CN106891017B - Modified Nano Zero-valent Iron and its preparation method and application - Google Patents
Modified Nano Zero-valent Iron and its preparation method and application Download PDFInfo
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- CN106891017B CN106891017B CN201710048158.XA CN201710048158A CN106891017B CN 106891017 B CN106891017 B CN 106891017B CN 201710048158 A CN201710048158 A CN 201710048158A CN 106891017 B CN106891017 B CN 106891017B
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- B22F9/00—Making metallic powder or suspensions thereof
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Abstract
The invention discloses a kind of modified Nano Zero-valent Iron and its preparation method and application, which includes rhamnolipid and nano zero valence iron, and in nano zero-valence iron surface, the mass ratio of rhamnolipid and nano zero valence iron is 0.1~2: 1 for rhamnolipid modification.Preparation method is to mix rhamnolipid solution with ferrous sulfate solution, is added dropwise to NaHB4Solution is reacted to obtain modified Nano Zero-valent Iron.Modified Nano Zero-valent Iron of the present invention has many advantages, such as that dispersion performance is good, stability is good, reactivity is high, permeability is high, there is good stabilization efficiency to the heavy metal lead in bed mud, secondary pollution will not be brought to environment, with good application value, it is with a wide range of applications in Heavy Metal Pollution in Sediments Treatment process field.
Description
Technical field
The invention belongs to the physical chemistry process field of heavy metal in polluted bed mud, be related to a kind of modified Nano material and its
A kind of preparation method, and in particular to modified Nano Zero-valent Iron and its preparation method and application.
Background technique
Sediments are the main accumulation libraries of river or lake pollution object, can also directly reflect the pollution history of water body,
The fast development of China's industry in recent years causes many rivers to receive more serious heavy metal pollution, especially its bed mud.
Heavy metal in bed mud not only generates pollution to water body, endangers the benthon in river, can also produce to the life of people and bring shadow
It rings.
Lead is a kind of important toxic pollutant in environment, it can make the activated protein deactivation in brain, make correlation
Functional activity disorder or stopping, or even make brain cell death, to cause that children's brain is permanent, irreversible damage.Lead
Be accumulated in skeleton, can hematological system, immune system, digestive system, nervous system etc. to human body have an impact.Research
Personnel also demonstrate that female intracorporal lead can leave a legacy of trouble to offspring, will affect the brain development of fetus, the diseases such as amentia, epilepsy occur, can also shadow
The development of fetus tooth bud is rung, child is susceptible to suffer from saprodontia after life.In addition, lead poisoning also results in sensory disturbance, such as many lead
Toxic patient will appear visual dysfunction: macular edema, retrobulbar neuritis, blind spot, eye abductor paralysis, optic nerve wither
Contracting, ocular motility disorder, pupil dysregulation, amblyopia or the visual field change；Or smell, dysgeusia etc..
The minimizing technology of heavy metal lead generally comprises physico-chemical process (pyrolysismethod, electrochemical process and extraction in bed mud
Method), biological restoration (microbial method, phytoremediation) etc..Although the above method in the repairing research of polluted bed mud
Certain progress is achieved, but there are still certain drawbacks for traditional restorative procedure.In recent years, it is restored and is removed with nano zero valence iron
Pollutant in environment becomes a very active research field.Nano zero valence iron have stronger reducing power, can
It is arranged in metal activity series table and is come out in metal replacement thereafter and be deposited on the surface of iron to achieve the purpose that depollution.
But due to the polarity of nano zero-valence iron particle itself, easily cause to reunite, reduce the absorption point of nano zero-valence iron particle,
And nano zero-valence iron particle easily reacts with the medium of surrounding (such as dissolved oxygen, water), is oxidized easily, to reduce it
Reactivity；Particle is usually all micron particles after reuniting simultaneously, this makes nano zero-valence iron particle moving in bed mud
Shifting property and active rapid decrease, are unfavorable for mobility of the nano zero-valence iron particle in environment water and soil, to environment dirt
The repair of dye is unfavorable.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide that a kind of dispersion performance is good, stability
Modified Nano Zero-valent Iron good, reactivity is high, permeability is high, additionally provides a kind of pair of experimental instrument and equipment requirement relatively
It is low, operation is simple, preparation cost is low and the preparation method of willing modified Nano Zero-valent Iron and the modification are received
Application of the rice Zero-valent Iron in stablizing bed mud in heavy metal lead, with low in cost, easy to operate, stablizing effect is good, cleaning nothing
The advantages that polluting, environment nonhazardous acted on.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of modified Nano Zero-valent Iron, the modified Nano Zero-valent Iron include rhamnolipid and nano zero valence iron, the mouse
Lee's sugar fat modification is in the nano zero-valence iron surface；Rhamnolipid described in the modified Nano Zero-valent Iron and the nano zero-valence
The mass ratio of iron is 0.1~2: 1.
In above-mentioned modified Nano Zero-valent Iron, it is preferred that the partial size of the modified Nano Zero-valent Iron is 100nm~120nm.
As a general technical idea, the present invention also provides a kind of preparation sides of above-mentioned modified Nano Zero-valent Iron
Method, comprising the following steps:
S1, rhamnolipid solution is mixed with ferrous sulfate solution, obtains mixed solution；
S2, by NaHB4Solution, which is added drop-wise in the mixed solution of step S1, to be reacted, and modified Nano Zero-valent Iron is obtained.
In above-mentioned preparation method, it is preferred that the concentration of the rhamnolipid solution is 0.2g/L~4g/L；The sulfuric acid
The concentration of ferrous iron solution is 0.07M~0.21M；The NaHB4The concentration of solution is 0.14M~0.42M.
In above-mentioned preparation method, it is preferred that the volume ratio of the rhamnolipid solution and ferrous sulfate solution is 2~3:
1；The ferrous sulfate solution and the NaHB4The volume ratio of solution is 1: 1；The NaBH4BH in solution4 -With the sulfuric acid
Fe in ferrous iron solution2+Molar ratio be 2: 1.
In above-mentioned preparation method, it is preferred that in the step S1: the rhamnolipid solution is mixed by rhamnolipid and water
It closes, it is sonicated to be prepared；The frequency of the ultrasonic treatment is 30KHz~50KHz；The time of the ultrasonic treatment is
5min~10min；
The mixing carries out in a nitrogen atmosphere；The revolving speed stirred in the mixed process is 300r/min~500r/
min；The time of the stirring is 15min~25min；
And/or in the step S2: the reaction carries out in a nitrogen atmosphere；The revolving speed stirred in the reaction process
For 300r/min~500r/min；The NaHB4After solution is added dropwise, continue to stir 15min~30min.
As a general technical idea, the present invention also provides a kind of above-mentioned modified Nano Zero-valent Irons to stablize bed mud
Application in middle heavy metal lead, comprising the following steps: modified Nano Zero-valent Iron is added to progress constant temperature standing in leaded bed mud
The processing to leaded bed mud is completed in reaction.
In above-mentioned application, it is preferred that the modified Nano Zero-valent Iron is added in leaded bed mud in the form of suspension,
The volume mass ratio of the suspension of modified Nano Zero-valent Iron and leaded bed mud is 5mL~10mL: 1g；The modified Nano Zero-valent Iron
Suspension in modified Nano Zero-valent Iron concentration be 0.5g/L~1g/L.
In above-mentioned application, it is preferred that in the leaded bed mud initial concentration of heavy metal lead be 250mg/kg~
300mg/kg；The pH value of the leaded bed mud is 6~8.
In above-mentioned application, it is preferred that the temperature that the constant temperature stands reaction is 20 DEG C~25 DEG C, and the time is 0d~42d.
Creativeness of the invention is:
The present invention is modified nano zero valence iron using rhamnolipid (RL) as dispersing agent, and wherein rhamnolipid improves
The dispersion performance of particle, mechanism is mainly by, in nano zero-valence iron surface, changing nano zero valence iron for rhamnolipid modification
Surface charge distribution, generate electrostatic stabilization effect, steric hindrance effect and electrostatic space stability ultimate load effect, so as to improve receiving
The dispersion effect of rice Zero-valent Iron, it is seen that make nano zero valence iron be uniformly dispersed by rhamnolipid modification, effectively prevent nanometer
Reuniting effect between Zero-valent Iron, improves the dispersibility, stability and permeability of nano zero valence iron, and solves due to nanometer
The problems such as reunion caused by the polarity of zero-valent iron particle itself, few absorption point；Meanwhile rhamnolipid modification is in nanometer
The surface of Zero-valent Iron is effectively reduced the contact area of the medium (such as dissolved oxygen, water) of nano zero-valence iron particle and surrounding,
Nano zero valence iron is prevented to react with surrounding medium, to maintain its higher reactivity.Therefore, pass through in the present invention
The modified obtained modified Nano Zero-valent Iron of rhamnolipid has dispersion performance is good, stability is good, reactivity is high, permeability is high etc.
Advantage has good stabilization efficiency to the heavy metal lead in bed mud, will not bring secondary pollution to environment, has good answer
With value.
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention is that dispersing agent is modified nano zero valence iron with rhamnolipid (RL), obtained modified Nano zero
Valence iron is the material that a kind of dispersion performance is good, stability is good, reactivity is high, permeability is high.Modified Nano zeroth order of the invention
Iron can penetrate into inside bed mud with solution, have biodegradable, act on environment nonhazardous, will not generate secondary dirt
Dye is suitble to large-scale application.
(2) in the present invention, rhamnolipid be it is a kind of it is cheap, biodegradable, to the yin of environment nonhazardous effect from
Sub- biosurfactant can be such that substance spreads, so that modified nano zero valence iron has by dispersion and wettability
There is good permeability；Rhamnolipid has distinctive carboxyl, hydroxyl structure simultaneously, this enables it to form chelating with heavy metal
Object especially has good stablizing effect to heavy metal lead.Compared to unmodified nano zero valence iron, the present invention passes through rhamnolipid
Modified obtained modified Nano Zero-valent Iron improves the stabilization efficiency to heavy metal lead, reduces migration of the heavy metal in bed mud
Property and biological effectiveness, reduce harm of the heavy metal to organism.
(3) the present invention also provides a kind of preparation method of modified Nano Zero-valent Iron, this method wants experimental instrument and equipment
Ask relatively low, operation is simple, preparation cost is low and is swift in response, a large amount of nanometer material can be generated in a short time
Material, modified Nano nulvalent iron particle obtained is evenly distributed, and shows spherical, and dispersibility is greatly improved, and does not occur
Iron oxides impurities, purity is high.
(4) modified Nano Zero-valent Iron of the invention can be used for administering heavy metal pollution polluted bed mud, low in cost, operation
Simplicity, stablizing effect is good, and cleanliness without any pollution, acts on environment nonhazardous, has in Heavy Metal Pollution in Sediments Treatment process field
Have wide practical use.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is the scanning electron microscope (SEM) photograph of unmodified nano zero valence iron (nZVI) in comparative example 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3.
Fig. 3 is the transmission electron microscope picture of unmodified nano zero valence iron (nZVI) in comparative example 1.
Fig. 4 is the transmission electron microscope picture of modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3.
Fig. 5 is unmodified nano zero-valence in modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3 and comparative example 1
The x-ray diffraction pattern of iron (nZVI), wherein a is RL-nZVI, b nZVI.
Fig. 6 is unmodified nano zero-valence in modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3 and comparative example 1
The FTIR spectrum figure of iron (nZVI), wherein a is nZVI, b RL-nZVI.
Fig. 7 is modified Nano Zero-valent Iron (RL-nZVI) R1, R2, R3, R4, R5 and comparative example 1 in the embodiment of the present invention 1~5
In unmodified nano zero valence iron (nZVI) to the stablizing effect figure of bed mud heavy metal lead, wherein ordinate is each form of heavy metal lead
Percentage, abscissa are the different stabilization processes times.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument are commercially available.
Embodiment 1:
A kind of modified Nano Zero-valent Iron, the modified Nano Zero-valent Iron include rhamnolipid (RL) and nano zero valence iron, sandlwood
Glycolipid modification is in nano zero-valence iron surface, and wherein rhamnolipid is dispersing agent.
In the present embodiment, the mass ratio of rhamnolipid and nano zero valence iron is 0.1: 1.
In the present embodiment, the partial size of modified Nano Zero-valent Iron is 120nm.
A kind of preparation method of modified Nano Zero-valent Iron in above-mentioned the present embodiment, comprising the following steps:
(1) solution is prepared:
FeSO4The preparation of solution: 0.496g FeSO is weighed4·7H2O is set in beaker, and appropriate ultrapure water solution transfer is added to arrive
In 25mL volumetric flask, it is settled to graduation mark with ultrapure water, is shaken up, obtains the FeSO that concentration is 0.07M4Solution.
The preparation of rhamnolipid solution: weighing 0.01g rhamnolipid and set in beaker, and appropriate ultrapure water is added to carry out at ultrasound
Reason, wherein the frequency being ultrasonically treated is 40KHZ, time 10min makes it dissolve, is then transferred into 50mL volumetric flask, with super
Pure water is settled to graduation mark, shakes up, and obtains the rhamnolipid solution that concentration is 0.2g/L.
NaBH4The preparation of solution: 0.136g NaBH is weighed4It sets in beaker, appropriate ultrapure water solution transfer is added to hold to 25mL
In measuring bottle, it is settled to graduation mark with ultrapure water, is shaken up, obtains the NaBH that concentration is 0.14M4Solution.
(2) modified Nano Zero-valent Iron (RL-nZVI) is prepared: by the FeSO of 25mL, 0.07M4Solution and 50mL, 0.2g/L's
Rhamnolipid solution is added in the three-necked flask of 250mL, is stirred 20min under being 300r/min in nitrogen protection and revolving speed, is obtained
To mixed solution；In the case where nitrogen protection and revolving speed are 300r/min, by BH4 -/Fe2+Molar ratio is 2: 1, by isometric 25mL's
NaBH4Solution at the uniform velocity instills in three-necked flask dropwise, reaction system blackening, there is bubble (hydrogen) generation, NaBH4After solution drips off
15min is stirred continuously and healthily, and obtaining modified Nano Zero-valent Iron (RL-nZVI) suspension, (its solvent is water, with embodiment 2-
5), number R1.The concentration of modified Nano Zero-valent Iron is 1g/L in the suspension.Since the cladding nanometer Zero-valent Iron is used for bottom
The processing of mud heavy metal, in order to guarantee its dispersibility in bed mud, therefore cladding nanometer Zero-valent Iron is usually with the shape of suspension
Formula saves.
Embodiment 2:
A kind of modified Nano Zero-valent Iron, essentially identical with the modified Nano Zero-valent Iron of embodiment 1, difference is only that: being implemented
The mass ratio of rhamnolipid and nano zero valence iron is 0.3: 1 in example 2.
A kind of preparation method of the modified Nano Zero-valent Iron of above-mentioned the present embodiment, the basic phase of preparation method with embodiment 1
Together, difference is only that: the concentration of rhamnolipid solution is 0.6g/L in embodiment 2.Modified Nano Zero-valent Iron made from this method
(RL-nZVI) suspension, number R2.
Embodiment 3:
A kind of modified Nano Zero-valent Iron, essentially identical with the modified Nano Zero-valent Iron of embodiment 1, difference is only that: being implemented
The mass ratio of rhamnolipid and nano zero valence iron is 0.5: 1 in example 3.
A kind of preparation method of the modified Nano Zero-valent Iron of above-mentioned the present embodiment, the basic phase of preparation method with embodiment 1
Together, difference is only that: the concentration of rhamnolipid solution is 1g/L in embodiment 3.Modified Nano Zero-valent Iron made from this method
(RL-nZVI) suspension, number R3.
Comparative example 1:
A kind of preparation method of unmodified nano zero valence iron (nZVI), difference essentially identical with the preparation method of embodiment 1
It is only that: rhamnolipid solution being not added in comparative example 1.
Unmodified nano zero valence iron in modified Nano Zero-valent Iron R3 obtained in the embodiment of the present invention 3 and comparative example 1 is set
Micro-Structure Analysis is carried out under scanning electron microscope.Fig. 1 is the scanning electron microscope of unmodified nano zero valence iron (nZVI) in comparative example 1
Figure.From Fig. 1 it is observed that chain structure is presented in unmodified nano zero valence iron, this is mainly due to nano zero valence irons itself
Caused by polarity.Fig. 2 is the scanning electron microscope (SEM) photograph of modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3.From figure
2 it is observed that particle dispersion is more uniform, shows spherical particle, shows that the modified nano zero valence iron of rhamnolipid has
It is good dispersibility and successfully modify in the surface of nano zero-valence iron particle.Fig. 3 is unmodified nano zero valence iron in comparative example 1
(nZVI) transmission electron microscope picture.From Fig. 3 it can be observed that nano zero valence iron can be presented chain form, but the partial size of each particle
One layer of translucent film can be observed in the extexine of nano zero-valence iron particle in respectively less than 100nm, this tunic belongs to nano zero-valence
The shell of iron, the mainly oxide and hydroxide of iron.Fig. 4 is modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3
Transmission electron microscope picture.Preferably, grain diameter is between 100nm-120nm for modified Nano Zero-valent Iron dispersibility as can be seen from Figure 4.
Fig. 5 is unmodified nano zero valence iron (nZVI) in modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3 and comparative example 1
X-ray diffraction pattern, wherein a be RL-nZVI, b nZVI.As seen from Figure 5, there is spreading out for 2 θ=44.9 ° in a and b
Peak is penetrated, which is the characteristic peak of nano zero valence iron；B is in 2 θ=30 ° of angle of diffraction, and 35 °, 62.25 ° occur significantly spreading out
Peak is penetrated, these peaks represent the oxide of iron, and do not occur in a, this shows modified Nano Zero-valent Iron not by oxygen
Change.Fig. 6 is unmodified nano zero valence iron in modified Nano Zero-valent Iron (RL-nZVI) in the embodiment of the present invention 3 and comparative example 1
(nZVI) FTIR spectrum figure, wherein a is nZVI, b RL-nZVI.Wave band 3600-3200cm-1Expression-OH, in RL-
Occurs the phenomenon that widening (curve b), and have no the phenomenon that widening in nZVI (curve a), this shows of the invention change in nZVI
Nano zero valence iron and rhamnolipid have carried out the combination of hydrogen bond in property nano zero valence iron.In 1635cm-1And 1405cm-1Place represents
- COOH, 3000-2800cm-1The peak of appearance represents c h bond, 1033cm-1Place represents C-O key, and-COOH, C-H and C-O this
A little functional groups and key are all that may indicate that rhamnolipid is successfully modified in nano zero-valence iron surface specific to rhamnolipid
(curve b).
Embodiment 4:
A kind of modified Nano Zero-valent Iron, essentially identical with the modified Nano Zero-valent Iron of embodiment 1, difference is only that: being implemented
The mass ratio of rhamnolipid and nano zero valence iron is 1: 1 in example 4.
A kind of preparation method of the modified Nano Zero-valent Iron of above-mentioned the present embodiment, the basic phase of preparation method with embodiment 1
Together, difference is only that: the concentration of rhamnolipid solution is 2g/L in embodiment 4.Modified Nano Zero-valent Iron made from this method
(RL-nZVI) suspension, number R4.
Embodiment 5:
A kind of modified Nano Zero-valent Iron, essentially identical with the modified Nano Zero-valent Iron of embodiment 1, difference is only that: being implemented
The mass ratio of rhamnolipid and nano zero valence iron is 2: 1 in example 5.
A kind of preparation method of the modified Nano Zero-valent Iron of above-mentioned the present embodiment, the basic phase of preparation method with embodiment 1
Together, difference is only that: the concentration of rhamnolipid solution is 4g/L in embodiment 5.Modified Nano Zero-valent Iron made from this method
(RL-nZVI) suspension, number R5.
Embodiment 6:
Application of the modified Nano Zero-valent Iron in stablizing bed mud in heavy metal lead, comprising the following steps:
(1) the leaded bed mud in Xiang River areas in Changsha section surface layer (0~20cm) is taken, leaded bed mud is air-dried under field conditions (factors), is ground,
Sieving, obtains the leaded bed mud of partial size≤75 μm.Then the basic physical and chemical of bed mud is measured, measurement result is shown in Table 1.
Table 1: the quality measurements table of leaded bed mud
As it can be seen from table 1 bed mud moisture content is higher, belong to solid-liquid mixed phase, therefore during pollution administration, holds
Complicated reaction easily occurs in solid liquid interface.
(2) do not change in modified Nano Zero-valent Iron R1, R2, R3, R4, the R5 and comparative example 1 being utilized respectively in Examples 1 to 5
Property nano zero valence iron handle leaded bed mud, method particularly includes:
Taking 0.5g through the pretreated leaded bed mud of step (1), (content of heavy metal lead is 274.1mg/kg, residual form lead
Content be 15.60mg/kg), be placed in 50mL centrifuge tube, then by the modified Nano Zero-valent Iron (RL- in Examples 1 to 5
NZVI) unmodified nano zero valence iron (nZVI) (being added in the form of suspension) is pressed in R1, R2, R3, R4, R5 and comparative example 1
It is added to the ratio of leaded bed mud volume mass ratio 5mL: 1g (nano zero valence iron suspension vol/bed mud absolute dry mass) above-mentioned
In centrifuge tube, constant temperature stands reaction 42 days at 24 DEG C.Using the various shapes of heavy metal lead in BCR continuous extraction measurement bed mud
The percentage composition of state, the results are shown in Table 2.Table 2 is the Pb content for repairing various forms in the bed mud of front and back.
Table 2: the Pb content of various forms in the bed mud of front and back is repaired
As can be known from the results of Table 2: modified Nano Zero-valent Iron R1, R2, R3, R4, R5 obtained are to leaded in Examples 1 to 5
The stabilization efficiency of residual form is above unmodified nano zero valence iron made from comparative example 1 and imitates to stablizing for leaded bed mud in bed mud
Rate, the weak acid extractable of lead and can the percentage of reduction-state reduce, residual form percentage increases, and illustrate to reduce to a certain degree again
The bioavilability of metallic lead reduces heavy metal lead to the harmfulness of organism.Modified Nano Zero-valent Iron made from embodiment 3
R3 is 56.09% to the residual form stabilization efficiency of heavy metal lead in bed mud, compared to preprosthetic, makes environmental pollution in bed mud
The content for endangering the smallest residual form rises 40.49%, be above it is other under the conditions of modified Nano Zero-valent Iron obtained, explanation
Modified Nano Zero-valent Iron R3 in embodiment 3 has better stablizing effect to the heavy metal lead in bed mud, is preferred embodiment.
Fig. 7 is modified Nano Zero-valent Iron (RL-nZVI) R1, R2, R3, R4, R5 and comparative example 1 in the embodiment of the present invention 1~5
In unmodified nano zero valence iron (nZVI) to the stablizing effect figure of bed mud heavy metal lead, wherein ordinate is each form of heavy metal lead
Percentage, abscissa are the different stabilization processes times.For abscissa, each time interval has 7 pillars, from left to right
It respectively represents: in the unmodified nano zero valence iron and Examples 1 to 5 before repairing in the value (original value), comparative example 1 of bed mud sample
Modified Nano Zero-valent Iron R1, R2, R3, R4, R5 stabilization treatment effect.Refer within the 0th day in Fig. 7 and measures lead on the day of added material
Metamorphosis, as shown in Figure 7, with the passage for stablizing the time, the weak acid extractable of heavy metal lead and can reduction-state percentage
It reducing, raised trend is presented in residual form percentage, it is above the residual form percentage of lead in bed mud before repairing, meanwhile, it can be with
Find out, when treated between after 35 days, residual form percentage change is little, has at this moment tended towards stability.Nano zero valence iron with
And the modified a degree of bioavilability for reducing heavy metal lead of nano zero valence iron, reduce heavy metal lead to biology
The harmfulness of body.In addition, within each sample time, it can be seen that R3 pairs of modified Nano Zero-valent Iron in the embodiment of the present invention 3
In bed mud the weak acid extractable of lead and can minimum, the residual form percentage highest of the sum of reduction-state percentage, this equally also illustrates this
Modified Nano Zero-valent Iron R3 in inventive embodiments 3 is best to the stablizing effect of heavy metal lead in bed mud.
Comparative example 2
Application of the modified Nano Zero-valent Iron in stablizing bed mud in heavy metal cadmium, wherein the source of the bed mud containing cadmium and its basic
Physicochemical property is identical as leaded bed mud in embodiment 6, and the modified Nano Zero-valent Iron R1 being utilized respectively in Examples 1 to 5,
In R2, R3, R4, R5 and comparative example 1 when unmodified nano zero valence iron processing bed mud containing cadmium, specific stabilization step also with reality
It is identical to apply example 6.
Using the percentage composition of the various forms of heavy metal cadmium in BCR continuous extraction measurement bed mud, as a result such as 3 institute of table
Show.Table 3 is the Cd content for repairing various forms in the bed mud of front and back.
Table 3: the Cd content of various forms in the bed mud of front and back is repaired
In conjunction with table 2 and table 3 it is found that modified Nano Zero-valent Iron obtained is to heavy metal in bed mud in 1-5 of the embodiment of the present invention
The stabilization effect of lead is obviously higher than their stabilization effects to heavy metal cadmium in bed mud.Changed with obtained in embodiment 3
Property nano zero valence iron R3 for, it is 56.08% to the residual form stabilization efficiency of heavy metal lead in bed mud, compares preprosthetic bottom
Mud, residual form stabilization efficiency improves 39.48%, and it is 36.02% to the residual form stabilization efficiency of heavy metal cadmium in bed mud,
Compared to preprosthetic bed mud, residual form stabilization efficiency improves only 34.15%, this also illustrates modified Nano Zero-valent Iron R3 of the present invention
It is more preferable to the stabilization effect of heavy metal lead in bed mud.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (2)
1. a kind of preparation method of modified Nano Zero-valent Iron, which comprises the following steps:
S1, rhamnolipid solution is mixed with ferrous sulfate solution, obtains mixed solution；It is described mixing in a nitrogen atmosphere into
Row；The revolving speed stirred in the mixed process is the r/min of 300 r/min~500；The time of the stirring is 15 min~25
min；
S2, by NaBH4Solution, which is added drop-wise in the mixed solution of step S1, to be reacted, and modified Nano Zero-valent Iron is obtained；The reaction
It carries out in a nitrogen atmosphere；The revolving speed stirred in the reaction process is the r/min of 300 r/min~500；The NaBH4Solution
After being added dropwise, continue to stir the min of 15 min~30；
The concentration of the rhamnolipid solution is the g/L of 0.6 g/L~1；The concentration of the ferrous sulfate solution be 0.07 M~
0.21 M；The NaBH4The concentration of solution is the M of 0.14 M~0.42；The body of the rhamnolipid solution and ferrous sulfate solution
Product is than being 2~3: 1；The ferrous sulfate solution and the NaBH4The volume ratio of solution is 1: 1；The NaBH4In solution
BH4 -With the Fe in the ferrous sulfate solution2+Molar ratio be 2: 1；
The modified Nano Zero-valent Iron includes rhamnolipid and nano zero valence iron, and the rhamnolipid modification is in the nano zero-valence
Iron surface；The mass ratio of rhamnolipid described in the modified Nano Zero-valent Iron and the nano zero valence iron is 0.3~0.5: 1；
The partial size of the modified Nano Zero-valent Iron is the nm of 100 nm~120.
2. preparation method according to claim 1, which is characterized in that in the step S1: the rhamnolipid solution by
Rhamnolipid is mixed with water, sonicated to be prepared；The frequency of the ultrasonic treatment is the KHz of 30 KHz~50；It is described super
The time of sonication is the min of 5 min~10.
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| CN109384299B (en) * | 2018-08-10 | 2022-02-01 | 华中师范大学 | Method for removing hexavalent chromium in water body by using sodium oxalate modified zero-valent iron |
| CN109848403A (en) * | 2018-11-24 | 2019-06-07 | 天津大学 | A kind of modified Nano Zero-valent Iron and preparation method thereof and the application for handling industrial seepage pit bed mud heavy metal |
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