CN109939651A - A kind of ZnO/PAN composite material, preparation method and application - Google Patents
A kind of ZnO/PAN composite material, preparation method and application Download PDFInfo
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- CN109939651A CN109939651A CN201811654251.6A CN201811654251A CN109939651A CN 109939651 A CN109939651 A CN 109939651A CN 201811654251 A CN201811654251 A CN 201811654251A CN 109939651 A CN109939651 A CN 109939651A
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Abstract
The present invention relates to a kind of ZnO/PAN composite materials, preparation method and application, belong to organic composite material technical field.The material is grafted on PAN fiber for ZnO and is made.Carboxylated PAN fiber is made in PAN fiber basic hydrolysis；Sodium hydroxide and four acetate hydrate zinc are dissolved in hybrid reaction in dehydrated alcohol, obtain ZnO seed colloidal sol；Carboxylated PAN fiber and ZnO seed colloidal sol are mixed, modified-reaction is simultaneously annealed, and modified PAN fiber is obtained；Modified PAN fiber is added in zinc nitrate hexahydrate and the mixed liquor of hexa and is reacted, washs, filter, dry, obtain the material.The material can be used as the adsorbent for extracting uranium, solves the problems such as traditional adsorbent material specific surface area is small, and space utilization rate is low, increases the adsorption site of adsorbent, significantly improves the uranium absorption performance of the material.The material is easily separated with reaction medium after absorption, reusable.
Description
Technical field
The present invention relates to a kind of ZnO/PAN composite materials, preparation method and application, belong to organic composite material technology neck
Domain.
Background technique
Stimulation with China's extensive development nuclear power and low-carbon economy to global nuclear power developing, the demand day of uranium resource
Beneficial urgent, " uranium diplomacy " will rise to the competition of national interests.The concentration of uranium in the seawater is about 3.3 μ gL-1Although concentration
It is extremely low, but world's seawater amount is huge, wherein contain about 4,500,000,000 tons of uranium, this for example than usual sources uranium resource for providing of land ore
It is about 1000 times more.China is ocean big country, therefore extraction of uranium from seawater technology will be to ensure that uranium resources in China stablizes effective way of supply
One of diameter.From the perspective of national long term growth, the visual field is turned into ocean, exploitation ocean uranium resource get the attention and
Research.
There are many kinds of the methods of the extraction of uranium from seawater, wherein absorption method it is low in cost, it is easy to operate, have stronger versatility,
The common method of seawater uranium enrichment is had become at present, but that there is thermal stability is poor, dynamics is slow, it for current adsorbent
The problems such as his ion interference.Therefore, preparing one kind has biggish adsorbance, faster adsorption time, resists other ion interferences
And reusable new material is very significant.
Summary of the invention
To overcome defect of the existing technology, one of the objects of the present invention is to provide a kind of ZnO/PAN composite material,
The material has excellent uranium absorption performance.
The second object of the present invention is to provide a kind of preparation method of ZnO/PAN composite material, prepared by the method
Journey is easy, easy to industrialized production.
The third object of the present invention is to provide a kind of application of ZnO/PAN composite material, and the material can be applied to uranium
Extraction.
To achieve the purpose of the present invention, following technical scheme is provided.
A kind of ZnO/PAN composite material, the material are grafted on polyacrylonitrile (PAN) fiber for zinc oxide (ZnO) and make
At.
A kind of preparation method of ZnO/PAN composite material of the present invention, the method comprises the following steps:
(1) by PAN fiber under the conditions of 60 DEG C~80 DEG C basic hydrolysis 1h~4h, be made carboxylated PAN fiber.
It is preferred that lye used in basic hydrolysis is sodium hydroxide (NaOH) solution that mass fraction is 1%~4%.
The selective hydrolysis reaction time is 2h~3h.
(2) by sodium hydroxide and four acetate hydrate zinc (Zn (NO3)2·4H2O it) is dissolved in dehydrated alcohol, 40 DEG C~60
DEG C hybrid reaction 3h~4h, obtains ZnO seed colloidal sol.
It is preferred that the mass ratio of sodium hydroxide and four acetate hydrate zinc is 1:1.
(3) carboxylated PAN fiber and ZnO seed colloidal sol are mixed, modified-reaction 5min~30min takes reaction product
It anneals out and at 140 DEG C~150 DEG C, obtains modified PAN fiber.
(4) modified PAN fiber is added in the mixed liquor of zinc nitrate hexahydrate and hexa, is placed in
Under 0.5MPa~2MPa, it is heated to 90 DEG C~95 DEG C reaction 3h~4h；Product washing, filtering are obtained after reaction, it is dried
Filter gained precipitating, obtains final product.
The solvent of the mixed liquor of the zinc nitrate hexahydrate and hexa is the water of deionized water purity or more.
It is preferred that the mass ratio of zinc nitrate hexahydrate and hexa is 1:1~1:5.
The washing, filtering can specifically: are first washed, filtered with dehydrated alcohol；Then will filtering gained precipitating spend from
More than sub- purity water washing, filtering.
A kind of application of ZnO/PAN composite material of the present invention, the application are the adsorbent for extracting uranium；Preferably mention
Take the adsorbent of URANIUM IN SEAWATER.
Beneficial effect
1. solving traditional adsorbent material specific surface area the present invention provides a kind of ZnO/PAN composite material and its application
It is small, the problems such as space utilization rate is low, the adsorption site of adsorbent is increased, the uranium absorption performance of the material is significantly improved,
Existing adsorbent material is substantially better than to uranium absorption aspect, and the material is easy to separate with reaction medium after absorption, it can
Recycling；
2. the method is easy and environmental pollution is small the present invention provides a kind of preparation method of ZnO/PAN composite material.
Detailed description of the invention
Fig. 1 is the Fourier transform infrared spectroscopy figure in embodiment before and after final product adsorption uranium liquid.
Specific embodiment
The present invention is described in detail in the following with reference to the drawings and specific embodiments, but not as the restriction to the invention patent.
In following embodiment:
The diameter of the polyacrylonitrile fibre is 1.8D.
Following adsorption effect detection is carried out to final product obtained in embodiment:
Using the final product after final product and adsorption uranium liquid as sample, using the production of Nicolet company, the U.S.
370 type Fourier Transform Infrared Spectrometer of Avater reaches the scanning times of sample 32 times per minute, and the wave-number range of test is
4000cm-1~400cm-1.The sample of examination of infrared spectrum cooperates tabletting sample preparation using KBr, takes the sample to be tested powder of 2mg~4mg
The KBr powder mixed grinding of body and 100mg~500mg by drying, grinding.To avoid experimental error caused by scattering because of light,
The hybrid solid powder after grinding is put into tablet press machine again and is pressurizeed, after ultimately forming transparent sheet, is put into detection in instrument.
Embodiment 1
(1) 10g polyacrylonitrile (PAN) fiber is dissolved in the NaOH solution that mass fraction is 1%, it is anti-in 60 DEG C of water-baths
1h is answered, carboxylated PAN fiber is made；
(2) 0.120g sodium hydroxide is dispersed in 100mL dehydrated alcohol, by the Zn (CH of 0.114g3COO)2·4H2O
It is dispersed in 75mL dehydrated alcohol, described two solution is mixed, 3h is stirred at 40 DEG C, obtains ZnO seed colloidal sol；
(3) carboxylated PAN fiber and ZnO seed colloidal sol are mixed, modified-reaction 5min, by reaction product take out and
It anneals at 140 DEG C, obtains modified PAN fiber；
(4) by the Zn (NO of 0.300g3)·6H2The hexa of O and 0.300g is dissolved in 100mL deionized water
Mixed liquor is made；The modified PAN fiber of 0.5g is added in the mixed liquor, uniform mixture is formed；Mixture is turned
It moves on in the autoclave of Teflon (Teflon) lining, 90 DEG C of reaction 3h is heated at pressure 0.5MPa, reaction terminates
After be cooled to room temperature；It first washed, filtered with dehydrated alcohol；Then filtering gained precipitating is washed with deionized, filtered；Finally
It is dried to obtain final product at 50 DEG C, is a kind of ZnO/PAN composite material of the present invention.
The final product ZnO/PAN composite material of 0.01g made from the present embodiment is added to the taper that volume is 100mL
In bottle, the uranium solution that 20mL concentration is 100ppm is then added thereto, is adjusted just with the dilute NaOH solution that mass fraction is 1%
The pH of beginning uranium solution is that oscillation reaches adsorption equilibrium at 6,25 DEG C, and the final product after obtaining adsorption uranium liquid does Fourier's change after drying
Change infrared spectroscopy.
Fourier transform infrared spectroscopy figure result is as shown in Figure 1, ZnO/PANF indicates that final product ZnO/PAN is compound in Fig. 1
Material, it can be seen from the figure that 2941cm-1Place is the stretching vibration peak of alkyl, 2243cm-1Place is cyano stretching vibration
Peak, 1453cm-1Place is alkyl stretching vibration peak, and the two remains the characteristic absorption peak of PAN fiber.
ZnO/PANF-U indicates the final product ZnO/PAN composite material after adsorption uranium liquid in Fig. 1, it can be seen from the figure that
For ZnO/PAN-U in 910cm-1There is O=U=O characteristic peak in place, and in 1650cm-1The absorption peak at place has occurred slight red
It moves, this phenomenon proves there is chelation between the-COOH and U (VI) of ZnO/PAN composite material surface.
Embodiment 2
(1) 10g PAN fiber is dissolved in the NaOH solution that mass fraction is 4%, reacts 3h in 80 DEG C of water-baths, be made
Carboxylated PAN fiber；
(2) 0.240g sodium hydroxide is dispersed in 200mL dehydrated alcohol, by the Zn (CH of 0.240g3COO)2·4H2O
It is dispersed in 150mL ethyl alcohol, described two solution is mixed, 4h is stirred at 60 DEG C, obtains ZnO seed colloidal sol；
(3) carboxylated PAN fiber and ZnO seed colloidal sol are mixed, modified-reaction 30min, by reaction product take out and
It anneals at 150 DEG C, obtains modified PAN fiber；
(4) by the Zn (NO of 0.600g3)·6H2The hexa of O and 3.000g is dissolved in 100mL deionized water
Mixed liquor is made；The modified PAN fiber of 0.5g is added in the mixed liquor, uniform mixture is formed；Mixture is turned
It moves on in the autoclave of Teflon (Teflon) lining, 95 DEG C of reaction 4h is heated at pressure 2MPa, after reaction
It is cooled to room temperature；It first washed, filtered with dehydrated alcohol；Then filtering gained precipitating is washed with deionized, filtered；Finally exist
It is dried to obtain final product at 50 DEG C, is a kind of ZnO/PAN composite material of the present invention.
The final product ZnO/PAN composite material of 0.01g made from the present embodiment is added to the taper that volume is 100mL
In bottle, the uranium solution that 20mL concentration is 100ppm is then added thereto, is adjusted just with the dilute NaOH solution that mass fraction is 1%
The pH of beginning uranium solution is that oscillation reaches adsorption equilibrium at 6,25 DEG C, and the final product after obtaining adsorption uranium liquid does Fourier's change after drying
Change infrared spectroscopy.
Fourier transform infrared spectroscopy figure result is as shown in Figure 1, ZnO/PANF indicates that final product ZnO/PAN is compound in Fig. 1
Material, it can be seen from the figure that 2941cm-1Place is the stretching vibration peak of alkyl, 2243cm-1Place is cyano stretching vibration
Peak, 1453cm-1Place is alkyl stretching vibration peak, and the two remains the characteristic absorption peak of PAN fiber.
ZnO/PANF-U indicates the final product ZnO/PAN composite material after adsorption uranium liquid in Fig. 1, it can be seen from the figure that
For ZnO/PAN-U in 910cm-1There is O=U=O characteristic peak in place, and in 1650cm-1The absorption peak at place has occurred slight red
It moves, this phenomenon proves there is chelation between the-COOH and U (VI) of ZnO/PAN composite material surface.
Claims (10)
1. a kind of ZnO/PAN composite material, it is characterised in that: the material is grafted on PAN fiber for ZnO and is made.
2. a kind of preparation method of ZnO/PAN composite material as described in claim 1, it is characterised in that: the method step
It is as follows:
(1) by PAN fiber under the conditions of 60 DEG C~80 DEG C basic hydrolysis 1h~4h, be made carboxylated PAN fiber；
(2) sodium hydroxide and four acetate hydrate zinc are dissolved in dehydrated alcohol, in 40 DEG C~60 DEG C hybrid reaction 3h~4h, are obtained
ZnO seed colloidal sol；
(3) carboxylated PAN fiber and ZnO seed colloidal sol are mixed, modified-reaction 5min~30min, reaction product is taken out simultaneously
It anneals at 140 DEG C~150 DEG C, obtains modified PAN fiber；
(4) modified PAN fiber is added in the mixed liquor of zinc nitrate hexahydrate and hexa, be placed in 0.5MPa~
Under 2MPa, it is heated to 90 DEG C~95 DEG C reaction 3h~4h；Product washing, filtering are obtained after reaction, are sunk obtained by dry filter
It forms sediment, obtains a kind of ZnO/PAN composite material；
The solvent of the mixed liquor of the zinc nitrate hexahydrate and hexa is the water of deionized water purity or more.
3. a kind of preparation method of ZnO/PAN composite material according to claim 2, it is characterised in that: in step (1),
Lye used in basic hydrolysis is the sodium hydroxide solution that mass fraction is 1%~4%.
4. a kind of preparation method of ZnO/PAN composite material according to claim 2, it is characterised in that: in step (1),
Hydrolysis time is 2h~3h.
5. a kind of preparation method of ZnO/PAN composite material according to claim 2, it is characterised in that: in step (2),
The mass ratio of sodium hydroxide and four acetate hydrate zinc is 1:1.
6. a kind of preparation method of ZnO/PAN composite material according to claim 2, it is characterised in that: in step (4),
The mass ratio of zinc nitrate hexahydrate and hexa is 1:1~1:5.
7. a kind of preparation method of ZnO/PAN composite material according to claim 2, it is characterised in that: step is washed in (4)
It washs, filter are as follows: first washed, filtered with dehydrated alcohol；Then filtering gained precipitating is spent to water washing, the mistake of ionic purity or more
Filter.
8. a kind of preparation method of ZnO/PAN composite material according to claim 2, it is characterised in that: in step (1),
Lye used in basic hydrolysis is the sodium hydroxide solution that mass fraction is 1%~4%；Hydrolysis time is 2h~3h；
In step (2), the mass ratio of sodium hydroxide and four acetate hydrate zinc is 1:1；
In step (4), the mass ratio of zinc nitrate hexahydrate and hexa is 1:1~1:5；Washing, filtering are as follows: first use nothing
Water-ethanol washing, filtering；Then filtering gained precipitating is spent into the water washing of ionic purity or more, filtering.
9. a kind of application of ZnO/PAN composite material as described in claim 1, it is characterised in that: the application is to extract uranium
Adsorbent.
10. a kind of application of ZnO/PAN composite material according to claim 9, it is characterised in that: the application is to extract
The adsorbent of URANIUM IN SEAWATER.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112281471A (en) * | 2020-11-02 | 2021-01-29 | 中国船舶重工集团公司第七一八研究所 | Method for catalytically hydrolyzing polyacrylonitrile material under alkaline condition |
| CN115440404A (en) * | 2021-06-03 | 2022-12-06 | 西南科技大学 | Method for treating high-temperature gas cooled reactor fuel element core preparation process wastewater by using novel functional fibers |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112281471A (en) * | 2020-11-02 | 2021-01-29 | 中国船舶重工集团公司第七一八研究所 | Method for catalytically hydrolyzing polyacrylonitrile material under alkaline condition |
| CN115440404A (en) * | 2021-06-03 | 2022-12-06 | 西南科技大学 | Method for treating high-temperature gas cooled reactor fuel element core preparation process wastewater by using novel functional fibers |
| CN115440404B (en) * | 2021-06-03 | 2024-04-26 | 西南科技大学 | Method for treating high-temperature gas cooled reactor fuel element core preparation process wastewater by using functionalized fibers |
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Application publication date: 20190628 |