CN107081125A - A kind of vulcanization nanometer zero-valent iron composite material of alta-mud load and preparation method and application - Google Patents
A kind of vulcanization nanometer zero-valent iron composite material of alta-mud load and preparation method and application Download PDFInfo
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Abstract
The present invention relates to the vulcanization of a kind of alta-mud load nanometer zero-valent iron composite material and preparation method and application, the composite is to load to the nano zero valence iron of sulfide modifier on bentonite, and described bentonite and the mass ratio of total iron content are 0.85 1.2：1, the mol ratio of element sulphur and total iron content is 0.05 0.065：1.The vulcanization nanometer zero-valent iron composite material of the alta-mud load of the present invention is more stablized and efficiently and suitable for the processing of multiple pollutant, sulfide modifier can accelerate the electron transmission of nano zero-valence iron surface to promote its corrosion to greatly improve the reactivity of the material, and sulfidation is simply pollution-free, loading on bentonite enables the material to be difficult reunion holding activity for a long time.The material reaches more than 97.5% in 2min to the clearance of 4 nitrophenols, to orange I clearance close to 100%.
Description
Technical field
The present invention relates to the vulcanization of a kind of alta-mud load nanometer zero-valent iron composite material and preparation method and application, category
In the Treatment process field of waste water.
Background technology
Iron is material very common during we live, and because its chemical property is active, abundance is cheap, electricity
Negativity is very big and is widely used to degrade and remove the organic pollution materials in environment with certain specific surface area
With inorganic pollution material.The development for being found to be Zero-valent Iron into nano zero valence iron since 21 century brings more wide sky
Between.Nano zero valence iron can reduce a variety of halogenated hydrocarbons, nitric acid/nitrite, high volence metal ion, Multiple Pesticides and herbicide
Deng, and the abundant raw material of nano zero valence iron is prepared, it is with low cost.In addition nano zero-valence iron particle can both be injected directly into ground
It is used for groundwater remediation down, can be directly used in mixed way again under oxygen deprivation and certain damp condition with contaminated soil.Due to its pole
Strong reactivity causes its surface to be readily formed oxide-film, also can slowly thicken with the increase oxide-film of holding time and
Its reactivity is reduced, smaller additionally, due to its molecule particles, molecular activity is larger and is easily caused nano zero valence iron and occurs group
Poly- phenomenon, this greatly influences its reactivity.Therefore, maintain the reactivity of nano zero valence iron and prevent it from occurring
Reunion will have vast potential for future development.Chinese patent document CN104827028A discloses composite Nano zero-valent iron particle, its
Composition form is nucleocapsid structure, and core is nano zero valence iron, and the shell of enhancing nano zero valence iron activity is coated with core,
It is characterized in that the composition of the shell is FeS, nano zero-valence iron layer is made in the nucleocapsid structure of described composite Nano zero-valent iron particle
The multiple layer combination structure being alternately present with FeS clads；The preparation method of modified Nano Zero-valent Iron, which is included in, prepares nano zero-valence
The chaotropic agent that elemental sulfur and elemental sulfur are added during iron particle forms FeS while iron ion is reduced.Though the method ensure that
The reactivity of nano zero valence iron, but it is smaller due to its molecule particles and cause its be still easy to aoxidize and reunite in atmosphere from
And influence its reactivity and cause its sulphur iron burden control more difficult due to sulphur simple substance content can not be monitored in real time.
Bentonite is a kind of nonmetallic minerals using montmorillonite as main mineral constituent, and smectite structure is by two silica
Tetrahedron presss from both sides the 2 of one layer of alumina octahedral composition：1 type crystal structure, because the layer structure of montmorillonite structure cell formation has certain
A little cations, such as Cu, Mg, Na, K, and the effect of these cations and montmorillonite structure cell is very unstable, easily by other cations
Exchange, therefore with preferable ion exchangeable.China's bentonite reserves rank first in the world and great variety of goods, widely distributed price
It is cheap to be a kind of green and have mineral products with broad prospects for development.
Chinese patent document CN101314496A discloses a kind of modified alta-mud loaded nano-hot metal treating agent, by modification
After bentonite uniformly mixes for 3: 7~9: 1 by weight with Nanoscale Iron, reduced using strong reductant, be prepared into modified alta-mud
Loaded nano-hot metal treating agent.It is due to bentonitic although this method can make the uniform and stable presence of nano zero valence iron
Suction-operated is limited and makes the mainly nano zero valence iron that the reaction plays a role, and simple nano zero valence iron reactivity is then
It is relatively low.
While nano zero valence iron sulfide modifier and it will load to its agglomeration traits can be not only solved on bentonite
Its activity can be improved.And while the nano zero valence iron prepared to Traditional liquid phase method carries out sulfide modifier and loaded
Following shortcoming is easily produced when on to bentonite：1st, the sodium thiosulfate added in one-step method sulfide modifier nano zero valence iron compared with
Proportioning for complicated sulphur iron whard to control causes complex operation, and sodium thiosulfate is easily influenceed most by bentonitic influence
Whole sulphur iron proportioning；2nd, the process of two-step method be will the nano zero valence iron that loaded immerse acid solution in discharge iron ion again with
The sulphion of addition is combined, this be easily caused the zeroth order iron loss of load and being come off from bentonite cause its structural instability from
And cause the reduction of reactivity.
The content of the invention
It is relatively low for simple in the prior art alta-mud loaded nano Zero-valent Iron activity, vulcanize modified Nano merely
Zero-valent Iron is easily reunited and simultaneously by nano zero valence iron sulfide modifier and the shortcoming and deficiency that load to technology on bentonite, sheet
Invention provides a kind of preparation method of vulcanization nano composite material of alta-mud load and its application in pollutant is removed.Knot
Fruit shows that the composite is evenly distributed the stable pollutant such as 4- nitrophenols and orange I and also of can quickly removing of performance
Have the advantages that environment-friendly, applicable pH range is relatively extensive, with low cost, efficiency is lasting.
Nano zero valence iron is loaded on bentonite and carries out sulfide modifier to it and then obtain the composite by the present invention,
The particle diameter of the composite applies to the material mould for removing nitrophenols containing 4- and orange I respectively between 50-150nm
Intend in waste water solution, excellent effect.
Term is explained
Bentonite：It is the nonmetallic minerals using montmorillonite as main mineral constituent, with good adsorptivity and necessarily
Ion-exchange capacity.
Nano zero valence iron：A kind of particle diameter Nano grade zeroth order iron powder, with good reproducibility and adsorptivity.Can
By FeCl3Prepared in a certain proportion of ethanol and the aqueous solution with sodium borohydride reduction, its reaction equation is
FeCl3·6H2O+3NaBH4→Fe+3B(OH)3+7.5H2↑+3NaCl。
Orange I：It is a kind of azo dyes, its chemical formula is C16H11N2NaO4S, it is in orange-yellow to be dissolved in color after water, by people
Carcinogenic risk is had after body suction.
4- nitrophenols：Also known as paranitrophenol, its chemical formula is C6H5NO3For medicine, agricultural chemicals, fuel etc., crystallize to be yellowish
Color, in acid condition close to colourless, yellow intensification in the basic conditions.Allergic reaction easily occurs for contact skin, sucks human body
It is harmful.
Technical scheme is as follows：
A kind of vulcanization nanometer zero-valent iron composite material of alta-mud load, the composite is by the nanometer zero of sulfide modifier
Valency iron is loaded on bentonite, and described bentonite and the mass ratio of total iron content are 0.85-1.2：1, element sulphur contains with total iron
The mol ratio of amount is 0.05-0.065：1.
, according to the invention it is preferred to, the microscopic appearance of described composite is：Zero-valent Iron is coated with iron sulfide
Spheric granules is formed, spheric granules rearranges chain structure, and chain structure free accumulation is supported on bentonite surface and swollen
The native molecule interlayer of profit.
, according to the invention it is preferred to, the particle diameter of described spheric granules is 50-150nm.
, according to the invention it is preferred to, the specific surface area of described composite is 30-35m2/ g, can evenly spread to water
In solution, reunion will not be produced.
According to the present invention, the preparation method of the vulcanization nanometer zero-valent iron composite material of above-mentioned alta-mud load, including step
It is as follows：
In the mixed solution that bentonite and trivalent iron salt are added to second alcohol and water, dispersed with stirring is equal under logical condition of nitrogen gas
It is even；Then sodium sulfide solution is added dropwise while adding sodium borohydride solution to be reacted, whole process is entered in the case of logical nitrogen
Go to ensure the anaerobic state of solution；Centrifuged after reaction completely, after solid cleaning, produce composite.
According to the preparation method of composite of the present invention, it is preferred that described trivalent iron salt is iron chloride or ferric sulfate.
According to the preparation method of composite of the present invention, it is preferred that the volume ratio of ethanol and water is (3- in ethanol water
5)：1, further preferred 4:1；
It is preferred that, the concentration of described sodium borohydride solution is 0.025-0.027g/mL；
It is preferred that, the volume ratio of ethanol water and sodium borohydride is 5：(1-3), further preferred 5:2；
According to the preparation method of composite of the present invention, it is preferred that described bentonite：Molysite：Sodium borohydride：Vulcanized sodium
Mass ratio be 1：4.83：2.0266：0.078.
According to the preparation method of composite of the present invention, it is preferred that sodium hydroxide is added in sodium borohydride solution makes hydrogen-oxygen
Change na concn is 2g/L, to prevent sodium borohydride and water from reacting consumption excessively, preferably adds 0.08g sodium hydroxides to 40mL boron hydrogen
Change in sodium solution；
According to the preparation method of composite of the present invention, it is preferred that Na2The concentration of S solution is 1mol/L, and volume is added dropwise and is
0.36-0.7mL, more preferably 0.5mL make the total iron mol ratio of sulphur be 0.056；
According to the preparation method of composite of the present invention, it is preferred that be 15-35min the time required to reaction completely, preferably instead
It is 30min between seasonable.
According to the preparation method of composite of the present invention, it is preferred that be continually fed into ordinary nitrogen in course of reaction to ensure
Solution anaerobic state, needs the nitrogen of logical certain time to ensure that Zero-valent Iron is not oxidized by oxygen before sodium borohydride solution is added dropwise.
It is preferred that in the case where 500mL/min flows are, maintaining nitrogen purge 30min；
The rotating speed stirred in course of reaction is 300rpm.
According to the preparation method of composite of the present invention, it is preferred that the dropwise addition speed of sodium borohydride solution and sodium sulfide solution
Rate is 1-2 drops/sec；
It is preferred that, Na is added dropwise again after sodium borohydride 1min is added dropwise2S solution.
According to the preparation method of composite of the present invention, it is preferred that the rotating speed of centrifugation is 4500 turns/min, during centrifugation
Between be 8~15min, more preferably 10min；
It is preferred that, cleaning is centrifuged again twice with the deionized water of anaerobic when cleaning the material, then again with anhydrous
Ethanol is cleaned once.
, according to the invention it is preferred to, the vulcanization nanometer zero-valent iron composite material of obtained alta-mud load is added to anaerobic
It is uniformly dispersed in deionized water, sealing preserve.It is preferred that, the concentration of composite is 20g/L.Composite described above makes
The material is set to be uniformly dispersed in anaerobic deionized water with ultrasonic 5min is both needed to before.
According to the vulcanization of alta-mud load of the present invention nanometer zero-valent iron composite material, a preferred embodiment is as follows：
80mL ethanol, 20mL water, 0.5g bentonites and 2.415g FeCl are added in four-neck flask3·6H2O exists
Stirred under 300rpm and logical nitrogen 30min is well mixed it, weigh 1.0133g sodium borohydrides and 0.08g sodium hydroxides
It is 0.025g/mL to be dissolved in gained sodium borohydride concentration in 40mL anaerobic deionized waters, is added drop-wise to constant pressure funnel with 1-2 drops/sec
In four-neck flask, 0.5mL 1mol/L Na is added dropwise after 1min with same speed2After S solution, reaction 30min, at 4500 turns
It is lower to use centrifuge separation cleaning, washed three times and washed again with ethanol solution one time with the deionization of anaerobic；It is eventually adding 50mL
Anaerobic deionized water ultrasound 5min is prepared into finely dispersed 20g/L composite.
According to the present invention, the vulcanization nanometer zero-valent iron composite material of above-mentioned alta-mud load processing nitrophenols containing 4- or/
With the application in the waste water of orange I pollutants.
Application according to the present invention, it is preferred that the pH value of regulation waste water is 5-7, further preferred pH=6.
Application according to the present invention, it is preferred that the concentration of 4- nitrophenols is 1-2mmol/L in waste water, further preferably
1.5mmol/L；Orange I concentration is (80-120) mg/L, further preferred 100mg/L.
Application according to the present invention, it is preferred that dosage of the composite in waste water is in 0.3-1.0g/L, in above-mentioned dirt
Contaminate preferably 1g/L under thing concentration.
Application according to the present invention, it is preferred that add after composite, reacted under agitation into waste water,
It is preferred that stir speed (S.S.) be 300-500r/min, further preferred 400r/min.
The technical characterstic and beneficial effect of the present invention
The present invention obtains this to its sulfide modifier and loading on bentonite while nano zero valence iron is prepared and is combined
Material, the process is simple and easy to get and is easy to control sulphur iron proportioning.Can be fast and efficiently in the case where being not added with cushioning liquid
Eliminate paranitrophenol and orange I.As a result show that the material has very strong reactivity, its specific surface area has reached 30-
35m2/ g, and can uniformly be distributed in the aqueous solution and be difficult to reunite, keep high reaction activity so as to prolonged.Sulphur
The corrosion of Zero-valent Iron can be accelerated by changing modification, promote Fe2+Release, while the ironing surface electron transmission of zeroth order can be accelerated, subtract
The passivation of weak Zero-valent Iron is so as to intensified response activity.Bentonite has certain absorption property and ion exchange energy in itself
Power, nano zero valence iron, which is loaded on bentonite, can prevent the reunion of nano zero valence iron so that material can be protected for a long time
Hold activity and enhance the absorption property of the composite.
Advantage is the present invention compared with prior art：
1st, the vulcanization nanometer zero-valent iron composite material of alta-mud load of the invention is more efficiently and suitable for a variety of
The processing of pollutant, sulfide modifier can accelerate the electron transmission of nano zero-valence iron surface and promote it to corrode, and greatly improve
The reactivity of the material, and sulfidation is simply pollution-free, and the clearance of 4- nitrophenols is reached in reaction 2min
More than 97.5%, to orange I clearance close to 100%.
2nd, bentonite can ensure that the composite keeps its activity to be difficult reunion for a long time in the present invention, and increase should
The absorption property of composite can adsorb multiple pollutant.
3rd, the invention provides a kind of method of simple easily controllable one-step method vulcanization and load, and the material is confirmed
Material has very strong reactivity and to environment non-secondary pollution.
4th, the vulcanization nanometer zero-valent iron composite material of alta-mud load of the invention can be in the range of broad pH to dirt
Dye thing is quickly removed, and it is more had the value of application.
Brief description of the drawings
Fig. 1 is the X-ray photoelectricity of the vulcanization nanometer zero-valent iron composite material of alta-mud load made from the embodiment of the present invention 1
Sub- power spectrum (XPS)；Abscissa is to combine energy (eV), and ordinate is relative intensity, is the umber of pulse of each second.
Fig. 2, Fig. 3 are the vulcanization nanometer zero-valent iron composite materials of alta-mud load made from the embodiment of the present invention 1 in difference
Scanning electron microscope (SEM) photograph (SEM) under multiplication factor.
Fig. 4 is bentonitic scanning electron microscope (SEM) photograph (SEM) used in the embodiment of the present invention 1.
Fig. 5 is the vulcanization nanometer zero-valent iron composite material of alta-mud load under different sulphur-iron ratios in the embodiment of the present invention 2 and 3
4- nitrophenols and orange I effect contrast figure are removed with alta-mud loaded nano Zero-valent Iron, wherein abscissa is the time (min)
Ordinate is C/C0Represent the concentration divided by its initial concentration of certain moment pollutant.
Fig. 6 is that sulphur and total iron mol ratio are 0.056 under different pH in test example 1 of the present invention：1, bentonite and total iron
Mass ratio is 1:The vulcanization nanometer zero-valent iron composite material of alta-mud load is to the removal effect comparison diagram of 4- nitrophenols when 1, its
Middle abscissa is that time (min) ordinate is C/C0Represent the concentration divided by its initial concentration of certain moment pollutant.
Embodiment
The embodiment of the present invention is described further with reference to case study on implementation, but application claims are protected
The scope of shield is not limited only to this.
Centrifuge used in embodiment is the low speed normal temperature desk centrifuge that Heng Nuo instrument companies produce, and ultrasound is shaken
It is the KQ-300B type ultrasonic washing instruments that Kunshan Ultrasonic Instruments Co., Ltd. produces to swing device.
The preparation of embodiment 1, the vulcanization nanometer zero-valent iron composite material of alta-mud load
By 80mL ethanol, 20mL water, 0.5g bentonites and 2.415g FeCl3·6H2O is added in four-neck flask,
300rpm, nitrogen flow rate weigh 1.0133g sodium borohydrides and 0.08g sodium hydroxides are molten to stir 30min under 500mL/min
In 40mL anaerobic deionized waters, it is added drop-wise to constant pressure funnel with 1-2 drops/sec in four-neck flask, while with 1-2 drops/sec of dropwise addition
0.5mL 1mol/L Na2S solution.React and centrifuged after 30min, and it is clear with anaerobic deionized water and ethanol solution difference
Wash, it is 0.056 to obtain sulphur iron mol ratio：The vulcanization nanometer zero-valent iron composite material of 1 alta-mud load.Composite is added
20g/L solution is made in 50mL anaerobics deionized water ultrasound 5min.
The x-ray photoelectron power spectrum of the vulcanization nanometer zero-valent iron composite material of gained alta-mud load in the present embodiment
(XPS) as shown in figure 1, its scanning electron microscope (SEM) photograph (SEM) as shown in Figure 2,3.Bentonitic ESEM (SEM) is as shown in Figure 4.
From Fig. 1, Fig. 2, Fig. 3, the Zero-valent Iron of the composite is coated with iron sulfide formation spheric granules, ball
Shape particle rearranges chain structure, and chain structure free accumulation is supported on bentonite surface.Spheric granules particle diameter is in 50-
150nm, and the material is evenly distributed without obvious agglomeration.The vulcanization nano zero valence iron of alta-mud load obtained by the present embodiment
The specific surface area of composite is 33.058m2The mass ratio of/g, bentonite and total iron content is 1:1, element sulphur in composite
Mol ratio with total iron content is 0.056：1.
Comparative example 1, without vulcanizing treatment
80mL ethanol, 20mL water, 0.5g bentonites and 2.415g FeCl are added in four-neck flask3·6H2O exists
Stirred under 300rpm and logical nitrogen 30min, weigh 1.0133g sodium borohydrides and 0.08g sodium hydroxides are dissolved in 40mL anaerobics
In deionized water, it is added drop-wise to constant pressure funnel with 1-2 drops/sec in four-neck flask, after reaction 30min, with centrifugation under 4500 turns
Machine centrifuges cleaning, is washed three times and is washed again with ethanol solution one time with the deionization of anaerobic, obtains the nanometer of alta-mud load
Zero-valent iron composite material.Composite addition 50mL anaerobics deionized water ultrasound 5min is prepared into finely dispersed 20g/L's
Composite solution.
It is total in bentonite and composite in the vulcanization nanometer zero-valent iron composite material of alta-mud load obtained by the present embodiment
The mass ratio of iron content is 1:1.
Comparative example 2, sulphur iron molar ratio are too low
By 80mL ethanol, 20mL water, 0.5g bentonites and 2.415g FeCl3·6H2O is added in four-neck flask,
300rpm, nitrogen flow rate weigh 1.0133g sodium borohydrides and 0.08g sodium hydroxides are molten to stir 30min under 500mL/min
In 40mL anaerobic deionized waters, it is added drop-wise to constant pressure funnel with 1-2 drops/sec in four-neck flask, while with 1-2 drops/sec of dropwise addition
0.36mL 1mol/L Na2S solution.React and centrifuged after 30min, and distinguished with anaerobic deionized water and ethanol solution
Cleaning, obtains the vulcanization nanometer zero-valent iron composite material for the alta-mud load that sulphur iron mol ratio is 0.056.Composite is added
20g/L solution is made in 50mL anaerobics deionized water ultrasound 5min.The vulcanization nano zero-valence of alta-mud load obtained by this comparative example
The bentonite of iron composite material and the mass ratio of total iron content are 1:1, the mol ratio of element sulphur and total iron content in composite
For 0.0404：1.
Comparative example 3, sulphur iron molar ratio are too high
By 80mL ethanol, 20mL water, 0.5g bentonites and 2.415g FeCl3·6H2O is added in four-neck flask,
300rpm, nitrogen flow rate weigh 1.0133g sodium borohydrides and 0.08g sodium hydroxides are molten to stir 30min under 500mL/min
In 40mL anaerobic deionized waters, it is added drop-wise to constant pressure funnel with 1-2 drops/sec in four-neck flask, while with 1-2 drops/sec of dropwise addition
0.7mL 1mol/L Na2S solution.React and centrifuged after 30min, and it is clear with anaerobic deionized water and ethanol solution difference
Wash, obtain the vulcanization nanometer zero-valent iron composite material for the alta-mud load that sulphur iron mol ratio is 0.056.Composite is added
20g/L solution is made in 50mL anaerobics deionized water ultrasound 5min.The vulcanization nano zero-valence of alta-mud load obtained by this comparative example
The bentonite of iron composite material and the mass ratio of total iron content are 1:1, the mol ratio of element sulphur and total iron content in composite
For 0.0784：1.
Embodiment 2, the application for removing 4- nitrophenols in waste water
The ultraviolet maximum absorption band of 4- nitrophenols is 317nm (under acid condition).
According to a series of 4- nitro phenol solutions of concentration knowns, corresponding ultraviolet absorptivity is measured, absorbance is obtained and dense
The standard curve of degree.
The 4- nitrophenols in agricultural chemicals waste water is removed using the composite prepared in embodiment 1 and its comparative example 1-3, it is described
The concentration of 4- nitrophenols is 1.5mmol/L in waste water, and step is as follows：
(1) agricultural chemicals waste waters of the 1L containing paranitrophenol is measured, in the reactor for being placed in opening, 0.1420g sodium sulphate is added (dense
Spend 1mM), adjust pH=6 with the NaOH solution and HCl solution of mass fraction 20%；
(2) obtained composite in embodiment 1 and its comparative example 1-3 respectively is added into solution, makes its concentration be
1.0g/L, 30min is reacted in 400rpm rotating speed lower open mouth；
(3) course of reaction described above is respectively in different point in time sampling, and sample point is 0,2,5,10,20 and 30min
Then the absorbance of 4- nitrophenols in solution is being determined under wavelength is 317nm with pH=2.9 5 times of acid dilution, and according to standard
Curve calculates corresponding concentration, and the concentration proportion curve for drawing 4- nitrophenols is as shown in Figure 5；
Embodiment 3, the application for removing orange I in waste water
Orange I ultraviolet maximum absorption band is 476nm.
According to a series of orange I solution of concentration knowns, corresponding ultraviolet absorptivity is measured, absorbance and concentration is obtained
Standard curve.
Removed using the composite prepared in embodiment 1 and comparative example 1 in the orange I in dyeing waste water, the waste water
Orange I concentration is 100mg/L, and step is as follows；
(1) orange I simulated wastewaters 1L is taken with open reactor, adding 0.1420g sodium sulphate (concentration 1mM), using matter
Measure the NaOH and HCl solution regulation pH=6.0 of fraction 20%；
(2) the vulcanization nanometer zero-valent iron composite material of alta-mud load made from embodiment 1 is added into reactor, makes it
Concentration is 1.0g/L, and rotating speed 400r/min, 25 DEG C of room temperature is sampled, and spend at 0,1,3,5,10,20 and 30min respectively
Ionized water dilutes 5 times and determines its absorbance using ultraviolet specrophotometer under 476nm wavelength afterwards, and is calculated according to standard curve
Go out corresponding concentration；The concentration proportion curve for drawing orange I is as shown in Figure 5.
As shown in Figure 5, the vulcanization nanometer zero-valent iron composite material of alta-mud load efficiently can quickly remove 4- nitrophenols
And orange I.
In simulation 4- nitrophenols concentration, concentration is respectively 15mmol/L, 100mg/L in orange I waste water, alta-mud load
The dosage for vulcanizing nanometer zero-valent iron composite material is 1g/L, and 2min 4- nitrophenols is reacted when sulphur-iron ratio mol ratio is 0.056
Clearance just reached 97.5%, orange I clearance is even more close to 100%.
Under identical circumstances, the composite in the case of sulphur iron mol ratio different in comparative example 2,3 removes 4- nitros
More than 15min is both needed to the time required to phenol, illustrates that the selection of sulphur iron mol ratio is most important for the process performance of composite,
Too high sulphur iron mol ratio or too low sulphur iron mol ratio are all unfavorable for improving the process performance of composite.
Simple alta-mud loaded nano Zero-valent Iron reaches the time difference needed for identical removal effect in comparative example 1
For：4- nitrophenols is 20min, and orange I is 10min.I.e.：The vulcanization nanometer zero-valent iron composite material of the alta-mud load of the present invention
Removal efficiency improves 10-15 times for simple alta-mud loaded nano Zero-valent Iron.
The influence of test example 1, pH value of waste water to pollutant removal
The initial of the simulated wastewater of the nitrophenols containing 4- is adjusted respectively with the NaOH solution and HCl solution of mass fraction 20%
PH=5.0,6.0,7.0, be in the vulcanization nanometer zero-valent iron composite material dosage of alta-mud load made from embodiment 1
According to the 4- nitros measured respectively under step same as Example 2 at 0,2,5,10,20 and 30min in the case of 0.5g/L
Phenol concentration.The mass ratio of bentonite and total iron content is 1 wherein in composite:1, sulphur iron mol ratio is 0.056：Isosorbide-5-Nitrae-nitro
Initial phenol concentration is 1.5mmol/L,；Curve is drawn, as shown in Figure 6.
It will be appreciated from fig. 6 that the vulcanization nanometer zero-valent iron composite material of alta-mud load is to 4- nitrophenols between pH=5-7
Removal reaches more than 95% in 2min and 15min respectively.Understand, it can quickly go decontamination in the wider scopes of pH
Contaminate thing.
Claims (10)
1. a kind of vulcanization nanometer zero-valent iron composite material of alta-mud load, the composite is by the nano zero-valence of sulfide modifier
Iron is loaded on bentonite, and described bentonite and the mass ratio of total iron content are 0.85-1.2：1, element sulphur and total iron content
Mol ratio be 0.05-0.065：1.
2. the vulcanization nanometer zero-valent iron composite material of alta-mud load according to claim 1, it is characterised in that described
The microscopic appearance of composite is：Zero-valent Iron is coated with iron sulfide formation spheric granules, and spheric granules rearranges chain
Shape structure, chain structure free accumulation is supported on bentonite surface and bentonite molecule interlayer.
3. the vulcanization nanometer zero-valent iron composite material of alta-mud load according to claim 2, it is characterised in that described
The particle diameter of spheric granules is 50-150nm, and the specific surface area of described composite is 30-35m2/g。
4. the preparation method of the vulcanization nanometer zero-valent iron composite material of the alta-mud load described in claim 1, including step is such as
Under：
In the mixed solution that bentonite and trivalent iron salt are added to second alcohol and water, dispersed with stirring is uniform under logical condition of nitrogen gas；
Then add sodium borohydride solution while be added dropwise sodium sulfide solution reacted, whole process lead to nitrogen in the case of carry out with
Ensure the anaerobic state of solution；Centrifuged after reaction completely, after solid cleaning, produce composite.
5. the preparation method of composite according to claim 4, it is characterised in that described trivalent iron salt is iron chloride
Or ferric sulfate.
6. the preparation method of composite according to claim 4, it is characterised in that ethanol and water in ethanol water
Volume ratio is (3-5)：1；
It is preferred that, the concentration of described sodium borohydride solution is 0.025-0.027g/mL；
It is preferred that, the volume ratio of ethanol water and sodium borohydride is 5：(1-3)；
It is preferred that, described bentonite：Molysite：Sodium borohydride：The mass ratio of vulcanized sodium is 1：4.83：2.0266：0.078；
It is preferred that, Na2The concentration of S solution is 1mol/L, and dropwise addition volume is 0.36-0.7mL, and more preferably 0.5mL makes sulphur total
Iron mol ratio is 0.056.
7. the preparation method of composite according to claim 4, it is characterised in that be 15- the time required to reaction completely
35min。
8. the preparation method of composite according to claim 4, it is characterised in that sodium borohydride solution and vulcanized sodium are molten
The drop rate of liquid is 1-2 drops/sec.
9. the alta-mud load described in claim 1 vulcanization nanometer zero-valent iron composite material processing nitrophenols containing 4- or/and
Application in the waste water of orange I pollutants.
10. application according to claim 9, it is characterised in that the pH value of regulation waste water is 5-7；
It is preferred that, the concentration of 4- nitrophenols is 1-2mmol/L in waste water, and orange I concentration is (80-120) mg/L；
It is preferred that, dosage of the composite in waste water is in 0.3g-1.0g/L.
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| CN112028131B (en) * | 2020-06-16 | 2024-03-12 | 暨南大学 | Vulcanized nano zero-valent iron and preparation method and application thereof |
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