CN107297386A - A kind of mechanochemistry reduction restorative procedure of hexavalent chromium polluted soil - Google Patents
A kind of mechanochemistry reduction restorative procedure of hexavalent chromium polluted soil Download PDFInfo
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- CN107297386A CN107297386A CN201710612501.9A CN201710612501A CN107297386A CN 107297386 A CN107297386 A CN 107297386A CN 201710612501 A CN201710612501 A CN 201710612501A CN 107297386 A CN107297386 A CN 107297386A
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- ball
- mechanochemistry
- hexavalent chromium
- polluted soil
- restorative procedure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Abstract
The invention belongs to heavy-metal contaminated soil processing technology field, the mechanochemistry reduction restorative procedure of specially a kind of hexavalent chromium polluted soil.It will sieve after the hexavalent chromium polluted soil mortar grinder of natural air drying first, then by the soil particle after screening, reducing agent（Such as ferrous sulfate, calcium polysulfide）And zirconium oxide balls are placed in ball grinder and carry out mechanico-chemical reaction in proportion, reduced by mechanochemistry and high toxicity, the easily high Cr VI of migration, bioavailability are changed into hypotoxicity, the easily low trivalent chromium of precipitation, bioavailability, realize the harmless treatment of hexavalent chromium polluted soil.The characteristics of the inventive method has efficient green, non-secondary pollution, is a kind of hexavalent chromium polluted soil remediation method of great application prospect.
Description
Technical field
The invention belongs to heavy-metal contaminated soil processing technology field, specifically a kind of machine of hexavalent chromium polluted soil
Tool electronation restorative procedure.
Background technology
With quickly propelling for human industryization process, chromium content in place is left in many industry severe overweight,
And have a strong impact on and threaten health and the sustainable development of environment of the mankind.Chromium two kinds of oxygen present in soil
It is trivalent chromium Cr respectively to change state（III）With Cr VI Cr（VI）, wherein with high toxicity, easily migration, bioavailable Cr VI
Harm is maximum.The characteristic that Cr VI is easily migrated so that Cr VI can not only expand pollution range, more can polluted surface water and underground
Water；In addition, although under normal physiological conditions, Cr VI will not react with DNA, the oxidation that Cr VI occurs is also
Original reaction can produce the extremely strong hydroxyl radical free radical of oxidability (OH), hydroxyl radical free radical meeting damaging cells, and then make cell bad
Extremely.
At present, the hexavalent chromium polluted agent, soil treatment method of " tradition " and existing many practical engineering applications has：Electronation
Method, elution method, heat treating process, electro reclamation and super enriching plant repairing method etc..These are in hexavalent chromium polluted soil
Restorative procedure all coming with some shortcomings inevitably of good result are obtained in actual place reparation, summary gets up to have：Such as
Reagent consumption amount is big, processing cost is high, produce secondary pollution, change larger, processing routine technique to the physicochemical property of soil answers
Miscellaneous, the process cycle not enough and shortcoming such as tediously long.
For the deficiency of existing treatment technology, seek at highly efficient green, the hexavalent chromium polluted soil of non-secondary pollution
Reason technology has very important significance.
The content of the invention
In order to make up and solve the deficiency of the existing hexavalent chromium polluted soil technology of processing, it is an object of the invention to provide
A kind of chemical method of reduction treatment of hexavalent chromium polluted soil by machines.It passes through the effect of mechanical ball mill so that reducing agent and sexavalence
Chromium-polluted soil has sufficient contact, and by the effect of mechanical force, realizes the parcel of pollutant and soil particle, so that
The solidification and stabilization processing of hexavalent chromium polluted soil is realized, is a kind of efficient green, innoxious process for treating.
The technical solution adopted by the present invention is as follows.
The present invention provides a kind of mechanochemistry reduction restorative procedure of hexavalent chromium polluted soil, comprises the following steps that：
Step one, the soil particle grinding of hexavalent chromium polluted soil, the sieving of natural air drying obtained adds after being mixed with reducing agent
Ball milling is carried out into zirconia ball mill, occurs mechanico-chemical reaction；Wherein：Reducing agent is one in ferrous sulfate or calcium polysulfide
Plant or two kinds；The mass ratio that the consumption of reducing agent accounts for total inventory is 1% ~ 5%；Rotational speed of ball-mill is 200 ~ 600 revs/min, ball
Consume time as 0.5 ~ 6 hour；
Step 2, after ball milling terminates, reaction product in zirconia ball mill and zirconium oxide balls is sieved, that is, repaired
Soil afterwards.
In the present invention, sieve and sieved for 2mm.
In the present invention, zirconia ball mill is planetary ball mill.
In the present invention, the mass ratio of total material and zirconium oxide balls is 1：6~1：18.
In the present invention, it is 2% ~ 4% that the consumption of reducing agent, which accounts for the mass ratio of total inventory,；Rotational speed of ball-mill be 400 ~ 600 turns/
Minute, Ball-milling Time is 1 ~ 3 hour.
Compared with existing actual place recovery technique, method provided by the present invention has the advantage that as follows：
In this method, with the Cr VI in contaminated soil sufficient reduction reaction occurs for reducing agent in the presence of mechanical ball mill,
And in the presence of mechanical force so that pollution products（Trivalent chromium and Cr VI）With soil particle formation aggregate, enhance
The stability of pollutant.In addition, the processing method is produced without any secondary pollution, before being a kind of efficient green, great application
The hexavalent chromium polluted soil remediation processing method of scape.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Fig. 1 is present invention process flow chart.
Embodiment 1
By 10g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, and according to GB 5085.3-2007, Cr VI is leached
Concentration is 22.58 mg/L）Planetary type ball-milling machine jar body is added to after being mixed with the calcium polysulfide of 0.2g ferrous sulfate and 0.1 g
In, zirconium oxide balls then are added to ball grinder, the wherein mass ratio of material and abrading-ball is 1:9.Set ball milling operation condition as：
Rotational speed of ball-mill is 500 revs/min, and Ball-milling Time is 2 hours, and ball milling method is ball milling 15 minutes, is spaced 15 minutes, follows successively
Ring is carried out.After mechanico-chemical reaction terminates, sampling carries out toxicity leaching experiment, and it is dense to measure the leaching of Cr VI in leaching liquor
Degree.
Through analysis, it is 0.92 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 2
By 10g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, and according to GB 5085.3-2007, Cr VI is leached
Concentration is 22.58 mg/L）It is added in planetary type ball-milling machine jar body, then adds to ball grinder after being mixed with 0.3 g ferrous sulfate
Enter zirconium oxide balls, the wherein mass ratio of material and abrading-ball is 1:9.Set ball milling operation condition as：Rotational speed of ball-mill be 600 turns/
Minute, Ball-milling Time is 2 hours, and ball milling method is ball milling 15 minutes, is spaced 15 minutes, circulation successively is carried out.Mechanochemistry is anti-
After should terminating, sampling carries out toxicity leaching experiment, and measures the leaching concentration of Cr VI in leaching liquor.
Through analysis, it is 0.38 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 3
By 10g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, and according to GB 5085.3-2007, Cr VI is leached
Concentration is 22.58 mg/L）It is added in planetary type ball-milling machine jar body, then adds to ball grinder after being mixed with 0.3 g calcium polysulfides
Enter zirconium oxide balls, the wherein mass ratio of material and abrading-ball is 1:9.Set ball milling operation condition as：Rotational speed of ball-mill be 500 turns/
Minute, Ball-milling Time is 2 hours, and ball milling method is ball milling 15 minutes, is spaced 15 minutes, circulation successively is carried out.Mechanochemistry is anti-
After should terminating, sampling carries out toxicity leaching experiment, and measures the leaching concentration of Cr VI in leaching liquor.
Through analysis, it is 0.51 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 4
By 10 g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, according to GB 5085.3-2007, Cr VI leaching
Go out concentration for 22.58 mg/L）Planetary ball mill tank is added to after being mixed with the calcium polysulfide of 0.2 g ferrous sulfate and 0.1 g
In body, zirconium oxide balls then are added to ball grinder, the wherein mass ratio of material and abrading-ball is 1:9.Set ball milling operation condition
For：Rotational speed of ball-mill is 500 revs/min, and Ball-milling Time is 4 hours, and ball milling method is ball milling 15 minutes, interval 15 minutes, successively
Circulation is carried out.After mechanico-chemical reaction terminates, sampling carries out toxicity leaching experiment, and it is dense to measure the leaching of Cr VI in leaching liquor
Degree.
Through analysis, it is 0.21 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 5
By 10 g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, according to GB 5085.3-2007, Cr VI leaching
Go out concentration for 22.58 mg/L）It is added to after being mixed with 0.3 g ferrous sulfate in planetary type ball-milling machine jar body, then to ball grinder
Zirconium oxide balls are added, the wherein mass ratio of material and abrading-ball is 1:9.Set ball milling operation condition as：Rotational speed of ball-mill is 600
Rev/min, Ball-milling Time is 4 hours, and ball milling method is ball milling 15 minutes, is spaced 15 minutes, circulation successively is carried out.Mechanization
After reaction terminates, sampling carries out toxicity leaching experiment, and measures the leaching concentration of Cr VI in leaching liquor.
Through analysis, it is 0.33 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 6
By 10 g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, according to GB 5085.3-2007, Cr VI leaching
Go out concentration for 22.58 mg/L）It is added to after being mixed with 0.3 g calcium polysulfides in planetary type ball-milling machine jar body, then to ball grinder
Zirconium oxide balls are added, the wherein mass ratio of material and abrading-ball is 1:9.Set ball milling operation condition as：Rotational speed of ball-mill is 500
Rev/min, Ball-milling Time is 4 hours, and ball milling method is ball milling 15 minutes, is spaced 15 minutes, circulation successively is carried out.Mechanization
After reaction terminates, sampling carries out toxicity leaching experiment, and measures the leaching concentration of Cr VI in leaching liquor.
Through analysis, it is 0.50 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 7
By 10 g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, according to GB 5085.3-2007, Cr VI leaching
Go out concentration for 22.58 mg/L）Planetary ball mill tank is added to after being mixed with the calcium polysulfide of 0.2 g ferrous sulfate and 0.1 g
In body, zirconium oxide balls then are added to ball grinder, the wherein mass ratio of material and abrading-ball is 1:12.Set ball milling operation condition
For：Rotational speed of ball-mill is 500 revs/min, and Ball-milling Time is 2 hours, and ball milling method is ball milling 15 minutes, interval 15 minutes, successively
Circulation is carried out.After mechanico-chemical reaction terminates, sampling carries out toxicity leaching experiment, and it is dense to measure the leaching of Cr VI in leaching liquor
Degree.
Through analysis, it is 0.48 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 8
By 10g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, and according to GB 5085.3-2007, Cr VI is leached
Concentration is 22.58 mg/L）It is added in planetary type ball-milling machine jar body, then adds to ball grinder after being mixed with 0.3 g ferrous sulfate
Enter zirconium oxide balls, the wherein mass ratio of material and abrading-ball is 1:15.Set ball milling operation condition as：Rotational speed of ball-mill be 500 turns/
Minute, Ball-milling Time is 2 hours, and ball milling method is ball milling 15 minutes, is spaced 15 minutes, circulation successively is carried out.Mechanochemistry is anti-
After should terminating, sampling carries out toxicity leaching experiment, and measures the leaching concentration of Cr VI in leaching liquor.
Through analysis, it is 0.31 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Embodiment 9
By 10 g contaminated soils（Original soil sample content of 6-valence Cr ions is 2360 mg/kg, according to GB 5085.3-2007, Cr VI leaching
Go out concentration for 22.58 mg/L）It is added to after being mixed with 0.3 g calcium polysulfides in planetary type ball-milling machine jar body, then to ball grinder
Zirconium oxide balls are added, the wherein mass ratio of material and abrading-ball is 1:15.Set ball milling operation condition as：Rotational speed of ball-mill is 500
Rev/min, Ball-milling Time is 2 hours, and ball milling method is ball milling 15 minutes, is spaced 15 minutes, circulation successively is carried out.Mechanochemistry
After reaction terminates, sampling carries out toxicity leaching experiment, and measures the leaching concentration of Cr VI in leaching liquor.
Through analysis, it is 0.05 mg/L to obtain hexavalent chromium concentration in leachate, less than leaching characteristic identification standard value（5.0
Mg/L, GB 5085.3-2007）.
Claims (5)
1. the mechanochemistry reduction restorative procedure of a kind of hexavalent chromium polluted soil, it is characterised in that comprise the following steps that：
Step one, the soil particle grinding of hexavalent chromium polluted soil, the sieving of natural air drying obtained adds after being mixed with reducing agent
Ball milling is carried out into zirconia ball mill, occurs mechanico-chemical reaction；Wherein：Reducing agent is one in ferrous sulfate or calcium polysulfide
Plant or two kinds；The mass ratio that the consumption of reducing agent accounts for total inventory is 1% ~ 5%；Rotational speed of ball-mill is 200 ~ 600 revs/min, ball
Consume time as 0.5 ~ 6 hour；
Step 2, after ball milling terminates, reaction product in zirconia ball mill and zirconium oxide balls is sieved, that is, repaired
Soil afterwards.
2. mechanochemistry as claimed in claim 1 reduces restorative procedure, it is characterised in that sieves and is sieved for 2mm.
3. mechanochemistry as claimed in claim 1 reduces restorative procedure, it is characterised in that zirconia ball mill is planetary ball
Grinding machine.
4. mechanochemistry as claimed in claim 1 reduces restorative procedure, it is characterised in that the matter of total material and zirconium oxide balls
Amount is than being 1：6~1：18.
5. mechanochemistry as claimed in claim 1 reduces restorative procedure, it is characterised in that the consumption of reducing agent accounts for total material
The mass ratio of amount is 2% ~ 4%；Rotational speed of ball-mill is 400 ~ 600 revs/min, and Ball-milling Time is 1 ~ 3 hour.
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| CN108746187A (en) * | 2018-05-25 | 2018-11-06 | 中国科学院沈阳应用生态研究所 | A kind of harmless, the recycling restorative procedure of chromium-polluted soil |
| CN108941189A (en) * | 2018-08-03 | 2018-12-07 | 祝定华 | A kind of mixed method of adsorbent for heavy metal and contaminated soil |
| CN109078563A (en) * | 2018-08-03 | 2018-12-25 | 祝定华 | A kind of mixing apparatus of adsorbent for heavy metal and contaminated soil |
| CN109092455A (en) * | 2018-07-31 | 2018-12-28 | 南京林业大学 | A method of using mechanochemical reaction degradation 5a,6,9,9a-hexahydro-6,9-methano-2,4 |
| CN110665956A (en) * | 2019-10-15 | 2020-01-10 | 上海第二工业大学 | Mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil |
| CN111234832A (en) * | 2020-01-14 | 2020-06-05 | 中南大学 | FeS-containing2Composite material and reduced iron, preparation method and application thereof |
| CN111889500A (en) * | 2020-06-16 | 2020-11-06 | 中南大学 | Detoxification method of chromium-containing residue soil, chromium-containing residue or chromium-containing soil |
| CN112044948A (en) * | 2020-10-10 | 2020-12-08 | 上海第二工业大学 | Method for restoring polychlorinated biphenyl polluted soil by mechanochemistry of nano zero-valent iron-oxide system |
| CN112705566A (en) * | 2020-11-24 | 2021-04-27 | 东南大学 | Method for restoring hexachlorobenzene polluted soil by mechanochemistry |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107353034A (en) * | 2017-07-27 | 2017-11-17 | 武汉理工大学 | A kind of method for preparing haydite using microwave sintering curing heavy metal chromium |
| CN108746187B (en) * | 2018-05-25 | 2020-07-31 | 中国科学院沈阳应用生态研究所 | Harmless and resource recovery method for chromium-polluted soil |
| CN108746187A (en) * | 2018-05-25 | 2018-11-06 | 中国科学院沈阳应用生态研究所 | A kind of harmless, the recycling restorative procedure of chromium-polluted soil |
| CN109092455A (en) * | 2018-07-31 | 2018-12-28 | 南京林业大学 | A method of using mechanochemical reaction degradation 5a,6,9,9a-hexahydro-6,9-methano-2,4 |
| CN108941189A (en) * | 2018-08-03 | 2018-12-07 | 祝定华 | A kind of mixed method of adsorbent for heavy metal and contaminated soil |
| CN109078563A (en) * | 2018-08-03 | 2018-12-25 | 祝定华 | A kind of mixing apparatus of adsorbent for heavy metal and contaminated soil |
| CN110665956A (en) * | 2019-10-15 | 2020-01-10 | 上海第二工业大学 | Mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil |
| CN111234832A (en) * | 2020-01-14 | 2020-06-05 | 中南大学 | FeS-containing2Composite material and reduced iron, preparation method and application thereof |
| CN111889500A (en) * | 2020-06-16 | 2020-11-06 | 中南大学 | Detoxification method of chromium-containing residue soil, chromium-containing residue or chromium-containing soil |
| CN111889500B (en) * | 2020-06-16 | 2022-07-12 | 中南大学 | Detoxification method of chromium-containing residue soil, chromium-containing residue or chromium-containing soil |
| CN112044948A (en) * | 2020-10-10 | 2020-12-08 | 上海第二工业大学 | Method for restoring polychlorinated biphenyl polluted soil by mechanochemistry of nano zero-valent iron-oxide system |
| CN112705566A (en) * | 2020-11-24 | 2021-04-27 | 东南大学 | Method for restoring hexachlorobenzene polluted soil by mechanochemistry |
| CN112705566B (en) * | 2020-11-24 | 2023-08-04 | 东南大学 | Method for repairing hexachlorobenzene-polluted soil by mechanochemical method |
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