018-11-28 | 2019-04-05 | 吉林大学 | A kind of preparation method and applications of the ZIF-8 functionalized nano-fiber film of poly-dopamine modification |
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| CN112619616A (en) * | 2020-12-31 | 2021-04-09 | 陕西科技大学 | High-load SA/GO/ZIFs composite adsorbent and preparation method and application thereof |
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Application publication date: 20180330 |