CN102276045A - Method for treating typical heavy metals and organochlorine waste water by using nano zerovalent iron as initiator - Google Patents
Method for treating typical heavy metals and organochlorine waste water by using nano zerovalent iron as initiator Download PDFInfo
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- CN102276045A CN102276045A CN 201010197587 CN201010197587A CN102276045A CN 102276045 A CN102276045 A CN 102276045A CN 201010197587 CN201010197587 CN 201010197587 CN 201010197587 A CN201010197587 A CN 201010197587A CN 102276045 A CN102276045 A CN 102276045A
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Abstract
The invention relates to environmental chemistry, in particular to a method for treating heavy metal ion and organochlorine containing waste water by using nano zerovalent iron as an initiator. In the invention, the mechanisms such as chemical reduction and competitive reaction in the initiator prepared by nano zerovalent iron are used to treat waste water; and the initiator is suitable for different kinds of waste water, such as waste water containing typical heavy metal ions, organochlorine such as Cr(VI), tetrachloroethylene and the like. The method comprises: preparing the initiator by pretreatment of the nano zerovalent iron; adding the initiator into a reactor containing waste water; oscillating in a water-bath constant-temperature oscillator at a temperature of 15 to 25 DEG C and at a speed of 160 to 180r/min; and reacting for a certain time period and realizing the treatment of different kinds of waste water. When the method is used, each gram of nano zerovalent iron can treat 70 to 200 mg of Cr(VI) and 5 to 15 mg of tetrachloroethylene respectively. Therefore, the method has a bright application prospect in repairing heavy metal ions and organochlorine containing waste water.
Description
Technical field
The present invention relates to environmental chemistry, specifically a kind of nano zero valence iron that utilizes is handled the method that contains heavy metal ion, organochlorine, waste water from dyestuff for initiator.
Background technology
The water pollution and prevention has become the serious problems that the whole world is paid close attention to.Contain all contaminations such as dyestuff, chlorinatedorganic, nitro-compound, heavy metal ion in the waste water.
In water polluted, heavy metal ion was wherein comparatively serious pollutent, especially chromium.Along with industrial expansion, chromium and compound thereof have obtained using widely as the important source material of industries such as metallurgy, plating, process hides, paint, pigment, printing and dyeing, pharmacy.Meanwhile, a large amount of contain chromium powder dirt, chromate waste water and chromium slags also enter in the environment, and atmosphere, water body, soil have been caused serious pollution.
Organochlorine is the very important pollutent of a class in the water surrounding, as various organochlorine pesticides and zellon, trieline etc.Wherein, zellon is a kind of difficult degradation chloro-alkenes compound, is widely used in dry-cleaning every field such as industry, metal cleaning, has replaced the oil series solvent that consumption is big, inflammable, soil removability is relatively poor.Along with the extensive use of zellon, atmosphere, underground water and soil are subjected to severe contamination simultaneously.
More than these toxic substances have teratogenesis, carcinogenic, mutagenic " three cause " effect, be a kind of serious threat to existent environment of people.The material general toxicity that can be degraded by microorganisms is lower, and easily handles, and the big and stable high pollutent of toxicity often is difficult to be degraded by microorganisms, and traditional sewage treatment process is very low to these organic degradation efficiencies.Therefore, developing low-cost, high efficiency sewage disposal technology become the focus and emphasis in the water pollution and the field of improvement.
Zero-valent Iron in recent years, the research of the heavy metal contamination in the water body is removed in begin one's study Zero-valent Iron material reduction of Chinese scholars, and has obtained certain effect.In recent years, Zero-valent Iron is a large amount of is used to handle various sewage, waste water from dyestuff, chlorinatedorganic, nitro-compound, heavy metal ion.In the Zero-valent Iron material of using, mainly contain iron filings, iron powder, nanometer iron powder and sponge iron.Some research group is devoted to improve the activity of Zero-valent Iron, improved method comprises and ultrasonic wave synergistic reaction, and hydridization heavy metal ion such as palladium, nickel carry out etching etc. with acid with the ironing surface passivation layer of zeroth order, studies show that these methods have all improved the activity of Zero-valent Iron to a certain extent.Yet, it is pointed out that hyperacoustic synergy can be restricted in the actual industrial process.The activity of nano zero valence iron and its preparation technology have substantial connection, and the fact shows that the nano zero valence iron of unpassivated can violent redox reaction take place with water itself, can't effectively handle waste water; There is a large amount of oxide compounds in the nano zero-valence iron surface of traditional method preparation, makes reaction efficiency reduce greatly.
The present invention utilizes nano zero valence iron to make initiator, the improvement cleverly that some problems of present existence have been carried out.As everyone knows, the dominant mechanism of zero valent ferri treating polluted water is to utilize its reducing power, can come out in metal replacement thereafter arranging in metal activity command table and be deposited on the surface of iron, also ion that can oxidisability is stronger or compound and some organism are reduced.In the initiator nano zero valence iron not only activity improved, and produced some other in the initiator and had the ion of reducing power, make the activity of nano zero valence iron improve greatly.
Summary of the invention
The object of the present invention is to provide a kind of nano zero valence iron that utilizes to handle the method that contains heavy metal ion, organochlorine waste water for initiator.
By the preparation initiator, utilize in the initiator and mechanism such as the direct chemical reduction of waste water, competing reaction, make the removal sewage that nano zero valence iron can be rapidly and efficiently, thereby realized purpose of the present invention.
For achieving the above object, the technical solution used in the present invention may further comprise the steps:
(1) gets the Cr (VI) of 1-10mL or zellon or methylene blue initial soln and nano zero-valence iron powder and join in the pretreating containers, drip 0-1mL H
2SO
4, H
2SO
4Concentration is 0.05-0.5mol/L, and is ultrasonic.
(2) initiator that contains nano zero valence iron that step (1) is obtained joins in Cr (VI) or zellon or the methylene blue solution, in the constant temperature water bath vibrator, vibrate, wherein temperature is 15-25 ℃, and hunting speed is 100-150r/min, and mode of oscillation is the vibration of winding formula.The reaction certain hour is realized the processing to various waste water.
The described nanoscale zero-valent iron of step (1) is our company's self-control product, and the nano zero-valence iron surface is covered with passivation layer.Purity 98%, particle diameter are 100-250nm, and specific surface area is 3-7m2/g.
The ratio that the addition of the described nano zero valence iron of step (1) accounts for wastewater treatment capacity is 1/100-1/2000, and preferable range is 1/400-1/1000.
The described ultrasonic temperature of step (1) is 15-25 ℃, and power is 100W-160W, and ultrasonic time is 2-15min.
The present invention utilizes in the initiator preparation process, and acid is removed multiple effect synergy such as surface passivation layer effect, ultransonic cleaning, chemical action, initial soln competition effect down, improves the activity that nano zero valence iron is removed waste water.Major advantage of the present invention has:
1. practical.This invention can be handled various wastewater, as heavy metal ion, organochlorine, dyestuff etc.
2. treatment effect is good.The method of handling waste water than general nano zero valence iron has improved several times or even tens times.
3. treatment rate is fast.Almost in preceding 30min, just wastewater treatment is reached balance.
4. technology is simple.The whole technology of the present invention only need join the preparation initiator in the waste water then, need not other complicated technical process.
5. process cost is low.No specific installation, only need common ultrasonic cleaning instrument just can, as long as ultrasonic 2-15min just can.
6. safety non-pollution.The present invention only needs nano zero valence iron, need not to add other poisonous and harmful chemical, and also can not produce secondary pollutent such as useless smoke waste gas after finishing dealing with.The SO42-that introduces is also less than the content standard (less than 250mg/L) of vitriol in the tap water.
Description of drawings
The initiator that contains nano zero valence iron is to Cr (VI) removal effect figure
Embodiment
Use method of the present invention to handle certain density typical heavy metal ion, organochlorine, dyestuff such as Cr (VI), zellon, methylene blue.Chromic measuring method utilizes diphenyl carbazide spectrophotometry, with reference to GB/T7467-1987.The measuring method of zellon utilizes vapor-phase chromatography, with reference to GB/T17130-1997, adopts external standard method that zellon is carried out quantitative analysis, and the gas chromatograph model is Tianjin, island 2010.
Following examples are to further specify of the present invention, are not limitations of the present invention.
Embodiment 1:
100mg/L Cr (VI) solution and the 0.15g nano zero-valence iron powder of getting 4mL join in the pretreating containers, drip 0.25mL H
2SO
4, H
2SO
4Concentration is 0.35mol/L, ultrasonic 5min.The initiator that contains nano zero valence iron that obtains is joined in 50mL 200mg/L Cr (VI) solution, vibrate in the constant temperature water bath vibrator, wherein temperature is 20 ℃, and hunting speed is 140-150r/min, and mode of oscillation is the vibration of winding formula.Reaction 5min, the removal effect of Cr (VI): clearance 100%, the amount that every gram nano zero valence iron is handled Cr (VI) is 66.67mg.
Embodiment 2
Difference from Example 1 is:
100mg/L Cr (VI) solution and the 0.15g nano zero-valence iron powder of getting 4mL join in the pretreating containers, drip 0.25mL H
2SO
4, H
2SO
4Concentration is 0.1mol/L, ultrasonic 5min.The initiator that contains nano zero valence iron that obtains is joined in 100mL 200mg/L Cr (VI) solution, vibrate in the constant temperature water bath vibrator, wherein temperature is 20 ℃, and hunting speed is 140-150r/min, and mode of oscillation is the vibration of winding formula.Reaction 30min realizes the processing to various waste water.The removal effect of Cr (VI): clearance 79.25%, the amount that every gram nano zero valence iron is handled Cr (VI) is 107.00mg.
Embodiment 3:
Difference from Example 1 is:
100mg/L Cr (VI) solution and the 0.15g nano zero-valence iron powder of getting 4mL join in the pretreating containers, drip 0.5mL H
2SO
4, H
2S0
4Concentration is 0.1mol/L, ultrasonic 5min.The initiator that contains nano zero valence iron that obtains is joined in 100mL 300mg/L Cr (VI) solution, vibrate in the constant temperature water bath vibrator, wherein temperature is 20 ℃, and hunting speed is 140-150r/min, and mode of oscillation is the vibration of winding formula.Reaction 30min realizes the processing to various waste water.The removal effect of Cr (VI): clearance 77.25%, the amount that every gram nano zero valence iron is handled Cr (VI) is 154.5mg.
Embodiment 4:
Get 5mL 16.31mg/L zellon solution and 0.6g nano zero-valence iron powder joins in the pretreating containers, drip 0.4mL H
2SO
4, H
2SO
4Concentration is 0.1mol/L, ultrasonic 5min.The initiator that contains nano zero valence iron that obtains is joined in the 100mL 32.6mg/L zellon solution, vibrate in the constant temperature water bath vibrator, wherein temperature is 20 ℃, and hunting speed is 140-150r/min, and mode of oscillation is the vibration of winding formula.Reaction 120min realizes the processing to various waste water.The treatment effect of zellon: clearance 88.35%, the amount that every gram nano zero valence iron is handled zellon is 5.57mg.
Embodiment 5:
Difference from Example 4 is:
Get 5mL 355mg/L zellon solution and 0.5g nano zero-valence iron powder joins in the pretreating containers, drip 0.25mL H
2SO
4, H
2SO
4Concentration is 0.1mol/L, ultrasonic 5min.The initiator that contains nano zero valence iron that obtains is joined in the 200mL 44.4mg/L zellon solution, vibrate in the constant temperature water bath vibrator, wherein temperature is 20 ℃, and hunting speed is 140-150r/min, and mode of oscillation is the vibration of winding formula.Reaction 120min realizes the processing to various waste water.The treatment effect of zellon: clearance 32.88%, the amount that every gram nano zero valence iron is handled zellon is 7.00mg.
Embodiment 6:
Difference from Example 4 is:
Get 5mL 355mg/L zellon solution and 0.5g nano zero-valence iron powder joins in the pretreating containers, drip 0.25mL H
2SO
4, H
2SO
4Concentration is 0.1mol/L, ultrasonic 5min.The initiator that contains nano zero valence iron that obtains is joined in the 200mL 83.9mg/L zellon solution, vibrate in the constant temperature water bath vibrator, wherein temperature is 20 ℃, and hunting speed is 140-150r/min, and mode of oscillation is the vibration of winding formula.Reaction 120min realizes the processing to various waste water.The treatment effect of zellon: clearance 36.59%, the amount that every gram nano zero valence iron is handled zellon is 13.58mg.
Claims (4)
1. one kind is utilized nano zero valence iron to handle the method that contains heavy metal ion, organochlorine waste water for initiator, and its step is as follows:
(1) gets the Cr (VI) of 1-10mL or zellon or methylene blue initial soln and nano zero-valence iron powder and join in the pretreating containers, drip 0-1mL H
2SO
4, H
2SO
4Concentration is 0.05-0.5mol/L, and is ultrasonic.
(2) initiator that contains nano zero valence iron that step (1) is obtained joins in Cr (VI) or zellon or the methylene blue solution, in the constant temperature water bath vibrator, vibrate, wherein temperature is 15-25 ℃, and hunting speed is 100-150r/min, and mode of oscillation is the vibration of winding formula.The reaction certain hour is realized the processing to various waste water.
2. to account for the ratio of wastewater treatment capacity be 1/100-1/2000 to the addition of right 1 described nano zero valence iron, and preferable range is 1/400-1/1000.
3. right 1 described ultrasonic temperature is 15-25 ℃, and power is 100W-160W, and ultrasonic time is 2-15min.
4. right 1 described nanoscale zero-valent iron is our company's self-control product, and the nano zero-valence iron surface is covered with passivation layer.Purity 98%, particle diameter are 100-250nm, and specific surface area is 3-7m
2/ g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194795A (en) * | 2014-06-10 | 2014-12-10 | 青岛华仁技术孵化器有限公司 | Novel in-situ passivation modifier and preparing method thereof |
| CN109209268A (en) * | 2018-10-19 | 2019-01-15 | 中国石油集团渤海钻探工程有限公司 | The method that drain is returned in acidification is handled using reproducibility iron powder |
| CN113262764A (en) * | 2021-03-12 | 2021-08-17 | 同济大学 | Application of iron-based cellulose nanocomposite in water environment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234812A (en) * | 2008-02-05 | 2008-08-06 | 中国科学院沈阳应用生态研究所 | Method for decoloring burned waste water by using zero-valent iron/ultrasonic wave synergistic reaction |
-
2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234812A (en) * | 2008-02-05 | 2008-08-06 | 中国科学院沈阳应用生态研究所 | Method for decoloring burned waste water by using zero-valent iron/ultrasonic wave synergistic reaction |
Non-Patent Citations (2)
| Title |
|---|
| 《环境保护》 20020430 梁震等 纳米级零价铁的制备及其用于污水处理的机理研究 第14-16页 1-4 , 第4期 * |
| 《科学通报》 20091215 侯春凤等 纳米铁颗粒物表征及其对2,4-二氯苯酚的脱氯降解性能 第3623-3629页 1-4 第54卷, 第23期 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194795A (en) * | 2014-06-10 | 2014-12-10 | 青岛华仁技术孵化器有限公司 | Novel in-situ passivation modifier and preparing method thereof |
| CN109209268A (en) * | 2018-10-19 | 2019-01-15 | 中国石油集团渤海钻探工程有限公司 | The method that drain is returned in acidification is handled using reproducibility iron powder |
| CN113262764A (en) * | 2021-03-12 | 2021-08-17 | 同济大学 | Application of iron-based cellulose nanocomposite in water environment |
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