CN106179277B - 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
- Publication number
- CN106179277B CN106179277B CN201610772031.8A CN201610772031A CN106179277B CN 106179277 B CN106179277 B CN 106179277B CN 201610772031 A CN201610772031 A CN 201610772031A CN 106179277 B CN106179277 B CN 106179277B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- polyvinyl alcohol
- solution
- sulfhydrylation
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
-
- 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
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation methods of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent.Graphite oxide is prepared using improved Hummers method first, graphene oxide is obtained by ultrasound removing, sulfhydrylation graphene oxide is prepared with 4- aminothiophenol covalent modification, sulfhydrylation graphene oxide is embedded in polyvinyl alcohol, a kind of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent is prepared, adsorbed water body heavy metal ion is used for.The introducing of sulfydryl of the present invention, reduces water solubility, is easy to be separated by solid-liquid separation, and improves product to the adsorption capacity of pollutant；By the way that sulfhydrylation graphene oxide to be embedded in polyvinyl alcohol, the usage amount of sulfhydryl oxidase graphene is not only reduced, and further solve it and be difficult to the shortcomings that being separated by solid-liquid separation；The macropore composite spherical structure of product has good mass transport, and polyvinyl alcohol also improves the mechanical strength of material, and the separation after being easy to adsorb improves its practical value.
Description
Technical field
The invention belongs to the preparation of polymer composite and field of environment engineering technology, and in particular to a kind of sulfhydrylation oxygen
Graphite alkene/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application.
Background technique
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 are discharged into water body, seriously threaten the health of the mankind.In general, often higher using having in water treatment technology
The adsorbent of specific surface area is made a return journey heavy metal and the pollutants such as dyestuff in water removal.
Graphene oxide specific surface area is high, is rich in the characteristics such as functional group, can not only pass through electrostatic or chemisorption etc.
Act on the functional group that combines, and be rich in water pollutant make it have good hydrophily and it is dispersed and with gather
The compatibility for closing object, so that it is with wide application potential.However individually graphene oxide is water-soluble preferably, practical application
It is difficult to the problems such as separating and recovering after adsorbing in the process, limits its application in actual production.Contain on polyvinyl alcohol molecule chain
There are a large amount of small sizes, highly polar hydroxyl, intermolecular formation hydrogen bond is easily cross-linked to form macromolecular network structure, and has low
Valence is nontoxic, good water solubility, bioaffinity, good mechanical strength and the features such as chemical stability, is widely used in
The fields such as gel rubber material science and biomedical material science.Currently, the whole world is compound to graphene oxide/polyvinyl alcohol
Material has carried out extensive research.
According to Coordinative Chemistry theoretical knowledge it is found that the adsorbent agent containing N, O and S has excellent absorption to heavy metal ion
Performance.Because heavy metal ion typically belongs to soft acid or intermediate acid, and organic sulfur compound and amine then belong to soft base or intermediate alkali,
According to hsab theory, both is easily combined into stable complex compound.During coagulant trap heavy metals, regardless of
Heavy metal coagulant is ionic or non-ionic, and really play trapping is coordinating group, and wherein determines coagulant
Bonded atom in the mainly coordinating group of Chelating Properties, it mainly determines and is combined whether substance has an effect, and
The size of selective action and active force.Influence of the heavy metal chelant bonded atom to Stability of Chelate, then mainly key
In action, heavy metal and the small bonded atom of electronegativity can form the more significant coordination of covalency to the electronegativity of conjunction atom
Key forms more stable chelate.The electronegativity difference of heavy metal and sulphur atom is minimum, that is to say, that it is formed with sulphur atom
Stability of Chelate highest, thus consideration first uses sulphur atom as bonded atom, and introducing strong coordinating group makes a removal huge sum of money
Belong to more efficient.
Graphene oxide is modified by sulfhydrylation, the functionalization of graphene oxide, Er Qieke not only may be implemented
Improve its dispersibility and stability, increase its to water pollutant removal ability simultaneously, make its water solubility reduce, be conducive to inhale
Attached separation.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the purpose of the present invention is to provide a kind of sulfhydrylations of high efficiency, low cost
Graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application.
To realize that goal of the invention, the technical solution adopted by the present invention are specific as follows:
A kind of preparation method of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, comprising the following steps:
(1) at room temperature, it disperses graphite oxide in deionized water, magnetic agitation is uniform, forms graphene oxide colloid
Suspension；Graphene oxide soliquid ultrasound is dissociated into 2 ~ 6h, forms the oxidation stone of 0.5 uniform and stable ~ 10.0mg/mL
Black alkene dispersion liquid；
(2) under stirring condition, 4- aminothiophenol is added in hydrochloric acid solution, 35 ~ 55 DEG C is gradually heated to, obtains 4- ammonia
Base benzenethiol solution；Sodium nitrite is dissolved in deionized water, sodium nitrite solution is obtained；Wherein, 4- aminothiophenol: sub-
Sodium nitrate: the molar ratio of hydrochloric acid is 1:1:1.0 ~ 1.5；Under the conditions of ice-water bath, sodium nitrite solution is slowly added dropwise while stirring
Into 4- aminothiophenol solution；Then graphene oxide dispersion is added reaction system, stirring 8 under ice bath ~ for 24 hours, wherein
4- aminothiophenol: the mass ratio of graphene oxide is 1 ~ 5:1；After reaction, reaction solution is used to acetone, dehydrated alcohol respectively
For several times with deionized water washing；Obtained solid is placed in 50 DEG C of vacuum ovens and is dried to get sulfhydrylation graphene oxide is arrived；
(3) by mass ratio be 10:1 ~ 5:10 ~ 20 polyvinyl alcohol, sodium alginate and calcium carbonate sequentially add fill from
In the reaction vessel of sub- water, stirs at 90 ~ 95 DEG C and be completely dissolved to solid, obtain mixed liquor A；Then add into mixed liquor A
Enter sulfhydrylation graphene oxide, 4 ~ 12h stirred at 75 ~ 95 DEG C, obtains sulfhydrylation graphene oxide/polyvinyl alcohol gel,
In, sulfhydrylation graphene oxide: the mass ratio of polyvinyl alcohol is 1:4 ~ 30；With syringe by sulfhydrylation graphene oxide/poly- second
Enol gel instills calcium chloride: in saturation boric acid solution=5g:100mL calcium chloride-saturation boric acid solution, moment forms black
Bead continues to harden 12h ~ 48h in calcium chloride-saturation boric acid solution；Then spherical product is transferred in deionized water, is dripped
Add hydrochloric acid solution, be slowly stirred, forms the composite balls with cavernous structure；Composite balls are washed into repeatedly with a large amount of distilled water
Property to get arrive sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent.
(1) under condition of ice bath, graphite powder is added in the concentrated sulfuric acid-phosphoric acid mixed liquor that volume ratio is 9:1, wherein every
0.5 ~ 4.0g graphite powder is added in the 100mL concentrated sulfuric acid-phosphoric acid mixed liquor, stirs evenly；
(2) by graphite powder: potassium permanganate=1:3 ~ 6 mass ratio is slowly added to potassium permanganate powder into reaction system, and
Temperature≤20 DEG C of reaction system are controlled, being slowly stirred dissolves potassium permanganate sufficiently；
(3) reaction system is placed in 35 ~ 55 DEG C of water-bath isothermal reaction 6 ~ 12 hours；
(4) reaction system is cooled to room temperature after reaction, by reaction solution: ice water=1:1 ~ 2 volume ratio is by reaction solution
Successively be transferred to ice water and 30% hydrogen peroxide in, obtain bright yellow solution, i.e. graphite oxide solution；
(5) solid product is filtered out, then washs solid product repeatedly with 10% hydrochloric acid solution, with the barium chloride of 10wt%
Solution detection, until cleaning solution is without white precipitate；Washing solid product to cleaning solution neutrality repeatedly with deionized water again is
Only；
(6) resulting solid product is dried in vacuo at 50 DEG C, obtains dry graphite oxide.
In the step (2), sodium nitrite solution volume is 1.2 ~ 1.5 times of 4- aminothiophenol liquor capacity.
In the step (3), mass fraction of the polyvinyl alcohol in mixed liquor A is 3% ~ 6%.
A kind of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, passes through above-mentioned sulfhydrylation graphite oxide
Alkene/polyvinyl alcohol macropore composite balls adsorbent preparation method is prepared.
Above-mentioned sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent answering in processing heavy metal containing sewage
With.
Compared with the existing technology, the invention has the advantages that and the utility model has the advantages that
(1) sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent of the present invention is prepared by covalent modification
Graphene oxide reduces its water solubility, is easy to be separated by solid-liquid separation；Meanwhile 4- aminothiophenol have the N of electron rich, S atom and
Sulfydryl, amino characteristic bifunctional, by aromatic mercaptans group group covalence graft in the sp of the electron rich of graphene oxide2Carbon
On skeleton, the functionalization of graphene oxide is realized, the mercapto groups being introduced into can occur complexing with heavy metal ion in water and make
With improving graphene oxide to the adsorption capacity of pollutant.
(2) it is difficult to separate and recover after the absorption of powdered adsorbent, although by after thiolated modified graphene oxide, mercapto
Base can be complexed with pollutant, reduce its water solubility, separate after being conducive to absorption, but macroscopically its appearance features or powder
Shape is scattered in solution after absorption, is unfavorable for recycling etc.；The present invention is by being embedded in polyvinyl alcohol for sulfhydrylation graphene oxide
In, composite balls are formed, are easily dispersed different from powdered form, composite balls volume, quality are big, are easy to separate after adsorbing, simultaneously because packet
Sulfhydrylation graphene oxide has been buried, and has kept higher absorption property.
(3) present invention not only reduces the usage amount of sulfhydryl oxidase graphene, reduces operating cost, and further solve
Having determined, it is difficult to the shortcomings that being separated by solid-liquid separation；The product of preparation is macropore composite spherical structure, has good mass transport；Together
When polyvinyl alcohol introducing improve the mechanical strength of material, the separation after being easy to adsorb improves its practical value.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below.
Embodiment 1: improved Hummers method prepares graphite oxide
The graphite powder of 6g is added in the three-neck flask of the phosphoric acid solution of the concentrated sulfuric acid and 80mL that fill 720mL, in ice
It is stirred evenly under water bath condition；Lasting stirring is slowly added to 36g potassium permanganate powder (control temperature of reaction system≤20 DEG C)；
After to be added, reaction system is put into thermostat water bath, the water bath with thermostatic control 12 hours under conditions of 50 DEG C；Wait react knot
After beam is cooled to room temperature, reaction solution is poured into 1000mL ice water, then transfers in a certain amount of 30% hydrogen peroxide, obtains
To bright yellow solution, reaction product is filtered；Above-mentioned filtration product is washed repeatedly with 10% hydrochloric acid solution, uses 10%(W/
V) barium chloride solution detects, and is washed until neutrality repeatedly until no white precipitate, then with deionized water；By resulting production
Object is placed in 50 DEG C of vacuum drying, and dry graphite oxide is made.
Embodiment 2
(1) it disperses graphite oxide prepared by 500mg embodiment 1 in 100mL deionized water, magnetic stirrer over night, shape
At graphene oxide soliquid；Then it is ultrasonically treated 4h under Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, formed uniformly steady
Fixed dispersion liquid is to get the graphene oxide dispersion for arriving 5mg/mL.
(2) under stirring condition, the 4- aminothiophenol of 12mmol is added in the hydrochloric acid solution of 15mL1mol/L, gradually
53 DEG C are warming up to, 4- aminothiophenol solution is obtained；Then, the sodium nitrite of 12mmol is dissolved in 20mL deionized water,
Obtain sodium nitrite solution；Sodium nitrite solution is slowly added dropwise to above-mentioned 4- aminobenzene sulphur while stirring under the conditions of ice-water bath
In phenol solution；Finally graphene oxide dispersion is added in above-mentioned reaction system, 24 h are stirred under the conditions of ice-water bath.Will
To mixed liquor washed for several times with acetone, dehydrated alcohol and deionized water respectively after, the vacuum that obtained solid is placed in 50 DEG C is done
It is dried in dry case to get sulfhydrylation graphite oxide ene product is arrived.
(3) 15.0g polyvinyl alcohol, 3.6g sodium alginate and 20.0 calcium carbonate are added to and fill 300mL deionized water
In beaker, at 90 DEG C stir 2h until solid be completely dissolved, obtain mixed liquor A；Then preparation in 2.5g step (2) is added
Sulfhydrylation graphene oxide, continue at 90 DEG C to stir 6h, obtain sulfhydrylation graphene oxide/polyvinyl alcohol gel；It has stirred
Sulfhydrylation graphene oxide/polyvinyl alcohol gel is instilled into 5%(W/V with syringe after finishing) in calcium chloride-saturation boric acid solution,
It can be seen that black ball moment is formed, and continue to harden 48h in calcium chloride-saturation boric acid solution；Then by spherical product
It is transferred in 1000mL distilled water, the hydrochloric acid solution of 1mol/L is added dropwise, is slowly stirred, makes complex spherical at cavernous structure；Finally,
Composite balls to cleaning solution is washed repeatedly with a large amount of distilled water to be in neutrality to get to final product sulfhydrylation graphene oxide/poly- second
Enol macropore composite balls adsorbent.
Embodiment 3
(1) it disperses graphite oxide prepared by 1000mg embodiment 1 in 100mL deionized water, magnetic stirrer over night, shape
At graphene oxide soliquid；Then it is ultrasonically treated 6h under Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, formed uniformly steady
Fixed dispersion liquid is to get the graphene oxide dispersion for arriving 10mg/mL.
(2) under agitation, the 4- aminothiophenol of 12mmol is added in the hydrochloric acid solution of 18mL1mol/L, gradually
35 DEG C are warming up to, 4- aminothiophenol solution is obtained；Then, the sodium nitrite of 12mmol is dissolved in 20mL deionized water,
Obtain sodium nitrite solution；Sodium nitrite solution is slowly added dropwise to above-mentioned 4- aminobenzene sulphur while stirring under the conditions of ice-water bath
In phenol solution；Finally graphene oxide dispersion is added in above-mentioned reaction system, 8 h are stirred under the conditions of ice-water bath.Will
To mixed liquor washed for several times with acetone, dehydrated alcohol and deionized water respectively after, the vacuum that obtained solid is placed in 50 DEG C is done
It is dried in dry case to get sulfhydrylation graphite oxide ene product is arrived.
(3) 15.0g polyvinyl alcohol, 7.5g sodium alginate and 30.0 calcium carbonate are added to and fill 300mL deionized water
In beaker, at 92 DEG C stir 2h until solid be completely dissolved, obtain mixed liquor A；Then preparation in 3.75g step (2) is added
Sulfhydrylation graphene oxide, continue at 95 DEG C to stir 4h, obtain sulfhydrylation graphene oxide/polyvinyl alcohol gel；It has stirred
Sulfhydrylation graphene oxide/polyvinyl alcohol gel is instilled into 5%(W/V with syringe after finishing) in calcium chloride-saturation boric acid solution,
It can be seen that black ball moment is formed, and continue to harden 30h in calcium chloride-saturation boric acid solution；Then by spherical product
It is transferred in 1000mL distilled water, the hydrochloric acid solution of 1mol/L is added dropwise, is slowly stirred, makes complex spherical at cavernous structure；Finally,
It is washed repeatedly to neutrality with a large amount of distilled water to get final product sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls are arrived
Adsorbent.
Embodiment 4
(1) it disperses graphite oxide prepared by 50mg embodiment 1 in 100mL deionized water, magnetic stirrer over night, is formed
Graphene oxide soliquid；Then it is ultrasonically treated 2h under Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, formed uniform and stable
Dispersion liquid to get arrive 0.5mg/mL graphene oxide dispersion.
(2) under agitation, the 4- aminothiophenol of 12mmol is added in the hydrochloric acid solution of 12mL1mol/L, by
40 DEG C are gradually warming up to, 4- aminothiophenol solution is obtained；Then, the sodium nitrite of 12mmol is dissolved in 20mL deionized water
In, obtain sodium nitrite solution；Sodium nitrite solution is slowly added dropwise to above-mentioned 4- amino while stirring under the conditions of ice-water bath
In benzenethiol solution；Finally graphene oxide dispersion is added in above-mentioned reaction system, 12h is stirred under the conditions of ice-water bath.
After obtained mixed liquor is washed for several times with acetone, dehydrated alcohol and deionized water respectively, obtained solid is placed in 50 DEG C true
It is dried in empty drying box to get sulfhydrylation graphite oxide ene product is arrived.
(3) 15.0g polyvinyl alcohol, 1.5g sodium alginate and 15.0 calcium carbonate are added to and fill 300mL deionized water
In beaker, at 95 DEG C stir 2h until solid be completely dissolved, obtain mixed liquor A；Then preparation in 0.5g step (2) is added
Sulfhydrylation graphene oxide, continue at 75 DEG C to stir 12h, obtain sulfhydrylation graphene oxide/polyvinyl alcohol gel；It has stirred
Sulfhydrylation graphene oxide/polyvinyl alcohol gel is instilled into 5%(W/V with syringe after finishing) in calcium chloride-saturation boric acid solution,
It can be seen that black ball moment is formed, and continue to harden 12h in calcium chloride-saturation boric acid solution；Then by spherical product
It is transferred in 1000mL distilled water, the hydrochloric acid solution of 1mol/L is added dropwise, is slowly stirred, makes complex spherical at cavernous structure；Finally,
It is washed repeatedly to neutrality with a large amount of distilled water to get final product sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls are arrived
Adsorbent.
The method of the present invention preparation is verified using static batch adsorption experiment, dynamic column adsorption experiment and parsing regeneration tests
Adsorbent and its absorption property.
(1) Staticadsorption experiment.Concrete operations are as follows: measure the Cu of 100mL prepared 50mg/L in advance2+Or 150mg/L
Pb2+Solution is 6.0 with the HCl/NaOH tune pH of 0.1mol/L in 200mL conical flask；Using 2 product of embodiment as removal
Cu2+、Pb2+Adsorbent, investigate influence of the different dosages to removal effect.25 DEG C, revolving speed 150rpm, constant temperature air bath vibration
It swings in device and vibrates；After balance to be adsorbed, after taking 0.22 μm of filtering with microporous membrane of supernatant, water sample is carried out with spectrophotometry
Analysis.The results are shown in Table 1:
Table 1
As shown in Table 1, the sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent pair of the method for the present invention preparation
Cu2+、Pb2+There is preferable removal effect.
(2) dynamic column adsorption experiment.Adsorb column length 20cm, internal diameter 3cm.Adsorbent is filled in adsorption column, it will
Know the Cu of solution concentration2+Or Pb2+Solution, by adsorption column, collects water outlet with certain flow rate at regular intervals, and measurement wherein weighs
The concentration of metal ion.The result shows that: in the case where flow velocity is 2.0mL/min, sulfhydrylation graphene oxide/polyvinyl alcohol is big
Hole composite balls adsorbent can adsorb the Cu of 80mg/L completely before its complete penetration2+With the Pb of 100mg/L2+The volume of solution
Respectively 1960 and 2480mL shows good column absorption feature, under lower water inlet concentration of metal ions and water inlet flow velocity
Adsorption rate is higher.
(3) regeneration tests are parsed: using the hydrochloric acid of 0.2mol/L as parsing agent, the adsorbent after absorption pollutant being put into
Into desorbed solution, 30 DEG C, revolving speed 150rpm are placed in, constant temperature oscillation for 24 hours, is tested according to Staticadsorption experiment condition experiment method later
Card, the results showed that sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent after 3 absorption-parsing circulation,
It is very fast to the removal rate decline of heavy metal, but as composite balls are mesh-structured more closely knit, recycled by 5 absorption-parsing
Afterwards, to Cu2+、Pb2+Adsorption rate still can reach 75% or more of initial adsorption amount, and composite balls still maintain good ball
Shape is not damaged.This illustrates that sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent has good stabilization
Property, it can cost-effectively remove the Cu in water removal2+、Pb2+, have potential practical value.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (6)
1. a kind of preparation method of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, which is characterized in that including
Following steps:
(1) at room temperature, it disperses graphite oxide in deionized water, magnetic agitation is uniform, forms graphene oxide colloidal suspension
Liquid；Graphene oxide soliquid ultrasound is dissociated into 2~6h, forms the graphite oxide of 0.5 uniform and stable~10.0mg/mL
Alkene dispersion liquid；
(2) under stirring condition, 4- aminothiophenol is added in hydrochloric acid solution, 35~55 DEG C is gradually heated to, obtains 4- amino
Benzenethiol solution；Sodium nitrite is dissolved in deionized water, sodium nitrite solution is obtained；Wherein, 4- aminothiophenol: nitrous
Sour sodium: the molar ratio of hydrochloric acid is 1:1:1.0~1.5；Under the conditions of ice-water bath, sodium nitrite solution is slowly dropped to while stirring
In 4- aminothiophenol solution；Then graphene oxide dispersion is added reaction system, stirring 8 under ice bath~for 24 hours, wherein
4- aminothiophenol: the mass ratio of graphene oxide is 1~5:1；After reaction, reaction solution is used to acetone, anhydrous second respectively
Pure and mild deionized water washing is for several times；Obtained solid is placed in 50 DEG C of vacuum ovens and is dried to get sulfhydrylation graphite oxide is arrived
Alkene；
(3) polyvinyl alcohol, sodium alginate and calcium carbonate that mass ratio is 10:1~5:10~20 are sequentially added and fills deionization
In the reaction vessel of water, stirs at 90~95 DEG C and be uniformly dispersed to solid, obtain mixed liquor A；Then it is added into mixed liquor A
Sulfhydrylation graphene oxide stirs 4~12h at 75~95 DEG C, obtains sulfhydrylation graphene oxide/polyvinyl alcohol gel,
In, sulfhydrylation graphene oxide: the mass ratio of polyvinyl alcohol is 1:4~30；With syringe by sulfhydrylation graphene oxide/poly- second
Enol gel instills calcium chloride: in saturation boric acid solution=5g:100mL calcium chloride-saturation boric acid solution, moment forms black
Bead continues to harden 12h~48h in calcium chloride-saturation boric acid solution；Then spherical product is transferred in deionized water,
Hydrochloric acid solution is added dropwise, is slowly stirred, forms the composite balls with cavernous structure；Composite balls are washed repeatedly with a large amount of distilled water to
Neutrality to get arrive sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent.
2. the preparation method of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent according to claim 1,
It is characterized by: the graphite oxide in the step (1) is prepared by following preparation method:
(1) under condition of ice bath, graphite powder is added in the concentrated sulfuric acid-phosphoric acid mixed liquor that volume ratio is 9:1, wherein every 100mL is dense
0.5~4.0g graphite powder is added in sulfuric-phosphoric mixed liquor, stirs evenly；
(2) by graphite powder: potassium permanganate=1:3~6 mass ratio is slowly added to potassium permanganate powder into reaction system, and controls
Temperature≤20 DEG C of reaction system processed, being slowly stirred dissolves potassium permanganate sufficiently；
(3) reaction system is placed in 35~55 DEG C of water-bath isothermal reaction 6~12 hours；
(4) reaction system is cooled to room temperature after reaction, by reaction solution: ice water=1:1~2 volume ratio by reaction solution according to
It is secondary be transferred to ice water and 30% hydrogen peroxide in, obtain bright yellow solution, i.e. graphite oxide solution；
(5) solid product is filtered out, then washs solid product repeatedly with 10% hydrochloric acid solution, it is molten with the barium chloride of 10wt%
Liquid detection, until cleaning solution is without white precipitate；Solid product is washed repeatedly with deionized water again until cleaning solution is neutral；
(6) resulting solid product is dried in vacuo at 50 DEG C, obtains dry graphite oxide.
3. the preparation method of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent according to claim 1,
It is characterized by: sodium nitrite solution volume is 1.2~1.5 times of 4- aminothiophenol liquor capacity in the step (2).
4. the preparation method of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent according to claim 1,
It is characterized by: mass fraction of the polyvinyl alcohol in mixed liquor A is 3%~6% in the step (3).
5. a kind of sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent, it is characterised in that: pass through claim 1-
The preparation method of 4 described in any item sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbents is prepared.
6. sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent described in claim 5 is heavy metal-polluted in processing
Application in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610772031.8A CN106179277B (en) | 2016-08-31 | 2016-08-31 | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610772031.8A CN106179277B (en) | 2016-08-31 | 2016-08-31 | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106179277A CN106179277A (en) | 2016-12-07 |
| CN106179277B true CN106179277B (en) | 2019-01-18 |
Family
ID=58088413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610772031.8A Active CN106179277B (en) | 2016-08-31 | 2016-08-31 | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106179277B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579628A (en) * | 2018-04-25 | 2018-09-28 | 北京师范大学 | A kind of kappa-carrageenan/graphene oxide gel bead and its preparation method and application |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107149928B (en) * | 2017-05-20 | 2021-02-26 | 复旦大学 | Preparation method of porous graphene-based composite material |
| CN108187641B (en) * | 2017-12-26 | 2019-08-20 | 武汉大学 | A kind of preparation method and applications of sodium alginate/polyvinyl alcohol@polyacrylamide core-shell structure gel ball |
| CN109371663B (en) * | 2018-09-14 | 2021-11-09 | 北京服装学院 | Modified bamboo fiber fabric and preparation method thereof |
| CN109453743A (en) * | 2018-12-12 | 2019-03-12 | 郑州大学 | A kind of graphene oxide/bentonite nano piece aeroge, preparation method and application |
| CN110102263A (en) * | 2019-04-10 | 2019-08-09 | 中国药科大学 | Mercaptoethylmaine functional magnetic graphene oxide adsorbent and its preparation method and application |
| CN110756175A (en) * | 2019-08-26 | 2020-02-07 | 河海大学 | Preparation method of ultralight efficient adsorbent foam for purifying dye wastewater |
| CN110564088A (en) * | 2019-08-26 | 2019-12-13 | 兰州理工大学 | self-healing graphene stealth film and preparation method thereof |
| CN110759412B (en) * | 2019-10-31 | 2021-04-23 | 中国科学院生态环境研究中心 | Method for synchronously treating desulfurization wastewater by in-situ crosslinking of double-network gel |
| CN110817849A (en) * | 2019-11-29 | 2020-02-21 | 无锡市惠山区川大石墨烯应用研究中心 | Sulfhydrylation graphene aerogel and preparation method and application thereof |
| CN112427026A (en) * | 2020-12-02 | 2021-03-02 | 邱芳璟 | Preparation method of polyvinyl alcohol functionalized carbon nanotube composite ball |
| CN112958056B (en) * | 2021-02-03 | 2022-04-15 | 中南大学 | Three-dimensional graphene oxide composite material and preparation method and application thereof |
| CN113578255A (en) * | 2021-08-17 | 2021-11-02 | 日月光半导体制造股份有限公司 | Method for treating porous silica |
| CN114471480A (en) * | 2022-03-01 | 2022-05-13 | 武汉科技大学 | Method for preparing chitosan-based adsorbent based on click chemical reaction |
| CN115193420B (en) * | 2022-09-13 | 2022-11-29 | 江苏米格新材料有限公司 | Graphene material and preparation method thereof |
| CN116272941A (en) * | 2023-03-23 | 2023-06-23 | 东南大学 | Graphene-based hydrogel sphere catalytic material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348782A (en) * | 2008-08-30 | 2009-01-21 | 兰州大学 | Macroreticular polyvinyl alcohol bead carrier and preparation thereof |
| CN103804828A (en) * | 2014-02-14 | 2014-05-21 | 江南大学 | Compound hydrogel capable of adsorbing heavy metal ions and preparation method of compound hydrogel |
| CN104226281A (en) * | 2014-10-13 | 2014-12-24 | 江南大学 | Composite hydrogel for adsorption of heavy metal ions and preparation method thereof |
| CN104973729A (en) * | 2015-06-20 | 2015-10-14 | 北京泰昌科睿环保科技有限公司 | Denitrification method for domestic sewage |
| CN105289539A (en) * | 2015-11-11 | 2016-02-03 | 华南理工大学 | Graphene/ polyvinyl alcohol nanofibers membrane adsorbent, preparation method and appliance |
| CN105833851A (en) * | 2016-05-18 | 2016-08-10 | 同济大学 | Method for preparing functional group modified alginate-graphene dual-network nano-composite gel beads |
-
2016
- 2016-08-31 CN CN201610772031.8A patent/CN106179277B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348782A (en) * | 2008-08-30 | 2009-01-21 | 兰州大学 | Macroreticular polyvinyl alcohol bead carrier and preparation thereof |
| CN103804828A (en) * | 2014-02-14 | 2014-05-21 | 江南大学 | Compound hydrogel capable of adsorbing heavy metal ions and preparation method of compound hydrogel |
| CN104226281A (en) * | 2014-10-13 | 2014-12-24 | 江南大学 | Composite hydrogel for adsorption of heavy metal ions and preparation method thereof |
| CN104973729A (en) * | 2015-06-20 | 2015-10-14 | 北京泰昌科睿环保科技有限公司 | Denitrification method for domestic sewage |
| CN105289539A (en) * | 2015-11-11 | 2016-02-03 | 华南理工大学 | Graphene/ polyvinyl alcohol nanofibers membrane adsorbent, preparation method and appliance |
| CN105833851A (en) * | 2016-05-18 | 2016-08-10 | 同济大学 | Method for preparing functional group modified alginate-graphene dual-network nano-composite gel beads |
Non-Patent Citations (3)
| Title |
|---|
| Functionalization of 4-aminothiophenol and 3-aminopropyltriethoxysilane with graphene oxide for potential dye and copper removal;Dan Chen et al;《Journal of Hazardous Materials》;20160222;第310卷;第179-187页 |
| Preparation of polyvinyl alcohol/chitosan hydrogel compounded with graphene oxide to enhance the adsorption properties for Cu(II) in aqueous solution;Luzhong Li et al;《J Polym Res》;20150710;第22卷;全文 |
| 聚乙烯醇／氧化石墨烯纳米复合材料的制备与表征;赵翠 等;《广州化工》;20120630;第40卷(第11期);第81-83页 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579628A (en) * | 2018-04-25 | 2018-09-28 | 北京师范大学 | A kind of kappa-carrageenan/graphene oxide gel bead and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106179277A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106179277B (en) | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application | |
| CN106311185B (en) | A kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls and its preparation method and application | |
| CN102161781B (en) | Modified chitosan material capable of absorbing heavy metal ions and preparation method thereof | |
| CN107243326B (en) | A kind of preparation method of graphene oxide/chitosan composite aerogel microballoon | |
| CN103769058B (en) | The preparation method of carbonization chitosan absorbent, product and application process | |
| KR101506094B1 (en) | Heavy Metal Adsorbent Using Biochar-Alginate Capsule, Preparation Method Thereof and Removal Method ofHeavy Metal in Aqueous Solution Using the Same | |
| CN106076279A (en) | A kind of adsorbent for heavy metal and its preparation method and application | |
| CN113426428B (en) | Polyaniline-sulfur nitrogen MXene/sodium alginate composite gel adsorbent and preparation method and application thereof | |
| CN104258817B (en) | The chitosan magnetic of melamine modification, preparation method and applications | |
| CN105601850A (en) | Preparation method of graphene oxide composite gel applicable to heavy metal adsorption | |
| CN113083238B (en) | Thiosemicarbazide functionalized graphene oxide/chitosan composite adsorbent and preparation method and application thereof | |
| CN107486132A (en) | A kind of preparation method of the porous heavy-metal adsorption material of nano ferriferrous oxide | |
| CN109092243A (en) | A kind of sulphur modification hydrotalcite adsorbent and preparation method thereof for the removal of mercury in acid waste water | |
| CN104014314B (en) | Bio-adsorbent, preparation method and application | |
| CN109261138A (en) | It is a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon and preparation method thereof | |
| CN114797783B (en) | Adsorbent for selectively removing Cr (VI) and preparation method and application thereof | |
| CN109012586A (en) | Uranium absorption agent and preparation method thereof | |
| CN102380348A (en) | Pectin modified magnetic nano-adsorbent and preparation method and application thereof | |
| CN104289200B (en) | A kind of preparation method and application of magnetic HACC/ oxidation multi-walled carbon nano-tubes adsorbent | |
| CN110589822A (en) | Method for preparing activated carbon from plastic waste and application of activated carbon | |
| Xiang et al. | Layered aerogel embedded with thiourea-resorcinol-formaldehyde resin for efficient adsorption of Au (III) | |
| Kuang et al. | Adsorption kinetics and adsorption isotherm studies of chromium from aqueous solutions by HPAM-chitosan gel beads | |
| Tran et al. | Facile synthesis of Fe3O4 nanoparticles loaded on activated carbon developed from Lotus seed pods for removal of Ni (II) ions | |
| CN106076289B (en) | A kind of preparation of the general liquid adsorbent of supper-fast metal ion and adsorption of metal ions device | |
| CN110124629A (en) | A kind of melamine sponge-graphene oxide adsorbent material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |