CN110451597A - A kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes - Google Patents
A kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes Download PDFInfo
- Publication number
- CN110451597A CN110451597A CN201910701672.8A CN201910701672A CN110451597A CN 110451597 A CN110451597 A CN 110451597A CN 201910701672 A CN201910701672 A CN 201910701672A CN 110451597 A CN110451597 A CN 110451597A
- Authority
- CN
- China
- Prior art keywords
- iron
- nano zero
- zero valence
- molecular sieve
- compound material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes; the following steps are included: preparing iron salt solutions; add molecular sieve into iron salt solutions, mechanical stirring exchanges to iron ion in molecular sieve under nitrogen protection, obtains the mixed liquor A of molecular sieve and molysite；Mixed liquor A is separated by solid-liquid separation, the solid after separation is mixed to get in mixed reaction solution with water, under conditions of nitrogen protection and mechanical stirring, reducing agent solution is added into mixed reaction solution, continues to stir, obtains mixed liquid B；Mixed liquid B is separated by solid-liquid separation, washing is carried out to the solid after separation and drying process obtains nano zero valence iron@molecular sieves compound material.The nano zero valence iron@molecular sieves compound material synthesized according to the method for the present invention combines the cation exchange property of molecular sieve and absorption-reducing property of nano zero valence iron, to Pb2+、Cu2+The equal anion such as heavy metal cations and arsenous anion have preferable removal effect.
Description
Technical field
The invention belongs to technical field of composite preparation, and in particular to a kind of nano zero valence iron@molecular sieves compound material
And preparation method thereof and purposes.
Background technique
Heavy metal is environmental pollution most serious and endangers maximum a class of pollutant to the mankind.Mining, metal smelting
The industries such as refining and processing, plating, process hides, pesticide, papermaking, paint, printing and dyeing, nuclear technology and petrochemical industry, can all generate containing a huge sum of money
The waste water of category, some heavy metal wastewater therebies are also simultaneously containing a variety of heavy (class) metal ions such as lead, arsenic, zinc, copper, cadmium, nickel, mercury, weight
The characteristics of toxic big, difficulty of metal is biodegradable, easy biological accumulation, be discharged into after environment can only be transferred, dilute, accumulating or
Change form, and cannot be eliminated.Currently, both at home and abroad heavy metal wastewater thereby processing method mainly have chemical precipitation, redox,
Absorption, ion exchange, UF membrane and electrochemical process etc..
Absorption method is widely used in the processing of heavy metal wastewater thereby due to adapting to wide, easy to operate, adsorption technology
Key is adsorbent material, and seeking efficient, cheap heavy-metal adsorption material in recent years becomes one of research and development hot spot both at home and abroad,
Such as: preparing adsorbent using agricultural residue or trade waste modification, utilize the organic polymers such as chitosan or natural porous mine
Object zeolite etc. makees adsorbent.However, these materials are respectively present certain limitation, for example, modified with agriculture and industry waste
The adsorbent prepared afterwards is smaller to the removal ability of heavy metal, and high molecular material chitosan is only applicable to specified conditions or ion,
Natural porous mineral adsorption capacity is small.Therefore the novel adsorbent with good adsorption effect is developed for removing removing heavy metals
Ion and other pollutants are of great significance.
Summary of the invention
Present invention solves the technical problem that are as follows: a kind of nano zero valence iron@molecular sieves compound material and preparation method thereof is provided,
Using molecular sieve as carrier, Fe is allowed2+Or Fe3+With the Na in molecular sieve+Ion exchange is carried out to enter in the internal gutter of molecular sieve,
After being separated by solid-liquid separation, reducing agent is added, thus only to the Fe for being stored in molecular sieve internal gutter2+Or Fe3+It is restored simultaneously
Nano zero valence iron after reduction is stored in molecular sieve internal gutter.The duct microenvironment of molecular sieve can not only reduce nanometer
The reunion of Zero-valent Iron also largely avoids it and contacts with air, it is suppressed that the surface oxidation of nano zero valence iron.According to this
The nano zero valence iron@molecular sieves compound material of invention synthesis combines the cation exchange property and nano zero valence iron of molecular sieve
Absorption-reducing property, to Pb2+、Cu2+The equal anion such as heavy metal cations and arsenous anion, dichromate ion all have preferably
Removal effect.
The present invention provides a kind of nano zero valence iron@molecular sieves compound material preparation method, the following steps are included:
1) compound concentration is the iron salt solutions of 0.2~1mol/L, by iron and molecular sieve quality ratio 1:(0.2~15) Xiang Suoshu
Molecular sieve is added in iron salt solutions, 1~5h of stirring exchanges to iron ion in molecular sieve, obtains the mixed liquor of molecular sieve and molysite
A, any one or a few in NaX, NaA or NaY of the molecular sieve.
2) mixed liquor A is separated by solid-liquid separation, solid after separation is mixed to get with the water of 30~60mL and is mixed instead
Answer in liquid, under conditions of nitrogen protection and mechanical stirring, according to the mass ratio of the material 1:(2~3 of iron and reducing agent) Xiang Suoshu
The reducing agent solution of 0.4~2mol/L is added in mixed reaction solution, continues 20~40min of stirring, obtains mixed liquid B；
3) mixed liquid B is separated by solid-liquid separation, washing is carried out to the solid after separation and drying process obtains nanometer
Zero-valent Iron@molecular sieves compound material.
The utility model has the advantages that
(1) porous structure and cation exchange property of molecular sieve are utilized according to the method for the present invention, is with molecular sieve
Carrier, allows Fe2+Or Fe3+With the Na in molecular sieve+It carries out ion exchange to enter in the internal gutter of molecular sieve, carries out solid-liquid point
From rear, reducing agent is added, thus only to the Fe for being stored in molecular sieve internal gutter2+Or Fe3+It carries out reduction and will be obtained after reduction
To nano zero valence iron be stored in molecular sieve internal gutter, the duct microenvironment of molecular sieve can not only reduce nano zero valence iron
Reunion, also largely avoid it and contacted with air, it is suppressed that the surface oxidation of nano zero valence iron.
(2) artificial synthesized molecular sieve, such as NaX, NaA and NaY, because having a porous structure, and large specific surface area, sun from
Sub- switching performance is strong, has received widespread attention.But molecular sieve can only remove heavy metal cation, to anion almost without
Removal effect；Nanoscale Iron has many advantages, such as that small grain diameter, absorption and reproducibility are strong, equal to the heavy metal anions and canons in water
There is good removal capacity, but Nanoscale Iron leads to problems such as activity reduce there are easy to reunite, oxidation, this makes Nanoscale Iron technology
Application in heavy metal containing wastewater treatment and contaminated underground/surface water reparation receives certain restrictions.According to the method for the present invention
The nano zero valence iron@molecular sieves compound material of preparation is using molecular sieve NaX, NaA or NaY of low silica-alumina ratio as embedding carrier, carrier
In Na with higher+Ion concentration, under the experiment condition of this experiment, obtained nano zero valence iron@molecular sieves compound material
In, it both include certain proportion Na+(there is cation exchange property), and include that certain nano zero valence iron (has absorption-
Reducing property), the nano zero valence iron@molecular sieves compound material synthesized according to the present invention combines the cationic exchangeability of molecular sieve
Absorption-reducing property of energy and nano zero valence iron, to Pb2+、Cu2+Equal heavy metal cations and arsenous anion, dichromate ion etc. are negative
Ion has preferable removal effect, has widened the removal range of molecular sieve, has also been superimposed molecular sieve and Nanoscale Iron to heavy metal
Removal ability, synergistic can play the effect for removing removing heavy metals, a variety of heavy (standards) are golden suitable for nonferrous smelting waste water
Belong to the removal of pollutant and the reparation of underground pollution water body.
(3) nano zero valence iron@molecular sieves compound material of the present invention has large specific surface area, good dispersion, activity
The features such as site is more, biggish specific surface area and pore volume are conducive to pollutant in the absorption of surface point and in material internal
The diffusion in gap, therefore nano zero valence iron@molecular sieves compound material has the faster rate of adsorption and preferably removal to pollutant
Effect.
On the basis of above scheme, the present invention can also be improved as follows:
Further, after the solid after the separation being rinsed solid 2~4 times with deionized water in step 2) again with 30~
The water of 60mL is mixed to get in mixed reaction solution.
In molecular sieve and iron salt solutions ion exchange process, part Fe2+Or Fe3+Replace the part Na in molecular sieve+Into
Enter into the internal gutter of molecular sieve, by filtering out extra iron salt solutions and repeatedly being washed, boron hydrogen is then added dropwise again
Change sodium to be restored, it is ensured that nano zero valence iron has fully embedded into molecular sieve in finally obtained material, rather than Nanoscale Iron
With the mixture of molecular sieve, the duct microenvironment of molecular sieve can reduce the reunion of nano zero valence iron, preferably avoid iron and sky
Gas catalytic oxidation, to improve the performance for removing heavy metal in water removal of material.
Further, it is molten to be selected from ferric chloride solution, ferrum sulfuricum oxydatum solutum, solution of ferrous chloride, ferrous sulfate for the iron salt solutions
Any one in liquid.
Under an inert atmosphere, above-mentioned iron salt solutions can be employed as source of iron and Na+Swap and enter the inside of molecular sieve
In duct.
Further, the solution of ferrous chloride, ferrous sulfate solution pH value be 2.8~3.2.
Specifically, concentrated hydrochloric acid or the concentrated sulfuric acid are added when preparing above-mentioned ferrous salt solution, the pH of the ferrous salt solution is adjusted
Value is 2.8~3.2, to prevent ferrous salt from aoxidizing.
Specifically, the progress under nitrogen protection when the iron salt solutions of addition are ferrous iron solution, in step 1).As a result,
Ferrous salt and oxidation can preferably be prevented.
Further, molecular sieve described in step 1) is pretreated molecular sieve, the molecular sieve pretreatment condition are as follows: In
Dry 1~3h at a temperature of 90~110 DEG C.
Molecular sieve has certain water imbibition, and molecular sieve is dried 1~3h at a temperature of 90~110 DEG C, can sufficiently remove institute
Water suction point guarantees the accuracy of the molecular sieve addition quality when prepared by material.
Further, any one of the reducing agent in potassium borohydride or sodium borohydride in step 2).
Specifically, solution of potassium borohydride or sodium borohydride solution are matched by the potassium borohydride or sodium borohydride and deionized water
It is made.
Further, the drying process in step 3) is freeze-drying, is freeze-dried condition are as follows: temperature -30~-45 DEG C, very
20~45Pa of reciprocal of duty cycle.
Nano zero valence iron@molecular sieves compound material is dried under conditions of freezing and completely cutting off air, can prevent from doing
Nanoscale Iron aoxidizes when dry.
The present invention also provides a kind of nano zero valence iron@molecular sieves compound materials, are prepared by preparation method as described above
It obtains.
Further, material includes molecular sieve carrier and the nano zero-valence that is distributed in the molecular sieve carrier internal gutter
Iron, the molar ratio of nano zero valence iron and sodium ion is (1~1.13) in nano zero valence iron@molecular sieves compound material: (1~
1.89)。
Nano zero valence iron@molecular sieves compound material according to the present invention has large specific surface area, iron good dispersion, active sites
The features such as point is more, since biggish specific surface area and pore volume are conducive to pollutant in the absorption in adsorption site and in material
Expect the diffusion of internal voids, therefore nano zero valence iron@molecular sieves compound material has the faster rate of adsorption and more preferable to pollutant
Removal effect；With molecular sieve NaX, NaA or NaY of low silica-alumina ratio, nano zero valence iron and sodium ion molar ratio has been prepared
For (1~1.13): the nano zero valence iron@molecular sieves compound material of (1~1.89), the composite material combine the sun of molecular sieve from
Absorption-reducing property of sub- switching performance and nano zero valence iron synergistic can play the effect for removing removing heavy metals.
The present invention also provides a kind of nano zero valence iron@molecular sieves compound material preparation methods as described above to be prepared
Nano zero valence iron@molecular sieves compound material purposes, be used for heavy-metal ion removal.
Nano zero valence iron molecular sieves compound material goes the principle of the heavy metal cation in water removal and process as follows:
(1) nano zero valence iron can be by Pb2+、Cu2+Etc. the chemical property metal that does not have iron active be reduced into heavy metal simple substance,
And nano zero valence iron can generate the ferriferous oxide (FeOOH) of different shape and the coordination ion (Fe (OH) of iron during the reaction2+,
Fe(OH)2 +), FeOOH specific surface area is larger, has preferable absorption property, Fe (OH) to various heavy metal cations2+, Fe
(OH)2 +Also adsorbable Zn2+、Cd2+Etc. heavy metal ion formed floccule precipitating.
(2) molecular sieve has stronger cation exchange property, can remove heavy metal cation by ion exchange.
Nano zero valence iron molecular sieves compound material goes the principle and mistake of the anion such as arsenous anion and chromate in water removal
Journey is as follows:
(1) nano zero valence iron is oxidized (such as the O dissolved in water2) produce Fe2+/Fe3+, and then generate hydrogen in statu nascendi
Iron oxide (Fe (OH)3) and unformed ferriferous oxide (FeOOH), As (III) (such as HAsO2And H2AsO3 -) and As (V) (such as
H2AsO4 -And HAsO4 2-) and Fe (OH)3Complex compound is formed with FeOOH to remove；In aqueous solution, nano zero valence iron and O2Reaction, also
HO and Fe (IV) with strong oxidizing property are produced, highly toxic As (III) can be oxidized to As (V) by these intermediate products, so
Afterwards by iron rot product (such as Fe2O3,Fe3O4,Fe(OH)3) adsorb through co-precipitation removal.
(2) nano zero valence iron has very strong reproducibility, by Cr (VI) (such as Cr2O7 2-、CrO4 -) it is reduced into Cr3+While
Generate Fe3+, Cr3+And Fe3+Generate Cr (OH) respectively later3With Fe (OH)3Co-precipitation removal.
Nano zero valence iron@molecular sieves compound material according to the present invention is to Pb2+、Cu2+Equal heavy metal cations and arsenous
The anion such as acid group all have preferable removal effect, and various metals pollutant has huge application prospect in going water removal.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is the SEM figure that embodiment 1 prepares material N aY used in nano zero valence iron@molecular sieves compound material.
Fig. 2 is the SEM figure for the nano zero valence iron@molecular sieves compound material that embodiment 1 is prepared.
Fig. 3 is the nano zero valence iron@molecular sieves compound material that embodiment 1 is prepared and material N aY molecular sieve to Pb
(II) comparison diagram of adsorbance.
Fig. 4 is the EDS map that nano zero valence iron@molecular sieves compound material is prepared in embodiment 1.
Fig. 5 is that nano zero valence iron@molecular sieves compound material and material N aX molecular sieve is prepared to AS in embodiment 2
(III) comparison diagram of adsorbance.
Specific embodiment
For a better understanding of the present invention, the present invention is furture elucidated for 1-5 and specific embodiment with reference to the accompanying drawing
Content, but the contents of the present invention are not limited solely to the following examples.
Embodiment 1
The preparation method is as follows:
(1) ferrous sulfate solution that compound concentration is 1mol/L, pH value is 3.0, by iron and molecular sieve quality ratio 1:0.2 to
Pretreated molecular sieve NaY is added in the iron salt solutions, mechanical stirring 2h exchanges to iron ion point under nitrogen protection
In son sieve, the mixed liquor A of molysite and molecular sieve is obtained.
(2) mixed liquor A suction filtration is separated by solid-liquid separation, after being rinsed solid 2 times after separation with deionized water, will be consolidated
Body is transferred in three-necked flask, and the distilled water that 40mL is added into three-necked flask obtains mixed reaction solution, in nitrogen protection and
Under conditions of mechanical stirring, into three-necked flask the mass ratio of the material 1:2 of iron and reducing agent into the mixed reaction solution at the uniform velocity
The sodium borohydride solution of 1mol/L is instilled, and continued mechanical stirs 20min after dripping, and obtains mixed liquid B.
(3) mixed liquid B is filtered, after being rinsed solid 2 times after separation with deionized water, it is dry that solid is placed in freezing
In dry case, under -35 DEG C, vacuum degree 40Pa, it is freeze-dried 5h, obtains nano zero valence iron@molecular sieves compound material.
As depicted in figs. 1 and 2, respectively material N aY molecular sieve and nano zero valence iron@molecular sieve composite wood obtained
The SEM of material schemes, and as can be seen from Figure 1 NaY molecular sieve is in irregular octahedronlike, and molecular sieve surface is loose and has porous
Structure can provide sufficient embedding load site for nano zero valence iron particle；Fig. 2 is prepared by embodiment 1 nano zero valence iron@points
Son sieve composite material, as can be seen from the figure nano zero-valence iron particle is embedding carries and is preferably dispersed in inside the duct of molecular sieve
Or on outer surface, partial size 9-12nm, partial size is small and dispersed height.It is compound to nano zero valence iron@molecular sieve by EDS energy disperse spectroscopy
Material carry out elemental analysis, as a result as shown in Figure 4 and Table 1, in nano zero valence iron@molecular sieves compound material containing element O, Si,
The percentage composition of Al, Fe, Na, Fe element and Na element is respectively 19.43% and 7.05%.
Table 1
The nano zero valence iron@molecular sieves compound material made from the present embodiment 1 and material N aY molecular sieve are in nitrogen respectively
It is handling containing Pb (II) waste water for 600mg/L to concentration that atmosphere, which is enclosed lower, as a result as shown in figure 3, Fig. 3 is nano zero valence iron@
Molecular sieves compound material and NaY molecular sieve are to the comparison diagram of the adsorbance of Pb (II), in nano zero valence iron@molecular sieves compound material
It with raw material NaY molecular sieve dosage is 1g/L and under conditions of the reaction time is 1h, absorption of the composite material to Pb (II)
Amount is 528.8mg/g, and NaY is 289.8mg/g to the adsorbance of Pb (II), and nano zero valence iron@molecular sieves compound material is to Pb
(II) adsorbance is about 2 times of NaY.
Embodiment 2
(1) solution of ferrous chloride that compound concentration is 0.5mol/L, pH value is 3.1, by iron and molecular sieve quality ratio 1:1 to
Pretreated molecular sieve NaY is added in the iron salt solutions, mechanical stirring 3h exchanges to iron ion point under nitrogen protection
In son sieve, the mixed liquor A of molysite and molecular sieve is obtained.
(2) mixed liquor A suction filtration is separated by solid-liquid separation, after being rinsed solid 3 times after separation with deionized water, will be consolidated
Body is transferred in three-necked flask, and the distilled water that 30mL is added into three-necked flask obtains mixed reaction solution, in nitrogen protection and
Under conditions of mechanical stirring, into three-necked flask the mass ratio of the material 1:2 of iron and reducing agent into the mixed reaction solution at the uniform velocity
The sodium borohydride solution of 0.5mol/L is instilled, and continued mechanical stirs 30min after dripping, and obtains mixed liquid B.
(3) mixed liquid B is filtered, after being rinsed solid 3 times after separation with deionized water, it is dry that solid is placed in freezing
In dry case, under -40 DEG C, vacuum degree 30Pa, it is freeze-dried 6h, obtains nano zero valence iron@molecular sieves compound material.
The percentage of Fe element and Na element contains in the nano zero valence iron@molecular sieves compound material that the present embodiment 2 is prepared
Amount is respectively 10.80% and 7.42%, respectively nano zero valence iron@molecular sieves compound material and original made from the present embodiment 2
Material NaY molecular sieve is under nitrogen atmosphere handling containing As (III) waste water for 10mg/L to concentration, as a result as shown in figure 4,
Fig. 4 is the comparison diagram of nano zero valence iron@molecular sieves compound material and NaY molecular sieve to the adsorbance of As (III), in nano zero-valence
Under conditions of iron@molecular sieves compound material and raw material NaY molecular sieve dosage are 1g/L and the reaction time is 1h, the composite wood
Expect to be 11.2mg/g to the adsorbance of As (III), NaY is 0.467mg/g, nano zero valence iron@molecular sieve to the adsorbance of As (III)
Composite material is to 24 times that the adsorbance of As (III) is about NaY.
Embodiment 3
(1) compound concentration is 0.2mol/L ferrum sulfuricum oxydatum solutum, by iron and molecular sieve quality ratio 1:5 into the iron salt solutions
Pretreated molecular sieve NaA is added, mechanical stirring 4h exchanges to iron ion in molecular sieve, obtains the mixed of molysite and molecular sieve
Close liquid A.
(2) mixed liquor A suction filtration is separated by solid-liquid separation, after being rinsed solid 3 times after separation with deionized water, will be consolidated
Body is transferred in three-necked flask, and the distilled water that 50mL is added into three-necked flask obtains mixed reaction solution, in nitrogen protection and
Under conditions of mechanical stirring, into three-necked flask the mass ratio of the material 1:3 of iron and reducing agent into the mixed reaction solution at the uniform velocity
The sodium borohydride solution of 0.4mol/L is instilled, and continued mechanical stirs 35min after dripping, and obtains mixed liquid B.
(3) mixed liquid B is filtered, after being rinsed solid 3 times after separation with deionized water, it is dry that solid is placed in freezing
In dry case, under -30 DEG C, vacuum degree 45Pa, it is freeze-dried 7h, obtains nano zero valence iron@molecular sieves compound material.
The percentage of Fe element and Na element contains in the nano zero valence iron@molecular sieves compound material that the present embodiment 3 is prepared
Amount is respectively 6.87% and 4.05%, and the nano zero valence iron@molecular sieves compound material being prepared with embodiment 3 is to concentration
100mg/L's is handled containing Zn (II) waste water, is 1g/L and anti-in the nano zero valence iron@molecular sieves compound material dosage
For under conditions of 1h, the composite material is to the removal rate of Zn (II) 85.5% or more between seasonable.
Embodiment 4
(1) ferrous sulfate solution that compound concentration is 0.8mol/L, pH value is 3.2, by iron and molecular sieve quality ratio 1:15
Pretreated molecular sieve NaX is added into the iron salt solutions, mechanical stirring 2.5h exchanges iron ion under nitrogen protection
Into molecular sieve, the mixed liquor A of molysite and molecular sieve is obtained.
(2) mixed liquor A suction filtration is separated by solid-liquid separation, after being rinsed solid 2 times after separation with deionized water, will be consolidated
Body is transferred in three-necked flask, and the distilled water that 35mL is added into three-necked flask obtains mixed reaction solution, in nitrogen protection and
Under conditions of mechanical stirring, into three-necked flask, the mass ratio of the material 1:2.5 of iron and reducing agent is even into the mixed reaction solution
Speed instills the solution of potassium borohydride of 2mol/L, and continued mechanical stirs 30min after dripping, and obtains mixed liquid B.
(3) mixed liquid B is filtered, after being rinsed solid 4 times after separation with deionized water, it is dry that solid is placed in freezing
In dry case, under -35 DEG C, vacuum degree 40Pa, it is freeze-dried 4h, obtains nano zero valence iron@molecular sieves compound material.
The percentage of Fe element and Na element contains in the nano zero valence iron@molecular sieves compound material that the present embodiment 4 is prepared
Amount is respectively 12.87% and 9.99%, and the nano zero valence iron@molecular sieves compound material obtained by the present embodiment 6 is to concentration
(VI) containing Cr of 10mg/L is handled, when the nano zero valence iron@molecular sieves compound material dosage is 1g/L and reaction
Between under conditions of 1h, the composite material is to the removal rate of Cr (VI) 95.3% or more.
Embodiment 5
(1) compound concentration is the ferric chloride solution of 1mol/L, by iron and molecular sieve quality ratio 1:3 into the iron salt solutions
Pretreated molecular sieve NaY is added, mechanical stirring 5h exchanges to iron ion in molecular sieve, obtains the mixed of molysite and molecular sieve
Close liquid A.
(2) mixed liquor A suction filtration is separated by solid-liquid separation, after being rinsed solid 3 times after separation with deionized water, will be consolidated
Body is transferred in three-necked flask, and the distilled water that 60mL is added into three-necked flask obtains mixed reaction solution, in nitrogen protection and
Under conditions of mechanical stirring, into three-necked flask the mass ratio of the material 1:3 of iron and reducing agent into the mixed reaction solution at the uniform velocity
The solution of potassium borohydride of 0.4mol/L is instilled, and continued mechanical stirs 40min after dripping, and obtains mixed liquid B.
(4) mixed liquid B is filtered, after being rinsed solid 3 times after separation with deionized water, it is dry that solid is placed in freezing
In dry case, under -45 DEG C, vacuum degree 20Pa, it is freeze-dried 8h, obtains nano zero valence iron@molecular sieves compound material.
(II) containing Cd that the nano zero valence iron@molecular sieves compound material obtained by the present embodiment 5 is 120mg/L to concentration
Waste water is handled, in the condition that the nano zero valence iron@molecular sieves compound material dosage is 1g/L and the reaction time is 1h
Under, the composite material is to the removal rate of Cd (II) 84.2% or more.
Embodiment 6
(1) ferrous sulfate solution that compound concentration is 0.6mol/L, pH value is 2.8, by iron and molecular sieve quality ratio 3:1 to
Pretreated molecular sieve NaY is added in the iron salt solutions, mechanical stirring 1h exchanges to iron ion point under nitrogen protection
In son sieve, the mixed liquor A of molysite and molecular sieve is obtained.
(2) mixed liquor A suction filtration is separated by solid-liquid separation, after being rinsed solid 2 times after separation with deionized water, will be consolidated
Body is transferred in three-necked flask, and the distilled water that 35mL is added into three-necked flask obtains mixed reaction solution, in nitrogen protection and
Under conditions of mechanical stirring, into three-necked flask the mass ratio of the material 1:2 of iron and reducing agent into the mixed reaction solution at the uniform velocity
The solution of potassium borohydride of 1mol/L is instilled, and continued mechanical stirs 30min after dripping, and obtains mixed liquid B.
(4) mixed liquid B is filtered, after being rinsed solid 2 times after separation with deionized water, it is dry that solid is placed in freezing
In dry case, under -35 DEG C, vacuum degree 40Pa, it is freeze-dried 4h, obtains nano zero valence iron@molecular sieves compound material.
(II) containing Cu that the nano zero valence iron@molecular sieves compound material obtained by the present embodiment 6 is 100mg/L to concentration
It is handled, under conditions of the nano zero valence iron@molecular sieves compound material dosage is 1g/L and the reaction time is 1h, institute
Composite material is stated to the removal rate of Cu (II) 90.2% or more.
Although the embodiment of the present invention is described in detail above, it will be understood by those skilled in the art that: In
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where not departing from the principle of the present invention and objective,
The scope of the present invention is defined by the claims and their equivalents.
Claims (10)
1. a kind of nano zero valence iron@molecular sieves compound material preparation method, which comprises the following steps:
1) compound concentration is the iron salt solutions of 0.2~1mol/L, by iron and molecular sieve quality ratio 1:(0.2~15) Xiang Suoshu molysite
Molecular sieve is added in solution, 1~5h of stirring exchanges to iron ion in molecular sieve, obtains the mixed liquor A of molecular sieve and molysite, institute
State any one or a few in NaX, NaA or NaY of molecular sieve；
2) mixed liquor A is separated by solid-liquid separation, the water of solid after separation and 30~60mL is mixed to get mixed reaction solution
In, under conditions of nitrogen protection and mechanical stirring, according to the mass ratio of the material 1:(2~3 of iron and reducing agent) it is mixed to described
The reducing agent solution of 0.4~2mol/L is added in reaction solution, continues 20~40min of stirring, obtains mixed liquid B；
3) mixed liquid B is separated by solid-liquid separation, washing is carried out to the solid after separation and drying process obtains nano zero-valence
Iron@molecular sieves compound material.
2. according to nano zero valence iron@molecular sieves compound material preparation method described in material 1, which is characterized in that will be in step 2)
Hybrid reaction is mixed to get with the water of 30~60mL again after solid after the separation is rinsed solid 2~4 times with deionized water
In liquid.
3. according to nano zero valence iron@molecular sieves compound material preparation method described in material 1, which is characterized in that the molysite is molten
Any one of liquid in ferric chloride solution, ferrum sulfuricum oxydatum solutum, solution of ferrous chloride, ferrous sulfate solution.
4. according to nano zero valence iron@molecular sieves compound material preparation method described in material 3, which is characterized in that the protochloride
Ferrous solution, ferrous sulfate solution pH value be 2.8~3.2.
5. according to nano zero valence iron@molecular sieves compound material preparation method described in material 1, which is characterized in that institute in step 1)
Stating molecular sieve is pretreated molecular sieve, the pretreatment condition of the molecular sieve are as follows: dry 1 at a temperature of 90~110 DEG C~
3h。
6. according to nano zero valence iron@molecular sieves compound material preparation method described in material 1, which is characterized in that in step 2)
Any one of the reducing agent in potassium borohydride or sodium borohydride.
7. according to nano zero valence iron@molecular sieves compound material preparation method described in material 1, which is characterized in that in step 3)
It is dried as freeze-drying, freeze-drying condition are as follows: temperature -30~-45 DEG C, 20~45Pa of vacuum degree.
8. a kind of nano zero valence iron@molecular sieves compound material, which is characterized in that by nanometer zero as claimed in claim 1 to 7
Valence iron@molecular sieves compound material preparation method is prepared.
9. nano zero valence iron@molecular sieves compound material according to claim 8, which is characterized in that including molecular sieve carrier
And it is distributed in the nano zero valence iron in the molecular sieve carrier internal gutter, it is received in nano zero valence iron@molecular sieves compound material
Rice Zero-valent Iron and the molar ratio of sodium ion are (1~1.13): (1~1.89).
10. the nanometer that nano zero valence iron@molecular sieves compound material preparation method as claimed in claim 1 is prepared
The purposes of Zero-valent Iron@molecular sieves compound material, which is characterized in that be used for heavy-metal ion removal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910701672.8A CN110451597A (en) | 2019-07-31 | 2019-07-31 | A kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910701672.8A CN110451597A (en) | 2019-07-31 | 2019-07-31 | A kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110451597A true CN110451597A (en) | 2019-11-15 |
Family
ID=68484287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910701672.8A Pending CN110451597A (en) | 2019-07-31 | 2019-07-31 | A kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110451597A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252879A (en) * | 2020-03-03 | 2020-06-09 | 天津师范大学 | Modified nano-iron and preparation method and application thereof |
| CN111559748A (en) * | 2020-04-02 | 2020-08-21 | 广东轻工职业技术学院 | Preparation method of silicon-aluminum molecular sieve |
| CN111633021A (en) * | 2020-06-08 | 2020-09-08 | 上海大学 | Nano zero-valent iron modified composite mesoporous material and preparation method and application thereof |
| CN112316896A (en) * | 2020-10-12 | 2021-02-05 | 昆明理工大学 | Resource utilization method of waste copper adsorbent |
| CN112755963A (en) * | 2020-12-15 | 2021-05-07 | 生态环境部华南环境科学研究所 | Green synthetic magnetic composite nano material, preparation method and application thereof |
| CN115106519A (en) * | 2022-06-09 | 2022-09-27 | 南开大学 | Superparamagnetic nano-iron material, composite material thereof, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941068A (en) * | 2009-07-10 | 2011-01-12 | 南开大学 | Silica micropowder loaded type nano zerovalent iron particle and preparation method thereof |
| CN102205419A (en) * | 2011-03-28 | 2011-10-05 | 北京师范大学 | Novel method for preparing load nano zero valent iron |
| CN102755883A (en) * | 2012-06-26 | 2012-10-31 | 南京大学 | Preparation method of attapulgite-loaded nanometre iron material |
| CN102923835A (en) * | 2012-11-09 | 2013-02-13 | 中国科学技术大学 | Nano zero-valent iron with montmorillonite serving as carrier, and preparation method and application thereof |
| US20160031766A1 (en) * | 2013-03-15 | 2016-02-04 | Ndsu Research Foundation | Calcium-alginate entrapped nanoscale zero-valent iron (nzvi) |
| CN108722344A (en) * | 2018-04-13 | 2018-11-02 | 安徽工程大学 | It is a kind of to load nano zero-valence iron-copper bi-metal molecular sieve, preparation method and its application of dephosphorization |
-
2019
- 2019-07-31 CN CN201910701672.8A patent/CN110451597A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941068A (en) * | 2009-07-10 | 2011-01-12 | 南开大学 | Silica micropowder loaded type nano zerovalent iron particle and preparation method thereof |
| CN102205419A (en) * | 2011-03-28 | 2011-10-05 | 北京师范大学 | Novel method for preparing load nano zero valent iron |
| CN102755883A (en) * | 2012-06-26 | 2012-10-31 | 南京大学 | Preparation method of attapulgite-loaded nanometre iron material |
| CN102923835A (en) * | 2012-11-09 | 2013-02-13 | 中国科学技术大学 | Nano zero-valent iron with montmorillonite serving as carrier, and preparation method and application thereof |
| US20160031766A1 (en) * | 2013-03-15 | 2016-02-04 | Ndsu Research Foundation | Calcium-alginate entrapped nanoscale zero-valent iron (nzvi) |
| CN108722344A (en) * | 2018-04-13 | 2018-11-02 | 安徽工程大学 | It is a kind of to load nano zero-valence iron-copper bi-metal molecular sieve, preparation method and its application of dephosphorization |
Non-Patent Citations (3)
| Title |
|---|
| WEI WANG: "Novel NaY zeolite-supported nanoscale zero-valent iron as an efficient", 《CATALYSIS COMMUNICATIONS》 * |
| 焦桓: "《无机材料化学实验》", 31 January 2014 * |
| 王世林: "多孔材料负载型纳米零价铁的制备及其在环境中的应用进展", 《山东化工》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252879A (en) * | 2020-03-03 | 2020-06-09 | 天津师范大学 | Modified nano-iron and preparation method and application thereof |
| CN111559748A (en) * | 2020-04-02 | 2020-08-21 | 广东轻工职业技术学院 | Preparation method of silicon-aluminum molecular sieve |
| CN111633021A (en) * | 2020-06-08 | 2020-09-08 | 上海大学 | Nano zero-valent iron modified composite mesoporous material and preparation method and application thereof |
| CN111633021B (en) * | 2020-06-08 | 2021-12-28 | 上海大学 | Nano zero-valent iron modified composite mesoporous material and preparation method and application thereof |
| CN112316896A (en) * | 2020-10-12 | 2021-02-05 | 昆明理工大学 | Resource utilization method of waste copper adsorbent |
| CN112316896B (en) * | 2020-10-12 | 2022-10-14 | 昆明理工大学 | Resource utilization method of waste copper adsorbent |
| CN112755963A (en) * | 2020-12-15 | 2021-05-07 | 生态环境部华南环境科学研究所 | Green synthetic magnetic composite nano material, preparation method and application thereof |
| CN115106519A (en) * | 2022-06-09 | 2022-09-27 | 南开大学 | Superparamagnetic nano-iron material, composite material thereof, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110451597A (en) | A kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes | |
| Liu et al. | Zeolitic imidazolate framework-based nanomaterials for the capture of heavy metal ions and radionuclides: A review | |
| Feng et al. | A review on heavy metal ions adsorption from water by layered double hydroxide and its composites | |
| Li et al. | Fabrication strategies and Cr (VI) elimination activities of the MOF-derivatives and their composites | |
| Lin et al. | A systematic review of metal organic frameworks materials for heavy metal removal: Synthesis, applications and mechanism | |
| Zhang et al. | Fabrication of L-cysteine stabilized α-FeOOH nanocomposite on porous hydrophilic biochar as an effective adsorbent for Pb2+ removal | |
| US10822259B2 (en) | Method for removing hexavalent chromium from water bodies by sodium oxalate-modified zero-valent iron | |
| Jiang et al. | Versatile core/shell-like alginate@ polyethylenimine composites for efficient removal of multiple heavy metal ions (Pb2+, Cu2+, CrO42-): Batch and fixed-bed studies | |
| CN109317091B (en) | Modified sepiolite heavy metal adsorption material and preparation method thereof | |
| CN103464091A (en) | Modified bentonite load nanometer iron material and preparation method thereof | |
| CN103769058B (en) | The preparation method of carbonization chitosan absorbent, product and application process | |
| Du et al. | La-doped activated carbon as high-efficiency phosphorus adsorbent: DFT exploration of the adsorption mechanism | |
| CN111718719B (en) | Vulcanized nano zero-valent iron-acid activated montmorillonite composite material and preparation method and application thereof | |
| CN101507915A (en) | Preparation method of alga biology absorbent | |
| Zheng et al. | Synergistic effect and mechanism of Cd (II) and As (III) adsorption by biochar supported sulfide nanoscale zero-valent iron | |
| CN105833831A (en) | A preparing method of an efficient hexavalent chromium adsorbent and applications of the adsorbent | |
| CN105148835B (en) | Granular pattern 13X molecular sieves/attapulgite loaded Nanoscale Iron nickel material and preparation method thereof | |
| CN112742340A (en) | S-ZVI magnetic environment restoration material and preparation method and application thereof | |
| Gao et al. | Graphene-based aerogels in water and air treatment: a review | |
| CN107790099B (en) | Adsorbing material for phosphorus and heavy metal polluted water and preparation method thereof | |
| CN114774130A (en) | Modified clay mineral for repairing arsenic-lead-antimony composite contaminated soil and preparation method and application thereof | |
| Wei et al. | Electrolytic manganese residue-biochar composite for simultaneous removal of antimony and arsenic from water: Adsorption performance and mechanisms | |
| CN111905702A (en) | Preparation method of porous particle filter material loaded with nano zero-valent iron for adsorbing and removing heavy metals in water | |
| CN113996315A (en) | Calcium polysulfide sulfide zero-valent iron nanocomposite and preparation method and application thereof | |
| Krstić | Some effective methods for treatment of wastewater from Cu production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191115 |