CN105797685A - Preparation method of sodium alginate-graphene oxide macroscopic sphere composite material - Google Patents

Preparation method of sodium alginate-graphene oxide macroscopic sphere composite material Download PDF

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CN105797685A
CN105797685A CN201610302347.0A CN201610302347A CN105797685A CN 105797685 A CN105797685 A CN 105797685A CN 201610302347 A CN201610302347 A CN 201610302347A CN 105797685 A CN105797685 A CN 105797685A
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graphene oxide
sodium alginate
macroscopic view
cross
preparation
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谢阿田
戴江栋
何劲松
常忠帅
李春香
闫永胜
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Jiangsu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to a preparation method of a sodium alginate-graphene oxide macroscopic sphere composite material, and belongs to the technical field of preparation of environment function materials. The method comprises the following steps: firstly, performing ultrasonic treatment to obtain mixed sol of sodium alginate and graphene oxide; secondly, carrying out cross-linking on the blended sol by divalent metal ions, carrying out secondary cross-linking with glutaraldehyde as a cross-linking agent, and then washing and removing metal ions with a dilute acid solution; and finally, drying the cross-linked spheres by a freeze-drying method to obtain the sodium alginate-graphene oxide macroscopic sphere composite material. Through a plurality of characterization methods, parameters of shape and form and the like of the composite material are disclosed. The removal property of the obtained material on tetracycline antibiotics in a water environment is researched by an adsorption experiment.

Description

A kind of preparation method of sodium alginate-graphene oxide macroscopic view sphere composite
Technical field
The present invention relates to the preparation method of a kind of sodium alginate-graphene oxide macroscopic view sphere composite, belong to ring Border functional material preparing technical field.
Background technology
The serious disease that Gram-positive and Gram-negative cause is had the most anti-by tetracycline antibiotics Bacterium activity, is therefore widely used in the disease prevention of human and animal and treatment or as livestock fodder additives. But, tetracycline digests and assimilates difference in vivo, and therefore major part is not engaged in metabolism and gets rid of external, still So remain biological activity, enter in environment, carry out shifting and propagating and produce toxic effect in microorganism.Excessively Dangerous residual in meat agricultural product, ecological environment is already led to tetracycline.Chinese scholars studies channel syndrome Real in soil and water environment, there is teracycline antibiotic residues, cause the extensive concern of environmental ecology. Therefore, set up and develop effective and economic and practical process means and carry out selectivity and remove tetracycline antibiotics in environment Residual is the most urgent.
Porous material is a kind of by being mutually communicated or blind bore hole constitutes the material of network structure, the border of hole Or surface is made up of pillar or flat board.Relatively for continuous media material, porous material typically has relative density Low, the advantage such as specific strength is high, specific surface area is high, lightweight, sound insulation, heat insulation, good penetrability.Porous material Possessing the specific surface area of the pore passage structure of open communication, superelevation, construction features determines it and possesses outstanding absorption Ability, owing to the diameter of every kind of gas or fluid molecule is different, the degrees of freedom of its motion are different, thus different The porous material in aperture is the most different to the absorbability of gas with various or liquid.The porous material of one-component, past Random in a jumble toward duct, pore-size distribution is uneven, and mechanical strength is not enough, and degradation property is the best, poor biocompatibility, Its construction features determines its performance deficiency, and seriously limits the application of such material.And utilize dissimilarity The raw material of matter is compound prepares porous material, can concentrate the advantage of each component, prepare combination property more superior Composite, to meet all kinds of performance requirements of environment functional material.Graphene oxide is the one of Graphene Important derivatives.Graphene oxide in this method is to use modified model Hummers method to prepare, i.e. at strong acid etc. Under strong oxidizer effect, oxygen atom intercalation enter graphite layers, by ultrasonic stripping, contained-C=O, The graphene oxide of the oxygen-containing functional groups such as-C-OH ,-COOH, these abundant oxy functional groups are oxidation stone The preparation of ink alkene composite provides the reaction site of abundance；Natural macromolecular material sodium alginate, biofacies Capacitive is good, itself is nontoxic, can be biodegradable into nontoxic little molecule and be excreted, mechanical property is good, easily become Type, is widely used.
The present invention prepares composite porous by compound to graphene oxide, sodium alginate, and this material can be by each component Advantageous combination optimizes, it is achieved the desired combination of inorganic and organic materials, and the machinery giving this composite good is strong Degree, preferable adsorptivity and biodegradability.
Summary of the invention
The present invention relates to the preparation method of a kind of sodium alginate-graphene oxide macroscopic view sphere composite, belong to ring Border functional material preparing technical field.First pass through supersound process and obtain being blended of sodium alginate and graphene oxide Colloidal sol；Secondly, utilizing bivalent metal ion to cross-link blended colloidal sol first, recycling glutaraldehyde is as friendship Connection agent carries out secondary cross-linking to it, then soaks with dilute acid soln and removes metal ion；Finally, with lyophilization The spheroid cross-linked is dried by method, obtains sodium alginate-graphene oxide macroscopic view sphere composite.By many Plant the parameters such as characterization method, the pattern of announcement composite and pore distribution.Adsorption experiment institute is utilized to obtain Material is to the removal capacity of tetracycline antibiotic in water environment.
The technical solution used in the present invention is: a kind of sodium alginate-graphene oxide macroscopic view sphere composite Preparation method, is carried out as steps described below:
(1) the miscible glue of graphene oxide/sodium alginate is prepared: divided by appropriate sodium alginate addition graphene oxide Dissipate in liquid, supersound process, obtain the miscible glue of graphene oxide/sodium alginate that thickness is homogeneous.
(2) miscible glue is cross-linked: utilize peristaltic pump that miscible for above-mentioned gained glue is added drop-wise to CaCl2Solution In and accompany by magnetic agitation and cross-link first, obtain macroscopic view spheroid and stand solidification；Then the spheroid being cured It is immersed in glutaraldehyde water solution and carries out secondary cross-linking, then dilute acid wash removes Ca2+Obtain hydrogel macroscopic view ball Body.
(3) sodium alginate-graphene oxide macroscopic view sphere composite is prepared: step (2) is removed Ca2+ After hydrogel macroscopic view spheroid rinse several times with deionized water, then carry out lyophilization, prepare sodium alginate- Graphene oxide porous macroscopic view spheroid aerogel composite.
In step 1, sodium alginate is 10:(1-10 with the mass ratio of graphene oxide), graphene oxide disperses The concentration of liquid is 1-10mg/mL, and the process conditions of supersound process are: power 500W, processes 1h.
In step 2, CaCl2The concentration of solution is 2mmol/L, and the time of magnetic agitation is for dripping to miscible glue Finishing, stir speed (S.S.) is that 10-50 turns/min, and the time of secondary cross-linking is 12h, and the quality of glutaraldehyde water solution is dense Degree is 0.5%-2%, and described diluted acid is dilute hydrochloric acid, and mass concentration is 5-15%.
In step 3, cryodesiccated process conditions are for be frozen into solid-state at a temperature of-10 DEG C～-50 DEG C, then Water sublimed is made in vacuum (1.3～13 handkerchief).
Described composite porous by the advantageous combination optimization of each component, make organic-inorganic rationality combine, be applied to Environmental wastewater processes, and, stable performance big to the adsorption capacity of antibiotic, regeneration reusing are good.
The beneficial effects of the present invention is:
(1) material therefor of the present invention is natural materials, abundance, cheap, environmental protection；
(2) prepare sodium alginate-graphene oxide macroscopic view sphere composite good mechanical property, organize regular, knot Structure is stable, porosity is high, and the repeatable utilization of this composite；
(3) in view of the sodium alginate-high-specific surface area of graphene oxide macroscopic view sphere composite, high composition activity, And biodegradability, can be widely used in the field such as adsorption filtration, pharmaceutical carrier；
(4) preparation method of the present invention is simple, flow process is shorter, easy controlled operation, is suitable to promote the use of.
Accompanying drawing explanation
Fig. 1 is the photo of sodium alginate-graphene oxide macroscopic hydrogel ball；Alginic acid as can be seen from Figure 1 Sodium-graphene oxide macroscopic hydrogel is the most homogeneous spheroid of size, its diameter be mainly distributed on 2-3mm it Between, provide convenience for the separation after absorption.Sodium alginate-graphene oxide hydrogel sphere is brown, shows Graphite oxide is evenly distributed in hydrogel sphere.
Fig. 2 is sodium alginate-graphene oxide macroscopic view airsetting glueballs；Water-setting after lyophilization as can be seen from Figure 2 Glue becomes aeroge, and its color has brown to become black, and its form remains in that spheroid.Sodium alginate-oxidation Its gel surface of Graphene is the most coarse, has a lot of folds and hole, is conducive to the absorption to tetracycline.
Fig. 3 sodium alginate-graphene oxide porous macroscopic view airsetting glueballs scanning electron microscope (SEM) photograph；As we can see from the figure Playing the main structure the most in the form of sheets of microstructure, surface is the most coarse, in accordion, with the structure of graphite oxide more Similar.Sodium alginate and graphite oxide are cross-linked with each other and cause its structure the most fluffy, are conducive to the absorption to tetracycline And interaction, provide substantial amounts of adsorption site for absorption.
Sodium alginate-graphene oxide porous macroscopic view ball adsorption isotherm line chart to tetracycline under Fig. 4 different temperatures, As shown in Figure 4: along with the rising of concentration, adsorbance increases therewith, and sodium alginate-graphene oxide porous is grand The adsorbance seeing ball increases comparatively fast when low concentration, and when tetracycline concentration reaches 140mg/L, absorption becomes It is bordering on balance.Additionally, when increase Contact Temperature be, adsorbance also responsive to increase, when temperature is 318K, Maximum equilibrium adsorption capacity reaches 72.01mg/g.
Sodium alginate-graphene oxide porous macroscopic view ball adsorption dynamics adsorption kinetics figure to TC under Fig. 5 different temperatures, As shown in Figure 5, adsorbing the starting stage, along with the increase of time of contact, adsorbance increases sharply.Temperature raises Time, the rate of adsorption and adsorbance are consequently increased, and adsorb and slowly tend to balance after adsorption took 120min, Show good adsorption dynamics adsorption kinetics performance.
Detailed description of the invention
1, in order to illustrate technical scheme and technical purpose, below in conjunction with specific embodiment the present invention done into The introduction of one step.
Embodiment 1:
It is in 10mg/mL graphene oxide solution by 100mg sodium alginate addition 10mL concentration, puts into merit Rate be 500W ultrasonic machine in supersound process 1h, the graphene oxide/sodium alginate obtaining thickness homogeneous is miscible Glue.
Utilize peristaltic pump that above-mentioned gained is blended colloidal sol and be added drop-wise to the CaCl of 2mmol/L2In solution and accompany by magnetic force Stirring, stir speed (S.S.) is 10 turns/min, obtains macroscopic view spheroid and stands solidification.Then the spheroid leaching being cured Bubble carries out secondary cross-linking in the glutaraldehyde of 2%, and the time of secondary cross-linking is 12h, then soaks with 15% diluted acid Remove Ca2+。
Ca will be removed2+After hydrogel macroscopic view spheroid rinse several times with deionized water, then carry out lyophilization, At a temperature of-50 DEG C, it is frozen into solid-state, then makes water sublimed at vacuum 13 handkerchief, prepare sodium alginate-oxidation stone Ink alkene macroscopic view sphere composite composite.
Embodiment 2:
It is in 1mg/mL graphene oxide solution by 100mg sodium alginate addition 10mL concentration, puts into merit Rate be 500W ultrasonic machine in supersound process 1h, the graphene oxide/sodium alginate obtaining thickness homogeneous is miscible Glue.
Utilize peristaltic pump that miscible for above-mentioned gained glue is added drop-wise to the CaCl of 2mmol/L2In solution and accompany by magnetic force Stirring, stir speed (S.S.) is 50 turns/min, obtains macroscopic view spheroid and stands solidification；Then the spheroid leaching being cured Bubble carries out secondary cross-linking in the glutaraldehyde of 0.5%, and the time of secondary cross-linking is 12h, then washes with 5% dilute hydrochloric acid Wash away Ca2+。
Ca will be removed2+After hydrogel macroscopic view spheroid rinse several times with deionized water, then carry out lyophilization, At a temperature of-10 DEG C, it is frozen into solid-state, then makes water sublimed at vacuum 1.3 handkerchief, prepare sodium alginate-oxidation stone Ink alkene macroscopic view sphere composite.
2, below in conjunction with being embodied as example, the present invention will be further described:
In the present invention, in specific embodiments, absorption property evaluation is carried out by the following method: utilize static adsorption real Test.The tetracycline of 10mL variable concentrations is joined in centrifuge tube, is added thereto to 2.0 respectively Mg sodium alginate-graphene oxide macroscopic view sphere composite, stands in water bath with thermostatic control, has investigated pH value of solution The impact that tetracycline is adsorbed by value, adsorbent amount, time of contact, temperature.Absorption reach saturated after, directly Collect the supernatant, record tetracycline molecule concentration not to be adsorbed in test solution with ultraviolet-visible photometer, meter Calculation obtains adsorption capacity (Qe)。
Q e = ( C 0 - C e ) V m
Wherein C0And C (mg/L)e(mg/L) being initial and equilibrium concentration respectively, m (mg) is adsorbent amount, V (mL) is liquor capacity.
Experimental example 1: take 10ml initial concentration be respectively 20,40,60,80,100,120,140mg/L Tetracycline join in centrifuge tube, be separately added into 2.0mg sodium alginate-graphene oxide macroscopic view spheroid Composite, after test fluid is placed in 298,308 and 318K water-bath standing 12.0h, collects upper strata clear Liquid, tetracycline molecule concentration ultraviolet-uisible spectrophotometer not to be adsorbed measures, and calculates according to result Adsorption capacity.Experimental result shows at Fig. 4.
Experimental example 2: take the tetracycline that 10ml initial concentration is 100mg/L and join in centrifuge tube, point Not Jia Ru 2.0mg sodium alginate-graphene oxide macroscopic view sphere composite, test fluid is placed on 298K's Water-bath stands 5,10,30,60,90,120 and 180 minutes respectively；After standing completes, in collection Layer clear liquid, tetracycline molecule concentration ultraviolet-uisible spectrophotometer not to be adsorbed measures, and according to result meter Calculate adsorption capacity.Experimental result shows at Fig. 5, shows: sodium alginate-graphene oxide macroscopic view spheroid is combined Material have preferable adsorption dynamics adsorption kinetics performance to Fourth Ring.

Claims (6)

1. the preparation method of sodium alginate-graphene oxide macroscopic view sphere composite, it is characterised in that: first pass through Supersound process obtains the blended colloidal sol of sodium alginate and graphene oxide；Secondly, utilize bivalent metal ion that blended colloidal sol is entered Row cross-links first, and recycling glutaraldehyde carries out secondary cross-linking as cross-linking agent to it, then soaks with dilute acid soln and removes metal Ion；Finally, with freeze-drying, the spheroid cross-linked is dried, obtains sodium alginate-graphene oxide macroscopic view spheroid and be combined Material.
The preparation method of a kind of sodium alginate the most as claimed in claim 1-graphene oxide macroscopic view sphere composite, it is special Levy and be to carry out in accordance with the following steps:
(1) the miscible glue of graphene oxide/sodium alginate is prepared: added by appropriate sodium alginate in graphene oxide dispersion, Supersound process, obtains the miscible glue of graphene oxide/sodium alginate that thickness is homogeneous；
(2) miscible glue is cross-linked: utilize peristaltic pump that miscible for above-mentioned gained glue is added drop-wise to CaCl2In solution and accompany by magnetic Power stirring cross-links first, obtains macroscopic view spheroid and stands solidification；Then the spheroid being cured is immersed in glutaraldehyde water solution In carry out secondary cross-linking, then dilute acid wash removes Ca2+Obtain hydrogel macroscopic view spheroid；
(3) sodium alginate-graphene oxide macroscopic view sphere composite is prepared: step (2) is removed Ca2+After hydrogel Macroscopic view spheroid deionized water rinses, then carries out lyophilization, prepares sodium alginate-graphene oxide porous macroscopic view spheroid airsetting Glue composite.
The preparation method of a kind of sodium alginate the most as claimed in claim 2-graphene oxide macroscopic view sphere composite, it is special Levying and be: in step 1, the mass ratio of sodium alginate and graphene oxide is 10:(1-10), graphene oxide dispersion dense Degree is 1-10mg/mL, and the process conditions of supersound process are: power 500W, processes 1h.
The preparation method of a kind of sodium alginate the most as claimed in claim 2-graphene oxide macroscopic view sphere composite, it is special Levy and be: in step 2, CaCl2The concentration of solution is 2mmol/L, and the time of magnetic agitation is complete to the dropping of miscible glue, Stir speed (S.S.) is that 10-50 turns/min, and the time of secondary cross-linking is 12h, and the mass concentration of glutaraldehyde water solution is 0.5%-2%, Described diluted acid is dilute hydrochloric acid, and mass concentration is 5-15%.
The preparation method of a kind of sodium alginate the most as claimed in claim 2-graphene oxide macroscopic view sphere composite, it is special Levying and be: in step 3, cryodesiccated process conditions are for be frozen into solid-state at a temperature of-10 DEG C～-50 DEG C, then in vacuum (1.3～13 handkerchief) makes water sublimed.
6. the sodium alginate that prepared by preparation method as described in claim 1-5 is arbitrary-graphene oxide macroscopic view sphere composite is gone Except the purposes of tetracycline antibiotic in water environment.
CN201610302347.0A 2016-05-09 2016-05-09 Preparation method of sodium alginate-graphene oxide macroscopic sphere composite material Pending CN105797685A (en)

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CN106633108A (en) * 2016-11-23 2017-05-10 辽宁石油化工大学 Preparation method of aminated graphene-sodium alginate composite gel ball
CN106853296A (en) * 2016-12-30 2017-06-16 福建农林大学 A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof
CN107583624A (en) * 2017-10-31 2018-01-16 南京林业大学 A kind of graphene oxide/sodium alginate composite microsphere and its preparation method and application
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CN113004570A (en) * 2021-03-01 2021-06-22 中国人民解放军陆军军医大学 Preparation method of aerogel for radioactive wastewater treatment, product and application thereof
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