CN106865720A - A kind of method of fast degradation selenite - Google Patents
A kind of method of fast degradation selenite Download PDFInfo
- Publication number
- CN106865720A CN106865720A CN201710012431.3A CN201710012431A CN106865720A CN 106865720 A CN106865720 A CN 106865720A CN 201710012431 A CN201710012431 A CN 201710012431A CN 106865720 A CN106865720 A CN 106865720A
- Authority
- CN
- China
- Prior art keywords
- zero
- selenite
- iron
- modified
- valent iron
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Classifications
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved 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
- C02F2101/106—Selenium compounds
Abstract
The invention discloses a kind of method of fast degradation selenite, belong to water-treatment technology field, the low problem of depollution speed caused by passivating film is also easy to produce in order to solve Zero-valent Iron, it is proposed that cover the new method that zeroth order iron surface improves its electron transport rate and then improves selenite clearance with the larger sulphur of conductive capability.The use of the method greatly improves the reactivity of Zero-valent Iron and the clearance of selenite waste water, and the method for modifying for being used is simple to operate, and course of reaction is easy to control, and the relatively low and modified zeroth order iron material of cost is more stable and is easy to preserve.
Description
Technical field：
The invention belongs to water-treatment technology field, it is related to a kind of water and wastewater treatment method, and in particular to a kind of fast degradation is sub-
The method of selenate.
Background technology：
With industrialized development, the phenomenon of selenium contamination water body is presented increasingly severe situation.China have now been found at present
Liang great natural selenium-rich area, one be Hubei Province Enshi, another is the Ziyang County in Shaanxi Province, particularly enshi fish pond
There is the Se fractionation of globally unique independent mineralization in dam area.Therefore, Enshi district and Ziyang County area selenium contamination event compared with
It is many, wherein the phenomenon in fish pond dam area selenosis of bestowing favour is the most notable.Se content is 0.06 ~ 400 μ in China, underground water
g•L-1, indivedual areas can reach 6000 μ g L-1.Selenium in the national regulation drinking water such as China, the U.S. and Canada contains
Amount must not exceed 10 μ g L-1.Selenium in natural water is main with selenate radical (SeO4 2-, Se (VI)) and selenite radical (SeO3 2-,
Se (IV)) form of both inorganic ions is present, and the toxicity of wherein Se (IV) is higher by 10 times than Se (VI), therefore, research and development warp
Effective selenite removal technology of helping is imperative.
The common method of the selenite pollution gone at present in water removal includes ion-exchange, coprecipitation, absorption method, life
Thing reducing process, abiotic reducing process, hyperfiltration etc..But all there is a problem of that removal efficiency is slower.Zero-valent Iron has price low
Honest and clean, safety is easy to get, will not produce secondary pollution to environment and can process the advantage of various hazardous contaminants, thus
Water treatment field is increasingly taken seriously.Although zero-valent iron technology has been obtained comparing and has been widely applied, there is also what is protruded
Shortcoming.Such as Zero-valent Iron during preparation, because the general surface of air oxidation can all cover one layer of passivating film.And passivating film
The ironing surface active site position of zeroth order can be covered, the speed that electronics is delivered to pollutant from Zero-valent Iron is reduced.Due to passivating film
Composition is different with thickness, and the increase degree to electron transmission resistance is different, and the reactivity reduction degree of Zero-valent Iron is also different.
Having researcher confirms that thick passivating film can reduce the reactivity of Zero-valent Iron or even the reactivity of Zero-valent Iron can be made to disappear completely
Lose.The significant obstacle and limitation Zero-valent Iron that the passivating film problem of Zero-valent Iron has turned into promotion zero-valent iron technology application permeate anti-
Answer the bottleneck of the sustainable application of wall technology.The passivation and raising for how effectively alleviating Zero-valent Iron have been passivated the reaction work of Zero-valent Iron
Property turned into the focus of current research.Patent 20120318103.3 discloses a kind of Zero-valent Iron of being strengthened with low-intensity magnetic field and removes selenium
The method of pollution, this method propose the method for low-intensity magnetic field depassivation, but there is a problem of that magnetic field addition is difficult.
The content of the invention：
For the problem that the removal pollutant for overcoming Zero-valent Iron surface passivated membrane to bring is slower, while improving the stronger sub- selenium of toxicity
Hydrochlorate pollution removal problem.It is an object of the invention to provide a kind of method of fast degradation selenite.
The technical scheme that the present invention takes is as follows：
A kind of method of fast degradation selenite, it is characterised in that comprise the following steps：
（1）At room temperature, to 150 mL distilled water are added in 500 mL there-necked flasks, mechanical agitator stirring controls rotating speed for 50-
200 r/min, it is 0 that whole process expose nitrogen to control dissolved oxygen, is subsequently adding 5g 1-30 microns of zero-valent iron particle；It is subsequently added weighing
Good ferrous sulfate solid powder stirring, is added dropwise over sodium sulfide solution, Fe in control ferrous sulfate and vulcanized sodium after 10 minutes2+
And S2-Mol ratio be 1：1, anaerobic reaction 1h is continued after dripping, vacuum filtration, 60 degree of steaming skies are drying to obtain modified Zero-valent Iron
Product；
（2）The modified zeroth order iron material 0.5g/L of synthesis is added in 500mL completes and is stirred, rotating speed 100-
500 r/min, 5-30 DEG C of temperature adds selenous acid waste water, and pH=3~10, reaction are controlled with acetic acid and sodium acetate buffer solution
Can remove selenite within 0.1-3.0 hours.
Further setting of the invention is as follows：
Zeroth order iron powder in modified Zero-valent Iron of the present invention before modified is micron order Zero-valent Iron, and particle diameter is 1-30 microns, preferably 1
Micron.
Modified Zero-valent Iron preparation process of the present invention is carried out at room temperature, and without the pH of control reaction.
Modified Zero-valent Iron preparation process of the present invention need to be stirred, and mixing speed is 50-200 r/min, preferably 200
r/min。
It is 0 mg/L that modified Zero-valent Iron preparation process of the present invention needs the concentration of whole-process control dissolved oxygen.
Fe in modified Zero-valent Iron preparation process control ferrous sulfate of the present invention and vulcanized sodium2+And S2-Mol ratio be
1：1.And vulcanized sodium rate of addition is strictly controlled to be added dropwise over.
The reaction time is 1 hour after modified Zero-valent Iron preparation process of the present invention drips vulcanized sodium.
Modified Zero-valent Iron preparation process of the present invention needs 60 degree of vacuum drying.
S in the modified Zero-valent Iron of preparation of the present invention：The mol ratio of Fe is 0.02-0.2.
The dosage of modified Zero-valent Iron removal selenous acid waste water of the present invention is 0.1-10.0 g/L, preferably 0.5 g/
L。
The concentration range of the modified Zero-valent Iron removal selenous acid Selenium in Wastewater of institute of the invention is 0.02-40 mg/L.
The speed of agitator of modified Zero-valent Iron removal selenous acid of the present invention is 100-500 r/min.Further preferably
Speed of agitator is 400 r/min.
Modified Zero-valent Iron of the present invention removes the pH=3-10 of selenous acid waste water.Further preferred pH=5.0.
The temperature of modified Zero-valent Iron removal selenous acid waste water of the present invention is 5-30 degree.Further preferred temperature is 25
Degree.
The hydraulic detention time of modified Zero-valent Iron removal selenous acid waste water of the present invention is 0.1-3.0 hours.
The present invention compared with the existing technology, has the following advantages that and beneficial effect：
1st, of the invention compared with existing technology, the removal effect of selenite is quick and clearance is high, and selenium is solved well
Pollute the problem of removal；
2nd, of the invention compared with existing technology, preparation method is simple, course of reaction is easy to control and reaction after without toxic metals from
Son residual, improves the value of commercial Application.
3rd, of the invention compared with existing technology, cost is relatively low and modified zeroth order iron material is more stable and is easy to protect
Deposit.
4th, by controlling to prepare the zero-valent iron particle particle diameter in Zero-valent Iron material technology, rotating speed and reaction time and temperature
Degree, S in the modified zeroth order iron material of preparation：The mol ratio of Fe is controlled in 0.02-0.2, is verified by experiments, and is gone for selenite
Except rate has remarkable result.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Brief description of the drawings：
Fig. 1 is the tetravalence selenium effect contrast figure that embodiment of the present invention Zero-valent Iron and modified Zero-valent Iron remove various concentrations；
Fig. 2 is the different modified Zero-valent Iron removal effect comparison diagrams of the present invention（The throwing amount of modified Zero-valent Iron is 0.5 g/L, pH=5,
Rotating speed 400r/min, 25 DEG C of room temperature, selenous acid concentration 5mg/L）.
Specific embodiment：
Embodiment 1：
At room temperature, to 150 mL distilled water are added in 500 mL there-necked flasks, mechanical agitator stirring controls rotating speed for 200 r/
Min, it is 0 that whole process expose nitrogen to control dissolved oxygen, is subsequently adding 5 g, 1 micron of zero-valent iron particle；It is subsequently added load weighted sulfuric acid
Ferrous solid powder stirring, is added dropwise over sodium sulfide solution, Fe in control ferrous sulfate and vulcanized sodium after 10 minutes2+And S2-'s
Mol ratio is 1：1, anaerobic reaction 2h is continued after dripping, vacuum filtration, 60 degree of steaming skies are drying to obtain, the sulphur of final modified product
Iron mol ratio is 0.111.
The modified g/L of zeroth order iron material 0.5 of synthesis is added in 500 mL completes and is stirred, rotating speed
400r/min, 25 DEG C of room temperature controls the concentration of selenite for 5 mg/L, sub- with acetic acid and sodium acetate buffer solution pH=5.0
Selenate can remove 99 more than % in 30 min.And react 30min at identical conditions using unmodified Zero-valent Iron and remove
Rate is only 7% result as shown in Figure 1.
Embodiment 2：
At room temperature, to 150 mL distilled water are added in 500 mL there-necked flasks, mechanical agitator stirring controls rotating speed for 200 r/
Min, it is 0 that whole process expose nitrogen to control dissolved oxygen, is subsequently adding 5 g, 1 micron of zero-valent iron particle；It is subsequently added load weighted sulfuric acid
Ferrous solid powder stirring, is added dropwise over sodium sulfide solution, Fe in control ferrous sulfate and vulcanized sodium after 10 minutes2+And S2-'s
Mol ratio is 1：1, anaerobic reaction 2h is continued after dripping, vacuum filtration, 60 degree of steaming skies are drying to obtain, the sulphur of final modified product
Iron mol ratio is 0.111.
The modified g/L of zeroth order iron material 0.5 of synthesis is added in 500 mL completes and is stirred, rotating speed
400r/min, 25 DEG C of room temperature controls the concentration of selenite for 10 mg/L, sub- with acetic acid and sodium acetate buffer solution pH=5.0
Selenate can remove 87 more than % in 30 min.And react 30min at identical conditions using unmodified Zero-valent Iron and remove
Rate is only 5% result as shown in Figure 1.
Embodiment 3：
At room temperature, to 150 mL distilled water are added in 500 mL there-necked flasks, mechanical agitator stirring controls rotating speed for 200 r/
Min, it is 0 that whole process expose nitrogen to control dissolved oxygen, is subsequently adding 5 g, 1 micron of zero-valent iron particle；It is subsequently added load weighted sulfuric acid
Ferrous solid powder stirring, is added dropwise over sodium sulfide solution, Fe in control ferrous sulfate and vulcanized sodium after 10 minutes2+And S2-'s
Mol ratio is 1：1, anaerobic reaction 2h is continued after dripping, vacuum filtration, 60 degree of steaming skies are drying to obtain, the sulphur of final modified product
Iron mol ratio is 0.111.
The modified g/L of zeroth order iron material 0.5 of synthesis is added in 500 mL completes and is stirred, rotating speed
400r/min, 25 DEG C of room temperature controls the concentration of selenite for 20mg/L, sub- with acetic acid and sodium acetate buffer solution pH=5.0
Selenate can remove 71 more than % in 30 min.And react 30min at identical conditions using unmodified Zero-valent Iron and remove
Rate is only 4 % results as shown in Figure 1.
Embodiment 4：
At room temperature, to 150 mL distilled water are added in 500 mL there-necked flasks, mechanical agitator stirring controls rotating speed for 200 r/
Min, it is 0 that whole process expose nitrogen to control dissolved oxygen, is subsequently adding 5 g, 1 micron of zero-valent iron particle；It is subsequently added load weighted sulfuric acid
Ferrous solid powder stirring, is added dropwise over sodium sulfide solution, Fe in control ferrous sulfate and vulcanized sodium after 10 minutes2+And S2-'s
Mol ratio is 1：1, anaerobic reaction 2h is continued after dripping, vacuum filtration, 60 degree of steaming skies are drying to obtain, the sulphur of final modified product
Iron mol ratio is 0.111.
The modified g/L of zeroth order iron material 0.5 of synthesis is added in 500 mL completes and is stirred, rotating speed
400r/min, 25 DEG C of room temperature controls the concentration of selenite for 40 mg/L, sub- with acetic acid and sodium acetate buffer solution pH=5.0
Selenate can remove 47 more than % in 30 min.And react 30min at identical conditions using unmodified Zero-valent Iron and remove
Rate is only 4 % results as shown in Figure 1.
Embodiment 5：S in modified zeroth order iron material：Influence of the mol ratio of Fe to clearance.
The different S that will be prepared：The modified zeroth order iron material of the mol ratio of Fe, and unmodified Zero-valent Iron, respectively to selenous acid
Salt is processed, and detects its removal effect, as shown in Figure 2.
Handling process is as follows：Zero-valent Iron/modified g/L of zeroth order iron material 0.5 is added in 500 mL completes
And stir, rotating speed 400r/min, 25 DEG C of room temperature, the concentration of selenite is controlled for 5mg/L, with acetic acid and sodium acetate buffer solution
Control pH=5.0.
In summary it can be seen：
1st, as shown in figure 1, improve the reactivity of Zero-valent Iron using the modified Zero-valent Iron of the present invention, Asia has been significantly speeded up
The removal of selenic acid；And the common Zero-valent Iron removal effect that is not modified is poor.
2nd, as shown in Fig. 2 by controlling to prepare the zero-valent iron particle particle diameter in Zero-valent Iron material technology, rotating speed and reaction
Time and temperature, S in the modified zeroth order iron material of preparation：The mol ratio of Fe is controlled in 0.02-0.2, is verified by experiments, for Asia
Selenate clearance has remarkable result（Work as S：The mol ratio of Fe is controlled at 0.2, is to be capable of achieving quick removal in 10min）.
Claims (10)
1. a kind of method of fast degradation selenite, it is characterised in that comprise the following steps：
（1）At room temperature, to 150 mL distilled water are added in 500 mL there-necked flasks, mechanical agitator stirring controls rotating speed for 50-
200 r/min, it is 0 that whole process expose nitrogen to control dissolved oxygen, is subsequently adding 5g 1-30 microns of zero-valent iron particle；It is subsequently added weighing
Good ferrous sulfate solid powder stirring, is added dropwise over sodium sulfide solution, Fe in control ferrous sulfate and vulcanized sodium after 10 minutes2+
And S2-Mol ratio be 1：1, anaerobic reaction 2h is continued after dripping, vacuum filtration, 60 degree of steaming skies are drying to obtain modified Zero-valent Iron
Product；
（2）The modified zeroth order iron material 0.5g/L of synthesis is added in 500mL completes and is stirred, rotating speed 100-
500 r/min, 5-30 DEG C of temperature adds selenous acid waste water, and pH=5.0 is controlled with acetic acid and sodium acetate buffer solution, reacts 0.1-
Can remove selenite within 3.0 hours.
2. the method for a kind of fast degradation selenite according to claim 1, it is characterised in that：The modified Zero-valent Iron
In zeroth order iron powder before modified be micron order Zero-valent Iron, particle diameter is 1-30 microns.
3. the method for a kind of fast degradation selenite according to claim 1, it is characterised in that：The modified Zero-valent Iron
Preparation process need to be stirred, and mixing speed is 200 r/min.
4. the method for a kind of fast degradation selenite according to claim 1, it is characterised in that：The modified Zero-valent Iron
Middle S：The mol ratio of Fe is 0.02-0.2.
5. the method for a kind of fast degradation selenite according to claim 1, it is characterised in that：Described modified zeroth order
The dosage of iron is 0.1-10.0 g/L.
6. the method for a kind of fast degradation selenite according to claim 5, it is characterised in that：Described modified zeroth order
The dosage of iron is 0.5 g/L.
7. a kind of method of fast degradation selenite according to claim 1 or 5, it is characterised in that：Described Ya Ya
The concentration range of selenic acid Selenium in Wastewater is 0.02-40 mg/L.
8. the method for a kind of fast degradation selenite according to claim 1, it is characterised in that：Described modified zeroth order
The speed of agitator of iron removal selenous acid is 400 r/min.
9. the method for a kind of fast degradation selenite according to claim 1, it is characterised in that：Described modified zeroth order
Iron removes pH=5.0 of selenous acid waste water.
10. the method for a kind of fast degradation selenite according to claim 1, it is characterised in that：Described modified zero
The temperature of valency iron removal selenous acid waste water is 25 degree.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110302807A (en) * | 2019-07-01 | 2019-10-08 | 山东大学 | A kind of preparation method and application of modified Zero-valent Iron liquid catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2635584A1 (en) * | 2005-12-29 | 2007-07-12 | Micronose Technologies, Inc. | Methods and compositions for removal of arsenic and heavy metals from water |
| CN105859015A (en) * | 2016-05-27 | 2016-08-17 | 山东大学 | Method for removing orange yellow I in printing and dyeing wastewater by using sulfurized modified zero-valent iron material under effect of low-intensity magnetic field |
-
2017
- 2017-01-09 CN CN201710012431.3A patent/CN106865720A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2635584A1 (en) * | 2005-12-29 | 2007-07-12 | Micronose Technologies, Inc. | Methods and compositions for removal of arsenic and heavy metals from water |
| CN105859015A (en) * | 2016-05-27 | 2016-08-17 | 山东大学 | Method for removing orange yellow I in printing and dyeing wastewater by using sulfurized modified zero-valent iron material under effect of low-intensity magnetic field |
Non-Patent Citations (1)
| Title |
|---|
| 梁丽萍等: "纳米零价铁去除地下水中***盐的动力学及机理", 《哈尔滨工业大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110302807A (en) * | 2019-07-01 | 2019-10-08 | 山东大学 | A kind of preparation method and application of modified Zero-valent Iron liquid catalyst |
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Application publication date: 20170620 |