CN110180510A - One kind slowing down the nano thin-film and device of reservoir " turning over library " phenomenon - Google Patents
One kind slowing down the nano thin-film and device of reservoir " turning over library " phenomenon Download PDFInfo
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- CN110180510A CN110180510A CN201910474916.3A CN201910474916A CN110180510A CN 110180510 A CN110180510 A CN 110180510A CN 201910474916 A CN201910474916 A CN 201910474916A CN 110180510 A CN110180510 A CN 110180510A
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Abstract
The present invention relates to the nano thin-films that one kind slows down reservoir " turning over library " phenomenon, it include three-decker, first layer is graphene oxide/water-soluble Arabic gum/polyvinyl alcohol nano film, and the second layer is charcoal adsorption layer, and third layer is polyacrylonitrile-charcoal nano-fiber film.The present invention achievees the purpose that slowing down reservoir " turning over library " phenomenon causes water quality deterioration by the special designing to nanometer thin film layer.
Description
Technical field
The present invention relates to the nano thin-films that a kind of nano thin-film more particularly to one kind slow down reservoir " turning over library " phenomenon.
Background technique
The first purpose that reservoir is built is exactly its emerging benefit effect, Runoff adjustment, flood storage mend it is withered, make natural water in the time and
The demand of people can be spatially better met, is supplied drinking water and irrigation water for neighbouring area.Reservoir " turning over library " (reservoir
" turning over bottom ") phenomenon concrete reason first is that the mud due to bottom storehouse in anaerobic state and exists a large amount of due to overstocking for a long time
Anaerobic bacteria, as temperature increases, dissolved oxygen is insufficient, mud Rapid Fermentation generate the anaerobic gas such as methane and constantly on gush, cause
Water body blacks, and may bring the polluter in mud into overlying water.It can be seen that " turning over library " phenomenon of reservoir influences whether
The water quality of water body.
Nano-fiber film is mainly prepared by high molecular polymer, and it is quiet for comparing attract attention in technology of preparing at present
Electrospinning.Since the nano-fiber film that is prepared has pulp freeness larger, aperture is small, associativity is good between hole
Many advantages, such as good, catalyst easily loads, and applicability is extensive, make it in terms of water process, medicine and the fields such as organizational project all
There is good application prospect.Wherein for nanofiber due to diameter refinement, fiber molecule segment or functional group are exposed to its surface
Probability improve, to also improve catalyst its area load a possibility that, propose nano-fiber film functionalization efficiency
The high application to satisfaction in terms of environmental improvement and reparation.
Charcoal is biological material under the conditions of limiting oxygen, low temperature (< 800 DEG C), a kind of virtue obtained by heat resolve
Fragrant carbon and mineral solid product abundant.Due to special porous structure and high-specific surface area, charcoal is not only used as soil
Renovation agent improves the fertility of soil, and carbon sequestration capacity can capture carbon to soil thus mitigation of climate change from atmosphere,
And it is as adsorbent, can pollutant effectively in adsorbed water body and soil, reduce pollutant to the utilizability of biology
And toxicity.Charcoal is made of different organic and inorganic components, can be by different mechanism and pollutant reaction, for example is matched
Position, absorption, aromatic rings-Π key and the reaction of cation-Π key and electrostatic attraction.Charcoal can remove the energy of pollutant in water
Power makes it one of suitable adsorbent in the water process especially complex wastewater containing multiple pollutant, due to its warp
Ji, efficient feature get more and more people's extensive concerning in terms of pollutant process and Drinking w ater reparation.
At present in the patent for charcoal for water process and soil remediation etc., the preparation and application of charcoal are deposited
In following problem:
(1) the charcoal characteristic prepared by different biomass is different, faces varying environment and pollution condition, application effect
Stability difference is larger.
(2) in charcoal preparation process, pyrolysis temperature has larger impact to its specific surface area and porosity, and influences it
Adsorption effect applied to pollutant.
(3) there are subsequent recycling problems after charcoal absorption pollutant.
Summary of the invention
The present invention provides one kind and slows down reservoir and " turn over to solve the problems, such as reservoir " turning over library " phenomena impair Reservoir Water Quality
The nano thin-film of library " phenomenon is reached by the special designing to nanometer thin film layer and is slowed down reservoir " turning over library " phenomenon water quality is caused to dislike
The purpose of change.
The technical solution used in the present invention are as follows: one kind slows down the nano thin-film of reservoir " turning over library " phenomenon, nano thin-film packet
Three-decker is included, first layer is graphene oxide/water-soluble Arabic gum/polyvinyl alcohol nano film (GO/GA/
PVA), i.e., first layer nano-fiber film includes GO, GA and PVA, and the second layer is charcoal adsorption layer, and third layer is polypropylene
Nitrile (PAN)-charcoal nano-fiber film.
Further, the polyacrylonitrile-charcoal nano-fiber film the preparation method comprises the following steps:
S1 will charcoal made from red cedar be added aqueous slkali in be thoroughly mixed after, by sample carry out high-temperature activation, cleaning,
Charcoal after being dried to obtain activation；
Polyacrylonitrile is dissolved in the mixed solution of n,N-Dimethylformamide and dimethyl sulfoxide (DMF/DMSO) by S2, is added
Charcoal after activation obtains mixture, and the mixture is prepared into PAN- biology carbon nanofibers by electrostatic spinning technique
Film, cleaning, drying.
Further, charcoal adsorption layer the preparation method comprises the following steps: dry leaf is put into atmosphere furnace, under argon atmosphere
800-1000 DEG C is warming up to the heating rate of 5-10 DEG C/min and keeps the temperature 1-2h, and after reaction, the leaf of charing is impregnated
In hydrochloric acid solution, then drying is made.
Further, graphene oxide/water-soluble Arabic gum/polyvinyl alcohol nano film the preparation method comprises the following steps:
S1 sulfuric acid and powdered graphite mixing and ice bath stirring, obtain homogeneous phase solution, Gao Meng then are added into the homogeneous phase solution
Sour potassium and sodium nitrate stirring, under strong acid environment, potassium permanganate and nitrate anion all have strong oxidizing property, after reacting a period of time,
Deionized water progress heating water bath is added, and the reaction was continued, is cooled to room temperature, is centrifuged after reaction after hydrogen peroxide stirring is added
Processing takes supernatant, is added deionized water and hydrochloric acid in Xiang Suoshu supernatant, stirring, centrifugation, dry graphene oxide；Sulfuric acid
It is strong protonic acid, graphite layers can be entered, sulfuric acid addition is to provide acidic environment, and potassium permanganate aoxidizes in acid condition
Property reinforce.It is to remove extra potassium permanganate that hydrogen peroxide, which is added,.It is because of dense sulphur that ice bath is used when preparing homogeneous phase solution
Acid reaction meeting heat release, ice bath can reduce environment temperature, make reaction should not excessively acutely.
Water-soluble Arabic gum and polyvinyl alcohol are dissolved separately in deionized water that obtain water-soluble Arabic gum molten by S2
Liquid and poly-vinyl alcohol solution, graphene oxide is added in water-soluble Arabic gum and obtains mixed solution, and stirring adds poly- second
GO/GA/PVA nano-fiber film is made using electrostatic spinning technique in enolate solution.
Further, the preparation method of the charcoal is to be pyrolyzed at 520-530 DEG C using red cedar, and pyrolysis time is
2-4min；The aqueous slkali is NaOH solution, and the concentration of the NaOH solution is 150-250g/L；The activation of the high-temperature activation
Condition is to be warming up to 800 DEG C with the heating rate of 5 ~ 10 DEG C/min and in 800 DEG C of holding 2h, and circulation has 200mL/ during activation
The nitrogen of the flow velocity of min；Drying condition is 18-24h at 50-60 DEG C.
Further, the n,N-Dimethylformamide and dimethyl sulfoxide volume ratio are 8:1-10:1；N, N- dimethyl
Formamide and dimethyl sulfoxide purity are 99.99%, and the charcoal of activation and the mass ratio of PAN, DMF/DMSO mixture are 1.5-
2%；Drying condition is to dry 8-12h at 50-60 DEG C.
Further, the mass ratio that the sulfuric acid is mixed with powdered graphite is 26:1-28:1, and potassium permanganate and nitric acid is added
Being stirred after sodium, stirring condition are to stir 20-30min at 35-45 DEG C；To sulfuric acid, powdered graphite, potassium permanganate and nitric acid
30-40min is reacted under 75-85 DEG C of water bath condition after deionized water is added in sodium mixture.
Further, the mass ratio of required water-soluble Arabic gum, polyvinyl alcohol and polyvinyl alcohol is 1:20:20-1:25:
25。
Further, in the electrostatic spinning technique electrospinning parameters be electric field strength: 1.0-1.2KV/cm, flow velocity:
1.2-1.4mL/h fiber collecting device revolving speed: 300-400rpm.
Further, it being fixed with hollow tube on the nano thin-film periphery, the hollow tube side wall is provided with several apertures,
The aperture is led to outside hollow tube by the hollow conduit body, and several apertures are set to nano thin-film and the hollow tube connects
Meet place.
Further, the hollow tube is PVC hose.
Beneficial effect caused by the present invention includes: that the present invention relates to the nanometer thins that one kind slows down reservoir " turning over library " phenomenon
Film essentially consists in the effect of multi-layer nano film.Upper layer is GO/GA/PVA nano-fiber film, and centre is that charcoal adsorbs
Layer, lower layer are PAN- charcoal nano-fiber film.When bottom storehouse mud anaerobic gas generation, which turns over, to be gushed, contact lower layer PAN- first is raw
Object carbon nanofibers film has mud and some of the contaminants certain barrier and adsorption effect, for entering in film
The pollutant of interbed, the charcoal of membrane middle layer has preferably the pollutant poured in due to its high-specific surface area at this time
Buffering and adsorption effect prevent pollutant from spreading to upper layer.Upper layer is GO/GA/PVA nano-fiber film, has certain dredge
It is aqueous, overlying water is contacted, the lower infiltration of overlying water is reduced.
Based on the above content, present invention has an advantage that
(1) present invention makes nano-fiber film using charcoal and graphene oxide, and high specific surface area and material basal plane are rich
Rich functional group, can be combined closely with large area and pollutant, achieve the effect that quickly and efficiently to remove pollutant.
(2) present invention materials environmental protection, to nano-fiber film, preparation process is optimized, using novel Static Spinning
Silk manufacturing technology, makes nano-fiber film have the features such as higher porosity, diameter are evenly distributed.
(3) the structure design that the present invention uses, situations such as fully taking into account applied to reservoir " turning over library ", PVC hose is with holes
Design, makes film while block contaminants, will not burst because accumulating excessive gas.
(4) the configuration of the present invention is simple, flexible arrangement, be easily recycled, and water environment will not be caused secondary pollution, tool
There are cleaning, efficient, environmental protection.
Detailed description of the invention
Fig. 1 is the structure horizontal section schematic diagram of present example；
Fig. 2 is PAN- charcoal nano-fiber film SEM figure；
Fig. 3 is P elements versus time curve figure in embodiment 2.
In Fig. 1, multi-layer nano fiber membrane 1, PVC hose 2, membrane holder 3.
Specific embodiment
Further details of explanation is done to the present invention with reference to the accompanying drawings and detailed description, it should be appreciated that
The protection scope of the present invention is not limited by the specific implementation manner.
Embodiment 1:
As shown in Figure 1, the present invention is directed to which reservoir " turning over library " bring pollutant is adsorbed and removed using nano thin-film,
Main structure body 1 is multi-layer nano fiber membrane, and as the major part of processing pollutant, upper layer is GO/GA/PVA nanofiber
Film, centre are charcoal adsorption layer, and lower layer is PAN- charcoal nano-fiber film.2 be PVC hose, with film junction
With aperture.
Fig. 2 is middle layer PAN- charcoal nano-fiber film SEM figure.It can see cashier clear and intuitively from SEM figure
The filamentary fibers of rice fiber membrane are tightly combined, and guarantee there is certain porosity.The ingredient of PAN- charcoal has pollutant
Preferable absorption combines effect, while hydrone can be made to pass through film again.
The preparation process of PAN- charcoal nano-fiber film is as follows in the present embodiment:
S1, red cedar is sawn into equal-sized fritter, is placed in atmosphere furnace the 3min at 520 DEG C and charcoal is made.It weighs
25gNaOH is dissolved in 100mL deionized water, and the above-mentioned charcoal of 10g is added and obtains mixture, the charcoal of addition is grinding
Charcoal powder afterwards, NaOH are activating agent.Mixture at room temperature with after 150rpm magnetic agitation 2h again 80 DEG C drying for 24 hours.
Sample after drying is put into atmosphere furnace, nitrogen is passed through as protection gas, with the liter of 10 DEG C/min using the flow velocity of 200mL/min
Warm rate is warming up to 800 DEG C and is cooled to room temperature after 800 DEG C of holding 2h.The HCl of sample deionized water and 0.1mol/L are washed
It washs to neutrality, then salting liquid is washed away with deionized water and dries the charcoal activated for 24 hours in 55 DEG C of baking oven.
S2, the polyacrylonitrile (PAN) of 2g is dissolved in n,N-Dimethylformamide/dimethyl sulfoxide (DMF/DMSO, volume
Than 10:1) mixed solution in, magnetic agitation is until obtaining clear solution.By the charcoal of activation compared to polyacrylonitrile matter
It measures the ratio than 2% and is added to magnetic agitation 56h in solution.At room temperature condition (25 DEG C of temperature, humidity 35%), electrostatic spinning skill is utilized
PAN- charcoal nano-fiber film is made by fiber collecting device (length 25cm, diameter 10cm) in art.Film is placed in first
120min washes away excess of solvent in alcohol, then in 60 DEG C of baking 8h after being washed with deionized water.
The preparation process of charcoal adsorption layer is as follows in the present embodiment: dry leaf being put into atmosphere furnace, argon atmospher
800 DEG C are warming up to the heating rate of 5 DEG C/min under enclosing and keep 2h.After reaction, by the leaf of charing in 2mol/L's
After HCl impregnates 12h to remove inorganic ions, it is put into 60 DEG C of baking 12h of baking oven.
The preparation process of GO/GA/PVA nano-fiber film is as follows in the present embodiment:
S1, addition 50mL sulfuric acid (96wt%) and 3g powdered graphite, ice bath stirring are mixed in the conical flask of 500mL
Liquid.It is slowly added to 7g potassium permanganate, is persistently added with stirring 1g sodium nitrate.30min is stirred with 300r/min revolving speed at 40 DEG C
Afterwards, the deionized water of 80mL is added and is transferred to 80 DEG C of water-bath 40min.It is initially added potassium permanganate, is reacted more acute
It is strong so can be reacted at a lower temperature, reaction is needed to improve reaction temperature to a certain extent afterwards to guarantee sufficiently instead
It answers, therefore selects 80 DEG C of water-baths, temperature raising can evaporate portions of de-ionized water, and then influence ion concentration, therefore need to add
Enter deionized water heating water bath.To after the reaction was completed be cooled to room temperature mixed solution, it is added 100mL hydrogen peroxide (30wt%)
Extra potassium permanganate is removed, since peroxidating is reacted acutely with potassium permanganate, thus need to be vigorously stirred to terminate reaction.With
After 7500r/min is centrifuged 5min, supernatant (i.e. graphene oxide) is scattered in deionized water again.40mL hydrochloric acid is added
(20wt%) stirring and centrifugation, this step is in triplicate with purified product.Product is scattered in after deionized water to be centrifuged obtains pH twice
For 7 solution, it is stand-by in drier that graphene oxide (GO) powder storage is obtained after solution freeze-drying.
S2, water-soluble Arabic gum (GA) and polyvinyl alcohol (PVA) are dissolved separately in deionized water, at 80 DEG C
GA (10wt%) aqueous solution and PVA (10wt%) aqueous solution is made in 300rpm magnetic agitation 5h.GA is added in GO (0.5wt%)
In (10wt%) solution, uniform dispersion is made in 90 DEG C of magnetic agitation 30min, adds isometric PVA (10wt%) aqueous solution,
GO/GA/PVA nano-fiber film is made using electrostatic spinning technique.
Embodiment 2
In view of the stability of the nano-fiber film prepared under different preparation conditions, to progress after the adjustment of film preparation condition
Preparation.Some parameters in PAN- charcoal nano-fiber film preparation condition are changed to as follows: N,N-dimethylformamide and
Dimethyl sulfoxide volume ratio is changed to 8:1, and drying condition is changed to 60 DEG C of baking 8h, and micro- 530 DEG C of red cedar pyrolysis temperature, pyrolysis time is
2min, NaoH solution concentration are 250g/L, and drying condition is 18h at 60 DEG C.Some preparation parameters of charcoal adsorption layer are changed
It is as follows: is warming up to 800 DEG C with 5 DEG C/min and keeps the temperature 2h.Some preparation parameters of GO/GA/PVA nano-fiber film are changed
Are as follows: sulfuric acid is 28:1 in powdered graphite ratio, and the mass ratio of graphene oxide, aqueous Arabic gum and polyvinyl alcohol is 1:20:
20.The lower preparation same as Example 1 of remaining preparation parameter.
Embodiment 3:
In view of the stability of the nano-fiber film prepared under different preparation conditions, to progress after the adjustment of film preparation condition
Preparation.Some parameters in PAN- charcoal nano-fiber film preparation condition are changed to as follows: N,N-dimethylformamide and
Dimethyl sulfoxide volume ratio is changed to 9:1, and drying condition is changed to 55 DEG C of baking 10h, and micro- 530 DEG C of red cedar pyrolysis temperature, pyrolysis time is
2min, Na OH solution concentration are 250g/L, and drying condition is 18h at 60 DEG C.Some preparation parameters of charcoal adsorption layer are changed
It is as follows: is warming up to 900 DEG C with 5 DEG C/min and keeps the temperature 2h.Some preparation parameters of GO/GA/PVA nano-fiber film are changed
Are as follows: sulfuric acid is 26:1 in powdered graphite ratio, and the mass ratio of graphene oxide, aqueous Arabic gum and polyvinyl alcohol is 1:23:
23.The lower preparation same as Example 1 of remaining preparation parameter.
Embodiment 4:
For study it is described the present invention in nano-fiber film absorption pollutant effect, with film prepared by embodiment 1 to phosphorus
Element is adsorbed as model.In the glass tube of 50mL, the KH of the charcoal of 50mg and the 10mg/L of 25mL is added2PO4Solution,
PH value of solution is adjusted to 5 with NaOH and HCl.Under room temperature, constant temperature oscillator is put into 200r/min speed oscillation.Absorption 1,
3, when 7d, reaction solution is acquired, 3000r/min uses 0.45 μm of membrane filtration after being centrifuged 15min, and it is first to measure remaining phosphorus in solution
Cellulose content.
Fig. 3 is P elements versus time curve figure in embodiment 4.As can be seen that life is added in 7d experimental period
The content of P elements is obviously reduced than being added without the blank control group of charcoal in the solution of object charcoal, illustrates to prepare in the present invention
Charcoal has good absorption and fixed effect to pollutant.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
The above is only a preferred embodiment of the present invention, and the present invention is not limited in the content of embodiment.For in this field
Technical staff for, can have various change and change within the scope of technical solution of the present invention, made any variation and
Change, within that scope of the present invention.
Claims (10)
1. the nano thin-film that one kind slows down reservoir " turning over library " phenomenon, it is characterised in that: nano thin-film includes three-decker, and first
Layer is graphene oxide/water-soluble Arabic gum/polyvinyl alcohol nano film, and the second layer is charcoal adsorption layer, third
Layer is polyacrylonitrile-charcoal nano-fiber film.
2. the nano thin-film according to claim 1 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: the polypropylene
Nitrile-charcoal nano-fiber film the preparation method comprises the following steps:
After S1 will be thoroughly mixed in the addition aqueous slkali of charcoal made from red cedar, sample is subjected to high-temperature activation, drying
Charcoal after being activated；
Polyacrylonitrile is dissolved in the mixed solution of n,N-Dimethylformamide and dimethyl sulfoxide by S2, the life after activation is added
Object charcoal obtains mixture, and the mixture is prepared into polyacrylonitrile-charcoal nano-fiber film by electrostatic spinning technique,
Drying.
3. the nano thin-film according to claim 2 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: the charcoal
Preparation method is to be pyrolyzed at 520-530 DEG C using red cedar, pyrolysis time 2-4min；
The aqueous slkali is NaOH solution, and the concentration of the NaOH solution is 150-250g/L；
The activation condition of the high-temperature activation is to be warming up to set temperature with the heating rate of 5 ~ 10 DEG C/min；Drying condition is
Dry 18-24h at 50-60 DEG C.
4. the nano thin-film according to claim 2 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: the N, N- bis-
Methylformamide and dimethyl sulfoxide volume ratio are 8:1-10:1；The charcoal of activation and the mass ratio of PAN, DMF/DMSO mixture
For 1.5-2%；Drying condition is to dry 8-12h at 50-60 DEG C.
5. the nano thin-film according to claim 1 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: charcoal adsorption layer
The preparation method comprises the following steps: dry leaf is put into atmosphere furnace, be warming up under argon atmosphere with the heating rate of 5-10 DEG C/min
It 800-1000 DEG C and keeps the temperature 1-2h and is carbonized, after charing, the leaf of charing is soaked in hydrochloric acid solution, is then dried
Drying.
6. the nano thin-film according to claim 1 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: graphene oxide/
Water-soluble Arabic gum/polyvinyl alcohol nano film the preparation method comprises the following steps:
S1 sulfuric acid and powdered graphite mixing and ice bath stirring, obtain homogeneous phase solution, Gao Meng then are added into the homogeneous phase solution
After sour potassium and sodium nitrate stirring carry out initial reaction, adds deionized water and carry out heating water bath the reaction was continued, reaction terminates
After be cooled to room temperature, centrifugal treating takes supernatant after hydrogen peroxide stirring is added, be added in Xiang Suoshu supernatant deionized water and
Hydrochloric acid, stirring, centrifugation, dry graphene oxide；
Water-soluble Arabic gum and polyvinyl alcohol are dissolved separately in deionized water by S2, obtain water-soluble Arabic gum solution
And poly-vinyl alcohol solution, graphene oxide is added in water-soluble Arabic gum and obtains mixed solution, stirs, adds polyethylene
Graphene oxide/water-soluble Arabic gum/polyvinyl alcohol nano film is made using electrostatic spinning technique in alcoholic solution.
7. the nano thin-film according to claim 4 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: the sulfuric acid and stone
The mass ratio of ink powder end mixing is 26:1-28:1.
8. the nano thin-film according to claim 4 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: it is required water solubility Ah
The mass ratio for drawing primary glue, polyvinyl alcohol and polyvinyl alcohol is 1:20:20-1:25:25.
9. the nano thin-film according to claim 4 for slowing down reservoir " turning over library " phenomenon, it is characterised in that: the electrostatic spinning
In technology electrospinning parameters be electric field strength: 1.0-1.2KV/cm, flow velocity: 1.2-1.4mL/h, fiber collecting device revolving speed:
300-400rpm。
10. a kind of device for slowing down reservoir " turning over library " phenomenon prepared using nano thin-film described in claim 1, feature are existed
In: it is fixed with hollow tube on the nano thin-film periphery, the hollow tube side wall is provided with several apertures, and the aperture is by described
Hollow conduit body leads to the junction of the hollow tube Yu the nano thin-film.
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