CN109847722A - A kind of compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol and preparation method thereof - Google Patents
A kind of compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol and preparation method thereof Download PDFInfo
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- CN109847722A CN109847722A CN201910067027.5A CN201910067027A CN109847722A CN 109847722 A CN109847722 A CN 109847722A CN 201910067027 A CN201910067027 A CN 201910067027A CN 109847722 A CN109847722 A CN 109847722A
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- polyvinyl alcohol
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Abstract
The present invention relates to compound carbon-based hydrophobic oil absorption materials of a kind of assemble in situ polyvinyl alcohol and preparation method thereof, the compound carbon-based hydrophobic oil absorption material of the assemble in situ polyvinyl alcohol has both good hydrophobic oleophilic oil characteristic (its water contact angle is up to 146 °), higher absorption multiplying power and mechanical strength, recycling can be realized by simply squeezing simultaneously, the preparation method of the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol is environmentally protective, cost is relatively low, has potential using value in environment protection fields such as the absorption of oils and organic solvent.
Description
Technical field
It is prepared the present invention relates to compound carbon-based hydrophobic oil absorption material of a kind of assemble in situ polyvinyl alcohol and preparation method thereof
The oil suction multiplying power of the compound carbon-based hydrophobic oil absorption material of polyvinyl alcohol is high, excellent in mechanical performance, while can repeatedly use, and belongs to
Environmental protection macromolecule field of compound material.
Background technique
The water contamination accident frequently occurred, including petroleum and chemicals overflow and caused accident and disaster make therefrom
The water quality for obtaining some areas in the world is contaminated.It includes physical method, chemical method and life that the method for oil product is removed usually from water
Object method, in these methods, physical absorption are considered as the method for the processing oil leak accident of most environment-friendly high-efficiency low cost.But
It is traditional inorganic adsorbing material (active carbon, expanded graphite, clay etc.), and synthetic polymer adsorbent material (polyurethane foam, three
Poly cyanamid sponge, macropore rubber gels etc.) and natural organic adsorption material (bombax cotton, cotton, stalk etc.) there is such as
Adsorbance is low, and oil-water selectivity is poor, the various deficiencies such as recyclability difference.Therefore, it is high to develop a kind of absorption multiplying power, grease selection
Property it is good, can be recycled, while there is the adsorbent material of lower cost to have a very important significance.
There are many excellent performances by the new carbon of representative of graphene.Such as high specific surface area, hydrophobic parent
Oily characteristic and good chemical stability become a kind of potentially adsorbent material for polluted-water processing.Pass through
CVD method, desivac, the methods of hydro-thermal method or 3D printing can prepare a variety of carbon-based three-dimensional knots with diverse microcosmic structure
Structure body, these aerogel three-dimensional structures have shown the absorption property of good oil product and organic solvent, such as absorption times
The characteristics such as rate is high, and adsorption rate is fast.For example, high oil product absorption multiplying power is come for three-dimensional structure graphene aerogel
Derived from the porous structure and extremely low density (usually less than 5 mg/cm of material3).But the lower intensity of material itself causes
It can not preferably maintain macrostructure after adsorbing oil type liquid, and then be difficult to adopt conventional mechanical fashion of extrusion and made profits again
With.In the report of the past, to recycling usually using heating distillation or combustive regeneration for carbon-based aeroge oil absorption material
Mode, and these modes have that efficiency is lower or secondary pollution in practical applications.At the same time, due to carbon-based
Aerogel material cost of material is higher, and preparation process is complicated, so that they are difficult to obtain scale application in practice.
The carbon-based aeroge of either traditional adsorbent material or novel high absorption multiplying power, in actual application
In there is different problems.It is therefore seen that realize the high hydrophobicity of adsorbent material, high oil absorption multiplying power, high mechanical property simultaneously
Can and the characteristics such as reusable be a great challenge project.
Summary of the invention
Present invention seek to address that existing adsorbent material hydrophobicity is poor, oil suction multiplying power is low, and recycling number is few, mechanical strength
The problems such as low, to provide a kind of excellent absorption to remove spilling oil product or other organic pollutions in water using physical method
Material.For this purpose, it is an object of the invention to propose a kind of compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol and its system
Preparation Method.
The compound carbon-based hydrophobic oil absorption material of a kind of assemble in situ polyvinyl alcohol proposed by the present invention, the hydrophobic oil suction material
Material is made of polyvinyl alcohol and c-based nanomaterial, is crosslinked in acidic environment through hydro-thermal, is cleaned and obtain after drying；It is carbon-based to receive
The dosage of rice material is the 2-10% of polyvinyl alcohol quality, and the concentration of polyvinyl alcohol water solution is 3-10%.
In the present invention, the c-based nanomaterial includes graphene oxide, graphene, carbon nanotube, carbon black or carbosphere
One of or it is several.
In the present invention, graphene, carbon nanotube, carbon black or carbosphere experienced acidification before the use, in turn
Realize that it is evenly dispersed in aqueous systems.
In the present invention, the acidic environment in the hydrophobic oil absorption material water-heat process is provided by 98% sulfuric acid solution, in system
The additive amount of 98% sulfuric acid is the 10-40% of polyvinyl alcohol quality.
In the present invention, hydro-thermal crosslinking control hydrothermal temperature is 150-240 DEG C, and the hydro-thermal time is 12-48h.
In the present invention, the drying mode includes supercritical drying, freeze-drying, is appointed in vacuum drying or natural drying
It is a kind of.
The preparation method of the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol proposed by the present invention, specific steps are such as
Under:
(1) PVA particle 95 DEG C at a temperature of be dissolved in water and to form transparent dispersion solution after, oxygen is added thereto after cooling
Graphite alkene solution or acidified modified graphene, carbon nanotube, carbon black or carbosphere solution, mechanical stirring is after mixing
Aqueous sulfuric acid is added, further mechanical stirring is uniformly mixed, and obtains mixed solution；
(2) mixed solution that step (1) obtains is placed in hydrothermal reaction kettle, is lauched heat cross-linking in the reaction temperature of setting, obtains
Obtain assemble in situ polyvinyl alcohol composite carbon-based material；
(3) the assemble in situ polyvinyl alcohol composite carbon-based material of the hydro-thermal preparation obtained step (2) immerses in pure water environment,
The complete raw material components of unreacted are removed, after being further dried, obtain the compound carbon-based hydrophobic oil absorption material of polyvinyl alcohol.
In the present invention, graphene oxide solution or acidified modified graphene in step (1), carbon nanotube, carbon black or
The dosage of carbosphere solution is the 2-10% of polyvinyl alcohol quality, and the concentration of polyvinyl alcohol water solution is 3-10%.
In the present invention, hydro-thermal crosslinking control hydrothermal temperature is 150-240 DEG C in step (2), and the hydro-thermal time is 12-48h.
The beneficial effects of the present invention are: the method for the invention is easy to operate, and prepared polyvinyl alcohol is compound carbon-based thin
Water oil absorption material excellent combination property, the environment protection fields such as potential absorption for being widely used in oils and organic solvent.
Other features and advantages of the present invention will be explained in the following detailed description section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following reality
It applies mode to be used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 shows the preparation method flow chart of the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol according to the present invention.
Fig. 2 shows the hydrophobic property (materials of the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol according to the present invention
The water contact angle of material is 146 °).
Fig. 3 shows the absorption of the hydrophobic oil absorption material of assemble in situ polyvinyl alcohol composite graphite olefinic carbon base according to the present invention not
With the absorption multiplying power histogram of organic solvent.
Fig. 4 shows the hydrophobic oil absorption material quick adsorption of assemble in situ polyvinyl alcohol composite graphite olefinic carbon base according to the present invention
Underwater chloroform drop experiment.
Specific embodiment
Below in conjunction with attached drawing, specific embodiments of the present invention will be described in detail.It should be understood that this place
The specific embodiment of description is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Embodiment 1
It weighs 5g PVA to be placed in the graphene oxide solution (concentration of graphene oxide is 0.5mg/ml) of 100 ml, in 95 DEG C
The aqueous sulfuric acid 5mL of 4 mol/L is further added in magnetic agitation dissolution in the solution after evenly mixing, and de- by mixing
After bubble, the above component is uniformly mixed and is placed in water heating kettle, hydro-thermal 24 hours, then obtains hydro-thermal under the conditions of 180 DEG C
Foam be placed in clear water and impregnate 3 days, it is primary to change within each 24 hours water, and then place the material in freeze-drying 72 in freeze drier is small
When, obtain the compound carbon-based hydrophobic oil absorption material 1 of polyvinyl alcohol.
Embodiment 2
It weighs 8g PVA to be placed in the aqueous solution for the carbon nanotube that 100 ml are dispersed with 120 mg acidifications, be stirred in 95 DEG C of magnetic force
Dissolution is mixed, the aqueous sulfuric acid 10ml of 3 mol/L is further added in mixed solution after evenly mixing, and by mixing deaeration
Afterwards, the above component is uniformly mixed and is placed in water heating kettle, the hydro-thermal 12 hours under the conditions of 200 DEG C then obtains hydro-thermal
Foam is placed in clear water and impregnates 3 days, and it is primary to change within each 24 hours water, and material is then carried out supercritical drying, obtains polyvinyl alcohol
Compound carbon-based hydrophobic oil absorption material 2.
Embodiment 3
It weighs 10g PVA to be placed in the aqueous solution for the graphene nanometer sheet that 100 ml are dispersed with 200 mg acidifications, in 95 DEG C
Magnetic agitation dissolution, is further added the aqueous sulfuric acid 5ml of 5 mol/L, and through overmulling in mixed solution after evenly mixing
After closing deaeration, the above component is uniformly mixed and is placed in water heating kettle, the hydro-thermal 24 hours under the conditions of 200 DEG C, then by hydro-thermal
The foam of acquisition is placed in clear water and impregnates 3 days, and it is primary to change within each 24 hours water, is then freeze-dried material, obtains poly- second
The compound carbon-based hydrophobic oil absorption material 3 of enol.
Comparative example 1
Weigh polyether polyol with high activity 100g, catalyst triethanolamine 3g, dibutyl tin dilaurate 1.5g, organosilyl surface
Activating agent 9g, physical blowing agent trifluorotrichloroethane 22.2g, deionized water 1g are placed in reaction vessel, are sufficiently stirred, and mix
Uniformly, mixed liquor is placed in a vacuum drying oven, after vacuumizing the bubble removed in mixed system twice, two is added in component
Isocyanates pours into mold rapidly after mixed system progress mechanical stirring is uniform, is placed in 60 DEG C of baking ovens and foams, and 120
After minute, polyurethane foam material is removed from the molds, obtains polyurethane foam oil absorption material.
Comparative example 2
1g PVA is weighed, 4g nano-cellulose is placed in 100ml deionized water, mixes 1 hour under the conditions of 90 DEG C, in system
The glutaraldehyde water solution that 250 microlitres of mass fractions are 25% is added, the dilution heat of sulfuric acid for being further 1% by the way that mass fraction is added
After the pH value adjustment value 4-6 of the above system, the gel solution of acquisition is poured into curing mold, 75 DEG C of vacuum drying oven is placed in
After middle solidification is crosslinked 3 hours, the hydrophobic oil suction foamed material of cellulose-polyvinyl alcohol is obtained.
The hydrophobic oil absorption material laboratory sample performance test data table of table 1.
| Apparent density (mg/cm3) | Oil suction multiplying power %(chloroform) | Water contact angle (hydrophobicity) | |
| Embodiment 1 | 77 mg/cm3 | 47 | 148 |
| Embodiment 2 | 84 mg/cm3 | 45 | 145 |
| Embodiment 3 | 101 mg/cm3 | 41 | 144 |
| Comparative example 1 | 95 mg/cm3 | 18 | 89 |
| Comparative example 2 | 117 mg/cm3 | 14 | 102 |
From upper table, it is apparent that the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol of the invention is with good
Hydrophobic oleophilic oil characteristic, while being much higher than other oil absorption materials by the oil suction multiplying power of case of chloroform.
It is noted that the above content is combine specific preferred embodiment made for the present invention further specifically
It is bright, and it cannot be said that a specific embodiment of the invention is only limitted to this, for the ordinary skill people of the technical field of the invention
For member, under the premise of not departing from design of the invention, several simple deductions or replacement can also be made, should all be regarded
Scope of patent protection is determined to belong to claims that the present invention is submitted.
Claims (9)
1. a kind of compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol, which is characterized in that the hydrophobic oil absorption material
It is made of polyvinyl alcohol and c-based nanomaterial, is crosslinked in acidic environment through hydro-thermal, cleaned and obtained after drying；Carbon-based nano
The dosage of material is the 2-10% of polyvinyl alcohol quality, and the concentration of polyvinyl alcohol water solution is 3-10%.
2. the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol according to claim 1, it is characterised in that described
C-based nanomaterial includes one of graphene oxide, graphene, carbon nanotube, carbon black or carbosphere or several.
3. the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol according to claim 2, which is characterized in that graphite
Alkene, carbon nanotube, carbon black or carbosphere experienced acidification before the use, and then realize that it is uniform in aqueous systems
Dispersion.
4. the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol according to claim 1, which is characterized in that described
Acidic environment in hydrophobic oil absorption material water-heat process is provided by 98% sulfuric acid solution, and the additive amount of 98% sulfuric acid is poly- second in system
The 10-40% of enol quality.
5. the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol according to claim 1, which is characterized in that hydro-thermal
It is 150-240 DEG C that hydrothermal temperature is controlled in cross-linking process, and the hydro-thermal time is 12-48h.
6. the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol according to claim 1, which is characterized in that described
Drying mode includes supercritical drying, freeze-drying, any in vacuum drying or natural drying.
7. a kind of preparation method of the compound carbon-based hydrophobic oil absorption material of assemble in situ polyvinyl alcohol as described in claim 1,
It is characterized in that specific step is as follows:
(1) PVA particle 95 DEG C at a temperature of be dissolved in water and to form transparent dispersion solution after, oxygen is added thereto after cooling
Graphite alkene solution or acidified modified graphene, carbon nanotube, carbon black or carbosphere solution, mechanical stirring is after mixing
Aqueous sulfuric acid is added, further mechanical stirring is uniformly mixed, and obtains mixed solution；
(2) mixed solution that step (1) obtains is placed in hydrothermal reaction kettle, is lauched heat cross-linking in the reaction temperature of setting, obtains
Obtain assemble in situ polyvinyl alcohol composite carbon-based material；
(3) the assemble in situ polyvinyl alcohol composite carbon-based material of the hydro-thermal preparation obtained step (2) immerses in pure water environment,
The complete raw material components of unreacted are removed, after being further dried, obtain the compound carbon-based hydrophobic oil absorption material of polyvinyl alcohol.
8. preparation method according to claim 7, it is characterised in that graphene oxide solution or acidification change in step (1)
Property graphene, carbon nanotube, the 2-10% that the dosage of carbon black or carbosphere solution is polyvinyl alcohol quality, polyvinyl alcohol is water-soluble
The concentration of liquid is 3-10%.
9. preparation method according to claim 7, it is characterised in that hydro-thermal crosslinking control hydrothermal temperature is in step (2)
150-240 DEG C, the hydro-thermal time is 12-48h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210114A (en) * | 2020-10-27 | 2021-01-12 | 福州大学 | Preparation method of ultrahigh-strength multifunctional polyvinyl alcohol-based oil gel elastomer |
| CN113083251A (en) * | 2021-03-30 | 2021-07-09 | 安徽光特新材料科技有限公司 | Preparation method and application of boron nitride modified polyvinyl alcohol composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN103145125A (en) * | 2013-04-01 | 2013-06-12 | 兰州大学 | Preparation method for high adsorptivity three-dimensional self-assembly graphene |
| CN106032274A (en) * | 2015-03-19 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene hydrogel, graphene aerogel as well as preparation method and application thereof |
| CN108715443A (en) * | 2018-08-23 | 2018-10-30 | 燕山大学 | A kind of preparation method of graphene hydrogel |
| CN108745290A (en) * | 2018-07-12 | 2018-11-06 | 山东佳星环保科技有限公司 | The preparation method of graphene/carbon nano-tube composite aerogel with efficient oil absorbency |
| CN108854977A (en) * | 2018-07-31 | 2018-11-23 | 李忠 | A kind of hydrophobic oil suction modified sponge composite material and preparation method |
-
2019
- 2019-01-24 CN CN201910067027.5A patent/CN109847722B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN103145125A (en) * | 2013-04-01 | 2013-06-12 | 兰州大学 | Preparation method for high adsorptivity three-dimensional self-assembly graphene |
| CN106032274A (en) * | 2015-03-19 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene hydrogel, graphene aerogel as well as preparation method and application thereof |
| CN108745290A (en) * | 2018-07-12 | 2018-11-06 | 山东佳星环保科技有限公司 | The preparation method of graphene/carbon nano-tube composite aerogel with efficient oil absorbency |
| CN108854977A (en) * | 2018-07-31 | 2018-11-23 | 李忠 | A kind of hydrophobic oil suction modified sponge composite material and preparation method |
| CN108715443A (en) * | 2018-08-23 | 2018-10-30 | 燕山大学 | A kind of preparation method of graphene hydrogel |
Non-Patent Citations (1)
| Title |
|---|
| JIAN DAI ET AL.: ""High structure stability and outstanding adsorption performance of graphene oxide aerogel supported by polyvinyl alcohol for waste water treatment"", 《MATERIALS AND DESIGN》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210114A (en) * | 2020-10-27 | 2021-01-12 | 福州大学 | Preparation method of ultrahigh-strength multifunctional polyvinyl alcohol-based oil gel elastomer |
| CN113083251A (en) * | 2021-03-30 | 2021-07-09 | 安徽光特新材料科技有限公司 | Preparation method and application of boron nitride modified polyvinyl alcohol composite material |
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