CN108862537A - Hydroxy functionalized Modified lift Fe0/Fe3O4Method of the composite material to Cr in waste water (VI) removal capacity - Google Patents
Hydroxy functionalized Modified lift Fe0/Fe3O4Method of the composite material to Cr in waste water (VI) removal capacity Download PDFInfo
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- CN108862537A CN108862537A CN201810663656.XA CN201810663656A CN108862537A CN 108862537 A CN108862537 A CN 108862537A CN 201810663656 A CN201810663656 A CN 201810663656A CN 108862537 A CN108862537 A CN 108862537A
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- composite material
- hydroxy functionalized
- zirconium oxide
- diameter
- waste water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of hydroxy functionalized Modified lift Fe0/Fe3O4Composite material is to the method for Cr in waste water (VI) removal capacity, the detailed process of hydroxy functionalized modification：By micron order Zero-valent Iron and micron order ferroso-ferric oxide according to mass ratio 1:0.05 ratio is uniformly mixed, and is added zirconium oxide balls by frequency conversion micro computer planetary ball mill progress mechanical ball mill and is obtained Fe0/Fe3O4Composite material, by Fe0/Fe3O4Composite material passes through mechanical stirring with dehydrated alcohol at room temperature and is reacted, with being dried with nitrogen to obtain hydroxy functionalized MODIFIED Fe after fully reacting0/Fe3O4Composite material, and saved under nitrogen atmosphere.By hydroxy functionalized modified Fe obtained in the present invention0/Fe3O4Composite material has significant effect to the removal of Cr in water (VI), and removal rate is significantly improved, and the modified solubility for increasing it in water reduces the hydrophobicity of milling material, it is made preferably to play its oxidation-reduction quality in the reaction.
Description
Technical field
The invention belongs to the hydroxylating technical field of modification of composite functional material, and in particular to a kind of hydroxy functionalized modification
Promote Fe0/Fe3O4Method of the composite material to Cr in waste water (VI) removal capacity.
Background technique
In recent years, with the continuous development of the modernization of industry, the industries process such as fuel, plating, mining, smelting further adds
Fastly.Waste water largely containing heavy metal can be discharged during these industry developments, serious pollution is caused to environment.Wherein
Pollution of chromium（Predominantly Cr VI）It is the most prominent.Due to the unreasonable discharge of Cr (VI) waste water, the serious of surface water environment is caused
Pollution, or even can also further endanger the health of animal, plant and the mankind.The processing technique of common Cr (VI) waste water has very much
Kind, including coagulant sedimentation, oxidation-reduction method, ion-exchange and membrane separation technique etc..In recent years, lot of domestic and foreign scholar couple
Fe0Reduction harmful heavy metal has carried out large-scale experiment and has probed into, and finds Fe0Chemical property is active, and reducing power is extremely strong, can incite somebody to action
Various metals cement out, and the oxidation-reduction potential of Cr (VI) is higher than Fe0, redox reaction can occur for the two.
Now, have and largely use Fe0The report of heavy metal in waste water is removed, but few scholars are by Fe0And Fe3O4In conjunction with
To handle Cr in waste water (VI).Using frequency conversion micro computer planetary ball mill by micron Fe0And Fe3O4It is fully ground, utilizes oxidation
Frictional force and shear stress are generated between zirconium sphere reinforcing material, both make to become that partial size is smaller, specific surface area is bigger is compound
Material.But it was found that although this composite material has Cr (VI) ability in stronger removal waste water, but due to its hydrophobicity, make its work
Property is by larger limitation.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of hydroxy functionalized Modified lift Fe0/Fe3O4Composite material pair
The method of Cr (VI) removal capacity in waste water, this method has the characteristics that economical and efficient and convenient for recycling heavy metal, in removal weight
New pollutant is not introduced while metal, and then avoids causing secondary pollution to environment.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, hydroxy functionalized Modified lift Fe0/Fe3O4It is multiple
Method of the condensation material to Cr in waste water (VI) removal capacity, it is characterised in that：Under the same conditions, hydroxy functionalized modified
Fe0/Fe3O4Composite material is superior to Fe before modified to Cr in waste water (VI) removal capacity0/Fe3O4Composite material, hydroxyl functional
Changing modified detailed process is：By micron order Zero-valent Iron and micron order ferroso-ferric oxide according to mass ratio 1:0.05 ratio mixing
Uniformly, zirconium oxide balls are added, Fe is obtained by frequency conversion micro computer planetary ball mill progress mechanical ball mill0/Fe3O4Composite wood
Material, by Fe0/Fe3O4Composite material passes through mechanical stirring with dehydrated alcohol at room temperature and is reacted, wherein Fe0/Fe3O4It is compound
The charge ratio of material and dehydrated alcohol is 1g:20mL, with being dried with nitrogen to obtain hydroxy functionalized MODIFIED Fe after fully reacting0/
Fe3O4Composite material, and saved under nitrogen atmosphere.
Preferably, the mechanical ball mill is interval alternately positive and negative rotation ball milling, i.e. ball milling 10min interval is further continued for after stopping 5s
Ball milling, repeatedly until ball milling accumulated time is equal to setting Ball-milling Time.
Preferably, the zirconium oxide balls include diameter is 1mm zirconium oxide balls, diameter is 2mm zirconium oxide balls, it is straight
The zirconium oxide balls that the zirconium oxide balls and diameter that diameter is 4mm are 8mm, wherein diameter is 1mm zirconium oxide balls, diameter 2mm
Zirconium oxide balls, diameter be 4mm zirconium oxide balls and diameter be 8mm the mass ratioes of zirconium oxide balls be 3:8:20:8.
Preferably, the churned mechanically revolving speed is 280rad/min, and the churned mechanically reaction time is for 24 hours.
Compared with the prior art, the present invention has the following advantages：
1, tradition Fe0/Fe3O4Composite material can not be produced in enormous quantities, and can not be generated according to the ratio of determination, and ball-milling method can
In high volume to synthesize, and can be synthesized according to a certain percentage；
2、Fe0/Fe3O4Composite material has magnetic properties, is easily recycled, while also reducing the pollution to environment, is
Environmentally friendly material；
3, by hydroxy functionalized modification, its surface is made to change, weakens its hydrophobicity, greatly strengthen its in water anti-
Answer activity.
Detailed description of the invention
Fig. 1 is that Fe is made in the embodiment of the present invention 10/Fe3O4The XRD spectrum of composite material；
Fig. 2 is that Fe is made in the embodiment of the present invention 10/Fe3O4Composite material hydrophilic and hydrophobic test result figure；
Fig. 3 is hydroxy functionalized modified obtained Fe in the embodiment of the present invention 20/Fe3O4The FT-IR map of composite material；
Fig. 4 is not hydroxy functionalized and hydroxy functionalized Fe in the embodiment of the present invention 30/Fe3O4Composite material removes Cr (VI)
The line chart of effect.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
It in this example, is in mass ratio 1 by micron order Zero-valent Iron and micron order ferroso-ferric oxide:0.05 ratio is sufficiently mixed
Raw mixture is obtained, abrading-ball includes tetra- kinds of Φ 1mm, Φ 2mm, Φ 4mm and Φ 8mm zirconium oxide balls, four kinds of zirconium oxide balls
Corresponding mass ratio is 3:8:20:8；Start mechanical ball mill positive and negative rotation alternating ball milling 8h and obtain ball milling product, wherein mechanical ball
The revolving speed of grinding machine is 375r/min；It grinds ball milling product to obtain Fe0/Fe3O4Composite material.
From XRD diagram（Fig. 1）It can be seen that Fe obtained0/Fe3O4Composite material maintains the main feature diffraction of Zero-valent Iron
Peak, and there is the diffraction maximum of fe at 2 θ=44.8 °, 65.2 °, there is not the diffraction maximum of the oxide of iron.
Embodiment 2
Weigh Fe obtained in a certain amount of example 10/Fe3O4Composite material is added in dehydrated alcohol, wherein 1g Fe0/Fe3O4It is multiple
The volume that condensation material corresponds to dehydrated alcohol is 20mL, is put into thermostat water bath（Temperature is 25 DEG C）In, mechanic whirl-nett reaction for 24 hours,
Mechanical stirring revolving speed is 280r/min.
From hydrophilic and hydrophobic test chart（Fig. 2）It can be seen that hydroxy functionalized Fe rear before modified0/Fe3O4Composite material surface
A series of variation has occurred, and makes it solubility greatly enhances in water.Material surface functional group is made in this variation
Further research is schemed from FT-IR（Fig. 3）Analysis is it is found that hydroxylating MODIFIED Fe0/Fe3O4Composite material is respectively in 631cm-1,
499cm-1：Fe-O, 1152cm-1、1020cm-1：Fe-O-H, 1390cm-1：FeOOH, 1630cm-1：Hydroxyl group.
Embodiment 3
Weigh a certain amount of not hydroxy functionalized and hydroxy functionalized Fe0/Fe3O4Composite material is respectively at 125mL polytetrafluoroethylene (PTFE) bottle
In, addition 100mL mass concentration is 50mg/L Cr (VI) solution, adjusts pH value of solution to 3, in constant temperature oscillation case instead with HCl
Answer, temperature be 25 DEG C, revolving speed 180r/min, respectively with 2min, 5min, 10min, 15min, 30min, 60min, 90min,
120min, 180min, 240min, 300min, 360min, 420min, 480min sampling, use diphenylcarbazide spectrophotometric
Method measures Cr (VI) content in solution.Figure 4, it is seen that through hydroxy functionalized modified, Fe0/Fe3O4Composite material pair
The removal ability of Cr (VI) is far longer than before modified.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (4)
1. hydroxy functionalized Modified lift Fe0/Fe3O4Composite material exists to the method for Cr in waste water (VI) removal capacity, feature
In：Under the same conditions, hydroxy functionalized modified Fe0/Fe3O4Composite material is excellent to Cr in waste water (VI) removal capacity
In Fe before modified0/Fe3O4The detailed process of composite material, hydroxy functionalized modification is：By micron order Zero-valent Iron and micron order
Ferroso-ferric oxide is according to mass ratio 1:0.05 ratio is uniformly mixed, and it is planetary by frequency conversion micro computer to add zirconium oxide balls
Ball mill carries out mechanical ball mill and obtains Fe0/Fe3O4Composite material, by Fe0/Fe3O4Composite material leads at room temperature with dehydrated alcohol
It crosses mechanical stirring to be reacted, wherein Fe0/Fe3O4The charge ratio of composite material and dehydrated alcohol is 1g:20mL, fully reacting
Afterwards with being dried with nitrogen to obtain hydroxy functionalized MODIFIED Fe0/Fe3O4Composite material, and saved under nitrogen atmosphere.
2. hydroxy functionalized Modified lift Fe according to claim 10/Fe3O4Composite material removes Cr in waste water (VI)
The method of performance, it is characterised in that：The mechanical ball mill is interval alternately positive and negative rotation ball milling, i.e. ball milling 10min interval stops 5s
After be further continued for ball milling, repeatedly until ball milling accumulated time be equal to setting Ball-milling Time.
3. hydroxy functionalized Modified lift Fe according to claim 10/Fe3O4Composite material removes Cr in waste water (VI)
The method of performance, it is characterised in that：The zirconium oxide balls include the zirconium oxide that diameter is 1mm zirconium oxide balls, diameter is 2mm
The zirconium oxide balls that the zirconium oxide balls and diameter that abrading-ball, diameter are 4mm are 8mm, wherein diameter is 1mm zirconium oxide balls, directly
The mass ratio for the zirconium oxide balls that the zirconium oxide balls and diameter that zirconium oxide balls that diameter is 2mm, diameter are 4mm are 8mm is 3:
8:20:8。
4. hydroxy functionalized Modified lift Fe according to claim 10/Fe3O4Composite material removes Cr in waste water (VI)
The method of performance, it is characterised in that：The churned mechanically revolving speed is 280rad/min, and the churned mechanically reaction time is for 24 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110282717A (en) * | 2019-07-03 | 2019-09-27 | 中国海洋大学 | A kind of method of mechanical ball mill activation zeroth order aluminium removal water pollutant |
| CN113264575A (en) * | 2021-05-07 | 2021-08-17 | 河南师范大学 | Electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in underground water by using AC material |
| CN114436389A (en) * | 2022-02-11 | 2022-05-06 | 盐城工学院 | Preparation method and application of magnetically separable zero-valent aluminum-ferroferric oxide compound |
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| CN107010638A (en) * | 2017-03-22 | 2017-08-04 | 河南师范大学 | A kind of mechanical attrition method prepares Fe0The method of the composites of/ZSM 5 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107010638A (en) * | 2017-03-22 | 2017-08-04 | 河南师范大学 | A kind of mechanical attrition method prepares Fe0The method of the composites of/ZSM 5 |
Non-Patent Citations (2)
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|---|
| ALMASRI D A , RHADFI T , ATIEH M A , ET AL: "High performance hydroxyiron modified montmorillonite nanoclay adsorbent for arsenite removal", 《CHEMICAL ENGINEERING JOURNAL》 * |
| COELHO F D S , ARDISSON J D , MOURA F C C , ET AL: "Potential application of highly reactive Fe0/Fe3O4 composites for the reduction of Cr(VI) environmental contaminants", 《CHEMOSPHERE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110282717A (en) * | 2019-07-03 | 2019-09-27 | 中国海洋大学 | A kind of method of mechanical ball mill activation zeroth order aluminium removal water pollutant |
| CN113264575A (en) * | 2021-05-07 | 2021-08-17 | 河南师范大学 | Electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in underground water by using AC material |
| CN114436389A (en) * | 2022-02-11 | 2022-05-06 | 盐城工学院 | Preparation method and application of magnetically separable zero-valent aluminum-ferroferric oxide compound |
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Application publication date: 20181123 |