CN106311185A - Polyvinyl alcohol/amino silanized graphene oxide macroporous compound spheres as well as preparation method and application of compound spheres - Google Patents
Polyvinyl alcohol/amino silanized graphene oxide macroporous compound spheres as well as preparation method and application of compound spheres Download PDFInfo
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses polyvinyl alcohol/amino silanized graphene oxide macroporous compound spheres as well as a preparation method and an application of the compound spheres. Firstly, graphite oxide is prepared with an improved Hummers method, graphene oxide is obtained through ultrasonic stripping and is silanized by 3-aminopropyltriethoxysilane, silanized graphene oxide is embedded in polyvinyl alcohol, and a target product is prepared and used for adsorbing heavy metal ions in a water body. Through silanization of graphene oxide, the water solubility of the product is reduced, and solid-liquid separation is easy to realize; introduced amino groups improve the adsorption capability of graphene oxide to pollutants, amino silanized graphene oxide is embedded in polyvinyl alcohol, the use amount of amino silanized graphene oxide is reduced, and the defect of difficulty in solid-liquid separation is further overcome; the macroporous compound spherical structure of the product has good quality transmission; besides, the mechanical strength of the material is improved due to introduction of polyvinyl alcohol, and separation after adsorption is facilitated.
Description
Technical field
The invention belongs to field of polymer composite material and field of environment engineering technology, be specifically related to a kind of for heavy metal
The preparation method of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls that ionic adsorption separates.
Background technology
Along with the development of the industry fields such as metallurgy, leather, weaving, chemical raw material and chemical product manufacturing, great Liang Chong
Metal or waste water from dyestuff enter water body, the health of the serious threat mankind.At present, in the various techniques to sewage disposal, due to
Absorption method has the advantages such as with low cost, simple to operate, sorbent material wide material sources, advantages of good adsorption effect it is considered to be to containing
One of most effectual way that metal ion or waste water from dyestuff purify.
Graphene oxide is big, rich in advantages such as functional groups, in heavy metal ion remaval owing to having specific surface area
Show preferable removal capacity, but individually graphene oxide water solublity is preferable, exist after processing stain disease and be difficult to point
From and cause secondary pollution, greatly limit its promote with application.
By Aminosilylation, graphene oxide is modified, not only can realize the functionalization of graphene oxide, and
And its dispersibility and stability can be improved, increasing it to water pollutant removal ability simultaneously so that it is water solublity reduces, favorably
Separation after absorption.But due to Aminosilylation graphene oxide still in powder, still deposit in actual application
Low in mechanical strength, quality is easily lost, adsorb after be difficult to the problems such as separation and recovery, limit its application in actual production.
Summary of the invention
The problems referred to above existed for prior art, the invention provides a kind of gathering for heavy metal ion adsorbed separation
Vinyl alcohol/Aminosilylation graphene oxide macropore composite balls and preparation method thereof.
The technical solution used in the present invention is specific as follows:
A kind of preparation of the polyvinyl alcohol for heavy metal ion adsorbed separation/Aminosilylation graphene oxide macropore composite balls
Method, comprises the following steps:
(1) under room temperature, being scattered in deionized water by graphite oxide, magnetic agitation is uniform, forms graphene oxide colloidal suspension
Liquid；By ultrasonic for the graphene oxide soliquid 2 ~ 6h that dissociates, form the graphene oxide of 0.5 uniform and stable ~ 10.0mg/mL
Dispersion liquid；
(2), under stirring condition, 3-aminopropyl triethoxysilane is added in deionized water, 3-aminopropyl triethoxysilane and
The volume ratio of deionized water is 1:10 ~ 100, is gradually heating to 40 ~ 80 DEG C, reacts 4 ~ 8 h；Then by graphene oxide dispersion
Add reaction system, stir 4 ~ 24 h under ice bath, obtain flocky precipitate；After reaction terminates, wad a quilt with cotton with deionized water cyclic washing
Shape precipitate, centrifugation, solid is placed in vacuum drying oven and is dried, obtain Aminosilylation graphene oxide solid；
(3) it is that the polyvinyl alcohol of 10:1 ~ 5:10 ~ 20, sodium alginate and calcium carbonate are sequentially added into and fill deionized water by mass ratio
Reaction vessel in, stir at 90 ~ 95 DEG C and be completely dissolved to solid, obtain mixed liquor A；Then in mixed liquor A, add ammonia
Base silane graphene oxide, stirs 4 ~ 12h at 75 ~ 95 DEG C, obtains polyvinyl alcohol/Aminosilylation graphene oxide and coagulates
Glue, wherein, Aminosilylation graphene oxide: the mass ratio of polyvinyl alcohol is 1:4 ~ 30；With syringe by Aminosilylation oxygen
Functionalized graphene/polyvinyl alcohol gel instillation calcium chloride: the calcium chloride of saturated boric acid solution=5g:100mL-saturated boric acid solution
In, moment forms black ball, and continue to harden 12h ~ 48h in calcium chloride-saturated boric acid solution；Then spherical product is shifted
To deionized water, drip hydrochloric acid solution, be slowly stirred, form the composite balls with cavernous structure；Will be multiple with a large amount of distilled water
Close ball cyclic washing the most neutral, i.e. obtain polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls.
Graphite oxide in described step (1) is prepared by following preparation method:
(1) under condition of ice bath, being added by graphite powder in concentrated sulphuric acid-phosphoric acid mixed liquor that volume ratio is 9:1, wherein, every 100mL is dense
Sulfuric-phosphoric mixed liquor adds 0.5 ~ 4.0g graphite powder, stirs；
(2) by graphite powder: the mass ratio of potassium permanganate=1:3 ~ 6 is slowly added to potassium permanganate powder in reaction system, and controls
Temperature≤20 DEG C of reaction system, are slowly stirred and make potassium permanganate fully dissolve；
(3) reaction system is placed in isothermal reaction 6 ~ 12 hours in the water-bath of 35 ~ 55 DEG C；
(4) reaction system is cooled to room temperature, by reactant liquor after terminating by reaction: the volume ratio of frozen water=1:1 ~ 2 is by reactant liquor successively
Be transferred to frozen water and 30% hydrogen peroxide in, obtain bright yellow solution, i.e. graphite oxide solution；
(5) filter out solid product, then with 10% hydrochloric acid solution cyclic washing solid product, with the barium chloride solution of 10wt%
Detection, till cleaning mixture is without white precipitate；Again with deionized water cyclic washing solid product to cleaning mixture neutrality；
(6) solid product of gained is vacuum dried at 50 DEG C, obtains the graphite oxide being dried.
In described step (3), polyvinyl alcohol mass fraction in mixed liquor A is 3% ~ 6%.
A kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls, by above-mentioned polyvinyl alcohol/amino silane
The preparation method changing graphene oxide macropore composite balls prepares.
The application in processing heavy metal containing sewage of the above-mentioned polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls.
Relative to prior art, the invention have the advantages that and beneficial effect:
(1) present invention utilizes silane coupler 3-aminopropyl triethoxysilane that graphene oxide is carried out silanization so that it is water
Dissolubility reduces, it is easy to solid-liquid separation；Meanwhile, containing substantial amounts of amino and epoxide in 3-aminopropyl triethoxysilane, it is achieved that
The functionalization of graphene oxide, the amino group of introducing can improve oxygen with the heavy metal ion generation complexing in water
The functionalized graphene absorbability to pollutant.
(2) present invention is by being embedded in Aminosilylation graphene oxide in polyvinyl alcohol, not only reduces amino silicone
The usage amount of alkanisation graphene oxide, reduces running cost, and solves its problem being difficult to solid-liquid separation further.System
Standby product is macropore composite spherical structure, has good mass transport；The introducing of polyvinyl alcohol simultaneously improves material
Mechanical strength, it is easy to the separation after absorption, improve its practical value.
Accompanying drawing explanation
Fig. 1 is polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls Adsorption of Cu2+Adsorption isothermal curve.
Fig. 2 is polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls absorption Pb2+Adsorption isothermal curve.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1: the Hummers method of improvement prepares graphite oxide
The graphite powder addition of 6g is filled in the three-neck flask of the concentrated sulphuric acid of 720mL and the phosphoric acid solution of 80mL, at ice-water bath bar
Stir under part；Continuously stirred, it is slowly added to 36g potassium permanganate powder (controlling temperature of reaction system≤20 DEG C)；To be added
After, reaction system is put in thermostat water bath, water bath with thermostatic control 12 hours under conditions of 50 DEG C；Question response terminates cooling
To room temperature, first mixed liquor is poured in the frozen water of 1000mL, transfer to subsequently, in the hydrogen peroxide of a certain amount of 30%, obtain
Bright yellow solution, filters product；With the above-mentioned solid product of hydrochloric acid solution cyclic washing of 10%, use 10wt% chlorination
Barium solution detection filtrate, till without white precipitate；Being neutrality with deionized water cyclic washing to cleaning mixture again；By institute
The solid product obtained is placed in 50 DEG C of vacuum drying, obtains the graphite oxide being dried.
Embodiment 2
(1) graphite oxide prepared by 200mg embodiment 1 is scattered in 100mL deionized water, magnetic stirrer over night, forms oxygen
Functionalized graphene soliquid；Then supersound process 6h in Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, is formed uniform and stable
Dispersion liquid, i.e. obtains the graphene oxide dispersion of 2mg/mL；
(2), under stirring condition, 10mL 3-aminopropyl triethoxysilane is added in the deionized water of 500mL, be gradually heating to
48 DEG C, react 6h；Then graphene oxide dispersion prepared by step (1) is joined stirring reaction in above-mentioned reaction system
12h, obtains flocky precipitate；With deionized water cyclic washing flocky precipitate, centrifugation, then solid is placed in vacuum and does
Dry case is dried, i.e. obtains Aminosilylation graphene oxide；
(3) 15.0g polyvinyl alcohol, 3.6g sodium alginate and 20.0g calcium carbonate are sequentially added into fill the burning of 300mL deionized water
In Bei, stirring 2h at 90 DEG C, solid is completely dissolved, and obtains mixed liquor A；Take Aminosilylation oxygen prepared by 2.5g step (2)
Functionalized graphene adds in mixed liquor A, continues stirring 4h, obtain polyvinyl alcohol/Aminosilylation graphene oxide gel at 95 DEG C；
With syringe, polyvinyl alcohol/Aminosilylation graphene oxide gel is instilled 5%(W/V after stirring) calcium chloride-saturated boron
In acid solution, it can be seen that black ball moment is formed, and in calcium chloride-saturated boric acid solution, continue hardening 48h；Then turn
Move in 1000mL distilled water, the hydrochloric acid solution of dropping 1mol/L, it is slowly stirred, makes complex spherical become cavernous structure；Finally, use
A large amount of distilled water cyclic washings, to neutral, i.e. obtain end product polyvinyl alcohol/Aminosilylation graphene oxide macropore and are combined
Ball.
Embodiment 3
(1) graphite oxide prepared by 1000mg embodiment 1 is dispersed in 100mL deionized water, magnetic stirrer over night, forms oxygen
Functionalized graphene soliquid；Then supersound process 4h in Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, is formed uniform and stable
Dispersion liquid, i.e. obtains the graphene oxide dispersion of 10mg/mL；
(2), under stirring condition, 10mL 3-aminopropyl triethoxysilane is added in the deionized water of 1000mL, gradually heat up
To 80 DEG C, react 4h；Then graphene oxide dispersion prepared by step (1) is joined stirring reaction in above-mentioned reaction system
24h, obtains flocky precipitate；With deionized water cyclic washing flocky precipitate, centrifugation, then solid is placed in vacuum and does
Dry case is dried, i.e. obtains Aminosilylation graphene oxide；
(3) 15.0g polyvinyl alcohol, 1.5g sodium alginate and 30.0g calcium carbonate are sequentially added into fill the burning of 300mL deionized water
In Bei, stirring 2h at 93 DEG C, solid is completely dissolved, and obtains mixed liquor A；Take Aminosilylation oxygen prepared by 3.75g step (2)
Functionalized graphene adds in mixed liquor A, continues stirring 12h at 85 DEG C, obtains polyvinyl alcohol/Aminosilylation graphene oxide and coagulates
Glue；With syringe, polyvinyl alcohol/Aminosilylation graphene oxide gel is instilled 5%(W/V after stirring) calcium chloride-full
With in boric acid solution, it can be seen that black ball moment formed, and in calcium chloride-saturated boric acid solution continue hardening 12h；So
After be transferred in 1000mL distilled water, dropping 1mol/L hydrochloric acid solution, be slowly stirred, make complex spherical become cavernous structure；?
After, with a large amount of distilled water cyclic washings to neutral, i.e. obtain end product polyvinyl alcohol/Aminosilylation graphene oxide macropore
Composite balls.
Embodiment 4
(1) graphite oxide prepared by 50mg embodiment 1 is dispersed in 100mL deionized water, magnetic stirrer over night, forms oxidation
Graphene soliquid；Then supersound process 2h in Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, forms uniform and stable dividing
Dissipate liquid, i.e. obtain the graphene oxide dispersion of 0.5mg/mL；
(2), under stirring condition, 10mL 3-aminopropyl triethoxysilane is added in the deionized water of 100mL, be gradually heating to
40 DEG C, react 8h；Then graphene oxide dispersion prepared by step (1) is joined stirring reaction in above-mentioned reaction system
4h, obtains flocky precipitate；With deionized water cyclic washing flocky precipitate, centrifugation, then solid is placed in vacuum and does
Dry case is dried, i.e. obtains Aminosilylation graphene oxide；
(3) 15.0g polyvinyl alcohol, 7.5g sodium alginate and 15.0g calcium carbonate are sequentially added into fill the burning of 300mL deionized water
In Bei, stirring 2h at 95 DEG C, solid is completely dissolved, and obtains mixed liquor A；Take Aminosilylation oxygen prepared by 0.5g step (2)
Functionalized graphene adds in mixed liquor A, continues stirring 24h at 75 DEG C, obtains polyvinyl alcohol/Aminosilylation graphene oxide and coagulates
Glue；With syringe, polyvinyl alcohol/Aminosilylation graphene oxide gel is instilled 5%(W/V after stirring) calcium chloride-full
With in boric acid solution, it can be seen that black ball moment formed, and in calcium chloride-saturated boric acid solution continue hardening 30h；So
After be transferred in 1000mL distilled water, dropping 1mol/L hydrochloric acid solution, be slowly stirred, make complex spherical become cavernous structure；?
After, with a large amount of distilled water cyclic washings to neutral, i.e. obtain end product polyvinyl alcohol/Aminosilylation graphene oxide macropore
Composite balls.
The present invention be applied to water process example:
(1) adsorbent prepared of batch type static state adsorption experiment method validation the inventive method and absorption property thereof are used.Concrete behaviour
As: measure the Cu of certain initial concentration that 100mL prepares in advance2+、Pb2+Solution, in 200mL conical flask, uses 0.1mol/
The HCl/NaOH solution of L adjusts pH to be 6.0；Using the product of embodiment 2 as removing Cu2+、Pb2+Adsorbent, according to necessarily adding
Amount adds；25 DEG C, rotating speed 150rpm, vibrates in constant temperature air bath agitator；After 24h adsorption equilibrium, take supernatant 0.22 μ
After m filtering with microporous membrane, carry out water sample analysis with spectrophotography.Result is as depicted in figs. 1 and 2.
From Fig. 1 and Fig. 2, Langmuir, Freundlich Isothermal Model can preferably describe product to Cu2+Or Pb2+Suction
Attached behavior, and calculated to Cu by model2+、Pb2+Maximum saturation adsorbance be respectively as follows: 96.22mg/g and
278.17mg/g, close to experiment value, the adsorbent that thus prepared by the explanation present invention is to Cu2+、Pb2+There is preferable removal effect.
(2) resolve regeneration tests: using the hydrochloric acid of 0.2mol/L as parsing agent, the adsorbent after pollutant will be adsorbed and put into
In desorbed solution, it is placed in 30 DEG C, rotating speed 150rpm, constant temperature oscillation 24h, test according to Staticadsorption experiment condition experiment method afterwards
Card, result shows: polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls is after 5 absorption-parsing circulation, right
Cu2+、Pb2+Adsorption rate still can reach more than the 75% of initial adsorption amount, and polyvinyl alcohol/Aminosilylation graphite oxide
Alkene macropore composite balls remains in that good spherical, is not damaged.This illustrates polyvinyl alcohol/Aminosilylation graphite oxide
Alkene macropore composite balls has good stability, can remove the Cu in water cost-effectively2+、Pb2+, possess potential practicality
It is worth.
Finally illustrating, above example is only in order to illustrate technical scheme and unrestricted, although with reference to relatively
The present invention has been described in detail by good embodiment, it will be understood by those within the art that, can be to the present invention's
Technical scheme is modified or equivalent, and without deviating from objective and the scope of technical solution of the present invention, it all should be contained
In the middle of scope of the presently claimed invention.
Claims (5)
1. the system for the polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls of heavy metal ion adsorbed separation
Preparation Method, it is characterised in that comprise the following steps:
(1) under room temperature, being scattered in deionized water by graphite oxide, magnetic agitation is uniform, forms graphene oxide colloidal suspension
Liquid；By ultrasonic for the graphene oxide soliquid 2 ~ 6h that dissociates, form the graphene oxide of 0.5 uniform and stable ~ 10.0mg/mL
Dispersion liquid；
(2), under stirring condition, 3-aminopropyl triethoxysilane is added in deionized water, 3-aminopropyl triethoxysilane and
The volume ratio of deionized water is 1:10 ~ 100, is gradually heating to 40 ~ 80 DEG C, reacts 4 ~ 8 h；Then by graphene oxide dispersion
Add reaction system, stir 4 ~ 24 h under ice bath, obtain flocky precipitate；After reaction terminates, wad a quilt with cotton with deionized water cyclic washing
Shape precipitate, centrifugation, solid is placed in vacuum drying oven and is dried, obtain Aminosilylation graphene oxide solid；
(3) it is that the polyvinyl alcohol of 10:1 ~ 5:10 ~ 20, sodium alginate and calcium carbonate are sequentially added into and fill deionized water by mass ratio
Reaction vessel in, stir at 90 ~ 95 DEG C and be completely dissolved to solid, obtain mixed liquor A；Then in mixed liquor A, add ammonia
Base silane graphene oxide, stirs 4 ~ 12h at 75 ~ 95 DEG C, obtains polyvinyl alcohol/Aminosilylation graphene oxide and coagulates
Glue, wherein, Aminosilylation graphene oxide: the mass ratio of polyvinyl alcohol is 1:4 ~ 30；With syringe by Aminosilylation oxygen
Functionalized graphene/polyvinyl alcohol gel instillation calcium chloride: the calcium chloride of saturated boric acid solution=5g:100mL-saturated boric acid solution
In, moment forms black ball, and continue to harden 12h ~ 48h in calcium chloride-saturated boric acid solution；Then spherical product is shifted
To deionized water, drip hydrochloric acid solution, be slowly stirred, form the composite balls with cavernous structure；Will be multiple with a large amount of distilled water
Close ball cyclic washing the most neutral, i.e. obtain polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls.
The preparation method of polyvinyl alcohol the most according to claim 1/Aminosilylation graphene oxide macropore composite balls, its
Being characterised by, the graphite oxide in described step (1) is prepared by following preparation method:
(1) under condition of ice bath, being added by graphite powder in concentrated sulphuric acid-phosphoric acid mixed liquor that volume ratio is 9:1, wherein, every 100mL is dense
Sulfuric-phosphoric mixed liquor adds 0.5 ~ 4.0g graphite powder, stirs；
(2) by graphite powder: the mass ratio of potassium permanganate=1:3 ~ 6 is slowly added to potassium permanganate powder in reaction system, and controls
Temperature≤20 DEG C of reaction system, are slowly stirred and make potassium permanganate fully dissolve；
(3) reaction system is placed in isothermal reaction 6 ~ 12 hours in the water-bath of 35 ~ 55 DEG C；
(4) reaction system is cooled to room temperature, by reactant liquor after terminating by reaction: the volume ratio of frozen water=1:1 ~ 2 is by reactant liquor successively
Be transferred to frozen water and 30% hydrogen peroxide in, obtain bright yellow solution, i.e. graphite oxide solution；
(5) filter out solid product, then with 10% hydrochloric acid solution cyclic washing solid product, with the barium chloride solution of 10wt%
Detection, till cleaning mixture is without white precipitate；Again with deionized water cyclic washing solid product to cleaning mixture neutrality；
(6) solid product of gained is vacuum dried at 50 DEG C, obtains the graphite oxide being dried.
The preparation method of polyvinyl alcohol the most according to claim 1/Aminosilylation graphene oxide macropore composite balls, its
It is characterised by: in described step (3), polyvinyl alcohol mass fraction in mixed liquor A is 3% ~ 6%.
4. polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls, it is characterised in that: by claim 1-3
The preparation method of the polyvinyl alcohol described in any one/Aminosilylation graphene oxide macropore composite balls prepares.
5. the polyvinyl alcohol described in claim 4/Aminosilylation graphene oxide macropore composite balls is processing heavy metal containing sewage
In application.
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| CN201610772033.7A CN106311185B (en) | 2016-08-31 | 2016-08-31 | A kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls and its preparation method and application |
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| CN106311185B CN106311185B (en) | 2019-01-18 |
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| CN113526495A (en) * | 2021-08-16 | 2021-10-22 | 内蒙古元瓷新材料科技有限公司 | Preparation method of magnetic graphene film with high electromagnetic wave absorption efficiency |
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| CN106902748A (en) * | 2017-03-29 | 2017-06-30 | 青岛辰达生物科技有限公司 | The preparation method and sewage-treating agent of a kind of adsorbent for heavy metal |
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| CN110893338A (en) * | 2019-08-26 | 2020-03-20 | 河海大学 | Preparation method of polymer nano composite gel |
| CN112341579A (en) * | 2020-11-26 | 2021-02-09 | 蚌埠市华东生物科技有限公司 | Adsorption resin for separating and purifying stevioside and application thereof |
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| CN112427026A (en) * | 2020-12-02 | 2021-03-02 | 邱芳璟 | Preparation method of polyvinyl alcohol functionalized carbon nanotube composite ball |
| CN113526495A (en) * | 2021-08-16 | 2021-10-22 | 内蒙古元瓷新材料科技有限公司 | Preparation method of magnetic graphene film with high electromagnetic wave absorption efficiency |
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