CN109467177A - A kind of preparation method of surface modifier Pluronic F-127 Modified Iron nickel bimetal - Google Patents
A kind of preparation method of surface modifier Pluronic F-127 Modified Iron nickel bimetal Download PDFInfo
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- CN109467177A CN109467177A CN201811288876.5A CN201811288876A CN109467177A CN 109467177 A CN109467177 A CN 109467177A CN 201811288876 A CN201811288876 A CN 201811288876A CN 109467177 A CN109467177 A CN 109467177A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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Abstract
The invention discloses a kind of preparation methods of surface modifier Pluronic F-127 Modified Iron nickel bimetal particle, it is modified to Fe ° of progress surface using F-127 as dispersing agent, utilize the particularity of the molecular structure of F-127, Fe ° of dispersion stabilization in water is improved in Zero-valent Iron space forming surface steric effect and electrostatic repulsion, simultaneously, iron nickel bimetal particle is formed in Fe ° of area load metallic nickel, improves particle to the removal efficiency of 2,4-DCP in water.Process of the present invention simplicity is easily operated, and manufacturing process ring makes quick, at low cost, particle to pollutants removal rate height.
Description
Technical field
The invention belongs to nano materials to environment remediation field, improve Fe with environmentally friendly material and bimetallic method0?
The stability of grain, and be applied in the processing of removal organo-chlorine pollutant waste water.
Background technique
China's water pollution is increasingly severe in recent years, and chlorophenol pollutant has the characteristics that high toxicity, refractory organics, and
There are oxygen atom in structure, making it in water has quite high solubility, enhances the ability of phenolic compound Transport And Transformation,
As one of main pollutant in environment.And chlorophenols organic pollutant meeting during drinking water carries out cholorination
2.4-DCP is generated with the chlorine in water, and the pollutant that 2,4-DCP are classified as priority acccess control by Environmental Protection Agency, therefore how
2,4-DCP of removal has become one of research hotspot of environment protection field.
Since the 1980s, Fe0 is gradually concerned by people as effective dechlorination agent, and partial size is small, compares
Surface area is big, reaction active site is high and not will cause the features such as secondary pollution, becomes the research of degrading chlorophenol class organic pollutant
Hot spot.But Fe0It is easy to reunite in water since there are own magnetic forces and effect between particle, cause specific surface area to reduce, reactivity
It reduces, it is therefore desirable to Fe0Particle surface is modified to improve Fe0The performance of particle, F-127 can improve Fe0 particle well
Dispersibility.But single Fe0The problem of particle removal chlorophenols organic pollutant is low equal there is also reaction time long removal rate,
Therefore to Fe0The modified carried metal nickel in surface is carried out, iron nickel bimetal particle is formed, realizes short time quick dechlorination.Consider
It is serious to China's problem of environmental pollution, therefore secondary pollution is avoided in modification.This experiment uses environmental-friendly profile
Expect Pluronic F-127 (hereinafter referred to as F-127), F-127 can gradually resolve into the small molecule object of environmental sound in water
Matter, therefore secondary pollution will not be caused to environment.With F-127 to Fe0Particle carries out surface and coats the double gold of the Modified Iron nickel to be formed
Metal particles are significantly increased in the removal rate of inoxidizability, dispersibility and parachlorphenol class organic pollutant.
Summary of the invention
The present invention provides a kind of preparation method of Pluronic F-127 Modified Iron nickel bimetal, this method provides one kind
Novel modifying agent, to Fe0It is modified to carry out surface, is improved its dispersibility and inoxidizability, while in being modified
Carried metal nickel on grain forms the modified bimetallic particle of good dispersion, while improving the removal rate to 2,4-DCP.
The present invention specific steps are as follows:
1) it weighs F-127 to be placed in the three-necked flask of 1000ml, the ultrapure water of 250ml is added, is continually fed into N2And it stirs
20min or more ensures deoxidation and Pluronic F-127 is evenly dispersed in water, and F-127 aqueous solution is made
2) it weighs ferrous sulfate to be added in F-127 solution, lasting stirring dissolves ferrous sulfate, and it is mixed that ferrous sulfate is made
Close solution；
3) it weighs sodium borohydride to be added in the ultrapure water of 250ml, be stirred evenly with glass bar, and logical N2Deoxygenation
Sodium borohydride solution is made in 10min or more.
4) use peristaltic pump with 5mlmin-1Rate by NaBH4It is mixed that solution is added drop-wise to the ferrous sulfate that (2) method obtains
It closes in solution, persistently stirred in dropwise addition with electric blender and leads to N2, continue to stir after being added dropwise, react it sufficiently,
Obtain modified black Fe0Aaerosol solution.
5) it weighs nickel sulfate and is added to MODIFIED Fe0In aaerosol solution, stirring 20min or more makes iron nickel reactant, the Fe of generation2+
Meeting and NaBH4Generate Fe0, form the Modified Iron nickel bimetal particle solution of favorable dispersibility.
6) solution that (5) obtain is filtered, and is cleaned 3 times with ultrapure water, remove the foreign ion in particle, filtered
Persistently lead to N to solution in the process2Deoxidation guarantees that particle is not oxidized, is carried out at the drying of sample after suction filtration with freeze drier
Reason, is sealed after sample drying, obtains Pluronic F-127 Modified Iron nickel bimetal particle of good performance.
Modified iron nickel bimetal particle is made using liquid phase reduction in the present invention, improves Fe0Itself dispersibility and
Inoxidizability improves the efficiency of removal organic polluter.
The Pluronic F-127 Modified Iron nickel bimetal particle that foregoing invention obtains is used for underground water hardly degraded organic substance
Application.
Compared with previous invention, present invention has an advantage that
(1) using Pluronic F-127 to Fe0Be modified, it is easy to operate, feasibility is high, selected materials be environment friend
Good profile material, not can cause environmental pollution.And solves Fe0Inoxidizability and problem easy to reunite, are conducive in water
Migration, have good application prospect in terms of underground water in-situ immobilization.
(2) present invention is improving Fe0After the dispersibility and stability of particle, also to bimetal granule is formed, effectively
Remove the chlorophenol pollutant in water removal.
Detailed description of the invention
Fig. 1 is the iron nickel bimetal granule preparing process figure for the modification that the present invention obtains
Fig. 2 is the SEM test result figure of the iron nickel bimetal particle for the modification that the present invention obtains
Fig. 3 is the XRD test result figure of the iron nickel bimetal particle for the modification that the present invention obtains
Fig. 4 is the different quality of the invention obtained than modified Fe0Subsidence curve in water
Fig. 5 is the different quality of the invention obtained than modified Fe0To the removal result figure of 2.4-DCP
Fig. 6 is removal result figure of the different loads rate Modified Iron nickel bimetal particle of the invention obtained to 2.4-DCP
Fig. 7 is that the optimal Modified Iron nickel bimetal particle that the present invention obtains changes concentration each in 2.4-DCP removal process
Figure
Specific embodiment
The present invention is described in further details with attached drawing below by example
Example 1: the selection of modifying agent mass ratio and the preparation of modified Nano Zero-valent Iron suspended particulate
The preparation of Pluronic F-127 modified nano zero valence iron, configuration F-127 solution concentration be 0g/l, 1.5g/l,
The F-127 solution 250ml of 2g/l, 2.25g/l and 2.4g/l stir 20min or more with electric blender, persistently lead in whipping process
Enter N2；7.448g, 3.72g, 2.484g, 1.86g and 1.49g ferrous sulfate is weighed to be added separately in above-mentioned F-127 solution,
Continue to stir 10min or more, be sufficiently mixed ferrous sulfate with F-127, ferrous sulfate mixed solution is made；It weighs respectively
2.233g, 1.122g, 0.746g, 0.561g and 0.448g sodium borohydride are added separately in the ultrapure water of 250ml, lead to N2
Sodium borohydride solution is made in 10min or more deoxidation；With peristaltic pump with 5mlmin-1Rate sodium borohydride solution is added drop-wise to
In ferrous sulfate solution, process is added dropwise and leads to N always2, persistently stirred with electric blender, continue to stir after being added dropwise
20min or more makes fully reacting, obtains modified nano zero valence iron suspension；Modified nano zero valence iron suspension is taken out
Filter, and cleaned 3 times with ultrapure water, the foreign ion in removal particle, persistently lead to N to solution during suction filtration2Deoxidation guarantee
Grain is not oxidized, carries out the drying process of sample after the completion of suction filtration with freeze drier, is sealed after sample drying.
Disperse suspension to probe into the F-NZVI of preparation, the F-NZVI particle formulation of the different quality ratio of above-mentioned preparation at
The suspension of 1g/l is stirred by ultrasonic 10min, draws uniformly mixed suspension in cuvette, cuvette is filled (cuvette
Top edge forms meniscus), plastic lid is covered, rocking makes internal solution be uniformly dispersed, and is put into UV, visible light spectrophotometric rapidly
In meter, scanning wavelength 508nm, sweep time 6000s, mechanical test of taking action obtain the sedimentation curve of spectrum.
Under the above conditions, Fe0It interacts to form F-NZVI particle with F-127.F-127 is three block macromolecule chemical combination
Object is made of hydrophilic radical with lipophilic group, when with Fe0Lipophilic group is externally formed with core in inside, hydrophilic radical when contact
Shell structure.The negatively charged generation repulsive interaction of hydrophilic radical, while F-127 is coated on particle surface and forms space steric effect,
F-NZVI is set to can be good at being dispersed in water.
Fig. 1 is the SEM figure of modified F-NZVI particle, and Fig. 4 is the subsidence curve of example 1, as can be seen from the experiment when
F-127 and Fe0Mass ratio be 4:1 and 2:1 when dispersion suspension it is good.
Example 2: the F-NZVI of different quality ratio tests the removal of 2,4-DCP
By beaker experiments, removal of the prepared material to 2,4-DCP is studied.By beaker experiments, 0.75g is weighed not
The F-NZVI particle of homogenous quantities ratio is put into respectively in 2, the 4-DCP solution that 250ml initial concentration is 20mg/l, and F-NZVI is dense
Degree control is 3g/l, and holding solution is neutrallty condition, is continually fed into N2Guarantee oxygen-free environment.At room temperature, with 200r
min-1Hunting speed reaction.Different time sections (0min, 5min, 10min, 20min, 40min, 60min, 2h, 3h, 4h,
5h, 6h) it is filtered with syringe sampling and by 0.45 μm of polyether sulfone water system filter, reach pollutant and F-NZVI particle
Centrifugation, be measured using concentration of the high performance liquid chromatograph to 2.4- Dichlorophenol.Fig. 5 is F- prepared by example 1
The pollutant concentration variation diagram that NZVI removes 2,4-DCP, the effect for removing 2,4-DCP when mass ratio 2:1 as seen from the figure are best.
The preparation of the F-127 of different nickel loads modified iron nickel bimetal and 2,4-DCP removal is probed into
The F-NZVI suspension for using example 1 to prepare mass ratio as 2:1, is added sulphur into the suspension prepared
Sour nickel, makes nickel and Fe0Mass ratio is 0,1:50,1:20,1:10,1:5, obtains the modified iron nickel pair of the F-127 of different quality ratio
Metallic particles.The F-127 of different quality ratio modified iron nickel bimetal particle removes 2,4-DCP by 2 method of example, Fig. 6
The removal of 2,4-DCP is studied for the F-127 of different quality ratio modified iron nickel bimetal particle, mass ratio is 1 as seen from the figure:
20 F-127 modified iron nickel bimetal is best to the removal effect of 2,4-dcp.
Example 4: Modified Iron nickel bimetal particle and to 2,4-DCP removal probe into
Probe into removal of the Modified Iron nickel bimetal particle to 2,4-DCP under optimum condition.Weigh the double gold of 0.75g Modified Iron nickel
Metal particles are put into 2, the 4-DCP solution that 250ml initial concentration is 20mg/l, and the control of F-NZVI concentration is 3g/l, are kept molten
Liquid is neutrallty condition, is continually fed into N2Guarantee oxygen-free environment.At room temperature, with 200rmin-1Hunting speed reaction.
It samples in different time sections and passes through 0.45 μm of polyether sulfone water system filter and be filtered, reach pollutant and F-NZVI particle
Centrifugation is measured using concentration and product concentration of the high performance liquid chromatograph to 2.4- Dichlorophenol.Fig. 7 is removal
The variation diagram of each material concentration in the process, as seen from the figure, the primary product that Modified Iron nickel bimetal particle removes 2,4-DCP is benzene
Phenol, phenol be largely formed by the direct dechlorination of 2,4-DCP, and be partially by 2,4-DCP dechlorination generate intermediate product after
Continuous dechlorination is formed.
Above example of the present invention is only the citing to preparation method of the present invention, is not for limiting the present invention.Therefore,
Rights protection scope of the present invention should be defined by the claims.
Claims (5)
1. a kind of preparation method of surface Modified Iron nickel bimetal, which is characterized in that specific step is as follows:
(1) it weighs F-127 to be dissolved in ultrapure water, is continually fed into N2And it stirs 20min or more and ensures deoxidation and Pluronic F-
127 is evenly dispersed in water, and F-127 aqueous solution is made；
(2) it weighs ferrous sulfate to be added in the solution of F-127, lasting stirring dissolves ferrous sulfate, and it is mixed that ferrous sulfate is made
Close solution；Fe in ferrous sulfate mixed solution0Mass ratio with F-127 is 2:1~1:1；
(3) it weighs a certain amount of sodium borohydride to be added in ultrapure water, be stirred evenly with glass bar, and logical N2Deoxygenation 10min with
On, sodium borohydride solution is made；The ratio between amount of sodium borohydride and ferrous sulfate substance is 2.2:1；
(4) by NaBH4Solution is added drop-wise in the ferrous sulfate mixed solution that step (2) method obtains, and electric mixing is used during being added dropwise
Machine is mixed to stir and persistently lead to N2, continue to stir 20min or more after being added dropwise, obtain MODIFIED Fe0Aaerosol solution；
(5) it weighs nickel sulfate and is added to MODIFIED Fe0In aaerosol solution, continues to stir 20min or more, make iron and nickel reactant, generation
Fe2+It can be with NaBH in solution4Generate Fe0, form Modified Iron nickel bimetal solution；Nickel and Fe in Modified Iron nickel bimetal solution0's
Mass ratio is 1:20~1:20；
(6) the Modified Iron nickel bimetal solution that (5) obtain is filtered, and is cleaned 3 times with ultrapure water, removal Modified Iron nickel is double
Foreign ion in metallic particles persistently leads to N to solution during suction filtration2Deoxidation guarantees that particle is not oxidized, after the completion of suction filtration
Sample is freeze-dried with freeze drier, obtains the modified iron nickel bimetal particle of Pluronic F-127, and by sample
Product are sealed preservation.
2. a kind of preparation method of surface Modified Iron nickel bimetal described in accordance with the claim 1, it is characterised in that: step (1)
Middle F-127 solution concentration is 1.5~2.0g/l.
3. a kind of preparation method of surface Modified Iron nickel bimetal described in accordance with the claim 1, it is characterised in that: step (4)
Middle sodium borohydride solution drop rate is 5mlmin-1。
4. Modified Iron nickel bimetal particle made from the preparation method of claims 1 to 3 any one.
5. removal of the Modified Iron nickel bimetal particle as claimed in claim 4 for chlorophenol type organic in water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111804930A (en) * | 2020-07-22 | 2020-10-23 | 成都理工大学 | Nano zero-valent ferro-manganese bimetal and preparation method and application thereof |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111804930A (en) * | 2020-07-22 | 2020-10-23 | 成都理工大学 | Nano zero-valent ferro-manganese bimetal and preparation method and application thereof |
| CN111804930B (en) * | 2020-07-22 | 2022-10-14 | 成都理工大学 | Nano zero-valent ferro-manganese bimetal and preparation method and application thereof |
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