CN106179277A - Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application - Google Patents
Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application Download PDFInfo
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- CN106179277A CN106179277A CN201610772031.8A CN201610772031A CN106179277A CN 106179277 A CN106179277 A CN 106179277A CN 201610772031 A CN201610772031 A CN 201610772031A CN 106179277 A CN106179277 A CN 106179277A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses the preparation method of a kind of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent.Graphite oxide is prepared initially with the Hummers method improved, graphene oxide is obtained by ultrasonic stripping, sulfhydrylation graphene oxide is prepared with 4 aminothiophenol covalent modifications, sulfhydrylation graphene oxide is embedded in polyvinyl alcohol, prepare a kind of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, use it for adsorbed water body heavy metal ion.The introducing of sulfydryl of the present invention, reduces water solublity, it is easy to solid-liquid separation, and improves the product absorbability to pollutant；By sulfhydrylation graphene oxide is embedded in polyvinyl alcohol, not only reduces the usage amount of sulfhydryl oxidase Graphene, and solve its shortcoming being difficult to solid-liquid separation further；The macropore composite spherical structure of product, has good mass transport, and polyvinyl alcohol also improves the mechanical strength of material, it is easy to the separation after absorption, improve its practical value.
Description
Technical field
The invention belongs to preparation and the field of environment engineering technology of polymer composite, be specifically related to a kind of sulfhydrylation oxygen
Functionalized graphene/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application.
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.Generally, in water technology, often utilization has higher
The adsorbent of specific surface area removes the pollutant such as the heavy metal in water and dyestuff.
Graphene oxide specific surface area is high, rich in characteristics such as functional groups, electrostatic or chemisorbed etc. can not only be passed through
Effect combine with water pollutant, and rich in functional group make it have good hydrophilic and dispersibility and with gather
The compatibility of compound so that it has wide application potential.But individually graphene oxide water solublity is preferable, actual application
During absorption after be difficult to the problems such as separation and recovery, limit its application in actual production.Contain on polyvinyl alcohol molecule chain
There are a large amount of small size, highly polar hydroxyl, intermolecular formation hydrogen bond, are easily cross-linked to form macromolecular network structure, and have low
The features such as water solublity, bioaffinity, good mechanical strength and chemical stability that valency is nontoxic, good, are widely used in
The fields such as gel rubber material science and biomedical material science.At present, graphene oxide/polyvinyl alcohol is combined by the whole world
Material has carried out widely studied.
According to Coordinative Chemistry theoretical knowledge, the adsorbent agent heavy metal ion containing N, O and S has excellent absorption
Performance.Because heavy metal ion typically belongs to soft acid or middle acid, organic sulfur compound and amine then belong to soft base or middle alkali,
According to hsab theory, both is easily combined into stable complex.During coagulant trap heavy metals, no matter
Heavy metal coagulant is ion-type or nonionic, and really play trapping effect is coordinating group, and wherein determines coagulant
Bonded atom in the mainly coordinating group of Chelating Properties, it mainly determines with whether combined material has an effect, and
Selective action and the size of active force.The impact on Stability of Chelate of the heavy metal chelant bonded atom, the most mainly key
Closing the electronegativity of atom in action, the bonded atom that heavy metal is little with electronegativity can form the coordination that covalency is more significant
Key, i.e. forms more stable chelate.Heavy metal is minimum with the electronegativity difference of sulphur atom, say, that it is formed with sulphur atom
Stability of Chelate the highest, thus first consideration sulphur atom is as bonded atom, introduces strong coordinating group and makes a removal huge sum of money
Belong to more efficient.
By sulfhydrylation, graphene oxide is modified, not only can realize the functionalization of graphene oxide, Er Qieke
Improve its dispersibility and stability, increasing it to water pollutant removal ability simultaneously so that it is water solublity reduces, be conducive to inhaling
Attached separation.
Summary of the invention
The problems referred to above existed for prior art, it is an object of the invention to provide the sulfhydrylation of a kind of high efficiency, low cost
Graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application.
For realizing goal of the invention, the technical solution used in the present invention is specific as follows:
The preparation method of a kind of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, 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, 4-aminothiophenol is added in hydrochloric acid solution, is gradually heating to 35 ~ 55 DEG C, obtains 4-aminobenzene
Thiophenol solution；Sodium nitrite is dissolved in deionized water, obtains sodium nitrite solution；Wherein, 4-aminothiophenol: nitrous acid
Sodium: the mol ratio of hydrochloric acid is 1:1:1.0 ~ 1.5；Under the conditions of ice-water bath, while stirring sodium nitrite solution is slowly dropped to 4-
In aminothiophenol solution；Then graphene oxide dispersion is added reaction system, under ice bath, stirs 8 ~ 24h, wherein, 4-ammonia
Base phenylmercaptan.: the mass ratio of graphene oxide is 1 ~ 5:1；After reaction terminates, by reactant liquor respectively with acetone, dehydrated alcohol with go
Ionized water washs for several times；Gained solid is placed in 50 DEG C of vacuum drying ovens and is dried, i.e. obtain sulfhydrylation graphene oxide；
(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 mercapto
Base graphene oxide, stirs 4 ~ 12h at 75 ~ 95 DEG C, obtains sulfhydrylation graphene oxide/polyvinyl alcohol gel, wherein, mercapto
Base graphene oxide: the mass ratio of polyvinyl alcohol is 1:4 ~ 30；With syringe, sulfhydrylation graphene oxide/polyvinyl alcohol is coagulated
Glue instills calcium chloride: in the calcium chloride of saturated boric acid solution=5g:100mL-saturated boric acid solution, and moment forms black ball,
Continue to harden 12h ~ 48h in calcium chloride-saturated boric acid solution；Then spherical product is transferred in deionized water, drips salt
Acid solution, is slowly stirred, and forms the composite balls with cavernous structure；With a large amount of distilled water by composite balls cyclic washing to neutral,
I.e. obtain sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent.
(1), under condition of ice bath, graphite powder is added in concentrated sulphuric acid-phosphoric acid mixed liquor that volume ratio is 9:1, wherein, often
100mL concentrated sulphuric acid-phosphoric acid 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 (2), sodium nitrite solution volume is 1.2 ~ 1.5 times of 4-aminothiophenol liquor capacity.
In described step (3), polyvinyl alcohol mass fraction in mixed liquor A is 3% ~ 6%.
A kind of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, by above-mentioned sulfhydrylation graphite oxide
The preparation method of alkene/polyvinyl alcohol macropore composite balls adsorbent prepares.
Above-mentioned sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent answering in processing heavy metal containing sewage
With.
Relative to prior art, the invention have the advantages that and beneficial effect:
(1) covalent modification that is prepared by of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent of the present invention aoxidizes
Graphene so that it is water solublity reduces, it is easy to solid-liquid separation；Meanwhile, 4-aminothiophenol has the N of electron rich, S atom and mercapto
Base, the characteristic of amino difunctional, by aromatic mercaptans group group covalence graft in the sp of the electron rich of graphene oxide2Carbon bone
On frame, it is achieved that the functionalization of graphene oxide, the mercapto groups of introducing can with heavy metal ion generation complexing in water,
Improve the graphene oxide absorbability to pollutant.
(2) it is difficult to separate and recover after the adsorbent of powder, although after passing through thiolated modified graphene oxide, mercapto
Base can be with pollutant complexation so that it is water solublity reduces, and separates after being conducive to absorption, but macroscopically its appearance features or powder
Shape, is scattered in after absorption in solution, is unfavorable for recovery etc.；The present invention is by being embedded in polyvinyl alcohol by sulfhydrylation graphene oxide
In, forming composite balls, be different from powdered form and easily disperse, composite balls volume, quality are big, it is easy to separate after absorption, simultaneously because bag
Bury sulfhydrylation graphene oxide, keep again higher absorption property.
(3) present invention not only reduces the usage amount of sulfhydryl oxidase Graphene, reduces running cost, and solves further
Determine its shortcoming being difficult to solid-liquid separation；The product of preparation is macropore composite spherical structure, has good mass transport；With
Time polyvinyl alcohol introducing improve the mechanical strength of material, it is easy to the separation after absorption, improve its practical value.
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 of 6g is joined in the three-neck flask of the phosphoric acid solution filling the concentrated sulphuric acid of 720mL and 80mL, at ice-water bath
Under the conditions of stir；Continuously stirred, it is slowly added to 36g potassium permanganate powder (controlling temperature of reaction system≤20 DEG C)；To be added
After entering, reaction system is put in thermostat water bath, water bath with thermostatic control 12 hours under conditions of 50 DEG C；Question response terminates cold
But to after room temperature, reactant liquor is poured in 1000mL frozen water, transfer to subsequently, in the hydrogen peroxide of a certain amount of 30%, obtain bright
Yellow solution, filters product；By the above-mentioned filtration product of hydrochloric acid solution cyclic washing of 10%, with 10%(W/V) chlorine
Change the detection of barium solution, till without white precipitate, then with deionized water cyclic washing to neutrality；The product of gained is put
In 50 DEG C of vacuum drying, prepare the graphite oxide being dried.
Embodiment 2
(1) graphite oxide prepared by 500mg embodiment 1 is scattered in 100mL deionized water, magnetic stirrer over night, forms oxygen
Functionalized graphene soliquid；Then supersound process 4h under 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 5mg/mL.
(2), under stirring condition, the 4-aminothiophenol of 12mmol is joined in the hydrochloric acid solution of 15mL1mol/L, gradually
It is warming up to 53 DEG C, obtains 4-aminothiophenol solution；Then, the sodium nitrite of 12mmol is dissolved in 20mL deionized water,
Obtain sodium nitrite solution；While stirring sodium nitrite solution is slowly added dropwise to above-mentioned 4-aminobenzene sulfur under the conditions of ice-water bath
In phenol solution；Finally graphene oxide dispersion is joined in above-mentioned reaction system, under the conditions of ice-water bath, stir 24 h.Will
After the mixed liquor arrived uses acetone, dehydrated alcohol and deionized water wash for several times respectively, the vacuum that gained solid is placed in 50 DEG C is done
Dry case is dried, i.e. obtains sulfhydrylation graphite oxide ene product.
(3) 15.0g polyvinyl alcohol, 3.6g sodium alginate and 20.0 calcium carbonate are joined fill 300mL deionized water
In beaker, at 90 DEG C, stirring 2h is until solid is completely dissolved, and obtains mixed liquor A；It is subsequently adding preparation in 2.5g step (2)
Sulfhydrylation graphene oxide, at 90 DEG C continue stirring 6h, obtain sulfhydrylation graphene oxide/polyvinyl alcohol gel；Stir
With syringe, sulfhydrylation graphene oxide/polyvinyl alcohol gel is instilled 5%(W/V after Biing) in calcium chloride-saturated boric acid solution,
It can be seen that black ball moment is formed, and in calcium chloride-saturated boric acid solution, continue hardening 48h；Then by spherical product
It is transferred in 1000mL distilled water, the hydrochloric acid solution of dropping 1mol/L, is slowly stirred, makes complex spherical become cavernous structure；Finally,
It is neutrality by a large amount of distilled water cyclic washing composite balls to cleaning mixture, i.e. obtains end product sulfhydrylation graphene oxide/poly-second
Enol macropore composite balls adsorbent.
Embodiment 3
(1) graphite oxide prepared by 1000mg embodiment 1 is scattered in 100mL deionized water, magnetic stirrer over night, forms oxygen
Functionalized graphene soliquid；Then supersound process 6h under 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 agitation, the 4-aminothiophenol of 12mmol is added in the hydrochloric acid solution of 18mL1mol/L, gradually
It is warming up to 35 DEG C, obtains 4-aminothiophenol solution；Then, the sodium nitrite of 12mmol is dissolved in 20mL deionized water,
Obtain sodium nitrite solution；While stirring sodium nitrite solution is slowly added dropwise to above-mentioned 4-aminobenzene sulfur under the conditions of ice-water bath
In phenol solution；Finally graphene oxide dispersion is joined in above-mentioned reaction system, under the conditions of ice-water bath, stir 8 h.Will
After the mixed liquor arrived uses acetone, dehydrated alcohol and deionized water wash for several times respectively, the vacuum that gained solid is placed in 50 DEG C is done
Dry case is dried, i.e. obtains sulfhydrylation graphite oxide ene product.
(3) 15.0g polyvinyl alcohol, 7.5g sodium alginate and 30.0 calcium carbonate are joined fill 300mL deionized water
In beaker, at 92 DEG C, stirring 2h is until solid is completely dissolved, and obtains mixed liquor A；It is subsequently adding preparation in 3.75g step (2)
Sulfhydrylation graphene oxide, at 95 DEG C continue stirring 4h, obtain sulfhydrylation graphene oxide/polyvinyl alcohol gel；Stir
With syringe, sulfhydrylation graphene oxide/polyvinyl alcohol gel is instilled 5%(W/V after Biing) in calcium chloride-saturated boric acid solution,
It can be seen that black ball moment is formed, and in calcium chloride-saturated boric acid solution, continue hardening 30h；Then by spherical product
It is transferred in 1000mL distilled water, the hydrochloric acid solution of dropping 1mol/L, is slowly stirred, makes complex spherical become cavernous structure；Finally,
With a large amount of distilled water cyclic washings to neutral, i.e. obtain end product sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls
Adsorbent.
Embodiment 4
(1) graphite oxide prepared by 50mg embodiment 1 is scattered in 100mL deionized water, magnetic stirrer over night, forms oxidation
Graphene soliquid；Then supersound process 2h under 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 agitation, the 4-aminothiophenol of 12mmol is joined in the hydrochloric acid solution of 12mL1mol/L, by
Gradually it is warming up to 40 DEG C, obtains 4-aminothiophenol solution；Then, the sodium nitrite of 12mmol is dissolved in 20mL deionized water
In, obtain sodium nitrite solution；While stirring sodium nitrite solution is slowly added dropwise to above-mentioned 4-amino under the conditions of ice-water bath
In phenylmercaptan. solution；Finally graphene oxide dispersion is joined in above-mentioned reaction system, under the conditions of ice-water bath, stir 12h.
By the mixed liquor that obtains respectively with acetone, dehydrated alcohol and deionized water wash for several times after, gained solid is placed in 50 DEG C true
Empty drying baker is dried, i.e. obtains sulfhydrylation graphite oxide ene product.
(3) 15.0g polyvinyl alcohol, 1.5g sodium alginate and 15.0 calcium carbonate are joined fill 300mL deionized water
In beaker, at 95 DEG C, stirring 2h is until solid is completely dissolved, and obtains mixed liquor A；It is subsequently adding preparation in 0.5g step (2)
Sulfhydrylation graphene oxide, at 75 DEG C continue stirring 12h, obtain sulfhydrylation graphene oxide/polyvinyl alcohol gel；Stir
With syringe, sulfhydrylation graphene oxide/polyvinyl alcohol gel is instilled 5%(W/V after Biing) in calcium chloride-saturated boric acid solution,
It can be seen that black ball moment is formed, and in calcium chloride-saturated boric acid solution, continue hardening 12h；Then by spherical product
It is transferred in 1000mL distilled water, the hydrochloric acid solution of dropping 1mol/L, is slowly stirred, makes complex spherical become cavernous structure；Finally,
With a large amount of distilled water cyclic washings to neutral, i.e. obtain end product sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls
Adsorbent.
Static batch adsorption experiment, dynamic column adsorption experiment and parsing regeneration tests is used to verify suction prepared by the inventive method
Attached dose and absorption property.
(1) Staticadsorption experiment.Concrete operations are: measure the Cu of the 50mg/L that 100mL prepares in advance2+Or 150mg/L
Pb2+Solution, in 200mL conical flask, adjusts pH to be 6.0 with the HCl/NaOH of 0.1mol/L；Using embodiment 2 product as removal
Cu2+、Pb2+Adsorbent, investigate the different dosage impact on removal effect.25 DEG C, rotating speed 150rpm, constant temperature air bath shakes
Swing in device and vibrate；After balance upon adsorption, take supernatant with after 0.22 μm filtering with microporous membrane, carry out water sample with spectrophotography
Analyze.Result is as shown in table 1:
Table 1
As shown in Table 1, the sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent that prepared by the inventive method is to Cu2 +、Pb2+There is preferable removal effect.
(2) dynamic column adsorption experiment.Adsorption column length 20cm, internal diameter 3cm.Adsorbent is filled in adsorption column, by
Know the Cu of solution concentration2+Or Pb2+Solution by adsorption column, collects water outlet with certain flow rate at regular intervals, measures and wherein weighs
The concentration of metal ion.Result shows: in the case of flow velocity is 2.0mL/min, and sulfhydrylation graphene oxide/polyvinyl alcohol is big
Hole composite balls adsorbent can adsorb the Cu of 80mg/L before it completely penetrates through completely2+Pb with 100mg/L2+The volume of solution
It is respectively 1960 and 2480mL, shows good post absorption feature, under relatively low water inlet concentration of metal ions and water inlet flow velocity
Adsorption rate is higher.
(3) 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: sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent after 3 absorption-parsing circulate,
The clearance of heavy metal declines very fast, but it is mesh-structured more closely knit to be as composite balls, through 5 absorption-parsing circulation
After, to Cu2+、Pb2+Adsorption rate still can reach more than the 75% of initial adsorption amount, and composite balls remains in that good ball
Shape, is not damaged.This explanation sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent has good stablizing
Property, the Cu in water can be removed cost-effectively2+、Pb2+, possess potential practical value.
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 skill of the present invention
Art 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 at this
In the middle of the right of invention.
Claims (6)
1. the preparation method of a sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, it is characterised in that include
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, 4-aminothiophenol is added in hydrochloric acid solution, is gradually heating to 35 ~ 55 DEG C, obtains 4-aminobenzene
Thiophenol solution；Sodium nitrite is dissolved in deionized water, obtains sodium nitrite solution；Wherein, 4-aminothiophenol: nitrous acid
Sodium: the mol ratio of hydrochloric acid is 1:1:1.0 ~ 1.5；Under the conditions of ice-water bath, while stirring sodium nitrite solution is slowly dropped to 4-
In aminothiophenol solution；Then graphene oxide dispersion is added reaction system, under ice bath, stirs 8 ~ 24h, wherein, 4-ammonia
Base phenylmercaptan.: the mass ratio of graphene oxide is 1 ~ 5:1；After reaction terminates, by reactant liquor respectively with acetone, dehydrated alcohol with go
Ionized water washs for several times；Gained solid is placed in 50 DEG C of vacuum drying ovens and is dried, i.e. obtain sulfhydrylation graphene oxide；
(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 mercapto
Base graphene oxide, stirs 4 ~ 12h at 75 ~ 95 DEG C, obtains sulfhydrylation graphene oxide/polyvinyl alcohol gel, wherein, mercapto
Base graphene oxide: the mass ratio of polyvinyl alcohol is 1:4 ~ 30；With syringe, sulfhydrylation graphene oxide/polyvinyl alcohol is coagulated
Glue instills calcium chloride: in the calcium chloride of saturated boric acid solution=5g:100mL-saturated boric acid solution, and moment forms black ball,
Continue to harden 12h ~ 48h in calcium chloride-saturated boric acid solution；Then spherical product is transferred in deionized water, drips salt
Acid solution, is slowly stirred, and forms the composite balls with cavernous structure；With a large amount of distilled water by composite balls cyclic washing to neutral,
I.e. obtain sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent.
The preparation method of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent the most according to claim 1,
It is characterized in that: 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 sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent the most according to claim 1,
It is characterized in that: in described step (2), sodium nitrite solution volume is 1.2 ~ 1.5 times of 4-aminothiophenol liquor capacity.
The preparation method of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent the most according to claim 1,
It is characterized in that: in described step (3), polyvinyl alcohol mass fraction in mixed liquor A is 3% ~ 6%.
5. a sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, it is characterised in that: by claim 1-
The preparation method of the sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent described in 4 any one prepares.
6. the sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent described in claim 5 is heavy metal-polluted in process
Application in water.
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