CN106563425A - Modified polyaniline composite adsorbent and application thereof to ciprofloxacin adsorption - Google Patents
Modified polyaniline composite adsorbent and application thereof to ciprofloxacin adsorption Download PDFInfo
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Abstract
The invention provides a modified polyaniline composite adsorbent and application thereof to ciprofloxacin adsorption. The modified polyaniline composite adsorbent comprises modified polyaniline, a carbon nano tube and clay, the modified polyaniline is of a micro-nano secondary structure, the micron-grade fibrous polyaniline serves as a supporting framework, and the nano-grade spherical granular polyaniline is distributed on the surface of the supporting framework. The specific preparation method of the modified polyaniline composite adsorbent includes the steps that oxidant, namely, ammonium persulfate and aniline monomers are dissolved in a proton acid solution respectively, the two types of solutions are mixed after being subjected to uniform ultrasonic dispersion and then being cooled to -5-0 DEG C, and a static oxidation polymerization reaction is conducted at the temperature of -5-0 DEG C; then a reaction product is filtered, washed, dried, ground and dispersed, and the modified polyaniline is obtained; then the carbon nano tube, the modified polyaniline and the clay are mixed and stirred, filtered and washed, subjected to vacuum drying and ground and dispersed, and the modified polyaniline composite adsorbent is obtained. A static adsorption method is adopted, and adsorption efficiency and adsorption capacity on ciprofloxacin are quite high.
Description
Technical field
The invention belongs to antibiotic sorbing material technical field, and in particular to a kind of modified polyaniline compound adsorbent and its
Application in Ciprofloxacin absorption.
Background technology
Antibiotic can prevent and treat human and animal's disease caused by the bacteria because of it, widely should obtain all over the world
With, but action time and metabolism time of the antibiotic in natural environment is longer, it is difficult to effectively degraded is realized, it is most anti-
Raw element is entered in environment with active compound or metabolisable form via the excretion of patient and livestock and poultry, is distributed in soil and water environment and is produced
Raw eco-toxicity, can suppress growth of animal and self immunity of reduction human body, cause the drug-fast enhancing of humans and animals.
Ciprofloxacin is a kind of typical broad-spectrum antibiotic, as the second generation product of fluoquinolone, in the yield of China
Very high with usage amount, Ciprofloxacin can produce substantial amounts of antibiotic waste water during manufacture and use, in antibiotic waste water
Organic matter containing difficult degradation and bio-toxicity material, deal with more difficult.At present main methods are biological treatment
Method, physical treatment process and multiple combination method, but high cost, actual effect is poor, and may produce secondary pollution.
With absorption method process Ciprofloxacin be a kind of new processing method, had at present by clay mineral, goethite,
In terms of activated sludge, soil, hydrous oxide, dissolved organic carbon, activated carbon and CNT are used for the absorption of Ciprofloxacin
Research.A kind of preparation side of the adsorbent of Selective Separation ciprofloxacin in water environment disclosed in Chinese patent CN103599759B
Method, obtains dry ferment yeast and connects bromine composite, then with Ciprofloxacin, methyl-prop as matrix grafting 2- bromine isobutyl acylbromides
Olefin(e) acid, hydroxyethyl methacrylate and ethylene glycol dimethacrylate are mixed to form pre-polymer solution, then successively add N,
N, N ', N ', N "-five methyl diethylentriamine and cuprous bromide, most after Jing centrifugal dryings extract membrane removal, obtain Ciprofloxacin table
Face imprinted polymer.A kind of utilization bamboo Charcoal Adsorption disclosed in Chinese patent CN 103613160A takes out Ciprofloxacin in water body
Method, by bamboo wood high-temperature firing into bamboo charcoal, adds in the waste water containing Ciprofloxacin, at continuous oscillation after bamboo charcoal is pulverized and sieved
Reason, then filters and removes powder bamboo charcoal from waste water, reaches the purpose for removing Ciprofloxacin in waste water.
Polyaniline is easy to get, closes as a kind of conducting polymer with structure diversification, mechanism of doping effect uniqueness, synthesis material
Into method it is simple the advantages of.Polyaniline can adapt to Various Complex absorption environment, and also solvent resistance is preferable, and surface is contained greatly
The amino and imido grpup functional group of amount, has application well at aspects such as Adsorption of Heavy Metals, coloring agents.Chinese patent CN
The preparation method of the disclosed Polymerization of Polyaniline/carbon Nanotube adsorbents with multi-level pore space structure of 102476046B, by carbon nanometer
Polyaniline is wrapped in carbon nano tube surface by pipe as support frame, and the compound adsorbent of preparation is used to adsorb having in waste water
Engine dyeing material.
From above-mentioned prior art, the research that current polyaniline is used to adsorb in terms of Ciprofloxacin is simultaneously few.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of modified polyaniline compound adsorbent and its inhales in Ciprofloxacin
The application enclosed, by chemical in situ oxidizing process, obtains the doped polyaniline particle of micro-nano secondary structure, is introduced into sulfonic group etc.
The modified polyaniline of functional group mixes with CNT and clay, obtains modified polyaniline compound adsorbent, the modified polyphenyl
Amine compound adsorbent has very high adsorption efficiency and adsorption capacity to Ciprofloxacin.
To solve above-mentioned technical problem, the technical scheme is that：
A kind of modified polyaniline compound adsorbent, the modified polyaniline compound adsorbent includes that modified polyaniline, carbon are received
Mitron and clay, the modified polyaniline has micro-nano secondary structure, and the micro-nano secondary structure is micron order polyaniline conduct
Support frame, nanoscale polyaniline is distributed in the surface of support frame, and it is 60- that the micron order polyaniline is average diameter
230nm length is 1-12 μm of fiber, and it is 20-50nm that the nanoscale polyaniline is average diameter, and specific surface area is 350-
770m2The form of spherical particles of/g, the modified polyaniline is prepared using chemical in situ oxidizing process.
As the preferred of above-mentioned technical proposal, in the modified polyaniline compound adsorbent by weight, including：It is modified
Polyaniline 40-50 parts, CNT 2-10 parts and clay 3-8 parts.
Used as the preferred of above-mentioned technical proposal, the clay is micro/nano level diatomite, and the CNT is many wall carbon
Nanotube, a diameter of 5-200nm, length is 1-50 μm.
As the preferred of above-mentioned technical proposal, the preparation method of the modified polyaniline compound adsorbent, including following step
Suddenly：
(1) oxidant ammonium persulfate is dissolved in protonic acid solution, is designated as solution A, taking aniline monomer, to be dissolved in Bronsted acid molten
In liquid, solution B is designated as, solution A and solution B are cooled to into -5～0 DEG C after respectively ultrasonic disperse is uniform；
(2) solution A prepared by step (1) is slowly dropped in the solution B of step (1) preparation, it is static at -5～0 DEG C
Oxidative polymerization 2-18h, obtains product；
(3) product prepared by step (2) is filtered and is washed, grinding distribution after vacuum drying is modified
Polyaniline；
(4) CNT is soluble in water, ultrasonic disperse is uniform, adds the modified polyaniline and clay of step (3) preparation,
Stirring, filtration washing, vacuum drying, grinding distribution obtains modified polyaniline compound adsorbent.
As the preferred of above-mentioned technical proposal, in the step (1) concentration of protonic acid solution be 0.5-2mol/L, over cure
It is 5-40% that sour ammonium accounts for the volume fraction of solution A, and it is 5-40% that aniline monomer accounts for the volume fraction of solution B.
Used as the preferred of above-mentioned technical proposal, protonic acid solution includes hydrochloric acid and detergent alkylate in the step (1)
The mol ratio of sulfonic acid, the hydrochloric acid and DBSA is 0.2-2:1.
As the preferred of above-mentioned technical proposal, aniline monomer in ammonium persulfate and solution B in solution A in the step (2)
Mol ratio be 0.8-1.2:1.
Used as the preferred of above-mentioned technical proposal, modified polyaniline has micro-nano secondary structure in the step (3), described micro-
Secondary structure of receiving is micron order polyaniline as support frame, and nanoscale polyaniline is distributed in the surface of support frame, described micro-
Meter level polyaniline is that average diameter is the fiber that 60-230nm length is 1-12 μm, and the nanoscale polyaniline is for average diameter
20-50nm, specific surface area is 350-770m2The form of spherical particles of/g.
As the preferred of above-mentioned technical proposal, in the step (4) clay be micro/nano level diatomite, the modified polyphenyl
The mass ratio of amine, CNT and clay is 40-50：2-10：3-8.
The present invention also provides a kind of application of modified polyaniline compound adsorbent in Ciprofloxacin absorption, and its feature exists
In, static adsorptive method is adopted during absorption, modified polyaniline compound adsorbent is 1 with the mass ratio of Ciprofloxacin:5-1000.
Compared with prior art, the invention has the advantages that：
(1) have containing modified polyaniline, modified polyaniline in modified polyaniline compound adsorbent prepared by the present invention
Unique micro-nano secondary structure, specific surface area is big, and surface also has the functional groups such as amino, imido grpup and sulfonic group, Ke Yiyu
Hydrogen bond is formed between amino and carboxyl on Ciprofloxacin molecule, good suction-operated, modified polyaniline composite adsorption is reached
Contain CNT in agent, CNT is hollow layer structure, draw ratio is big, specific surface area is big, and chemical stability is good, is modified
Also contain micro/nano level diatomite in polyaniline compound adsorbent, diatomite contains nano level loose structure, with larger
Micropore area, CNT and diatomite it is all hydrophobic, hydrophobic effect can occur with Ciprofloxacin molecule and reach the purpose of absorption,
Therefore the modified polyaniline compound adsorbent that prepared by the present invention can adsorb from the angle of physics and chemistry to Ciprofloxacin,
Effectively remove the Ciprofloxacin in waste water.
(2) preparation method of the invention is simple, and controllability is strong, can be had very to Ciprofloxacin using static adsorptive method
Good adsorption effect, up to 95%, adsorption capacity reaches 48mg/g to removal effect, and modified polyaniline prepared by the present invention is combined
Adsorbent is environmentally friendly, does not result in secondary pollution.
Specific embodiment
Describe the present invention, the illustrative examples of the here present invention and explanation in detail below in conjunction with specific embodiment
It is for explaining the present invention but not as a limitation of the invention.
Embodiment 1：
(1) oxidant ammonium persulfate is dissolved in the protonic acid solution of 0.5mol/L, is designated as solution A, wherein ammonium persulfate
The volume fraction for accounting for solution A is 5%, takes aniline monomer and is dissolved in the protonic acid solution of 0.5mol/L, is designated as solution B, wherein benzene
It is 5% that amine monomers account for the volume fraction of solution B, and solution A and solution B are cooled to into -5 DEG C after respectively ultrasonic disperse is uniform, wherein,
The mol ratio of hydrochloric acid and DBSA is 0.2 in protonic acid solution:1.
(2) solution A is slowly dropped in solution B, wherein in solution A in ammonium persulfate and solution B aniline monomer mole
Than for 0.8:1, at -5 DEG C, static oxidative polymerization 2-18h obtains product.
(3) product is filtered and is washed, grinding distribution after vacuum drying is obtained with micro-nano secondary structure
Modified polyaniline, wherein average diameter are 60nm, length be 1 μm of fibrous micron order polyaniline as support frame, averagely
A diameter of 20nm, specific surface area is 350m2The form of spherical particles nanoscale polyaniline of/g is distributed in the surface of support frame.
(4) by weight, 2 parts of CNT is soluble in water, ultrasonic disperse is uniform, adds 40 parts of modified polyphenyl
Amine and 3 parts of micro/nano level diatomite clay, stirring, filtration washing, vacuum drying, grinding distribution obtains modified polyaniline and answers
Close adsorbent.
Adsorption method：Using static adsorptive method, the ciprofloxacin solution of 50mg/L is configured, will with hydrochloric acid or NaOH
PH value tone pitch 4, adds modified polyaniline compound adsorbent, the wherein mass ratio of modified polyaniline compound adsorbent and Ciprofloxacin
For 1:5, under the conditions of lucifuge, at 25 DEG C, rotating speed is that under conditions of 100rpm, sealed thermostat vibrates, standing adsorption.According to
The when segmentum intercalaris of 10min, 20min, 30min, 60min, 120min, 300min, 480min, 1440min, 2880min, 4320min
Point sampling, by sample centrifugal filtration, Jing high effective liquid chromatography for measuring, is calculated modified polyaniline compound adsorbent
The adsorption rate of adsorption capacity and Ciprofloxacin.
Measurement result is as shown in the table：
Embodiment 2：
(1) oxidant ammonium persulfate is dissolved in the protonic acid solution of 2mol/L, is designated as solution A, wherein ammonium persulfate is accounted for
The volume fraction of solution A is 40%, takes aniline monomer and is dissolved in the protonic acid solution of 2mol/L, is designated as solution B, wherein aniline list
It is 40% that body accounts for the volume fraction of solution B, and solution A and solution B are cooled to into 0 DEG C after respectively ultrasonic disperse is uniform, wherein, proton
The mol ratio of hydrochloric acid and DBSA is 2 in acid solution:1.
(2) solution A is slowly dropped in solution B, wherein in solution A in ammonium persulfate and solution B aniline monomer mole
Than for 1.2:1, at 0 DEG C, static oxidative polymerization 18h obtains product.
(3) product is filtered and is washed, grinding distribution after vacuum drying is obtained with micro-nano secondary structure
Modified polyaniline, wherein average diameter be 230nm, length be 12 μm of fibrous micron order polyaniline as support frame, put down
A diameter of 50nm, specific surface area is 770m2The form of spherical particles nanoscale polyaniline of/g is distributed in the surface of support frame.
(4) by weight, 10 parts of CNT is soluble in water, ultrasonic disperse is uniform, adds 50 parts be modified poly-
Aniline and 8 parts of micro/nano level diatomite clay, stirring, filtration washing, vacuum drying, grinding distribution obtains modified polyaniline
Compound adsorbent.
Adsorption method：Using static adsorptive method, the ciprofloxacin solution of 100mg/L is configured, with hydrochloric acid or NaOH
By pH value tone pitch 5, modified polyaniline compound adsorbent, the wherein quality of modified polyaniline compound adsorbent and Ciprofloxacin are added
Than for 1:1000, under the conditions of lucifuge, at 25 DEG C, rotating speed is that under conditions of 100rpm, sealed thermostat vibrates, standing adsorption.Press
According to the time of 10min, 20min, 30min, 60min, 120min, 300min, 480min, 1440min, 2880min, 4320min
Node sample, by sample centrifugal filtration, Jing high effective liquid chromatography for measuring, is calculated modified polyaniline compound adsorbent
Adsorption capacity and Ciprofloxacin adsorption rate.
Measurement result is as shown in the table：
Embodiment 3：
(1) oxidant ammonium persulfate is dissolved in the protonic acid solution of 1mol/L, is designated as solution A, wherein ammonium persulfate is accounted for
The volume fraction of solution A is 25%, takes aniline monomer and is dissolved in the protonic acid solution of 1.5mol/L, is designated as solution B, wherein aniline
It is 15% that monomer accounts for the volume fraction of solution B, and solution A and solution B are cooled to into -3 DEG C after respectively ultrasonic disperse is uniform, wherein,
The mol ratio of hydrochloric acid and DBSA is 0.5 in protonic acid solution:1.
(2) solution A is slowly dropped in solution B, wherein in solution A in ammonium persulfate and solution B aniline monomer mole
Than for 1:1, at -30 DEG C, static oxidative polymerization 8h obtains product.
(3) product is filtered and is washed, grinding distribution after vacuum drying is obtained with micro-nano secondary structure
Modified polyaniline, wherein average diameter are 150nm, length be 8 μm of fibrous micron order polyaniline as support frame, averagely
A diameter of 35nm, specific surface area is 600m2The form of spherical particles nanoscale polyaniline of/g is distributed in the surface of support frame.
(4) by weight, 7 parts of CNT is soluble in water, ultrasonic disperse is uniform, adds 45 parts of modified polyphenyl
Amine and 5 parts of micro/nano level diatomite clay, stirring, filtration washing, vacuum drying, grinding distribution obtains modified polyaniline and answers
Close adsorbent.
Adsorption method：Using static adsorptive method, the ciprofloxacin solution of 50mg/L is configured, will with hydrochloric acid or NaOH
PH value tone pitch 7, adds modified polyaniline compound adsorbent, the wherein mass ratio of modified polyaniline compound adsorbent and Ciprofloxacin
For 1:5-1000, under the conditions of lucifuge, at 25 DEG C, rotating speed is that under conditions of 100rpm, sealed thermostat vibrates, standing adsorption.Press
According to the time of 10min, 20min, 30min, 60min, 120min, 300min, 480min, 1440min, 2880min, 4320min
Node sample, by sample centrifugal filtration, Jing high effective liquid chromatography for measuring, is calculated modified polyaniline compound adsorbent
Adsorption capacity and Ciprofloxacin adsorption rate.
Measurement result is as shown in the table：
Embodiment 4：
(1) oxidant ammonium persulfate is dissolved in the protonic acid solution of 1.2mol/L, is designated as solution A, wherein ammonium persulfate
The volume fraction for accounting for solution A is 30%, takes aniline monomer and is dissolved in the protonic acid solution of 0.8mol/L, is designated as solution B, wherein benzene
It is 15% that amine monomers account for the volume fraction of solution B, and solution A and solution B are cooled to into -2 DEG C after respectively ultrasonic disperse is uniform, its
In, the mol ratio of hydrochloric acid and DBSA is 1.2 in protonic acid solution:1.
(2) solution A is slowly dropped in solution B, wherein in solution A in ammonium persulfate and solution B aniline monomer mole
Than for 0.9:1, at -3 DEG C, static oxidative polymerization 6h obtains product.
(3) product is filtered and is washed, grinding distribution after vacuum drying is obtained with micro-nano secondary structure
Modified polyaniline, wherein average diameter are 120nm, length be 3 μm of fibrous micron order polyaniline as support frame, averagely
A diameter of 25nm, specific surface area is 450m2The form of spherical particles nanoscale polyaniline of/g is distributed in the surface of support frame.
(4) by weight, 7 parts of CNT is soluble in water, ultrasonic disperse is uniform, adds 42 parts of modified polyphenyl
Amine and 5 parts of micro/nano level diatomite clay, stirring, filtration washing, vacuum drying, grinding distribution obtains modified polyaniline and answers
Close adsorbent.
Adsorption method：Using static adsorptive method, the ciprofloxacin solution of 50mg/L is configured, will with hydrochloric acid or NaOH
PH value tone pitch 9, adds modified polyaniline compound adsorbent, the wherein mass ratio of modified polyaniline compound adsorbent and Ciprofloxacin
For 1:100, under the conditions of lucifuge, at 25 DEG C, rotating speed is that under conditions of 100rpm, sealed thermostat vibrates, standing adsorption.According to
The when segmentum intercalaris of 10min, 20min, 30min, 60min, 120min, 300min, 480min, 1440min, 2880min, 4320min
Point sampling, by sample centrifugal filtration, Jing high effective liquid chromatography for measuring, is calculated modified polyaniline compound adsorbent
The adsorption rate of adsorption capacity and Ciprofloxacin.
Measurement result is as shown in the table：
Embodiment 5：
(1) oxidant ammonium persulfate is dissolved in the protonic acid solution of 0.7mol/L, is designated as solution A, wherein ammonium persulfate
The volume fraction for accounting for solution A is 15%, takes aniline monomer and is dissolved in the protonic acid solution of 1.3mol/L, is designated as solution B, wherein benzene
It is 35% that amine monomers account for the volume fraction of solution B, and solution A and solution B are cooled to into -5 DEG C after respectively ultrasonic disperse is uniform, its
In, the mol ratio of hydrochloric acid and DBSA is 0.6 in protonic acid solution:1.
(2) solution A is slowly dropped in solution B, wherein in solution A in ammonium persulfate and solution B aniline monomer mole
Than for 0.9:1, at -2 DEG C, static oxidative polymerization 10h obtains product.
(3) product is filtered and is washed, grinding distribution after vacuum drying is obtained with micro-nano secondary structure
Modified polyaniline, wherein average diameter are 110nm, length be 5 μm of fibrous micron order polyaniline as support frame, averagely
A diameter of 30nm, specific surface area is 650m2The form of spherical particles nanoscale polyaniline of/g is distributed in the surface of support frame.
(4) by weight, 7 parts of CNT is soluble in water, ultrasonic disperse is uniform, adds 42 parts of modified polyphenyl
Amine and 6 parts of micro/nano level diatomite clay, stirring, filtration washing, vacuum drying, grinding distribution obtains modified polyaniline and answers
Close adsorbent.
Adsorption method：Using static adsorptive method, the ciprofloxacin solution of 50mg/L is configured, will with hydrochloric acid or NaOH
PH value tone pitch 10, adds modified polyaniline compound adsorbent, the wherein quality of modified polyaniline compound adsorbent and Ciprofloxacin
Than for 1:50, under the conditions of lucifuge, at 25 DEG C, rotating speed is that under conditions of 100rpm, sealed thermostat vibrates, standing adsorption.According to
The when segmentum intercalaris of 10min, 20min, 30min, 60min, 120min, 300min, 480min, 1440min, 2880min, 4320min
Point sampling, by sample centrifugal filtration, Jing high effective liquid chromatography for measuring, is calculated modified polyaniline compound adsorbent
The adsorption rate of adsorption capacity and Ciprofloxacin.
Measurement result is as shown in the table：
Embodiment 6：
(1) oxidant ammonium persulfate is dissolved in the protonic acid solution of 0.9mol/L, is designated as solution A, wherein ammonium persulfate
The volume fraction for accounting for solution A is 20%, takes aniline monomer and is dissolved in the protonic acid solution of 1.3mol/L, is designated as solution B, wherein benzene
It is 35% that amine monomers account for the volume fraction of solution B, and solution A and solution B are cooled to into -5 DEG C after respectively ultrasonic disperse is uniform, its
In, the mol ratio of hydrochloric acid and DBSA is 0.6 in protonic acid solution:1.
(2) solution A is slowly dropped in solution B, wherein in solution A in ammonium persulfate and solution B aniline monomer mole
Than for 1.1:1, at -5 DEG C, static oxidative polymerization 5h obtains product.
(3) product is filtered and is washed, grinding distribution after vacuum drying is obtained with micro-nano secondary structure
Modified polyaniline, wherein average diameter are 80nm, length be 3 μm of fibrous micron order polyaniline as support frame, averagely
A diameter of 45nm, specific surface area is 600m2The form of spherical particles nanoscale polyaniline of/g is distributed in the surface of support frame.
(4) by weight, 7 parts of CNT is soluble in water, ultrasonic disperse is uniform, adds 43 parts of modified polyphenyl
Amine and 5 parts of micro/nano level diatomite clay, stirring, filtration washing, vacuum drying, grinding distribution obtains modified polyaniline and answers
Close adsorbent.
Adsorption method：Using static adsorptive method, the ciprofloxacin solution of 100mg/L is configured, with hydrochloric acid or NaOH
By pH value tone pitch 7, modified polyaniline compound adsorbent, the wherein quality of modified polyaniline compound adsorbent and Ciprofloxacin are added
Than for 1:20, under the conditions of lucifuge, at 25 DEG C, rotating speed is that under conditions of 100rpm, sealed thermostat vibrates, standing adsorption.According to
The when segmentum intercalaris of 10min, 20min, 30min, 60min, 120min, 300min, 480min, 1440min, 2880min, 4320min
Point sampling, by sample centrifugal filtration, Jing high effective liquid chromatography for measuring, is calculated modified polyaniline compound adsorbent
The adsorption rate of adsorption capacity and Ciprofloxacin.
Measurement result is as shown in the table：
As seen from the above table, the modified polyaniline compound adsorbent that prepared by the present invention has good adsorptivity to Ciprofloxacin
Can, and adsorption capacity and adsorption rate highest of the pH value of solution 7 or so.
The principle and its effect of above-described embodiment only illustrative present invention, it is of the invention not for limiting.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and the scope without prejudice to the present invention to above-described embodiment.Cause
This, such as those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of modified polyaniline compound adsorbent, it is characterised in that：The modified polyaniline compound adsorbent includes modified poly-
Aniline, CNT and clay, the modified polyaniline has micro-nano secondary structure, and the micro-nano secondary structure is poly- for micron order
Used as support frame, nanoscale polyaniline is distributed in the surface of support frame to aniline, and the micron order polyaniline is average diameter
For the fiber that 60-230nm length is 1-12 μm, it is 20-50nm that the nanoscale polyaniline is average diameter, and specific surface area is
350-770m2The form of spherical particles of/g, the modified polyaniline is prepared using chemical in situ oxidizing process.
2. a kind of modified polyaniline compound adsorbent according to claim 1, it is characterised in that the modified polyaniline is answered
Close adsorbent in by weight, including：Modified polyaniline 40-50 parts, CNT 2-10 parts and clay 3-8 parts.
3. a kind of modified polyaniline compound adsorbent according to claims 1 or 2, it is characterised in that：The clay is
Micro/nano level diatomite, the CNT is multi-walled carbon nano-tubes, and a diameter of 5-200nm, length is 1-50 μm,.
4. a kind of modified polyaniline compound adsorbent according to claims 1 or 2, it is characterised in that described modified poly-
The preparation method of aniline compound adsorbent, comprises the following steps：
(1) oxidant ammonium persulfate is dissolved in protonic acid solution, is designated as solution A, taken aniline monomer and be dissolved in protonic acid solution,
Solution B is designated as, solution A and solution B are cooled to into -5～0 DEG C after respectively ultrasonic disperse is uniform；
(2) solution A prepared by step (1) is slowly dropped in the solution B of step (1) preparation, at -5～0 DEG C, static state oxidation
Polymerisation 2-18h, obtains product；
(3) product prepared by step (2) is filtered and is washed, grinding distribution after vacuum drying is obtained modified polyphenyl
Amine；
(4) CNT is soluble in water, ultrasonic disperse is uniform, adds the modified polyaniline and clay of step (3) preparation, stirs
Mix, filtration washing, be vacuum dried, grinding distribution obtains modified polyaniline compound adsorbent.
5. a kind of modified polyaniline compound adsorbent according to claim 4, it is characterised in that：Matter in the step (1)
The concentration of sub- acid solution is 0.5-2mol/L, and it is 5-40% that ammonium persulfate accounts for the volume fraction of solution A, and aniline monomer accounts for solution B
Volume fraction be 5-40%.
6. a kind of modified polyaniline compound adsorbent according to claim 4, it is characterised in that：Matter in the step (1)
Sub- acid solution includes that the mol ratio of hydrochloric acid and DBSA, the hydrochloric acid and DBSA is 0.2-2:1.
7. a kind of modified polyaniline compound adsorbent according to claim 4, it is characterised in that：It is molten in the step (2)
Ammonium persulfate and the mol ratio of aniline monomer in solution B are 0.8-1.2 in liquid A:1.
8. a kind of modified polyaniline compound adsorbent according to claim 4, it is characterised in that：Change in the step (3)
Property polyaniline there is micro-nano secondary structure, the micro-nano secondary structure be micron order polyaniline as support frame, nanoscale gathers
Aniline is distributed in the surface of support frame, and it is 60-230nm length for 1-12 μm of fibre that the micron order polyaniline is average diameter
Dimension, it is 20-50nm that the nanoscale polyaniline is average diameter, and specific surface area is 350-770m2The form of spherical particles of/g.
9. a kind of modified polyaniline compound adsorbent according to claim 4, it is characterised in that：Stick in the step (4)
Soil is micro/nano level diatomite, and the mass ratio of the modified polyaniline, CNT and clay is 40-50：2-10：3-8.
10. application of a kind of modified polyaniline compound adsorbent in Ciprofloxacin absorption, it is characterised in that：Using quiet during absorption
State absorption method, modified polyaniline compound adsorbent is 1 with the mass ratio of Ciprofloxacin:5-1000.
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