CN104226987B - A kind of modified Nano Zero-valent Iron and preparation method thereof - Google Patents
A kind of modified Nano Zero-valent Iron and preparation method thereof Download PDFInfo
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- CN104226987B CN104226987B CN201410521018.6A CN201410521018A CN104226987B CN 104226987 B CN104226987 B CN 104226987B CN 201410521018 A CN201410521018 A CN 201410521018A CN 104226987 B CN104226987 B CN 104226987B
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Abstract
The invention discloses a kind of modified Nano Zero-valent Iron and preparation method thereof, wherein modified Nano Zero-valent Iron includes nano zero valence iron and sodium lauryl sulphate, sodium lauryl sulphate is wrapped in nano zero-valence iron surface, and sodium lauryl sulphate is 0.01～0.07 with the mass ratio of nano zero valence iron.The preparation method of modified Nano Zero-valent Iron comprises the following steps: by ultrasonic disperse, nano zero valence iron granule is obtained in sodium dodecyl sulfate solution modified Nano Zero-valent Iron.The advantages such as the present invention uses sodium lauryl sulphate to be modified nano zero valence iron, passes through space steric effect, it is achieved the stabilisation to nano material, has dispersive property good, has good stability, and reactivity is high.
Description
Technical field
The invention belongs to pollute the physical chemistry process field of heavy metal in environment, particularly relate to a kind of new modified nano material and
Its preparation method.
Background technology
Nano zero valence iron is as the effective reducing agent of one and adsorbent, and it is little that nano zero valence iron has particle diameter, the specific surface area of granule
Big and surface can be big, thus has superior absorption property and the highest reducing activity.Utilize the distinctive skin effect of nano-particle
And small-size effect, reactivity and the treatment effeciency of zero-valent iron particle can be improved.Therefore, in environment remediation and the field of improvement
Get more and more people's extensive concerning.But owing to nano zero valence iron is the most unstable, it is easy to mutually perikinetic aggregation aggregates into bulky grain, and
It is prone to react with the water in environment, oxygen, causes its reactivity, animal migration to reduce, leverage nano zero valence iron
Reactivity and treatment effeciency.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of dispersive property is good, reactivity is high and
The modified Nano Zero-valent Iron that animal migration is good, also provides for a kind of method preparing modified Nano Zero-valent Iron, and the method has principle letter
Characteristic single, easy to operate, that preparation cost is low, properties of product are good.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of modified Nano Zero-valent Iron, including nano zero valence iron and sodium lauryl sulphate, aforementioned sodium lauryl sulphate is wrapped in
Aforementioned nano zero-valence iron surface forms core-shell structure, the mass ratio of aforementioned sodium lauryl sulphate and nano zero valence iron be 0.01～
0.07∶1。
As a total inventive concept, present invention also offers the preparation method of a kind of aforementioned modified nano zero valence iron, including with
Lower step: nano zero valence iron granule is obtained modified Nano Zero-valent Iron by ultrasonic disperse in sodium dodecyl sulfate solution.
Further, the concentration of aforementioned sodium dodecyl sulfate solution is 0.1g/L～0.7g/L.
Further, aforementioned nano zero valence iron is by isopyknic NaBH4And FeSO4Prepare after mixing.
Further, aforementioned NaBH4The concentration of solution is 0.2M～0.4M.
Further, aforementioned FeSO4The concentration of solution is 0.05M～0.1M.
Further, aforementioned NaBH4Solution and aforementioned FeSO4Solution is sufficiently stirred for 25min～30min and obtains nano zero valence iron.
Further, the aforementioned ultrasonic scattered time is 30min～60min, the scattered frequency of aforementioned ultrasonic be 20kHZ～
30kHZ。
The creativeness of the present invention is:
The invention provides a kind of modified Nano Zero-valent Iron and preparation method thereof, first by isopyknic NaBH4Solution at the uniform velocity drips
To FeSO4Preparing nano zero valence iron in solution, its reaction equation is as follows:
Then nano zero valence iron reaction obtained in sodium dodecyl sulfate solution, makes lauryl sulphate acid by ultrasonic disperse
Sodium more fully adsorbs at nano zero-valence iron surface, and forms core-shell structure with nano zero valence iron.Due to sodium lauryl sulphate
It is wrapped in the surface of nano zero valence iron, changes the surface charge distribution of nano zero valence iron, at electrostatic repulsion and the work of steric effect
Under with, make nano zero valence iron more disperse, be not susceptible to reunite；Secondly, sodium lauryl sulphate prevents nano zero valence iron table
The high activity site in face reacts with surrounding medium, thus maintains its high response；Finally, stabilizer SDS is wrapped in nanometer
Zero-valent Iron surface, prevents the formation of nano zero valence iron particle surface passivation layer, thus extends nano zero valence iron and reduce
The time of reaction.Therefore, the nano zero valence iron particle diameter modified by sodium lauryl sulphate is less, has good skin effect
And small-size effect, its dispersibility in aqueous strengthens simultaneously, is not susceptible to reunite, and stability strengthens, it is possible to effectively
Stop nano zero-valence iron surface high activity site to react with the medium (dissolved oxygen and water) of surrounding, there is good permeability
Preferable with dispersive property, nontoxic, biological degradability, secondary pollution will not be brought to environment, and low price, be applicable to big
The use of scale, has good use value.
Compared with prior art, it is an advantage of the current invention that:
1, nano zero valence iron is modified as stabilizer by the present invention using sodium lauryl sulphate (SDS), and the modification obtained is received
It is good that rice Zero-valent Iron is that one has dispersive property, has good stability, the material that reactivity is high.
2, nano zero valence iron of the present invention is by isopyknic NaBH4And FeSO4Prepare after mixing, it is possible to make Fe2+Fully
Reaction, is completely reduced as Fe0, reaction efficiency is high；Secondly, the reagent used is prone to obtain, and preparation cost is low；Finally,
Reacted product is respectively nano zero valence iron precipitation, hydrogen and the material of solubility, is relatively easy to carry out product separation, to receiving
The cleaning of rice Zero-valent Iron is easier, and the purity of the nano zero valence iron finally given is higher.
3, the present invention provide modified Nano Zero-valent Iron preparation method to experimental instrument and equipment require relatively low, simple to operate easily
Row, preparation cost are low；And being swift in response, preparation is quick, can produce substantial amounts of nano material, and material at short notice
It is prone to deposit, is suitable for industrialized production.
4, new modified nano zero valence iron prepared by the present invention can be used for administering heavy metal pollution polluted bed mud and waste water, and it operates letter
Just, processing the cycle short, reactivity is high, and rehabilitation cost is low, and cleanliness without any pollution, to environment nonhazardous effect, therefore at ring
Process and the environment remediation field of environment pollution are with a wide range of applications.
Accompanying drawing explanation
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, attached below in conjunction with in the embodiment of the present invention
Figure, carries out clear, complete description to the technical scheme in the embodiment of the present invention.
Fig. 1 is the micro-structure diagram of modified Nano Zero-valent Iron (SDS-nZVI) in the present embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of nano zero valence iron (Bare-nZVI) granule of unmodified.
Fig. 3 is the scanning electron microscope (SEM) photograph of modified Nano Zero-valent Iron (SDS-nZVI) in the embodiment of the present invention 2.
Fig. 4 is energy spectrogram (EDS) of the nano zero valence iron (Bare-nZVI) of unmodified.
Fig. 5 is energy spectrogram (EDS) of modified Nano Zero-valent Iron (SDS-nZVI) in the present embodiment 2.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but the most therefore limits this
The protection domain of invention.
Raw material and instrument employed in following example are commercially available.
Embodiment 1
Seeing the modified Nano Zero-valent Iron of Fig. 1: a kind of present invention, this modified Nano Zero-valent Iron includes nano zero valence iron and dodecane
Base sodium sulfate, sodium lauryl sulphate is wrapped in the surface of nano zero valence iron and forms core-shell structure, and sodium lauryl sulphate is to nanometer
Zero-valent Iron carries out the physical modification on surface；In this modified Nano Zero-valent Iron, sodium lauryl sulphate with the mass ratio of nano zero valence iron is
0.01∶1。
The preparation method of a kind of above-mentioned modified Nano Zero-valent Iron, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 0.7000g FeSO4·7H2O puts in beaker, adds appropriate ultra-pure water solution transfer
In 50mL volumetric flask, it is settled to graduation mark, shakes up, i.e. can get 0.05M FeSO4Solution.
(2)NaBH4The preparation of solution: weigh 0.3783g NaBH4Put in beaker, add appropriate ultra-pure water solution transfer to 50mL
In volumetric flask, it is settled to graduation mark, shakes up, i.e. can get 0.2M NaBH4Solution.
(3) preparation of nano zero valence iron (Bare-nZVI) granule: by 50mL, 0.05M FeSO4Solution joins 250mL
There-necked flask in, under conditions of the protection and mechanical agitation of nitrogen, by isopyknic 0.2M NaBH4Solution is the evenest
Speed instills in there-necked flask, at the uniform velocity titrate complete after, treat that both react 30min, obtain black suspension；Finally by black
Suspension is transferred in centrifuge tube, under 3000rmp, centrifugal 15min, removes supernatant and obtains black solid, use deionization
Water cleans 3 times, then with 5% ethanol purge 1 time, obtains nano zero valence iron (Bare-nZVI) granule, save it in 10mL
In ethanol solution.
(4) preparation of modified Nano Zero-valent Iron (SDS-nZVI): 0.7g nano zero valence iron (Bare-nZVI) granule is disperseed
In sodium lauryl sulphate (SDS) solution that 70mL concentration is 0.1g/L, under the conditions of 20kHZ, supersound process 40min,
Can be prepared by 10g/L modified Nano Zero-valent Iron (SDS-nZVI) suspension.
In the present embodiment, supersonic frequency is 20kHZ～30kHZ, and the time of ultrasonic disperse is that 30min～60min all can implement.
Embodiment 2
A kind of modified Nano Zero-valent Iron of the present invention, this modified Nano Zero-valent Iron includes nano zero valence iron and sodium lauryl sulphate,
Sodium lauryl sulphate is wrapped in the surface of nano zero valence iron and forms core-shell structure, and nano zero valence iron carries out the physical modification on surface；
In this modified Nano Zero-valent Iron, sodium lauryl sulphate is 0.03: 1 with the mass ratio of nano zero valence iron.
The preparation method of a kind of above-mentioned modified Nano Zero-valent Iron, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 1.4000g FeSO4·7H2O puts in beaker, adds appropriate ultra-pure water solution transfer
In 50mL volumetric flask, it is settled to graduation mark, shakes up, i.e. can get 0.1M FeSO4Solution.
(2)NaBH4The preparation of solution: weigh 0.7566g NaBH4Put in beaker, add appropriate ultra-pure water solution transfer to 50mL
In volumetric flask, it is settled to graduation mark, shakes up, i.e. can get 0.4M NaBH4Solution.
(3) preparation of nano zero valence iron (Bare-nZVI) granule: by 50mL, 0.1M FeSO4Solution joins 250mL
There-necked flask in, under conditions of the protection and mechanical agitation of nitrogen, by isopyknic 0.4M NaBH4Solution is the evenest
Speed instills in there-necked flask, at the uniform velocity titrate complete after, treat that both react 30min, obtain black suspension；Finally by black
Suspension is transferred in centrifuge tube, under 3000rmp, centrifugal 15min, removes supernatant and obtains black solid, use deionization
Water cleans 3 times, then with 5% ethanol purge 1 time, obtains nano zero valence iron (Bare-nZVI) granule, save it in 10mL
In ethanol solution.
(4) preparation of modified Nano Zero-valent Iron (SDS-nZVI): 0.7g nano zero valence iron (Bare-nZVI) granule is disperseed
In sodium lauryl sulphate (SDS) solution that 70mL concentration is 0.3g/L, under the conditions of 20kHZ, supersound process 30min,
Can be prepared by 10g/L modified Nano Zero-valent Iron (SDS-nZVI) suspension.
In the present embodiment, supersonic frequency is 20kHZ～30kHZ, and the time of ultrasonic disperse is that 30min～60min all can implement.
Embodiment 3
A kind of modified Nano Zero-valent Iron of the present invention, this modified Nano Zero-valent Iron includes nano zero valence iron and sodium lauryl sulphate,
Sodium lauryl sulphate is wrapped in the surface of nano zero valence iron and forms core-shell structure, and nano zero valence iron carries out the physical modification on surface；
In this modified Nano Zero-valent Iron, sodium lauryl sulphate is 0.05: 1 with the mass ratio of nano zero valence iron.
The preparation method of a kind of above-mentioned modified Nano Zero-valent Iron, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 3.9200g FeSO4·7H2O puts in beaker, adds appropriate ultra-pure water and dissolves, will
Above-mentioned solution is transferred to, in 200mL volumetric flask, be settled to graduation mark, shake up, and i.e. can get 0.07M FeSO4Solution.
(2)NaBH4The preparation of solution: weigh 2.1437g NaBH4Put in beaker, add appropriate ultra-pure water and dissolve, by above-mentioned molten
Liquid is transferred to, in 200mL volumetric flask, be settled to graduation mark, shake up, and i.e. can get 0.28M NaBH4Solution.
(3) preparation of nano zero valence iron (Bare-nZVI) granule: by 200mL, 0.07M FeSO4Solution joins 500mL
There-necked flask in, under conditions of the protection and mechanical agitation of nitrogen, by isopyknic 0.28M NaBH4Solution is the evenest
Speed instills in there-necked flask, at the uniform velocity titrate complete after, treat that both react 25min, obtain black suspension；Finally by black
Suspension is transferred in centrifuge tube, under 3000rmp, centrifugal 15min, removes supernatant and obtains black solid, use deionization
Water cleans 3 times, then with 5% ethanol purge 1 time, obtains nano zero valence iron (Bare-nZVI) granule, save it in 10mL
In ethanol solution.
(4) preparation of modified Nano Zero-valent Iron (SDS-nZVI): 2.8g nano zero valence iron (Bare-nZVI) granule is disperseed
In sodium lauryl sulphate (SDS) solution that 280mL concentration is 0.5g/L, under the conditions of 20kHZ, supersound process 45min,
Can be prepared by 10g/L modified Nano Zero-valent Iron (SDS-nZVI) suspension.
In the present embodiment, supersonic frequency is 20kHZ～30kHZ, and the time of ultrasonic disperse is that 30min～60min all can implement.
Embodiment 4
A kind of modified Nano Zero-valent Iron of the present invention, this modified Nano Zero-valent Iron includes nano zero valence iron and sodium lauryl sulphate,
Sodium lauryl sulphate is wrapped in the surface of nano zero valence iron and forms core-shell structure, and nano zero valence iron carries out the physical modification on surface；
In this modified Nano Zero-valent Iron, sodium lauryl sulphate is 0.07: 1 with the mass ratio of nano zero valence iron.
The preparation method of a kind of above-mentioned modified Nano Zero-valent Iron, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 1.2600g FeSO4·7H2O puts in beaker, adds appropriate ultra-pure water and dissolves, will
Above-mentioned solution is transferred to, in 50mL volumetric flask, be settled to graduation mark, shake up, and i.e. can get 0.09M FeSO4Solution.
(2)NaBH4The preparation of solution: weigh 0.6809g NaBH4Put in beaker, add appropriate ultra-pure water and dissolve, by above-mentioned molten
Liquid is transferred to, in 50mL volumetric flask, be settled to graduation mark, shake up, and i.e. can get 0.36M NaBH4Solution.
(3) preparation of nano zero valence iron (Bare-nZVI) granule: by 50mL, 0.09M FeSO4Solution joins 250mL
There-necked flask in, under conditions of the protection and mechanical agitation of nitrogen, by isopyknic 0.36M NaBH4Solution is the evenest
Speed instills in there-necked flask, at the uniform velocity titrate complete after, treat that both react 27min, obtain black suspension；Finally by black
Suspension is transferred in centrifuge tube, under 3000rmp, centrifugal 15min, removes supernatant and obtains black solid, use deionization
Water cleans 3 times, then with 5% ethanol purge 1 time, obtains nano zero valence iron (Bare-nZVI) granule, save it in 10mL
In ethanol solution.
(4) preparation of modified Nano Zero-valent Iron (SDS-nZVI): 0.7g nano zero valence iron (Bare-nZVI) granule is disperseed
In sodium lauryl sulphate (SDS) solution that 70mL concentration is 0.7g/L, under the conditions of 20kHZ, supersound process 30min,
Can be prepared by 10g/L modified Nano Zero-valent Iron (SDS-nZVI) suspension.
In the present embodiment, supersonic frequency is 20kHZ～30kHZ, and the time of ultrasonic disperse is that 30min～60min all can implement.
Comparative example 1
Unmodified nano zero valence iron (Bare-nZVI), its preparation method is according to the preparation method of nano zero valence iron in embodiment 1
Carry out, but without stabilizer sodium lauryl sulphate (SDS).
Comparative example 2
A kind of modified Nano Zero-valent Iron includes that nano zero valence iron and dodecylbenzene sodium sulfonate, dodecylbenzene sodium sulfonate absorption are being received
The surface of rice Zero-valent Iron, carries out the physical modification on surface to nano zero valence iron；DBSA in this modified Nano Zero-valent Iron
Sodium is 0.03: 1 with the mass ratio of nano zero valence iron.
Comparative example 3
A kind of modified Nano Zero-valent Iron includes nano zero valence iron and sodium carboxymethyl cellulose, and sodium carboxymethyl cellulose adsorbs in nanometer zero
The surface of valency ferrum, carries out the physical modification on surface to nano zero valence iron；In this modified Nano Zero-valent Iron sodium carboxymethyl cellulose with receive
The mass ratio of rice Zero-valent Iron is 0.01: 1.
Comparative example 4
A kind of modified Nano Zero-valent Iron includes nano zero valence iron and rhamnolipid, and rhamnolipid adsorbs on the surface of nano zero valence iron,
Nano zero valence iron is carried out the physical modification on surface；In this modified Nano Zero-valent Iron, rhamnolipid with the mass ratio of nano zero valence iron is
0.7: 1 (wherein the concentration of rhamnolipid is the cubage according to total organic carbon).
Comparative example 5
A kind of modified Nano Zero-valent Iron includes nano zero valence iron and Metal Palladium, and Metal Palladium is adsorbed on the surface of nano zero valence iron, to receiving
Rice Zero-valent Iron carries out the physical modification on surface；In this modified Nano Zero-valent Iron, Metal Palladium is 0.01 with the mass ratio of nano zero valence iron:
1。
Microstructure analysis to modified Nano Zero-valent Iron:
The modified Nano Zero-valent Iron of embodiment 2 is carried out microexamination analysis, finds under the environmental scanning electronic microscope of 30000 times,
Compared with the nano material of unmodified, the modified Nano Zero-valent Iron of the present invention has special microstructure.Fig. 2 is unmodified
The scanning electron microscope (SEM) photograph of nano zero valence iron (Bare-nZVI) granule, from Fig. 2 it is observed that the nano-particle of unmodified, granule
Disperseing uneven, granule is bigger, and this has magnetic mainly due to material itself, occurs reunion to cause.Fig. 3 is the present invention
The scanning electron microscope (SEM) photograph of modified Nano Zero-valent Iron (SDS-nZVI), from Fig. 3 it is observed that modified Nano Zero-valent Iron (SDS-nZVI)
Granule dispersion ratio is more uniform, and granule is less, forms dendritic morphology, and this adsorbs in nanometer zero mainly due to sodium lauryl sulphate
The surface of valency ferrum granule, and change the performance of particle surface, change granule and the phase interaction between liquid phase medium, granule and granule
With；And it is owing to sodium lauryl sulphate is a kind of anion surfactant, by space steric effect and electrostatic, finally real
Dispersibility that existing system is good and the good stability of nano material.Fig. 4 and Fig. 5 is respectively the nano zero valence iron of unmodified
(Bare-nZVI) and modified Nano Zero-valent Iron (SDS-nZVI) can spectrogram (EDS), from can spectrogram (EDS) analyze
Arriving, in Fig. 5, the content of Fe, S is more, is difficult to by rapid oxidation, can preserve 14d, shows prepared new modified receive
Rice material moderately good.Thus, sodium lauryl sulphate enhances the stability of nano zero valence iron, effectively improves nanometer
Zero-valent Iron is the most oxidized and particle agglomeration problem, greatly improves the nano zero valence iron efficiency to processing heavy metal.
After modified Nano Zero-valent Iron (SDS-nZVI) is vacuum dried, can preserve for a long time, and will
SDS-nZVI is saved in 5% ethanol solution, it is also possible to place the long period in the lab.
The modified Nano Zero-valent Iron of different stabilizers concentration is to the clearance of heavy metal chromium in bed mud:
Respectively with modified Nano Zero-valent Iron (SDS-nZVI) and the nano zero valence iron (Bare-nZVI) of comparative example 1 of embodiment 1 to 4
Processing the bed mud containing chromium, concrete operation step is as follows:
(1) bed mud being carried out pretreatment, it concretely comprises the following steps: will contain chromium bed mud in freeze dryer with cold under subzero 40 degrees Celsius
Lyophilizing is dry；Then carrying out mechanical grinding, the first sieve of 1mm excessively, then < sieve of 0.63mm completes the pretreatment of bed mud excessively.
(2) the modified Nano Zero-valent Iron (SDS-nZVI) of the present embodiment is added to 5g heavy metal chromium according to weight in wet base 1.0g/kg
(Cr6+) concentration is 50mg/kg, pH value be 6 containing in chromium bed mud, 25 DEG C, to carry out constant temperature oscillation under the conditions of 300rpm anti-
Should.After 24h, the bed mud after processing carries out extraction process, and concrete leach step is:
By the bed mud after oscillation treatment, at 105 DEG C, process 6h in an oven, dry, remove the moisture in sample；Weigh
The dried bed mud of 0.5g, in 50mL centrifuge tube, adds 10mL 1M pH=8.2 NaOAC solution and (adds MgCl2Molten
Liquid also can reach same or analogous technique effect), constant temperature oscillation 1h at 22 DEG C；Centrifugal 20min under 5000g,
Obtain bed mud lixiviating solution；The lixiviating solution filter of 0.45 μm is filtered.With determined by ultraviolet spectrophotometry filtrate at different bars
Cr is remained under part6+Concentration, result see table 1.
Table 1: the clearance of the modified Nano Zero-valent Iron heavy metal chromium of different stabilizers concentration
| Embodiment | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The concentration (g/L) of SDS | 0 | 0.1 | 0.3 | 0.5 | 0.7 |
| Clearance (%) | 78.94 | 90.26 | 98.48 | 94.74 | 89.67 |
As can be known from Table 1: stabilizer (SDS) concentration is the modified Nano Zero-valent Iron (SDS-nZVI) of 0.1g/L～0.7g/L
Heavy metal chromium (Cr6+) process all preferable, when wherein stabilizer (SDS) concentration is 0.3g/L, treatment effect is best,
Heavy metal chromium (Cr6+) clearance be 98.48%.
The treatment effeciency of modified Nano Zero-valent Iron process variable concentrations heavy metal chromium:
Respectively with the nano zero valence iron (Bare-nZVI) of comparative example 1, embodiment 3 modified Nano Zero-valent Iron (SDS-nZVI) is right
Bed mud containing heavy metal chromium processes, and concrete operation step is as follows:
The modified Nano Zero-valent Iron of the nano zero valence iron of comparative example 1 and embodiment 3 is added respectively to 50mL not by 1.0g/kg weight in wet base
Heavy metal chromium (Cr with concentration6+) (carry out pretreatment containing chromium bed mud according to preceding method) containing in chromium bed mud, regulate bed mud pH
Value is 6,25 DEG C, carry out constant temperature oscillation reaction under the conditions of 300rpm.After 24h, the bed mud after processing, after processing
Bed mud carry out extraction process, take the lixiviating solution filter in 0.45 μm aperture and filter, the filtrate obtained.Use ultraviolet spectrometry light
Degree method measures the heavy metal chromium (Cr in filtrate6+) content.Result see table 2.
Table 2: the treatment effeciency of variable concentrations heavy metal bed mud
| Chromium initial concentration | 20mg/L | 50mg/L | 80mg/L | 100mg/L | 200mg/L |
| Bare-nZVI | 76.3% | 73.92% | 68.85% | 65.36% | 60.68% |
| SDS-nZVI | 100% | 94.72% | 91.6% | 84.12% | 79.56% |
Knowable to the testing result of table 2: the treatment effeciency of modified Nano Zero-valent Iron (SDS-nZVI) heavy metal of embodiment 3
Nano zero valence iron (Bare-nZVI) apparently higher than comparative example 1.
Modified Nano Zero-valent Iron is to the treatment effeciency detection of heavy metal chromium in bed mud:
Respectively by modified Nano Zero-valent Iron and the nano zero valence iron (Bare-nZVI) of comparative example 1, the comparative example 2 to 5 of embodiment 2
Modified Nano Zero-valent Iron be applied to the process of heavy metal chromium in bed mud, concrete processing method is:
20g heavy metal chromium (Cr is added to by 1.0g/kg weight in wet base6+) concentration be 80mg/kg containing chromium bed mud (containing chromium bed mud according to
Preceding method carries out pretreatment) in, regulation pH value of waste water is 6,25 DEG C, carry out constant temperature oscillation reaction under the conditions of 300rpm.
After 24h, the bed mud after processing carries out extraction process, takes the lixiviating solution filter in 0.45 μm aperture and filters, obtains
Filtrate.With heavy metal Cr not processed in determined by ultraviolet spectrophotometry filtrate6+。
Heavy metal Cr6+Assay method be diphenyl carbazide spectrophotometry, with ultraviolet spectrophotometer measure, the specifically side of detection
Method is:
A) take 50mL color comparison tube 9, be separately added into Cr VI standard solution (1mg/L) 0,0.2,0.5,1.0,2.0,
4.0,6.0,8.0 and 10.0mL add pure water to graduation mark obtain hexavalent chromium concentration be respectively 0,0.004,0.01,0.02,0.04,
0,08,0.12,0.16, the chromium standard solution of 0.2mg/L；
B) take 50mL water sample, as in 50mL color comparison tube, be diluted with water to graticule；
C) in water sample and mark liquid, it is separately added into (1+1) sulphuric acid 2.5mL, adds 2.5mL diphenylcarbazide solution, immediately
Mixing, after placing 10min, at 540nm wavelength, with the cuvette of 3cm, makees reference with pure water, measures absorbance and make
Blank correction, sets up equation of linear regression, by equation of linear regression determination of hexavalent chromium content.
Testing result shows: the modified Nano Zero-valent Iron of embodiment 2 is to the Cr in bed mud6+Clearance to can reach be 93%, right
The nano zero valence iron of ratio 1 to 5 is to Cr6+Clearance all below 90%, removal effect is undesirable.
Modified Nano Zero-valent Iron is to the treatment effeciency detection of heavy metal chromium in bed mud:
Take the sediments (0～20cm) of Xiang River areas in Changsha section, and pH in detection bed mud, organic matter, moisture content, with much money respectively
The indexs such as genus, testing result is shown in Table 3.
Table 3: the quality measurements table of sediments
In bed mud, moisture content is higher as can be seen from Table 3, belongs to solid-liquid mixed phase, therefore when pollution administration, easily exists
Complicated reaction is there is at solid liquid interface.
Respectively by modified Nano Zero-valent Iron and the nano zero valence iron (Bare-nZVI) of comparative example 1, the comparative example 2 to 5 of embodiment 2
Modified Nano Zero-valent Iron be applied to the process of heavy metal chromium in above-mentioned sediments, concrete processing method is:
Add in above-mentioned sediments (sediments carries out pretreatment according to preceding method) according to 1.0g/kg weight in wet base, regulation
PH is 6, and at 25 DEG C, constant temperature oscillation 24h under 300rmp, the bed mud after processing carries out extraction process, takes lixiviating solution with 0.45
The filter in μm aperture filters, the filtrate obtained.With the content of heavy metal chromium in ultraviolet spectrophotometry filtrate, calculate chromium
Clearance, result of calculation is shown in Table 4.
Table 4: the clearance result table of heavy metal chromium in bed mud
| The stabilizer used | The clearance (%) of chromium | |
| Embodiment 1 | Sodium lauryl sulphate | 94.58 |
| Comparative example 1 | Nothing | 70.62 |
| Comparative example 2 | Dodecylbenzene sodium sulfonate | <85 |
| Comparative example 3 | Sodium carboxymethyl cellulose | <90 |
| Comparative example 4 | Rhamnolipid | <90 |
| Comparative example 5 | Metal Palladium | <90 |
As can be known from the results of Table 4: the modified Nano Zero-valent Iron of embodiment 2 to the chromium clearance in bed mud apparently higher than comparative example 1
To 4, removal efficiency is high, has a good permeability, dispersive property, nontoxic and biological degradability preferable, will not give environment
Bringing secondary pollution, and low price, cost performance is high, it is adaptable to uses on a large scale, has good use value.If
Use CMC as the stabilizer of nano zero valence iron, owing to CMC is mainly used in thickening agent, adhesive, therefore can cause nanometer
Material transition is deteriorated, and causes effect when the process of polluted river bed mud to be deteriorated.And use SDBS as stabilizer, change
The dispersion effect of property nano zero valence iron is poor, and SDBS use in a large number can cause the secondary pollution of environment；And rhamnolipid and
Metal Palladium raw material sources difficulty, cost is high, and a large amount of use can produce secondary pollution to environment, is the most all not suitable as modification
The stabilizer of nano zero valence iron.
The above, be only presently preferred embodiments of the present invention, and the present invention not makees any pro forma restriction.Although this
Invention discloses as above with preferred embodiment, but is not limited to the present invention.Any those of ordinary skill in the art,
In the case of the spirit of the present invention and technical scheme, all may utilize the method for the disclosure above and technology contents to this
Bright technical scheme makes many possible variations and modification, or is revised as the Equivalent embodiments of equivalent variations.Therefore, every do not take off
From the content of technical solution of the present invention, the technical spirit of the foundation present invention is to any simple modification made for any of the above embodiments, equivalent
Replace, equivalence changes and modifies, and all still falls within the range of technical solution of the present invention protection.
Claims (6)
1. the preparation method of a modified Nano Zero-valent Iron, it is characterized in that, described modified Nano Zero-valent Iron includes nano zero valence iron and sodium lauryl sulphate, described sodium lauryl sulphate is wrapped in described nano zero-valence iron surface and forms core-shell structure, described sodium lauryl sulphate is 0.01～0.07: 1 with the mass ratio of nano zero valence iron, and its preparation method comprises the following steps:
By isopyknic NaBH4And FeSO4Blended obtain nano zero valence iron；After described nano zero valence iron priority deionized water and ethanol purge, obtaining modified Nano Zero-valent Iron by ultrasonic disperse in sodium dodecyl sulfate solution, the concentration of described sodium dodecyl sulfate solution is 0.1g/L～0.7g/L.
Preparation method the most according to claim 1, it is characterised in that described NaBH4The concentration of solution is 0.2M～0.4M.
Preparation method the most according to claim 1, it is characterised in that described FeSO4The concentration of solution is 0.05M～0.1M.
Preparation method the most according to claim 1, it is characterised in that described NaBH4Solution and described FeSO4Solution is sufficiently stirred for 25min～30min and obtains nano zero valence iron.
5. according to the preparation method described in Claims 1-4 any one, it is characterised in that the time of described ultrasonic disperse is 30min～60min.
6. according to the preparation method described in Claims 1-4 any one, it is characterised in that the frequency of described ultrasonic disperse is 20kHZ～30kHZ.
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| CN104478004B (en) * | 2014-12-31 | 2016-06-15 | 湖南大学 | MODIFIED Fe S nanoparticle and its preparation method and application |
| CN104827028B (en) * | 2015-04-15 | 2016-04-20 | 刘骁勇 | Composite nano zero-valent iron particle |
| CN104909443B (en) * | 2015-06-26 | 2017-09-05 | 湖南大学 | The method for removing Heavy Metals in Waters chromium |
| CN106000335B (en) * | 2016-05-17 | 2018-10-19 | 湖南大学 | Cladding nanometer Zero-valent Iron and its preparation method and application |
| CN106891017B (en) * | 2017-01-20 | 2019-05-14 | 湖南大学 | Modified Nano Zero-valent Iron and its preparation method and application |
| CN106986669B (en) * | 2017-03-01 | 2020-03-27 | 沃邦环保有限公司 | Passivator for reducing activity of heavy metals in livestock and poultry manure and application thereof |
| CN106984641B (en) * | 2017-03-01 | 2020-03-27 | 沃邦环保有限公司 | Chemical stabilizer for repairing heavy metal contaminated soil and repairing method of heavy metal contaminated soil |
| CN106984642B (en) * | 2017-03-01 | 2020-03-31 | 沃邦环保有限公司 | Remediation method of heavy metal contaminated soil |
| CN106986514B (en) * | 2017-03-01 | 2020-02-11 | 沃邦环保有限公司 | Heavy metal polluted bottom mud remediation method |
| CN108043188B (en) * | 2017-11-23 | 2020-08-18 | 浙江海洋大学 | Organic waste gas purification process for adhesive products |
| CN107899388B (en) * | 2017-11-23 | 2020-08-18 | 浙江海洋大学 | Fluorine-containing waste gas treatment process |
| CN109513266A (en) * | 2018-05-23 | 2019-03-26 | 新州华美环保 | Poroid Particles dispersed iron for pollutant in treatment liquid and gas |
| CN109652080B (en) * | 2019-01-09 | 2020-05-05 | 中国农业大学 | Soil remediation agent and preparation method thereof |
| CN112139508A (en) * | 2020-09-23 | 2020-12-29 | 中国科学院地理科学与资源研究所 | Amphoteric surface micron zero-valent iron, and preparation method and application thereof |
| CN113477937B (en) * | 2021-07-05 | 2023-04-07 | 扬州工业职业技术学院 | Method for green synthesis of composite nano iron particles and application thereof |
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