CN106311185B - A kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls and its preparation method and application - Google Patents
A kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls and preparation method thereof.Graphite oxide is prepared using improved Hummers method first, graphene oxide is obtained by ultrasound removing, using 3- aminopropyl triethoxysilane to graphene oxide silanization, silanization graphene oxide is embedded in polyvinyl alcohol, target product is prepared, adsorbed water body heavy metal ion is used for.The present invention reduces the water solubility of product, is easy to be separated by solid-liquid separation by carrying out silanization to graphene oxide；The amino of introducing improves graphene oxide to the adsorption capacity of pollutant, the graphene oxide of Aminosilylation is embedded in polyvinyl alcohol, the usage amount of Aminosilylation graphene oxide is not only reduced, and further solves it and is difficult to the shortcomings that being separated by solid-liquid separation；The macropore composite spherical structure of product has good mass transport, and the introducing of polyvinyl alcohol improves the mechanical strength of material, the separation after being easy to adsorb.
Description
Technical field
The invention belongs to field of polymer composite material and field of environment engineering technology, and in particular to one kind is used for heavy metal
Polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls preparation method of ionic adsorption separation.
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.Currently, in the various techniques to sewage treatment, due to
Absorption method has many advantages, such as that low in cost, easy to operate, sorbent material is from a wealth of sources, adsorption effect is good, it is considered to be to containing
Metal ion or one of the most effectual way of waste water from dyestuff purification.
Graphene oxide is due to having many advantages, such as large specific surface area, being rich in functional group, in removal of heavy metal ions
Preferable removal capacity is shown, however individually graphene oxide is water-soluble preferably, in the presence of being difficult to point after handle stain disease
From and cause secondary pollution, greatly limit its promote and application.
Graphene oxide is modified by Aminosilylation, the functionalization of graphene oxide not only may be implemented, and
And can be improved its dispersibility and stability, increase its to water pollutant removal ability simultaneously, make its water solubility reduce, favorably
Separation after absorption.But due to Aminosilylation graphene oxide be still in it is powdered, still deposit in actual application
It is difficult to the problems such as separating and recovering after mechanical strength is low, quality is easily lost, adsorbs, limits its application in actual production.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of for the poly- of heavy metal ion adsorbed separation
Vinyl alcohol/Aminosilylation graphene oxide macropore composite balls and preparation method thereof.
The technical solution adopted by the present invention is specific as follows:
It is a kind of for heavy metal ion adsorbed isolated polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls
Preparation method, 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, 3- aminopropyl triethoxysilane is added in deionized water, 3- aminopropyl-triethoxy silicon
The volume ratio of alkane and deionized water is 1:10 ~ 100, is gradually heated to 40 ~ 80 DEG C, reacts 4 ~ 8 h；Then by graphene oxide point
Reaction system is added in dispersion liquid, stirs 4 ~ 24 h under ice bath, obtains flocky precipitate；After reaction, it is washed repeatedly with deionized water
Flocky precipitate is washed, is centrifugated, solid is placed in a vacuum drying oven drying, it is solid to obtain Aminosilylation graphene oxide
Body；
(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 Aminosilylation graphene oxide, 4 ~ 12h is stirred at 75 ~ 95 DEG C, obtains polyvinyl alcohol/Aminosilylation graphene oxide
Gel, wherein Aminosilylation graphene oxide: the mass ratio of polyvinyl alcohol is 1:4 ~ 30；With syringe by Aminosilylation
Graphene oxide/polyvinyl alcohol gel instills calcium chloride: saturation boric acid solution=5g:100mL calcium chloride-saturation boric acid solution
In, moment forms black ball, continues to harden 12h ~ 48h in calcium chloride-saturation boric acid solution；Then spherical product is shifted
Into deionized water, hydrochloric acid solution is added dropwise, is slowly stirred, forms the composite balls with cavernous structure；It will be answered with a large amount of distilled water
Ball is closed to be washed repeatedly to neutrality to get polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls are arrived.
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
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.
Mass fraction of the polyvinyl alcohol in mixed liquor A is 3% ~ 6% in the step (3).
A kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls, pass through above-mentioned polyvinyl alcohol/amino silane
The preparation method for changing graphene oxide macropore composite balls is prepared.
Application of the above-mentioned polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls in processing heavy metal containing sewage.
Compared with the existing technology, the invention has the advantages that and the utility model has the advantages that
(1) present invention carries out silanization to graphene oxide using silane coupling agent 3- aminopropyl triethoxysilane, makes
Its water solubility reduces, and is easy to be separated by solid-liquid separation；Meanwhile containing a large amount of amino and oxygroup in 3- aminopropyl triethoxysilane, it is real
The functionalization for having showed graphene oxide, the amino group being introduced into can occur complexing with the heavy metal ion in water, be promoted
Adsorption capacity of the graphene oxide to pollutant.
(2) present invention not only reduces amino silicone by the way that Aminosilylation graphene oxide to be embedded in polyvinyl alcohol
The usage amount of alkanisation graphene oxide reduces operating cost, and further solves it and be difficult to the problem of being separated by solid-liquid separation.System
Standby product is macropore composite spherical structure, has good mass transport；The introducing of polyvinyl alcohol improves material simultaneously
Mechanical strength, be easy to adsorb after separation, improve its practical value.
Detailed description of the invention
Fig. 1 is polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls Adsorption of Cu2+Adsorption isothermal curve.
Fig. 2 is that polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls adsorb Pb2+Adsorption isothermal curve.
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 water
It is stirred evenly under the conditions of bath；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；To anti-
It should terminate after being cooled to room temperature, first pour into mixed liquor in the ice water of 1000mL, then transfer to a certain amount of 30% dioxygen
In water, bright yellow solution is obtained, reaction product is filtered；Above-mentioned solid product is washed repeatedly with 10% hydrochloric acid solution, is used
10wt% barium chloride solution detects filtrate, until no white precipitate；It is washed to cleaning solution and is in neutrality repeatedly with deionized water again
Until；Resulting solid product is placed in 50 DEG C of vacuum drying, obtains dry graphite oxide.
Embodiment 2
(1) it disperses graphite oxide prepared by 200mg embodiment 1 in 100mL deionized water, magnetic stirrer over night, shape
At graphene oxide soliquid；Then it is ultrasonically treated 6h in Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, is formed uniformly steady
Fixed dispersion liquid is to get the graphene oxide dispersion for arriving 2mg/mL；
(2) under stirring condition, 10mL 3- aminopropyl triethoxysilane is added in the deionized water of 500mL, is gradually risen
Temperature reacts 6h to 48 DEG C；Then graphene oxide dispersion prepared by step (1) is added in above-mentioned reaction system and is stirred instead
12h is answered, flocky precipitate is obtained；Flocky precipitate is washed repeatedly with deionized water, is centrifugated, solid is then placed in vacuum
It is dried in drying box to get Aminosilylation graphene oxide is arrived；
(3) 15.0g polyvinyl alcohol, 3.6g sodium alginate and 20.0g calcium carbonate are sequentially added and fills 300mL deionized water
Beaker in, 2h is stirred at 90 DEG C, solid is completely dissolved, and obtains mixed liquor A；The amino silane for taking 2.5g step (2) to prepare
Change graphene oxide to be added in mixed liquor A, continues to stir 4h at 95 DEG C, obtain polyvinyl alcohol/Aminosilylation graphene oxide
Gel；Polyvinyl alcohol/Aminosilylation graphene oxide gel is instilled into 5%(W/V with syringe after stirring) calcium chloride-
It is saturated in boric acid solution, it can be seen that black ball moment is formed, and continues to harden 48h in calcium chloride-saturation boric acid solution；
It is then 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, being washed repeatedly to neutrality with a large amount of distilled water to get big to final product polyvinyl alcohol/Aminosilylation graphene oxide
Hole composite balls.
Embodiment 3
(1) graphite oxide prepared by 1000mg embodiment 1 is dispersed in 100mL deionized water, magnetic stirrer over night, shape
At graphene oxide soliquid；Then it is ultrasonically treated 4h in Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, is formed uniformly steady
Fixed dispersion liquid is to get the graphene oxide dispersion for arriving 10mg/mL；
(2) under stirring condition, 10mL 3- aminopropyl triethoxysilane is added in the deionized water of 1000mL, gradually
80 DEG C are warming up to, 4h is reacted；Then graphene oxide dispersion prepared by step (1) is added in above-mentioned reaction system and is stirred
Reaction for 24 hours, obtains flocky precipitate；Flocky precipitate is washed repeatedly with deionized water, is centrifugated, is then placed in solid very
It is dried in empty drying box to get Aminosilylation graphene oxide is arrived；
(3) 15.0g polyvinyl alcohol, 1.5g sodium alginate and 30.0g calcium carbonate are sequentially added and fills 300mL deionized water
Beaker in, 2h is stirred at 93 DEG C, solid is completely dissolved, and obtains mixed liquor A；The amino silane for taking 3.75g step (2) to prepare
Change graphene oxide to be added in mixed liquor A, continues to stir 12h at 85 DEG C, obtain polyvinyl alcohol/Aminosilylation graphene oxide
Gel；Polyvinyl alcohol/Aminosilylation graphene oxide gel is instilled into 5%(W/V with syringe after stirring) calcium chloride-
It is saturated in boric acid solution, it can be seen that black ball moment is formed, and continues to harden 12h in calcium chloride-saturation boric acid solution；
It is then 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, being washed repeatedly to neutrality with a large amount of distilled water to get big to final product polyvinyl alcohol/Aminosilylation graphene oxide
Hole composite balls.
Embodiment 4
(1) graphite oxide prepared by 50mg embodiment 1 is dispersed in 100mL deionized water, magnetic stirrer over night, is formed
Graphene oxide soliquid；Then it is ultrasonically treated 2h in Ultrasound Instrument, makes the thin peeling of oxidized graphite flake, is formed uniform and stable
Dispersion liquid to get arrive 0.5mg/mL graphene oxide dispersion；
(2) under stirring condition, 10mL 3- aminopropyl triethoxysilane is added in the deionized water of 100mL, is gradually risen
Temperature reacts 8h to 40 DEG C；Then graphene oxide dispersion prepared by step (1) is added in above-mentioned reaction system and is stirred instead
4h is answered, flocky precipitate is obtained；Flocky precipitate is washed repeatedly with deionized water, is centrifugated, solid is then placed in vacuum
It is dried in drying box to get Aminosilylation graphene oxide is arrived；
(3) 15.0g polyvinyl alcohol, 7.5g sodium alginate and 15.0g calcium carbonate are sequentially added and fills 300mL deionized water
Beaker in, 2h is stirred at 95 DEG C, solid is completely dissolved, and obtains mixed liquor A；The amino silane for taking 0.5g step (2) to prepare
Change graphene oxide to be added in mixed liquor A, continues stirring at 75 DEG C for 24 hours, obtain polyvinyl alcohol/Aminosilylation graphene oxide
Gel；Polyvinyl alcohol/Aminosilylation graphene oxide gel is instilled into 5%(W/V with syringe after stirring) calcium chloride-
It is saturated in boric acid solution, it can be seen that black ball moment is formed, and continues to harden 30h in calcium chloride-saturation boric acid solution；
It is then 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, being washed repeatedly to neutrality with a large amount of distilled water to get big to final product polyvinyl alcohol/Aminosilylation graphene oxide
Hole composite balls.
The example that the present invention is applied to water process:
(1) using the adsorbent and its absorption property of the preparation of batch type static state adsorption experiment method validation the method for the present invention.Tool
Gymnastics as: measure 100mL in advance prepared certain initial concentration Cu2+、Pb2+Solution is used in 200mL conical flask
The HCl/NaOH solution tune pH of 0.1mol/L is 6.0；Using the product of embodiment 2 as removal Cu2+、Pb2+Adsorbent, according to
Certain dosage adds；It 25 DEG C, revolving speed 150rpm, vibrates in constant temperature air bath oscillator；For 24 hours after adsorption equilibrium, supernatant is taken
After 0.22 μm of filtering with microporous membrane of liquid, water sample analysis is carried out with spectrophotometry.As a result as depicted in figs. 1 and 2.
By Fig. 1 and Fig. 2 it is found that Langmuir, Freundlich Isothermal Model can preferably describe product to Cu2+Or Pb2+
Absorption behavior, and by model be calculated to Cu2+、Pb2+Maximum saturation adsorbance be respectively as follows: 96.22mg/g and
Thus 278.17mg/g illustrates adsorbent prepared by the present invention to Cu close to experiment value2+、Pb2+There is preferable removal effect.
(2) 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 polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls are right after 5 absorption-parsing circulation
Cu2+、Pb2+Adsorption rate still can reach 75% or more of initial adsorption amount, and polyvinyl alcohol/Aminosilylation graphite oxide
Alkene macropore composite balls still maintain good spherical shape, are not damaged.This illustrates polyvinyl alcohol/Aminosilylation graphite oxide
Alkene macropore composite balls are with good stability, 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
Invention is explained in detail for good embodiment, those skilled in the art should understand that, it can be to of the invention
Technical solution is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered
In scope of the presently claimed invention.
Claims (5)
1. a kind of for heavy metal ion adsorbed isolated polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls system
Preparation Method, which comprises the 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, by 3- aminopropyl triethoxysilane be added deionized water in, 3- aminopropyl triethoxysilane and
The volume ratio of deionized water is 1:10~100, is gradually heated to 40~80 DEG C, reacts 4~8h；Then graphene oxide is dispersed
Reaction system is added in liquid, and stirring 4 under ice bath~for 24 hours, obtain flocky precipitate；After reaction, it is washed repeatedly with deionized water
Flocky precipitate, centrifuge separation, is placed in a vacuum drying oven drying for solid, obtains Aminosilylation graphene oxide solid；
(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
Aminosilylation graphene oxide stirs 4~12h at 75~95 DEG C, obtains polyvinyl alcohol/Aminosilylation graphene oxide
Gel, wherein Aminosilylation graphene oxide: the mass ratio of polyvinyl alcohol is 1:4~30；With syringe by Aminosilylation
Graphene oxide/polyvinyl alcohol gel instills calcium chloride: saturation boric acid solution=5g:100mL calcium chloride-saturation boric acid solution
In, moment forms black ball, continues to harden 12h~48h in calcium chloride-saturation boric acid solution；Then spherical product is turned
It moves in deionized water, hydrochloric acid solution is added dropwise, is slowly stirred, form the composite balls with cavernous structure；It will with a large amount of distilled water
Composite balls wash repeatedly to neutrality to arrive polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls.
2. polyvinyl alcohol according to claim 1/Aminosilylation graphene oxide macropore composite balls preparation method,
It is characterized in that, 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. polyvinyl alcohol according to claim 1/Aminosilylation graphene oxide macropore composite balls preparation method,
Be characterized in that: mass fraction of the polyvinyl alcohol in mixed liquor A is 3%~6% in the step (3).
4. a kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls, it is characterised in that: pass through claim 1-3
Described in any item polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls preparation method is prepared.
5. polyvinyl alcohol as claimed in claim 4/Aminosilylation graphene oxide macropore composite balls are in 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 true CN106311185B (en) | 2019-01-18 |
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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 |
| CN106824118A (en) * | 2017-03-29 | 2017-06-13 | 邱发龙 | A kind of adsorbent for heavy metal for sewage disposal and preparation method thereof |
| CN107746054A (en) * | 2017-11-10 | 2018-03-02 | 西安近代化学研究所 | A kind of synthetic method of 3 aminopropyltriethoxywerene werene modified graphene oxide |
| CN108246268A (en) * | 2018-01-08 | 2018-07-06 | 兰州理工大学 | A kind of graphene oxide adsorbing material of Aminosilylation and preparation method thereof |
| CN110756175A (en) * | 2019-08-26 | 2020-02-07 | 河海大学 | Preparation method of ultralight efficient adsorbent foam for purifying dye wastewater |
| CN110893338A (en) * | 2019-08-26 | 2020-03-20 | 河海大学 | Preparation method of polymer nano composite gel |
| CN112341579B (en) * | 2020-11-26 | 2023-07-25 | 蚌埠市华东生物科技有限公司 | Adsorption resin for stevioside separation and purification and application thereof |
| CN112427026A (en) * | 2020-12-02 | 2021-03-02 | 邱芳璟 | Preparation method of polyvinyl alcohol functionalized carbon nanotube composite ball |
| CN113526495B (en) * | 2021-08-16 | 2022-09-06 | 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 |
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 |
| CN103877953A (en) * | 2014-03-30 | 2014-06-25 | 河南城建学院 | Hydrogel for sewage treatment as well as preparation method thereof |
| 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 |
| 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 CN201610772033.7A patent/CN106311185B/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 |
| CN103877953A (en) * | 2014-03-30 | 2014-06-25 | 河南城建学院 | Hydrogel for sewage treatment as well as preparation method thereof |
| 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 |
| 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 and3-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;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 |
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