CN102188949B - Method for removing arsenic (III) in water by utilizing composite MnO2/Fe3O4 adsorbent - Google Patents
Method for removing arsenic (III) in water by utilizing composite MnO2/Fe3O4 adsorbent Download PDFInfo
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- CN102188949B CN102188949B CN 201110091212 CN201110091212A CN102188949B CN 102188949 B CN102188949 B CN 102188949B CN 201110091212 CN201110091212 CN 201110091212 CN 201110091212 A CN201110091212 A CN 201110091212A CN 102188949 B CN102188949 B CN 102188949B
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Abstract
The invention relates to a method for removing arsenic (III) in water by utilizing the MnO2/Fe3O4 composite adsorbent. The invention mainly solves the technical problems that MnO2 is difficult to separate and an application of MnO2 on water treatment is limited. The composite adsorbent is prepared by the following steps of: dissolving FeSO4. 7H2O in deionized water at room temperature, placing the solution in an anaerobic operating platform, adding NaOH, rapidly stirring to be uniform by virtue of a glass rod after blue-green flocculation is produced, pouring the solution into a breaker filled with KMnO4, stirring, standing and sinking, removing a supernate by filtering, flushing repeatedly, then drying, and grinding to obtain the MnO2/Fe3O4 composite adsorbent. The method for removing arsenic (III) comprises the following steps of: controlling the pH value of arsenic (III) containing sewage to be more than 5, and adding the composite adsorbent to carry out turbulent flow contact adsorption. The composite adsorbent adsorbed with heavy metals can be separated from water by adopting a magnet, the separation method is simple, and the operation is easy.
Description
Technical field
The present invention relates to a kind of compound adsorbent and remove the method for arsenic (III) in the water.
Background technology
MnO
2Suction-operated is owing to its efficient adsorption to low-concentration heavy metal, and high economic benefit and strong operability receive much concern always.Compare MnO with metal oxides such as Fe, Al, Mn, Zn
2The strongest with heavy metal ion affinity.But MnO
2Apparent density lower, in water, form easily the shortcoming such as ultra-fine grain, not easily separated, limited the application in water treatment.
Summary of the invention
The present invention will solve MnO
2Not easily separated, limit the technical problem that it is used in water treatment; And provide MnO
2/ Fe
3O
4Compound adsorbent is removed the method for arsenic (III) in the water.
MnO
2/ Fe
3O
4The preparation method of compound adsorbent carries out in the steps below: at room temperature with 0.45molFeSO
47H
2O is dissolved in the 200mL ionized water, with being placed in the anaerobic operation platform, then adds 1.2molNaOH, occurs stirring and evenly mixing rapidly with glass bar after the blue-green flocculation, then pours into 0.1molKMnO is housed
4In the beaker, be stirred to KMnO
4Till dissolving fully, quiet heavy 1～2h, the filtering supernatant washes sediment until washing lotion becomes neutrality repeatedly with deionized water, then sediment is put in the vacuum drying chamber and dries 5～7h under 40～60 ℃ of conditions, is ground into powder, and obtains MnO
2/ Fe
3O
4Compound adsorbent.
MnO
2/ Fe
3O
4Compound adsorbent is removed the method for arsenic (III) in the water and is finished in the steps below: will contain the wastewater pH control of arsenic (III) more than 5, and then add the MnO of said method preparation
2/ Fe
3O
4Compound adsorbent carried out turbulent Contact-sorption more than 12 hours; Namely finished the removal of arsenic (III).
The present invention by coprecipitation with MnO
2Load to and obtain MnO on the tri-iron tetroxide
2/ Fe
3O
4Compound adsorbent, MnO in the compound adsorbent of the present invention's preparation
2It is comparatively even to distribute, and particle diameter is distributed in 1～100 μ m and does not wait, and manganese dioxide is with amorphous MnO
2Form exists.Adopt magnet just the compound adsorbent of Adsorption of Heavy Metals can be separated to come from water, simple, the easily operation of separation method.Arsenic in the water (III) initial concentration is 50mg/L, adds present embodiment MnO
2/ Fe
3O
4Compound adsorbent, described compound adsorbent consumption is 200mg/L, the maximal absorptive capacity of described adsorbent is about 72.83mg/g.
Description of drawings
Fig. 1 is MnO
2/ Fe
3O
4Compound adsorbent is mixed in the design sketch of water; Fig. 2 is the design sketch with quiet heavy 2min behind the magnet adsorption; Fig. 3 is the MnO of the specific embodiment five preparations
2/ Fe
3O
4The electron-microscope scanning figure of compound adsorbent, Fig. 4 are the MnO of the specific embodiment five preparations
2/ Fe
3O
4The XRD diffraction spectrogram of compound adsorbent, Fig. 5 are the MnO of the specific embodiment five preparations
2/ Fe
3O
4The X-ray diffraction spectrogram of compound adsorbent; Fig. 6 is the specific embodiment six MnO
2/ Fe
3O
425 ° of adsorption isotherm line charts of compound adsorbent, ▼ represents different arsenic (III) concentration solution samplings (from 10mg/l-50mg/l) among the figure,---expression Freundlich adsorption curve ,-expression Langmuir adsorption curve; Fig. 7 is the specific embodiment six MnO
2/ Fe
3O
4Compound adsorbent 2 curve of adsorption kinetics figure, loose point is 10mg/l arsenic (III) solution different time absorption sample point among the figure.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: MnO in the present embodiment
2/ Fe
3O
4The preparation method of compound adsorbent carries out in the steps below: at room temperature with 0.45molFeSO
47H
2O is dissolved in the 200mL ionized water, with being placed in the anaerobic operation platform, then adds 1.2mol NaOH, occurs stirring and evenly mixing rapidly with glass bar after the blue-green flocculation, then pours into 0.1molKMnO is housed
4In the beaker, be stirred to KMnO
4Till dissolving fully, quiet heavy 1～2h, the filtering supernatant washes sediment until washing lotion becomes neutrality repeatedly with deionized water, then sediment is put in the vacuum drying chamber and dries 5～7h under 40～60 ℃ of conditions, is ground into powder, and obtains MnO
2/ Fe
3O
4Compound adsorbent.
MnO in the compound adsorbent of present embodiment method preparation
2It is comparatively even to distribute, and particle diameter is distributed in 1～100 μ m and does not wait, and manganese dioxide is with amorphous MnO
2Form exists.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: the described quiet heavy time is 1h.Other step is identical with the specific embodiment one with parameter.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is: described bake out temperature is 50 ℃.Other step is identical with the specific embodiment one or two with parameter.
The specific embodiment four: what present embodiment and the specific embodiment three were different is: described drying time is 6h.Other is identical with the specific embodiment three.
The specific embodiment five: present embodiment MnO
2/ Fe
3O
4The preparation method of compound adsorbent carries out in the steps below: at room temperature with 0.45molFeSO
47H
2O is dissolved in the 200mL ionized water, with being placed in the anaerobic operation platform, then add 1.2mol NaOH, occur stirring and evenly mixing rapidly (dissolved oxygen in all solution is fully reacted completely) with glass bar after the blue-green flocculation, then pour into 0.1molKMnO is housed
4In the beaker, be stirred to KMnO
4Till dissolving fully, quiet heavy 1h, filtering supernatant, sediment is washed until washing lotion becomes neutrality repeatedly with deionized water, then sediment is put in the vacuum drying chamber (prevent Surface Contact air from heating oxidized) and under 50 ℃ of conditions, dries 6h, be ground into powder, obtain MnO
2/ Fe
3O
4Compound adsorbent (Fig. 5).
MnO in the compound adsorbent of present embodiment method preparation
2Distribute comparatively evenly (Fig. 3), particle diameter is distributed in 1～100 μ m and does not wait (Fig. 4), and manganese dioxide is with amorphous MnO
2Form exists.
MnO with the present embodiment preparation
2/ Fe
3O
4Compound adsorbent is mixed in the 100ml deionized water (sees Fig. 1), magnet is attached on bottle wall, original muddy adsorbent mixing material is limpid gradually, sorbent particles is close to magnet rapidly, effect illustrates that the compound adsorbent of present embodiment preparation has very superior performance aspect mud-water separation behind the quiet heavy 2min shown in Fig. 2.
The specific embodiment six: MnO
2/ Fe
3O
4Compound adsorbent is removed the method for arsenic (III) in the water and finished in the steps below: the pH value that will contain the sewage of arsenic (III) is controlled more than 5, then adds the MnO of the specific embodiment one described method preparation
2/ Fe
3O
4Compound adsorbent carried out turbulent Contact-sorption more than 12 hours; Namely finished the removal of arsenic (III).
Arsenic-adsorbing (III) the results are shown in Figure 6-7.
Fig. 6 is 25 ° of adsorption isotherms of adsorbent, illustrate when the concentration of adsorbent in solution is 200mg/l, when arsenic (III) concentration is that 50mg/l can reach best removal effect, the mass ratio of adsorbent and arsenic (III) is 4: 1 o'clock by that analogy, and adsorbent substantially reaches maximal absorptive capacity and is about 72.83mg/g.
Fig. 7 is curve of adsorption kinetics, and when adsorption time reaches 12 hours, adsorbance can not change substantially, and adsorbent is saturated to reach absorption, and 24 hours is optimum reacting time.
The specific embodiment seven: what present embodiment and the specific embodiment six were different is: press MnO
2/ Fe
3O
4Compound adsorbent and arsenic (III) are that 4: 1 mass ratio adds MnO
2/ Fe
3O
4Compound adsorbent.Other step is identical with the specific embodiment six with parameter.
The effect that adopts following verification experimental verification that heavy metal arsenic (III) is adsorbed: arsenic in the water (III) initial concentration is 50mg/L, adds present embodiment MnO
2/ Fe
3O
4Compound adsorbent, described compound adsorbent consumption is 200mg/L, the maximal absorptive capacity of described adsorbent is about 72.83mg/g.
Claims (2)
1.MnO
2/ Fe
3O
4Compound adsorbent is removed the method for arsenic (III) in the water, it is characterized in that MnO
2/ Fe
3O
4Compound adsorbent is removed the method for arsenic (III) in the water and finished in the steps below: the pH value that will contain the sewage of arsenic (III) is controlled more than 5, then adds MnO
2/ Fe
3O
4Compound adsorbent carried out turbulent Contact-sorption more than 12 hours; Namely finished the removal of arsenic (III); Described MnO
2/ Fe
3O
4The preparation method of compound adsorbent carries out in the steps below: at room temperature with 0.45molFeSO
47H
2O is dissolved in the 200mL ionized water, with being placed in the anaerobic operation platform, then adds 1.2molNaOH, occurs stirring and evenly mixing rapidly with glass bar after the blue-green flocculation, then pours into 0.1molKMnO is housed
4In the beaker, be stirred to KMnO
4Till dissolving fully, quiet heavy 1～2h, the filtering supernatant washes sediment until washing lotion becomes neutrality repeatedly with deionized water, then sediment is put in the vacuum drying chamber and dries 5～7h under 40～60 ℃ of conditions, is ground into powder, and obtains MnO
2/ Fe
3O
4Compound adsorbent.
2. described MnO according to claim 1
2/ Fe
3O
4Compound adsorbent is removed the method for arsenic (III) in the water, it is characterized in that by MnO
2/ Fe
3O
4Compound adsorbent and arsenic (III) are that 4: 1 mass ratio adds MnO
2/ Fe
3O
4Compound adsorbent.
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| CN 201110091212 CN102188949B (en) | 2011-04-12 | 2011-04-12 | Method for removing arsenic (III) in water by utilizing composite MnO2/Fe3O4 adsorbent |
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| CN 201110091212 CN102188949B (en) | 2011-04-12 | 2011-04-12 | Method for removing arsenic (III) in water by utilizing composite MnO2/Fe3O4 adsorbent |
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| CN102188949B true CN102188949B (en) | 2013-01-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941057B (en) * | 2012-11-12 | 2014-10-08 | 北京大学 | Preparation method and application of magnetic compound arsenic adsorption agent |
| CN104772105A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院大学 | Preparation of MnO2 loaded fly ash adsorbent and application of adsorbent in removal of water body As (III) |
| CN104353407B (en) * | 2014-11-19 | 2016-03-23 | 中南大学 | A kind of Fe-Mn system adsorbent and methods for making and using same thereof |
| CN104773839B (en) * | 2015-04-12 | 2017-03-08 | 北京工业大学 | A kind of arsenic removing apparatus with iron and manganese oxides granulation as carrier |
| CN105036262B (en) * | 2015-07-02 | 2018-06-22 | 华北电力大学 | A kind of method that ferro manganese composite oxides arsenic removal efficiency is improved using magnetic field |
| CN105688793A (en) * | 2016-01-25 | 2016-06-22 | 华东交通大学 | Preparation method of MnO2-based magnetic nano Fe3O4 heavy metal adsorbing material |
| CN105771877A (en) * | 2016-04-23 | 2016-07-20 | 上海大学 | Method for preparing composite adsorption material MnO2-Fe3O4 with core-shell structure |
| CN106268646A (en) * | 2016-10-13 | 2017-01-04 | 沈阳建筑大学 | A kind of PAC Fe3O4/MnO2 magnetic active carbon and preparation method thereof |
| CN109289762B (en) * | 2018-11-28 | 2021-05-11 | 常熟理工学院 | Preparation method of manganese-activated amorphous iron-based adsorbent |
| CN110665512B (en) * | 2019-09-27 | 2020-12-11 | 浙江大学 | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172511A (en) * | 2011-04-01 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of MnO2/Fe3O4 compound adsorbent |
| CN102172510A (en) * | 2011-04-01 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of MnO2/Fe3O4 compound adsorbent and method for removing lead in water with compound adsorbent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172511A (en) * | 2011-04-01 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of MnO2/Fe3O4 compound adsorbent |
| CN102172510A (en) * | 2011-04-01 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of MnO2/Fe3O4 compound adsorbent and method for removing lead in water with compound adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| Gaosheng Zhang et al.Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal.《Water Research》.2007,第41卷第1921-1928页. * |
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