CN105797692A - Magnetic-beta-cyclodextrin-graphene oxide composition, preparation method and application thereof - Google Patents

Magnetic-beta-cyclodextrin-graphene oxide composition, preparation method and application thereof Download PDF

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CN105797692A
CN105797692A CN201610274844.4A CN201610274844A CN105797692A CN 105797692 A CN105797692 A CN 105797692A CN 201610274844 A CN201610274844 A CN 201610274844A CN 105797692 A CN105797692 A CN 105797692A
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magnetic
beta
graphene oxide
schardinger dextrin
oxide complex
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纪靓靓
邓丽萍
白朝暾
杜俊洋
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Hohai University HHU
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229Compounds of Fe
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002Solid 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
    • B01J20/28009Magnetic properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/288Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46Materials comprising a mixture of inorganic and organic materials
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds

Abstract

The invention discloses a magnetic-beta-cyclodextrin-graphene oxide composition, a preparation method and an application thereof. The composition adopts graphene oxide as a main body material, is loaded with magnetic nanoparticles and beta-cyclodextrin on the surface, and is prepared by the following steps of adopting the graphene oxide as the main body material, leading ferric trichloride hexahydrate and ferrous chloride tetrahydrate to carry out mixing reaction with ammonia water, then obtaining magnetic nanoparticles, uniformly mixing and stirring the magnetic nanoparticles and beta-cyclodextrin in acetic acid solution to obtain a black product, then carrying out constant-temperature reaction on the product and activated graphene oxide, and finally washing and drying by utilizing sodium hydroxide solution and deionized water to prepare magnetic-beta-cyclodextrin-graphene oxide. The magnetic-beta-cyclodextrin-graphene oxide composition can absorb and remove medicines and personal skin-care products in water under the condition that pH is equal to 5-8, the prepared composite material shows excellent absorbing performance superior to that of the traditional absorbing material, can be recovered for reuse by an external magnetic field, is used for removing PPCPs in micropolluted water and has good environmental benefit.

Description

Magnetic -β- Cyclodextrin - Graphene oxide complex and preparation method and application
Technical field
The invention belongs to environment functional material and water processes new technical field, particularly relate to a kind of magnetic-beta-schardinger dextrin--graphene oxide complex and preparation method thereof application of PPCPs in processing water.
Background technology
Medicine and personal-care supplies (Pharmaceuticals and Personal Care Products, PPCPs) a series of chemical substances including various medicines (such as antibiotic, amcinonide, antibiotic medicine etc.) and personal-care supplies (such as perfume, skin care item etc.), the life with the mankind is closely related.Along with people's life, the raising of medical level, PPCPs is widely used.But, being applied in the medicine major part with human or animal body can not be fully absorbed by body, how to excrete with feces, urine etc. with the form of body or metabolite, enters in water body environment.Research shows, detects the micro quantity organic pollutants such as multiple PPCPs in municipal sewage, and the drug variety being detected at present more than 80 kinds, is even also detected in water environment in indivedual local drinking waters.
It is long to there is the time in PPCPs class material in ecosystem, and biodegradation is slow, has biological activity and bioaccumulation, has potential risks in ecological environment, the health being chronically exposed to various biology therein and the mankind is had the biggest danger.PPCPs pollutant produces various impacts to the target organism in environment, the physiological structure etc. presented in anatomic course such as the probability of success of hatching of biochemistry local circulation change procedure, the improvement of plant growing, the sex ratio of higher organism, the decortication of insecticide or young baby of the earth, the lopsided life entity of appearance.But most of PPCPs is water miscible, some PPCPs are also with acid or alkaline functional group, although the half-life of PPCPs is not the longest, but owing to individual and animal husbandry use in a large number and continually, cause PPCPs to form false persistence phenomenon.The Chinese country big as drug use and comparision of production, water environment Chinese medicine pollution problem is the severeest.The intensification recognized PPCPs class material to environment and mankind's potential hazard along with people, increasing Chinese scholars begins to focus on PPCPs at sewage and the minimizing technology of drinking water.
The process technique that traditional waste water treatment plant is specifically designed for PPCPs is the most less, and most PPCPs clearance does not reaches 50% and even can not be degraded.The processing method of PPCPs class material mainly has biological degradation method, advanced oxidation processes (O at present3, H2O2/O3、ClO2, electrochemical oxidation process, photocatalytic degradation, ultraviolet method etc.), membrane processing method, absorption method etc..Several method comparatively, biological degradation method the most not produce by-product, removal effect good, but bigger by environmental influence, it is achieved scale application difficult;Advanced oxidation processes advanced technology, high treating effect, but mechanism is relative complex, studies the most perfect, processes object the most single, the most also rests on the experimental stage.Membrane processing method also exists and easily generates the defects such as secondary pollution, cost is high, operating cost is high.Similarly, since the broad applicability of absorption method, and removal effect is stable, absorption method is universal in the field application removing water pollutant.
Absorption method is most commonly used that activated carbon, montmorillonite, kaolinite, adsorbent resin etc. are also widely studied.These materials are excellent effect when processing heavy metal wastewater thereby and incretion interferent waste water respectively.And for the stronger PPCPs of stability, above method can not solve well.Graphene oxide, as the representative of novel nano-material, itself has specific surface area and the loose structure of super large, stable chemical nature, and electric conductivity and adsorptivity are good, it is possible to achieve such material in absorption waste water, respond well.
Although graphene oxide is with the obvious advantage in terms of absorption, but owing to its particle diameter is little, it is difficult to filter and precipitation, so the separation and recovery of graphene oxide is a great problem of absorption at present, is also to limit its industrialized committed step.In the urgent need to seeking a kind of simple and easy to do method to realize the sharp separation of graphene oxide.Obviously, graphene oxide is given magnetic behavior and can realize efficiently separating between graphene oxide and waste water.But in magnetic history, some adsorption sites of surface of graphene oxide are occupied by magnetic nano-particle, thus causing magnetic oxygenated Graphene adsorption site to reduce, absorbability also reduces.In order to improve its absorbability, it is necessary to increase the adsorption site that organic pollution is had stronger chelation on its surface.Beta-schardinger dextrin-is a kind of cyclic oligosaccharide comprising 7 glucose unit molecules, and a lot of oxy radical is carried on its surface, and the hydrophobic cavity in molecule can also produce good tetra-inclusion complex to organic pollution.Therefore, it can by certain method, beta-schardinger dextrin-is grafted onto magnetic oxygenated graphenic surface, increase its adsorption site, thus improve its absorbability.
Summary of the invention
For existing problem, it is an object of the invention to provide and a kind of the most easily separated, with low cost can be used for the magnetic-beta-schardinger dextrin--graphene oxide complex of PPCPs in adsorption treatment water;
It is a further object of the present invention to provide the preparation method that a kind of technique is simple, prepare quick magnetic-beta-schardinger dextrin--graphene oxide complex;
The present invention also provides for the method that above-mentioned complex is applied to remove PPCPs.
In order to achieve the above object, the present invention is by the following technical solutions:
Magnetic-beta-schardinger dextrin--graphene oxide complex, this complex with graphene oxide as material of main part, its surface loaded magnetic nanoparticle and beta-schardinger dextrin-.
Wherein based on graphene oxide, load a certain amount of magnetic nano-particle and beta-schardinger dextrin-, wherein the ratio of composite shared by graphene oxide is 70%-90%, magnetic nano-particle accounts for 2%-10%, beta-schardinger dextrin-accounts for 8%-20%, wherein preferred scope, and graphene oxide, magnetic nano-particle and beta-schardinger dextrin-account for the ratio of composite and be respectively 80%-85%, 4%-6%, 11%-14%.
The preparation method of above-mentioned magnetic-beta-schardinger dextrin--graphene oxide complex, it is first beta-schardinger dextrin-to be grafted on magnetic nano-particle by glutaraldehyde, then graphene oxide matrix is cross-linked with magnetic beta-schardinger dextrin-by activated carboxyl, forms last combination product magnetic beta-schardinger dextrin--graphene oxide.
Comprise the following steps:
1) FeCl in double distilled water will be dissolved in3·6H2O and FeCl2·4H2O solution is added dropwise in ammonia, heated and stirred, Magnetic Isolation, cleans, dried Magnet nanoparticle Fe3O4
2), after beta-schardinger dextrin-being completely dissolved in acetum, the Magnet nanoparticle Fe described in step 1) is added3O4And ultrasonic disperse, regulation pH value of solution is between 8.0 ~ 9.0;Add glutaraldehyde mixing, at 55 ~ 65 DEG C, stir 1.5 ~ 2.5 h, obtain precipitate, clean the most neutral and be dried, obtaining magnetic beta-schardinger dextrin-;
3) graphene oxide is dissolved in ultrasonic disperse in ultra-pure water, adds water-soluble carbodiimide and N-hydroxy-succinimide solution stirring, the carboxyl on active oxidation Graphene, and keep whole pH value of solution for neutrality;It is subsequently adding step 2) the magnetic beta-schardinger dextrin-of gained and glutaraldehyde, ultrasonic 10 ~ 30 minutes, continuously stirred 1.0 ~ 2.0 h at 60 ~ 70 DEG C, obtain precipitate, rinse until pH is neutral, be dried after Magnetic Isolation, obtain magnetic beta-schardinger dextrin--graphene oxide complex.
Step 2) in beta-schardinger dextrin-and Magnet nanoparticle Fe3O4Mass ratio be 1.5 ~ 6:1.
In step 3), the concentration of water-soluble carbodiimide is 0.05 ~ 0.1 mol/L, and the concentration of N-hydroxy-succinimide solution is 0.05 ~ 0.1 mol/L。
Described preparation method is specifically described as comprising the following steps:
(1) being joined by the ammonia spirit that concentration is 1.5 ~ 2.5 mol/L with in dropper and magnetic stirrer four neck round-bottom flask, meanwhile, nitrogen removes other gases in being linked into reaction flask.Afterwards, the FeCl in double distilled water will be dissolved in3·6H2O and FeCl2·4H2O solution is added dropwise in ammonia, reacted mixture continuous heating stir 1.5 ~ 3 in the water-bath of 85 ~ 95 DEG C H, separates finally by extraneous Magnet, clean, be vacuum dried after Magnet nanoparticle Fe3O4
(2) 0.3 ~ 0.6 g beta-schardinger dextrin-is completely dissolved in 50 ~ 100 mL(3%) acetum after pour in round-bottomed flask, afterwards, add magnetic-particle described in 0.1 ~ 0.2 g step (1) ultrasonic disperse 10 ~ 30 minutes, pH value of solution is regulated so that it is be maintained between 8.0 ~ 9.0 with low concentration ammonia.The pure glutaraldehyde of 1.0 ~ 3.0 mL is joined in reaction flask after completing and mixes by above-mentioned steps, and at 55 ~ 65 DEG C, stir 1.5 ~ 2.5 h, finally cleaning gained precipitate benzin, methanol and deionized water to neutrality and be dried, products therefrom is magnetic beta-schardinger dextrin-.
(3) at room temperature, graphene oxide is dissolved in ultra-pure water ultrasonic 2h to reach dispersion effect, the water-soluble carbodiimide (EDC) of 0.05 ~ 0.1 mol/L and 0.05 ~ 0.1 N-hydroxy-succinimide (NHS) solution of mol/L is added simultaneously in dispersion liquid, and continuously stirred 2h is to reach the carboxyl on active oxidation Graphene, and keeps whole pH value of solution for neutrality.Afterwards, the magnetic beta-schardinger dextrin-(0.1 ~ 0.2 g) of step (2) gained and 2 ~ 5 mL glutaraldehydes are successively joined in dispersion liquid ultrasonic 10 ~ 30 minutes, and continuously stirred 1.0 ~ 2.0 h at 60 ~ 70 DEG C, last deposit with 2% (w/v) NaOH and deionized water rinsing until pH is neutrality, last dry after separation under external magnet effect, gained end product magnetic beta-schardinger dextrin--graphene oxide.
The present invention also provides for a kind of above-mentioned magnetic-beta-schardinger dextrin--graphene oxide composite material and is applied to remove the method for PPCPs in waste water, comprise the following steps: utilize and can remove PPCPs in water by Magnetic Isolation Composite Adsorbent Absorbing, composite is 1:2000~5000 with the mass ratio containing PPCPs waste water, after absorption terminates, by external magnetic field, composite is separated with waste water, and detect the content of PPCPs in water, determine the adsorption rate of compound adsorbent.
In above-mentioned application, the pH value of described adsorption reaction is preferably 5~8;
In above-mentioned application, described sorption reaction time is preferably 2~48h;
In above-mentioned application, adsorption reaction temperature is preferably 298~308 K.
Compared with prior art, it is an advantage of the current invention that:
1. the magnetic beta-schardinger dextrin--graphene oxide complex of the present invention, there is specific surface area is big, surface adsorption site is many and is easily combined with organic pollution feature, adsorption efficiency height, and it has magnetic, being easy to the waste water after processing separate, the improvement removing Organic Pollutants in Wastewater provides new theory;
2. raw material sources enrich, low cost, and its preparation method and technique simple, it is possible to effectively realize industrialized production;
3. the beta-schardinger dextrin-of the present invention-graphene oxide complex is high to the removal efficiency of PPCPs, processes technique simple and easily operated.
Accompanying drawing explanation
Fig. 1 is the magnetic beta-schardinger dextrin--graphene oxide complex scanning electron microscope (SEM) photograph of the embodiment of the present invention 1;
Fig. 2 is the magnetic-beta cyclodextrin-graphene oxide complex scanning electron microscope (SEM) photograph of the embodiment of the present invention 3;
Fig. 3 position embodiment of the present invention 1 and the magnetic intensity comparison diagram of embodiment 3 products therefrom magnetic-beta cyclodextrin-graphene oxide complex.
Detailed description of the invention
The invention will be further described below.Following example are only used for clearly illustrating technical scheme, and can not limit the scope of the invention with this.
In following example, graphene oxide is purchased from Nanjing Xian Feng material Science and Technology Ltd., and beta-schardinger dextrin-is purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
A kind of magnetic-beta-schardinger dextrin--graphene oxide complex, with graphene oxide as material of main part, its surface loaded magnetic nanoparticle Fe3O4With this complex of beta-schardinger dextrin-, prepare following methods:
(1) being joined by the ammonia spirit that concentration is 1.5 mol/L with in dropper and magnetic stirrer four neck round-bottom flask, meanwhile, nitrogen removes other gases in being linked into reaction flask.Afterwards, the FeCl in double distilled water will be dissolved in3·6H2O and FeCl2·4H2O solution (FeCl3·6H2O and FeCl2·4H2The mol ratio of O is 1 ~ 1.5:1) be added dropwise in ammonia, reacted mixture continuous heating stir 1.5h in the water-bath of 90 DEG C, separate finally by extraneous Magnet, clean, be vacuum dried after Magnet nanoparticle Fe3O4
(2) 0.3g beta-schardinger dextrin-is completely dissolved in 50 mL(3%) acetum after pour in round-bottomed flask, afterwards, add the Magnet nanoparticle Fe of 0.1 g step (1) gained3O4And ultrasonic disperse 10 minutes, gained solution low concentration ammonia (0.1 ~ 1.0 mol/L) solution regulation pH, making solution be maintained at pH is between 8.0 ~ 9.0, the pure glutaraldehyde of 1.0mL is joined in reaction flask after completing and mixes by previous step, and at 55 DEG C, stir 1.5h, last precipitate benzin, methanol and water wheels stream rinse until pH is 7, and dry in 40 DEG C of vacuum drying ovens, and products therefrom is magnetic beta-schardinger dextrin-;
(3) at room temperature, graphene oxide is dissolved in ultra-pure water ultrasonic 2h to reach dispersion effect, the water-soluble carbodiimide (EDC) (100mL, 1.197g) of 0.1 mol/L and N-hydroxy-succinimide (NHS) solution (100ml of 0.1 mol/L 1.151g) being added simultaneously in dispersion liquid, continuously stirred 2h, to reach the carboxyl on active oxidation Graphene, keeps whole pH value of solution to be 7 by NaOH solution afterwards.Afterwards, magnetic-the beta-schardinger dextrin-(0.1 g) of step (2) gained and 5 mL glutaraldehydes are successively joined in dispersion liquid ultrasonic 10 minutes, and continuously stirred 2h at 65 DEG C, last deposit with 2% (w/v) NaOH and deionized water rinsing until pH is 7, finally separate under external magnet effect and dry in 50 DEG C of vacuum drying ovens, gained end product magnetic-beta-schardinger dextrin--graphene oxide.
Above-mentioned prepared magnetic-beta-schardinger dextrin--graphene oxide complex is placed under scanning electron microscope observation, and its structure is as shown in Figure 1, it can be seen that a large amount of magnetic Fe of its surface distributed3O4Nanoparticle.
Embodiment 2
Magnetic-beta-schardinger dextrin--graphene oxide complex embodiment 1 prepared is applied to the process containing PPCPs waste water, with this complex as adsorbent, with ibuprofen and triclosan for adsorbed agent, comprise the following steps: adsorb in closing container, constant temperature oscillation.The initial concentration of ibuprofen and triclosan is respectively 2.0 mg/L and 1.8mg/L, the mass ratio of adsorbent and micro-polluted water takes 1:2500, absorption is carried out under the conditions of pH=6.0, adsorption temp 298K, this complex is separated and separately sampled, with triclosan not to be adsorbed in high-performance liquid chromatogram determination each sample and the content of ibuprofen after starting 12h, 24h, 48h from waste water by adsorption reaction with extraneous Magnet.
Testing result shows, after 12h, 24h and 48h adsorption reaction, the adsorbance of triclosan is respectively 3.2 mg/g, 4.4 mg/g and 4.5mg/g, clearance is 72%, 98% and 99%, the adsorbance of ibuprofen is respectively 3.25 mg/g, 4.8 mg/g and 4.85mg/g, and clearance is 65%, 96% and 97%.
Contrast understands, and magnetic-beta-schardinger dextrin--graphene oxide Composite Adsorbent Absorbing PPCPs has reached adsorption equilibrium when 24 h, illustrates that the application in terms for the treatment of of Organic Wastewater of this magnetic composite adsorbent is feasible.
Embodiment 3
A kind of magnetic-beta-schardinger dextrin--graphene oxide complex, first two steps are with described in example 1, and the 3rd step changes, following methods prepare:
At room temperature, graphene oxide is dissolved in ultra-pure water ultrasonic 2h to reach dispersion effect, water-soluble carbodiimide (the EDC) (100mL of 0.1 mol/L, 1.917) N-hydroxy-succinimide (NHS) solution (100mL.151) of and 0.1 mol/L is added simultaneously in dispersion liquid, continuously stirred 2h, to reach the carboxyl on active oxidation Graphene, keeps whole pH value of solution to be 7 by NaOH solution afterwards.Afterwards, magnetic-the beta-schardinger dextrin-(0.2 g) of step (2) gained and 5 mL glutaraldehydes are successively joined in dispersion liquid ultrasonic 10 minutes, and continuously stirred 2h at 65 DEG C, last deposit with 2% (w/v) NaOH and deionized water rinsing until pH is 7, finally separate under external magnet effect and dry in 50 DEG C of vacuum drying ovens, gained end product magnetic-beta-schardinger dextrin--graphene oxide.
Above-mentioned prepared beta-schardinger dextrin--graphene oxide complex is placed under scanning electron microscope observation, and its structure is as shown in Figure 2, it can be seen that the further amounts of magnetic ferroferric oxide nano-particles of its surface distributed, substantially keeps consistent with embodiment 1 result.Fig. 3 is embodiment 1(a) with embodiment 3(b) hysteresis graph of gained end product, as seen from the figure, two kinds of example products therefrom magnetic are all put up a good show, and embodiment 3 product is more higher than embodiment 1 magnetic.
Embodiment 4
Magnetic-beta-schardinger dextrin--graphene oxide complex embodiment 3 prepared is applied to the process containing PPCPs waste water, with this complex as adsorbent, with ibuprofen and triclosan for adsorbed agent, comprise the following steps: adsorb in closing container, constant temperature oscillation.The initial concentration of ibuprofen and triclosan is respectively 2.0 mg/L and 1.8mg/L, the mass ratio of adsorbent and micro-polluted water takes 1:2500, absorption is carried out under the conditions of pH=6.0, adsorption temp 298K, this complex is separated and separately sampled after starting 12h, 24h, 48h from waste water by adsorption reaction with extraneous Magnet, and utilizes the content of triclosan not to be adsorbed in high-performance liquid chromatogram determination each sample and ibuprofen.
Testing result shows, after 12h, 24h and 48h adsorption reaction, the adsorbance of triclosan is respectively 2.70 mg/g, 4.05 mg/g and 4.06 mg/g, and clearance is 60%, 90% and 91%, and the adsorbance of ibuprofen is respectively 2.75 Mg/g, 4.40 mg/g and 4.45 mg/g, clearance is 55%, 88% and 89%.
Contrast understands, and the magnetic-beta-schardinger dextrin-of embodiment 3 gained-graphene oxide Composite Adsorbent Absorbing PPCPs has reached adsorption equilibrium when 24 h, illustrates that the application in terms for the treatment of of Organic Wastewater of this magnetic composite adsorbent is feasible.
Embodiment 5
With embodiment 2, wherein with graphene oxide as adsorbent, with ibuprofen and triclosan for adsorbed agent, the initial concentration of ibuprofen and triclosan is 2.0 mg/L and 1.8mg/L, the mass ratio of adsorbent and micro-polluted water takes 1:2500, absorption is carried out under the conditions of pH=6.0, adsorption temp 298K, after absorption 48h, the adsorbance of ibuprofen is 4.05 mg/g, clearance is 81%, and the adsorbance of triclosan is 3.74 mg/g, and clearance is 83%.
Understand with embodiment 2 contrast, more better than graphene oxide to the removal effect of PPCPs at identical adsorption conditions magnetic beta-schardinger dextrin--graphene oxide compound adsorbent, illustrate that this magnetic oxygenated Graphene application in terms for the treatment of of Organic Wastewater is also the most promising.
Embodiment 6
With embodiment 2, the initial concentration of ibuprofen is 3.6 mg/L, and other condition is constant, and the adsorbance of ibuprofen is respectively 7.47mg/g, and clearance is 83%.
Embodiment 7
With embodiment 2, the initial concentration of ibuprofen is 5.4 mg/L, and other condition is constant, and the adsorbance of ibuprofen is respectively 12.16mg/g, and clearance is 76%.
Visible, in the range of low concentration, the clearance of PPCPs is improved by magnetic beta-schardinger dextrin--graphene oxide adsorbent along with the reduction of concentration.
Embodiment 8
With embodiment 2, wherein with activated carbon and montmorillonite as adsorbent, with ibuprofen and triclosan as adsorbent, the initial concentration of ibuprofen and triclosan is 2.0 mg/L and 1.8mg/L, the mass ratio of adsorbent and micro-polluted water takes 1:2500, absorption is carried out under the conditions of pH=6.0, adsorption temp 298K, after absorption 48h, activated carbon is 3.50 mg/g to the adsorbance of ibuprofen, clearance is 70%, the adsorbance of triclosan is 3.37 mg/g, clearance is 75%, montmorillonite is 2.20 mg/g to the adsorbance of ibuprofen, clearance is 40%, the adsorbance of triclosan is 2.03 mg/g, clearance is 45%.
Understand with embodiment 2 contrast, more preferable than general water treatment absorbent (activated carbon, montmorillonite etc.) to the removal effect of PPCPs at identical adsorption conditions magnetic-beta-schardinger dextrin--graphene oxide compound adsorbent, this result illustrates that this composite magnetic graphene oxide composite material is to being the most promising in the process containing organic pollution (especially PPCPs) waste water.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, on the premise of without departing from the technology of the present invention principle; can also make some improvement and deformation, these improve and deformation also should be regarded as protection scope of the present invention.

Claims (10)

1. magnetic-beta-schardinger dextrin--graphene oxide complex, it is characterised in that this complex with graphene oxide as material of main part, its surface loaded magnetic nanoparticle and beta-schardinger dextrin-.
2. the preparation method of the magnetic-beta-schardinger dextrin--graphene oxide complex described in claim 1, it is characterized in that, beta-schardinger dextrin-grafts on magnetic nano-particle by glutaraldehyde, then graphene oxide matrix is cross-linked with magnetic beta cyclodextrin by activated carboxyl, forms combination product magnetic beta-schardinger dextrin--graphene oxide complex.
The preparation method of magnetic-beta-schardinger dextrin--graphene oxide complex the most according to claim 2, it is characterised in that comprise the following steps:
1) FeCl in double distilled water will be dissolved in3·6H2O and FeCl2·4H2O solution is added dropwise in ammonia, heated and stirred, Magnetic Isolation, cleans, dried Magnet nanoparticle Fe3O4
2), after beta-schardinger dextrin-being completely dissolved in acetum, the Magnet nanoparticle Fe described in step 1) is added3O4And ultrasonic disperse, regulation pH value of solution is between 8.0 ~ 9.0;Add glutaraldehyde mixing, at 55 ~ 65 DEG C, stir 1.5 ~ 2.5 h, obtain precipitate, clean the most neutral and be dried, obtaining magnetic beta-schardinger dextrin-;
3) graphene oxide is dissolved in ultrasonic disperse in ultra-pure water, adds water-soluble carbodiimide and N-hydroxy-succinimide solution stirring, the carboxyl on active oxidation Graphene, and keep whole pH value of solution for neutrality;It is subsequently adding step 2) the magnetic beta-schardinger dextrin-of gained and glutaraldehyde, ultrasonic 10 ~ 30 minutes, continuously stirred 1.0 ~ 2.0 h at 60 ~ 70 DEG C, obtain precipitate, rinse until pH is neutral, be dried after Magnetic Isolation, obtain magnetic beta-schardinger dextrin--graphene oxide complex.
The preparation method of magnetic-beta-schardinger dextrin--graphene oxide complex the most according to claim 3, it is characterised in that the FeCl described in step 1)3·6H2O and FeCl2·4H2The ratio of the molal quantity of O is 1 ~ 1.5:1.
The preparation method of magnetic-beta-schardinger dextrin--graphene oxide complex the most according to claim 3, it is characterised in that step 2) in beta-schardinger dextrin-and Magnet nanoparticle Fe3O4Mass ratio be 1.5 ~ 6:1.
The preparation method of magnetic-beta-schardinger dextrin--graphene oxide complex the most according to claim 3, it is characterised in that in step 3), the concentration of water-soluble carbodiimide is 0.05 ~ 0.1 The concentration of mol/L, N-hydroxy-succinimide solution is 0.05 ~ 0.1 mol/L.
7. magnetic-the beta-schardinger dextrin-described in claim 1-graphene oxide complex application in the treatment of waste water.
Application the most according to claim 7, it is characterized in that, magnetic-beta-schardinger dextrin--graphene oxide complex removes PPCPs in waste water as adsorbent, magnetic-beta-schardinger dextrin--graphene oxide complex is joined in the waste water containing PPCPs, sorption reaction time is 2~48h, adsorption reaction temperature is 298~308 K, after absorption terminates, is separated with waste water by composite by external magnetic field.
Application the most according to claim 7, it is characterised in that magnetic-beta-schardinger dextrin--graphene oxide complex is 1:2000~5000 with the mass ratio containing PPCPs waste water.
Application the most according to claim 7, it is characterised in that adsorption reaction control ph is 5~8.
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