CN104941996A - Remediation method for chromium-contaminated soil - Google Patents
Remediation method for chromium-contaminated soil Download PDFInfo
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- CN104941996A CN104941996A CN201510314301.6A CN201510314301A CN104941996A CN 104941996 A CN104941996 A CN 104941996A CN 201510314301 A CN201510314301 A CN 201510314301A CN 104941996 A CN104941996 A CN 104941996A
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Abstract
The invention belongs to the field of regeneration of contaminated soil, and provides a remediation method for chromium-contaminated soil. The remediation method comprises the following steps: (1) juicing sugarcane, and crushing and screening the juiced sugarcane into sugarcane bagasse with the size of 10-100 meshes; (2) uniformly mixing the sugarcane bagasse with the chromium-contaminated soil to obtain a mixture, and controlling moisture content of the mixture to 20%-60% so to obtain a chromium-contaminated soil mixture; and (3) carrying out remediation culture on the chromium-contaminated soil mixture at a temperature of 20-45 DEG C. According to the remediation method for chromium-contaminated soil provided by the invention, the sugarcane bagasse is taken as a treatment agent, so that agricultural waste is utilized; the removal rate for hexavalent chromium in the soil can be up to 99.99%, so that the remediation method is suitable for different types of chromium-contaminated soil; compared with a solidification and stabilization method adopted in the prior art, the removal rate for the hexavalent chromium is higher, the remediation period is shorter, the secondary pollution is avoided, and the soil quality can be improved; and moreover, the method disclosed by the invention is simple to operate and high in applicability, and the remediation agent is wide in source, easy to obtain and low in price.
Description
Technical field
The present invention relates to contaminated soil regeneration field, particularly relate to a kind of by the restorative procedure of the soil of pollution of chromium.
Background technology
Chromium existing mainly with Cr (VI) and Cr (III) two kind of valence state at occurring in nature, both toxicity and chemical behavior differ very large, mainly exist with trivalent chromium compound in soil, after they enter soil, wherein more than 90% fixed by adsorption by soil rapidly, be difficult to move again in soil.Soil is lower to chromic absorption crystallized ability, is only 8.5%-36.2%.Trivalent chromium is the trace element of needed by human, is the chief component of GTF (GTF).Cr VI, due to its oxidisability and the high osmosis to skin, is poisoned very large, has been identified carcinogenesis.The repairing and treating of chromium-polluted soil is mainly for chromic process.Such as use solidification and stabilization technology governance chromium-polluted soil.Solidification and stabilization technology is by adding hexavalent chrome reduction to be become chromic reparation medicament and then utilize curing agent by the technology of soil solidification in soil.Reparation medicament conventional at present mainly contains iron system thing, sulphur system thing and low molecule organic matter.
Although existing research and utilization iron system's thing and the reparation of thing to chromium-polluted soil of sulphur system have good effect, as ferrous sulfate, iron sulfide, sodium dithionite etc., but it easily causes secondary pollution, and on the physicochemical property of soil, there is negative impact, soil function is caused to lack, Technique Popularizing limited space.Bagasse is a kind of common, is prevalent in occurring in nature, is easy to obtain, cheap, the debirs of the sugar industry of wide material sources, but any report that is current and that have no about bagasse reparation chromium-polluted soil.
Summary of the invention
The object of the invention is to utilize ferrous salt, sulfide etc. to repair medicament for prior art repair chromium-polluted soil and easily cause secondary pollution and the problem of negative effect can be caused soil physico-chemical property, propose a kind of environmental friendliness and be applicable to the restorative procedure of the chromium-polluted soil of different pollution level and mode.
For realizing above-mentioned purpose of the present invention, the technical scheme of employing is:
For a restorative procedure for chromium-polluted soil, described method is using bagasse as soil remediation medicament.
The present invention is using bagasse as a kind of brand-new soil remediation medicament, surprisingly find that it effectively can repair chromium-polluted soil, and obtain desirable treatment effect, the concrete mode of process can adopt conventional multiple of prior art, can repair being mixed in an appropriate form in chromium-polluted soil to complete as the bagasse of soil remediation medicament.
Specifically, the restorative procedure for chromium-polluted soil of the present invention, preferably includes following steps:
(1) be the bagasse of 10 ~ 100 order sizes by crushing and screening after sugar cane crushing;
(2) mixed with chromium-polluted soil by described bagasse, controlling its moisture content is 20% ~ 60%, obtains chromium-polluted soil mixture;
(3) carry out reparation under described chromium-polluted soil mixture being placed on 20 ~ 45 DEG C of temperature to cultivate.
Above-mentioned restorative procedure is more outstanding compared with the treatment effect of additive method.
Method of the present invention, in step (1), preferably by air-dry after sugar cane crushing be crush and screen after 1 ~ 10% to moisture content.
Method of the present invention, step (2) can according to the actual conditions of chromium-polluted soil and bagasse, select by adding the mode such as water or appropriateness evaporation to control its final moisture content for 20% ~ 60% in chromium-polluted soil mixture, concrete means are grasped by those skilled in the art, and the present invention is not particularly limited this.
Method of the present invention, in described step (2), by percentage to the quality, the consumption of bagasse is 2.5% ~ 100% of chromium-polluted soil dry weight.
The present invention, by the optimal control to chromium-polluted soil water content and soil remediation medicament (bagasse) consumption, can take into account repair ability and cost further simultaneously.Experimental result shows, the bagasse adding 2.5 ~ 100% in chromium-polluted soil all can realize good repairing effect.
Further, in described step (2), the moisture content preferably controlling chromium-polluted soil mixture is 20% ~ 50%, and the consumption of bagasse is 2.5% ~ 30% of chromium-polluted soil dry weight.
Further preferably, in described step (2), the moisture content controlling chromium-polluted soil mixture is 30% ~ 40%, and the consumption of bagasse is 2.5% ~ 15% of chromium-polluted soil dry weight.。
The present invention is by the control to the moisture content of chromium-polluted soil mixture, and the consumption in conjunction with chromium content in the relative chromium-polluted soil of bagasse controls, and more contributes to guaranteeing repairing effect.Wherein, in described step (3), it is 20 ~ 30 DEG C that chromium-polluted soil mixture repairs cultivation temperature, is conducive to bagasse to chromic effect under this cultivation temperature.
Method of the present invention, in step (3), repairs incubation time and was advisable with 3 days ~ 1 year.
Method of the present invention, find in experimentation, if when hexavalent chromium concentration is at 1000mg/kg add 2.5% bagasse reparation after 28 days chromic clearance can reach more than 97%, and add 5% bagasse reparation after 3 days chromic clearance just can reach more than 97%; When hexavalent chromium concentration is at 1500mg/kg, the bagasse reparation of interpolation 5% can reach the clearance of more than 97% after 28 days, and when hexavalent chromium concentration is 3000mg/kg, the bagasse adding 5% then needs to reach the clearance of more than 97% repair time more grown.
Consider that the chromium-polluted soil of different pollution level has different requirements for concrete repairing condition, for guaranteeing that the method for the invention has more specific aim, inventor further provides as follows for the preferred restorative procedure of different pollution level on the basis of lot of experiments, can be suitable for obtain desirable repairing effect (repair rate all reaches more than 97%) under repairing condition to make the chromium-polluted soil of different pollution level:
When hexavalent chromium concentration is at below 1000mg/kg in chromium-polluted soil, adds the bagasse reparation accounting for soil dry weight 1 ~ 3% and cultivate 15 ~ 28 days; Or add account for soil dry weight 3 ~ 10% bagasse reparation cultivate 3 ~ 15 days.
When hexavalent chromium concentration in chromium-polluted soil is at 1000 ~ 3000mg/kg, adds the bagasse reparation accounting for soil dry weight 3 ~ 10% and cultivate 25 ~ 30 days; Or add account for soil dry weight 10 ~ 15% bagasse reparation cultivate 10 ~ 25 days.
When hexavalent chromium concentration is greater than 3000mg/kg in chromium-polluted soil, adds the bagasse reparation accounting for soil dry weight 5 ~ 20% and cultivate 28 days ~ 0.5 year; Or add the bagasse reparation accounting for soil dry weight 20 ~ 100% and cultivate 15 days ~ 28 days.
Wherein, the control of the moisture content of cultivation temperature and chromium-polluted soil mixture can continue to use above-mentioned condition of the present invention.
Beneficial effect of the present invention is:
Bagasse after flour adds in chromium-polluted soil by the present invention, control soil moisture content, by the chromium generation chemical reaction in the effect such as complexing, oxidationreduction and soil environment, hexavalent chrome reduction in soil is become trivalent chromium, form stable chemical form, reduce animal migration in soil of chromic content in soil, total chromium and chromic leaching concentration and chromium and the degree of murder by poisoning.And in soil extract, hexavalent chromium concentration meets the standard of " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) " after repairing.
The restorative procedure of chromium-polluted soil provided by the invention, is treatment agent with bagasse, makes agricultural wastes obtain utilization; More than 95% is reached to clearance chromic in soil, be applicable to DIFFERENT Cr contaminated soil, compare with the solidification and stabilization method adopted in prior art, the clearance of chromium is higher, repairing efficiency is shorter, non-secondary pollution, can improve soil quality and method of the present invention is simple to operate, applicability is strong, repair medicament source wide, be easy to obtain, cheap.
Accompanying drawing explanation
Fig. 1 is before embodiment 1 is repaired and repairs the test light spectrogram of rear soil.
Detailed description of the invention
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.
In embodiment of the present invention, the bagasse of employing is that to crush and screen after sugar cane crushing be the bagasse of 10 ~ 100 order sizes, or after squeezing the juice first through air-dry to moisture content be 1 ~ 10%, after to carry out crushing and screening be the bagasse of 10 ~ 100 order sizes.
The present invention only considers the objectivity of experiment and conformity provides unified specific examination soil as reparation object, but those skilled in the art are it is understood that the method for the invention is applicable to the chromium-polluted soil of multiple degree.
Specifically, provided by the invention as follows for examination soil:
Experiment soil collecting is not comtaminated region from Henan, and the content of beary metal in this regional soil top layer meets a class standard of " standard of soil environment quality " (GB15618-1995).For reaching requirement of experiment, in soil, adding potassium bichromate, according to dry weight, in every 10KG soil, adding 16.96g potassium bichromate, make Chromium in Soil content be 600mg/kg.After aging 2 months, in soil, chromic content is 502mg/kg, soil of must taking an entrance examination (chromium-polluted soils namely in following examples).
The restorative procedure of chromium-polluted soil provided by the invention is described in detail below by way of 20 embodiments.
Embodiment 1:
Present embodiments provide a kind of restorative procedure for chromium-polluted soil, comprise the steps:
(1) crushing and screening after sugar cane crushing is the bagasse of 10 ~ 100 order sizes.
(2) described bagasse is mixed with chromium-polluted soil, obtained moisture content is the chromium-polluted soil mixture of 40% (controlling moisture content by the water adding suitable amounts wherein), wherein, chromium-polluted soil dry weight is 20kg, and the quality of bagasse is 1kg.
(3) repair cultivation 28 days under described chromium-polluted soil mixture being placed in 25 DEG C of conditions, complete reparation.
The present embodiment provides the X-ray abosrption spectrogram of the soil before and after repairing simultaneously, sees Fig. 1.Because Cr (VI) has an obvious limit leading peak in border area, trivalent chromium does not have, can observe to repair in front soil by this figure thus and have more Cr VI, and Cr VI distinctive limit leading peak do not detected in soil after the technical scheme reparation of the present embodiment, in the detectable limit of this experimental facilities, can't detect chromic being present in.Therefore, the Cr VI after repairing in soil obtains good removal.
Embodiment 2
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, the consumption of bagasse is 0.5kg.
Embodiment 3
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, the consumption of bagasse is 3kg.
Embodiment 4
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, the consumption of bagasse is 20kg.
Embodiment 5
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, the moisture content being controlled chromium-polluted soil mixture by the addition adjusting water is 20%.
Embodiment 6
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, the moisture content being controlled chromium-polluted soil mixture by the addition adjusting water is 30%.
Embodiment 7
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, the moisture content being controlled chromium-polluted soil mixture by the addition adjusting water is 50%.
Embodiment 8
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, repair and cultivate at described chromium-polluted soil mixture is placed in 20 DEG C.
Embodiment 9
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, repair and cultivate at described chromium-polluted soil mixture is placed in 30 DEG C.
Embodiment 10
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, repair and cultivate at described chromium-polluted soil mixture is placed in 45 DEG C.
Embodiment 11
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 2, and difference is, in step (3), the reparation of described chromium-polluted soil mixture are cultivated 3 days.
Embodiment 12
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, in step (3), the reparation of described chromium-polluted soil mixture are cultivated 0.5 year.
Embodiment 13
In the present embodiment, the chromium-polluted soil source chosen, operating procedure, reaction mechanism are all with embodiment 1, and difference is, in step (3), the reparation of described chromium-polluted soil mixture are cultivated 1 year.
Embodiment 14
In the present embodiment, operating procedure, reaction mechanism are all with embodiment 1, difference is, the chromium-polluted soil that the present embodiment is chosen is originated, pollution of chromium concentration is all different, and the present embodiment chromium-polluted soil used is that actual pollution of chromium place soil without the need to adding potassium bichromate and carrying out alternation of wetting and drying aging 2 months in soil.
Specifically, in the present embodiment, chromium-polluted soil collection is from pollution of chromium region, Henan, this regional soil reach many decades by the pollution of chromium time and content of beary metal in upper soll layer far away higher than the grade III Standard of " standard of soil environment quality " (GB15618-1995), the content of Chromium in Soil is 1690mg/kg, chromic content is 1050mg/kg, for meeting the soil of pollution or heavily contaminated.
Embodiment 15
In the present embodiment, the distinctive points compared with embodiment 1 is that concrete restorative procedure is: in chromium-polluted soil, hexavalent chromium concentration is at 600mg/kg, adds the bagasse reparation accounting for soil dry weight 3% and cultivates 28 days.
Embodiment 16
In the present embodiment, the distinctive points compared with embodiment 1 is that concrete restorative procedure is: in chromium-polluted soil, hexavalent chromium concentration is at 800mg/kg, adds the bagasse reparation accounting for soil dry weight 8% and cultivates 6 days.
Embodiment 17
In the present embodiment, the distinctive points compared with embodiment 1 is that concrete restorative procedure is: in chromium-polluted soil, hexavalent chromium concentration is at 1000mg/kg, adds the bagasse reparation accounting for soil dry weight 3% and cultivates 25 days.
Embodiment 18
In the present embodiment, the distinctive points compared with embodiment 1 is that concrete restorative procedure is: in chromium-polluted soil, hexavalent chromium concentration is when 2000mg/kg, adds the bagasse reparation accounting for soil dry weight 12% and cultivates 18 days.
Embodiment 19
In the present embodiment, the distinctive points compared with embodiment 1 is that concrete restorative procedure is: in chromium-polluted soil, hexavalent chromium concentration is 3000mg/kg, adds the bagasse reparation accounting for soil dry weight 20% and cultivates 28 days.
Embodiment 20
In the present embodiment, the distinctive points compared with embodiment 1 is that concrete restorative procedure is: in chromium-polluted soil, hexavalent chromium concentration is 4000mg/kg, adds the bagasse reparation accounting for soil dry weight 50% and cultivates 20 days.
Experimental example 1
Through adopting the method disclosed in " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) " and " the chromic mensuration alkali of solid waste clears up/atomic absorption spectrophotometry (HJ687-2014) ", detect chromic leaching concentration and content to the rehabilitating soil that above-described embodiment 1 ~ 14 obtains respectively, testing result is listed in table 1 ~ table 3.
Table 1 repairs chromic leaching concentration, content and clearance in rear soil
| Leaching concentration mg/kg | Content mg/kg | Clearance |
| Before reparation | 48.8 | 502 | \ |
| Embodiment 1 | <0.004 | <0.16 | 99.99％ |
| Embodiment 2 | <0.004 | <0.16 | 99.99％ |
| Embodiment 3 | <0.004 | <0.16 | 99.99％ |
| Embodiment 4 | <0.004 | <0.16 | 99.99％ |
| Embodiment 5 | <0.004 | <0.16 | 99.99％ |
| Embodiment 6 | <0.004 | <0.16 | 99.99％ |
| Embodiment 7 | <0.004 | <0.16 | 99.99％ |
| Embodiment 8 | <0.004 | <0.16 | 99.99％ |
| Embodiment 9 | <0.004 | <0.16 | 99.99％ |
| Embodiment 10 | <0.004 | <0.16 | 99.99％ |
| Embodiment 11 | 22.2 | 24.1 | 95.20％ |
| Embodiment 12 | <0.004 | <0.16 | 99.99％ |
| Embodiment 13 | <0.004 | <0.16 | 99.99％ |
Table 2 repairs chromic leaching concentration, content and clearance in rear soil
| Leaching concentration mg/kg | Content mg/kg | Clearance | |
| Before reparation | 124 | 1050 | \ |
| Embodiment 14 | <0.004 | <0.16 | 99.99％ |
Table 3 repairs chromic leaching concentration, content and clearance in rear soil
| Leaching concentration mg/kg | Content mg/kg | Clearance | |
| Before reparation | 56.08 | 600 | \ |
| Embodiment 15 | <0.004 | <0.16 | 99.99％ |
| Before reparation | 75.48 | 800 | \ |
| Embodiment 16 | 0.12 | 1.42 | 99.82％ |
| Before reparation | 98.31 | 1000 | \ |
| Embodiment 17 | 5.81 | 16.53 | 98.35％ |
| Before reparation | 190.42 | 2000 | \ |
| Embodiment 18 | 19.20 | 27.78 | 98.61％ |
| Before reparation | 292.46 | 3000 | \ |
| Embodiment 19 | 13.01 | 25.45 | 99.15％ |
| Before reparation | 401.23 | 4000 | \ |
| Embodiment 20 | 21.44 | 43.82 | 98.90％ |
In 14 embodiments, chromic clearance reaches more than 95% as can be seen from Table 1 and Table 2, reach as high as 99.99% and leaching concentration except embodiment 11, all the other all reach " Groundwater Environmental Quality standard " (GB/T14848-93) I class standard.Compared with the additive method simultaneously adopted with prior art, repairing efficiency has foreshortened to 3 days ~ 28 days by 3 months ~ 1 year, has saved time cost.
As can be seen from Table 3, embodiment 15-20 all achieves desirable repairing effect, and chromic clearance all reaches more than 98%.
In addition, the content of soil with organic matter is the leading indicator characterizing soil fertility.The restorative procedure that the present invention proposes also has positive effect to improving soil quality, repair the correction data of rear soil with organic matter content before embodiment 1 ~ 13 reparation listed by table 4 and table 5 with embodiment 14, the correction data that embodiment 15 ~ 20 repairs front and back soil with organic matter content listed by table 6.
Rear soil with organic matter content repaired by table 4
| Organic g/kg | |
| Before reparation | 20.2 |
| Embodiment 1 | 48.8 |
| Embodiment 2 | 32.4 |
| Embodiment 3 | 82.6 |
| Embodiment 4 | 283.0 |
| Embodiment 5 | 42.2 |
| Embodiment 6 | 39.6 |
| Embodiment 7 | 38.9 |
| Embodiment 8 | 42.6 |
| Embodiment 9 | 39.9 |
| Embodiment 10 | 43.1 |
| Embodiment 11 | 39.6 |
| Embodiment 12 | 43.1 |
| Embodiment 13 | 40.5 |
Rear soil with organic matter content repaired by table 5
| Organic g/kg | |
| Before reparation | 21.6 |
| Embodiment 14 | 44.8 |
Rear soil with organic matter content repaired by table 6
| Organic g/kg | |
| Before reparation | 19.8 |
| Embodiment 15 | 30.1 |
| Before reparation | 20.4 |
| Embodiment 16 | 58.5 |
| Before reparation | 21.3 |
| Embodiment 17 | 37.6 |
| Before reparation | 19.5 |
| Embodiment 18 | 76.3 |
| Before reparation | 20.6 |
| Embodiment 19 | 91.7 |
| Before reparation | 19.6 |
| Embodiment 20 | 187 |
Although above with general explanation, detailed description of the invention and test, the present invention is described in detail, on basis of the present invention, can make some amendments to it or improve, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. for a restorative procedure for chromium-polluted soil, it is characterized in that, using bagasse as soil remediation medicament.
2. restorative procedure according to claim 1, is characterized in that, comprises step:
(1) be the bagasse of 10 ~ 100 order sizes by crushing and screening after sugar cane crushing;
(2) mixed with chromium-polluted soil by described bagasse, controlling its moisture content is 20% ~ 60%, obtains chromium-polluted soil mixture;
(3) carry out reparation under described chromium-polluted soil mixture being placed on 20 ~ 45 DEG C of temperature to cultivate.
3. restorative procedure according to claim 2, is characterized in that, in step (1), by air-dry after sugar cane crushing be crush and screen after 1 ~ 10% to moisture content.
4. restorative procedure according to claim 2, is characterized in that, in described step (2), by percentage to the quality, the consumption of bagasse is 2.5% ~ 100% of chromium-polluted soil dry weight.
5. restorative procedure according to claim 2, is characterized in that, in described step (2), the moisture content controlling chromium-polluted soil mixture is 20% ~ 50%, and the consumption of bagasse is 2.5% ~ 30% of chromium-polluted soil dry weight; The moisture content of preferred control chromium-polluted soil mixture is 30% ~ 40%, and the consumption of bagasse is 2.5% ~ 15% of chromium-polluted soil dry weight.
6. according to the arbitrary described restorative procedure of claim 2 ~ 5, it is characterized in that, in described step (3), repairing cultivation temperature is 20 ~ 30 DEG C.
7. according to the arbitrary described restorative procedure of claim 2 ~ 5, it is characterized in that, in described step (3), repairing incubation time is 3 days ~ 1 year.
8. according to the arbitrary described restorative procedure of claims 1 to 3, it is characterized in that, when hexavalent chromium concentration is at below 1000mg/kg in chromium-polluted soil, adds the bagasse reparation accounting for soil dry weight 1 ~ 3% and cultivate 15 ~ 28 days; Or add account for soil dry weight 3 ~ 10% bagasse reparation cultivate 3 ~ 15 days.
9. according to the arbitrary described restorative procedure of Claims 1 to 5, it is characterized in that, when hexavalent chromium concentration in chromium-polluted soil is at 1000 ~ 3000mg/kg, adds the bagasse reparation accounting for soil dry weight 3 ~ 10% and cultivate 25 ~ 30 days; Or add account for soil dry weight 10 ~ 15% bagasse reparation cultivate 10 ~ 25 days.
10. according to the arbitrary described restorative procedure of Claims 1 to 5, it is characterized in that, when hexavalent chromium concentration is greater than 3000mg/kg in chromium-polluted soil, adds the bagasse reparation accounting for soil dry weight 5 ~ 20% and cultivate 28 days ~ 0.5 year; Or add the bagasse reparation accounting for soil dry weight 20 ~ 100% and cultivate 15 days ~ 28 days.
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