CN104941996B - A kind of restorative procedure for chromium-polluted soil - Google Patents
A kind of restorative procedure for chromium-polluted soil Download PDFInfo
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- CN104941996B CN104941996B CN201510314301.6A CN201510314301A CN104941996B CN 104941996 B CN104941996 B CN 104941996B CN 201510314301 A CN201510314301 A CN 201510314301A CN 104941996 B CN104941996 B CN 104941996B
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Abstract
The invention belongs to contaminated soil regeneration field, there is provided a kind of restorative procedure for chromium-polluted soil, including step：(1) will be crushed and screened after sugar cane crushing as the bagasse of 10~100 mesh sizes；(2) bagasse is well mixed with chromium-polluted soil, it is 20%~60% to control its moisture content, obtains chromium-polluted soil mixture；(3) reparation culture is carried out at a temperature of the chromium-polluted soil mixture being placed on into 20~45 DEG C.The restorative procedure of chromium-polluted soil provided by the invention, using bagasse as treatment agent, utilized agricultural wastes；99.99% is reached as high as to the clearance of Cr VI in soil, suitable for different chromium-polluted soils, compared with the solidification and stabilization method used in the prior art, the clearance of Cr VI is higher, and repairing efficiency is shorter, non-secondary pollution, soil quality can be improved, and the method for the present invention is simple to operate, strong applicability, reparation medicament source is wide, is easily obtained, is cheap.
Description
Technical field
The present invention relates to the restorative procedure of contaminated soil regeneration field, more particularly to a kind of soil by pollution of chromium.
Background technology
Chromium is more with (III) two kind of valence state presence of Cr (VI) and Cr, both toxicity and chemical behavior differences in nature
It is very big, mainly exist in soil with trivalent chromium compound, after they enter soil, wherein 90% sharply above by soil
Absorption is fixed, and is difficult to migrate again in soil.Absorption crystallized ability of the soil to Cr VI is relatively low, only 8.5%-36.2%.
Trivalent chromium is the essential trace elements of the human body, is GTF (GTF) chief component.Cr VI is due to its oxygen
The property changed and the high osmosis to skin, murder by poisoning is very big, has been identified carcinogenesis.The repairing and treating of chromium-polluted soil is mainly pin
Processing to Cr VI.Such as with solidification and stabilization technology governance chromium-polluted soil.Solidification and stabilization technology is by soil
Hexavalent chrome reduction can be repaired medicament and then recycling curing agent by the technology of soil solidification by middle addition into trivalent chromium.Often at present
Reparation medicament mainly has iron system thing, sulphur system thing and low molecule organic matter.
Although the existing reparation of research and utilization iron system's thing and sulphur system thing to chromium-polluted soil has good effect, such as sulfuric acid
Ferrous iron, iron sulfide, sodium dithionite etc., but it easily causes secondary pollution, and there is negative shadow to the physicochemical property of soil
Ring, cause soil function to lack, Technique Popularizing limited space.Bagasse is a kind of common, is prevalent in nature, easily
It is cheap in acquisition, the debirs of the sugar industry of wide material sources, but at present and have no on bagasse repair pollution of chromium
Any report of soil.
The content of the invention
It is an object of the invention to repair medicament using ferrous salt, sulfide etc. for prior art to repair chromium-polluted soil
The problem of easily causing secondary pollution and being adversely affected to soil physico-chemical property, propose a kind of environment-friendly and be applied to not
With pollution level and the restorative procedure of the chromium-polluted soil of mode.
To realize above-mentioned purpose of the present invention, the technical scheme used for：
A kind of restorative procedure for chromium-polluted soil, methods described are used as soil remediation medicament using bagasse.
The present invention has been surprisingly found that it can effectively repair pollution of chromium using bagasse as a kind of brand-new soil remediation medicament
Soil, and obtain preferable treatment effect, it is a variety of that the concrete mode of processing can use prior art to commonly use, and can will be used as soil
The bagasse that earth repairs medicament mixes into chromium-polluted soil completion reparation in an appropriate form.
Specifically, the restorative procedure of the present invention for chromium-polluted soil, preferably includes following steps：
(1) will be crushed and screened after sugar cane crushing as the bagasse of 10~100 mesh sizes；
(2) bagasse is well mixed with chromium-polluted soil, it is 20%~60% to control its moisture content, obtains pollution of chromium
Soil mixture；
(3) reparation culture is carried out at a temperature of the chromium-polluted soil mixture being placed on into 20~45 DEG C.
Above-mentioned restorative procedure is more prominent compared with the treatment effect of other method.
Method of the present invention, in step (1), will preferably be air-dried after sugar cane crushing to moisture content is 1~10% laggard
Row crushes and screens.
Method of the present invention, step (2) can according to the actual conditions of chromium-polluted soil and bagasse, select pass through to
The mode such as water or appropriateness evaporation is added in chromium-polluted soil mixture to control its final moisture content as 20%~60%, specific hand
Section is grasped by those skilled in the art, and the present invention is not particularly limited to this.
Method of the present invention, in the step (2), by percentage to the quality, the dosage of bagasse is pollution of chromium soil
The 2.5%~100% of earth dry weight.
The present invention, can by the optimal control to chromium-polluted soil water content and soil remediation medicament (bagasse) dosage
Further take into account repair ability and cost simultaneously.Test result indicates that 2.5~100% sugarcane is added in chromium-polluted soil
Slag can realize good repairing effect.
Further, in the step (2), the moisture content for preferably controlling chromium-polluted soil mixture is 20%~50%,
The dosage of bagasse is the 2.5%~30% of chromium-polluted soil dry weight.
It is further preferred that in the step (2), the moisture content for controlling chromium-polluted soil mixture is 30%~40%,
The dosage of bagasse is the 2.5%~15% of chromium-polluted soil dry weight..
Control of the invention by the moisture content to chromium-polluted soil mixture, with reference to bagasse with respect in chromium-polluted soil
The dosage control of chromium content, is more conducive to ensure repairing effect.Wherein, in the step (3), chromium-polluted soil mixture reparation
Cultivation temperature is 20~30 DEG C, is advantageous to effect of the bagasse to Cr VI under the cultivation temperature.
Method of the present invention, in step (3), repair incubation time was advisable with 3 days~1 year.
Method of the present invention, finds in experimentation, if being added when hexavalent chromium concentration is in 1000mg/kg
The clearance of Cr VI can reach more than 97% after 2.5% bagasse reparation 28 days, and add after 5% bagasse repairs 3 days
The clearance of Cr VI just can reach more than 97%；When hexavalent chromium concentration is in 1500mg/kg, the bagasse of addition 5% repairs 28
Its rear can reach more than 97% clearance, and when hexavalent chromium concentration is 3000mg/kg, adding 5% bagasse then needs
Want the clearance that longer repair time can reach more than 97%.
There is different requirements for specific repairing condition in view of the chromium-polluted soil of different pollution levels, to ensure this
Invention methods described has more specific aim, and inventor further provides on the basis of lot of experiments is directed to different dirts as follows
The preferred restorative procedure of dye degree, to cause the chromium-polluted soil of different pollution levels to be obtained in the case where suitably obtaining repairing condition
Preferable repairing effect (repair rate is up to more than 97%)：
When hexavalent chromium concentration is in below 1000mg/kg in chromium-polluted soil, addition accounts for the sugarcane of soil dry weight 1~3%
Slag reparation culture 15~28 days；Or addition accounts for the bagasse reparation culture 3~15 days of soil dry weight 3~10%.
When hexavalent chromium concentration is in 1000~3000mg/kg in chromium-polluted soil, addition accounts for the sweet of soil dry weight 3~10%
Bagasse reparation culture 25~30 days；Or addition accounts for the bagasse reparation culture 10~25 days of soil dry weight 10~15%.
When hexavalent chromium concentration is more than 3000mg/kg in chromium-polluted soil, addition accounts for the bagasse of soil dry weight 5~20%
Repair culture 28 days~0.5 year；Or addition accounts for the bagasse reparation culture 15 days~28 days of soil dry weight 20~100%.
Wherein, the control of the moisture content of cultivation temperature and chromium-polluted soil mixture can continue to use above-mentioned bar of the present invention
Part.
The beneficial effects of the present invention are：
Bagasse after flour is added in chromium-polluted soil by the present invention, controls soil moisture content, passes through complexing, oxygen
The effects such as change-reduction chemically react with the chromium in soil environment, by the hexavalent chrome reduction in soil into trivalent chromium, are formed steady
Fixed chemical form, reduce the migration of the content, the leaching concentration and chromium of total chromium and Cr VI of Cr VI in soil in soil
Property and poison degree.And hexavalent chromium concentration meets in soil extract after repairing《Hazardous waste judging standard Leaching reflects
Not (GB5085.3-2007)》Standard.
The restorative procedure of chromium-polluted soil provided by the invention, using bagasse as treatment agent, obtain agricultural wastes
Utilize；More than 95% is reached to the clearance of Cr VI in soil, suitable for different chromium-polluted soils, with adopting in the prior art
Solidification and stabilization method compares, and the clearance of chromium is higher, and repairing efficiency is shorter, non-secondary pollution, can improve soil quality and
The method of the present invention is simple to operate, strong applicability, and reparation medicament source is wide, is easily obtained, is cheap.
Brief description of the drawings
Fig. 1 is the test light spectrogram with soil after reparation before embodiment 1 is repaired.
Embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.
In embodiment of the present invention, the bagasse that uses for sugar cane crushing after crush and screen as 10~100 mesh sizes
Bagasse, or after squeezing the juice first through air-dry to moisture content be 1~10%, after crushed and screened as 10~100 mesh sizes
Bagasse.
The present invention takes into consideration only the objectivity of experiment and conformity provides unified specific examination soil as reparation pair
As, but it will be appreciated to those of skill in the art that the method for the invention is applicable to the chromium-polluted soil of a variety of degree.
Specifically, it is provided by the invention as follows for examination soil：
Experiment soil collection meets from the content of beary metal in the not comtaminated region in Henan, the regional soil top layer《Soil
Earth environmental quality standards》(GB15618-1995) a class standard.To reach requirement of experiment, potassium bichromate is added into soil,
According to dry weight, 16.96g potassium bichromates are added in every 10KG soil, it is 600mg/kg to make chromium content in soil.After aging 2 months
The content of Cr VI is 502mg/kg in soil, the soil that must take an entrance examination (chromium-polluted soil i.e. in following examples).
Describe the restorative procedure of chromium-polluted soil provided by the invention in detail below by way of 20 embodiments.
Embodiment 1：
A kind of restorative procedure for chromium-polluted soil is present embodiments provided, is comprised the following steps：
(1) crushed and screened after sugar cane crushing as the bagasse of 10~100 mesh sizes.
(2) bagasse is well mixed with chromium-polluted soil, moisture content is made as 40% (by adding conjunction thereto
The water of dosage controls moisture content) chromium-polluted soil mixture, wherein, chromium-polluted soil dry weight is 20kg, bagasse
Quality is 1kg.
(3) culture 28 days is repaired under the conditions of the chromium-polluted soil mixture being placed in into 25 DEG C, completes to repair.
The present embodiment provides the X-ray absorption spectrogram for repairing front and rear soil simultaneously, sees Fig. 1.Because Cr (VI) exists
There is an obvious side leading peak in border area and trivalent chromium does not have, be observed that from there through this figure before reparation have in soil it is more
Cr VI, and before the distinctive side of Cr VI is not detected in the soil after the technical scheme reparation of the present embodiment
Peak, the presence of Cr VI is can't detect in the detectable limit of this experimental facilities.Therefore, the sexavalence after reparation in soil
Chromium has obtained good removal.
Embodiment 2
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In the dosage of bagasse is 0.5kg.
Embodiment 3
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In the dosage of bagasse is 3kg.
Embodiment 4
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In the dosage of bagasse is 20kg.
Embodiment 5
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In it is 20% that the addition by adjusting water, which controls the moisture content of chromium-polluted soil mixture,.
Embodiment 6
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In it is 30% that the addition by adjusting water, which controls the moisture content of chromium-polluted soil mixture,.
Embodiment 7
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In it is 50% that the addition by adjusting water, which controls the moisture content of chromium-polluted soil mixture,.
Embodiment 8
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In, by the chromium-polluted soil mixture be placed at 20 DEG C repair cultivate.
Embodiment 9
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In, by the chromium-polluted soil mixture be placed at 30 DEG C repair cultivate.
Embodiment 10
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In, by the chromium-polluted soil mixture be placed at 45 DEG C repair cultivate.
Embodiment 11
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 2, are distinguished
In by the chromium-polluted soil mixture reparation culture 3 days in step (3).
Embodiment 12
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In by the chromium-polluted soil mixture reparation culture 0.5 year in step (3).
Embodiment 13
In the present embodiment, the chromium-polluted soil source of selection, operating procedure, reaction mechanism with embodiment 1, are distinguished
In by the chromium-polluted soil mixture reparation culture 1 year in step (3).
Embodiment 14
In the present embodiment, with embodiment 1, difference is for operating procedure, reaction mechanism, the pollution of chromium that the present embodiment is chosen
Soil sources, pollution of chromium concentration are different, and chromium-polluted soil used in the present embodiment is that actual pollution of chromium place soil need not be to soil
Potassium bichromate is added in earth and carries out alternation of wetting and drying aging 2 months.
Specifically, chromium-polluted soil collection is dirty by chromium from Henan pollution of chromium region, the regional soil in the present embodiment
The dye time is significantly larger than up to the content of beary metal in many decades and upper soll layer《Standard of soil environment quality》(GB15618-
1995) grade III Standard, the content of chromium is 1690mg/kg in soil, and the content of Cr VI is 1050mg/kg, to meet pollution
Or the soil of heavily contaminated.
Embodiment 15
In the present embodiment, distinctive points compared with Example 1 are that specific restorative procedure is：Sexavalence in chromium-polluted soil
For chromium concn in 600mg/kg, addition accounts for the bagasse reparation culture 28 days of soil dry weight 3%.
Embodiment 16
In the present embodiment, distinctive points compared with Example 1 are that specific restorative procedure is：Sexavalence in chromium-polluted soil
For chromium concn in 800mg/kg, addition accounts for the bagasse reparation culture 6 days of soil dry weight 8%.
Embodiment 17
In the present embodiment, distinctive points compared with Example 1 are that specific restorative procedure is：Sexavalence in chromium-polluted soil
For chromium concn in 1000mg/kg, addition accounts for the bagasse reparation culture 25 days of soil dry weight 3%.
Embodiment 18
In the present embodiment, distinctive points compared with Example 1 are that specific restorative procedure is：Sexavalence in chromium-polluted soil
For chromium concn in 2000mg/kg, addition accounts for the bagasse reparation culture 18 days of soil dry weight 12%.
Embodiment 19
In the present embodiment, distinctive points compared with Example 1 are that specific restorative procedure is：Sexavalence in chromium-polluted soil
Chromium concn is 3000mg/kg, and addition accounts for the bagasse reparation culture 28 days of soil dry weight 20%.
Embodiment 20
In the present embodiment, distinctive points compared with Example 1 are that specific restorative procedure is：Sexavalence in chromium-polluted soil
Chromium concn is 4000mg/kg, and addition accounts for the bagasse reparation culture 20 days of soil dry weight 50%.
Experimental example 1
Through using《Hazardous waste judging standard leaching characteristic identification (GB5085.3-2007)》With《Solid waste Cr VI
Measure alkali resolution/atomic absorption spectrophotometry (HJ687-2014)》The method of middle disclosure, respectively to above-described embodiment
1~14 rehabilitating soil obtained detect the leaching concentration and content of Cr VI, and testing result is listed in 1~table of table 3.
Table 1 repair after in soil Cr VI leaching concentration, content and clearance
| 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 repair after in soil Cr VI leaching concentration, content and clearance
| Leaching concentration mg/kg | Content mg/kg | Clearance | |
| Before reparation | 124 | 1050 | \ |
| Embodiment 14 | <0.004 | <0.16 | 99.99% |
Table 3 repair after in soil Cr VI leaching concentration, content and clearance
| 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% |
The clearance of Cr VI reaches more than 95% in 14 embodiments as can be seen from Table 1 and Table 2, reaches as high as
99.99% and leaching concentration in addition to embodiment 11 remaining reach《Groundwater Environmental Quality standard》(GB/T14848-93) I class
Standard.Repairing efficiency was foreshortened to 3 days~28 days by 3 months~1 year compared with the other method that prior art uses simultaneously, was saved
About time cost.
From table 3 it is observed that embodiment 15-20 realizes preferable repairing effect, the clearance of Cr VI reaches
To more than 98%.
In addition, the content of soil with organic matter is to characterize the leading indicator of soil fertility.Restorative procedure proposed by the present invention
Also there is positive effect to improving soil quality, table 4 and table 5 list embodiment 1~13 and repair soil after preceding and embodiment 14 is repaired
The correction data of the middle content of organic matter, table 6 list the correction data of soil with organic matter content before and after embodiment 15~20 is repaired.
Soil with organic matter content after table 4 is repaired
| Organic matter 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 |
Soil with organic matter content after table 5 is repaired
| Organic matter g/kg | |
| Before reparation | 21.6 |
| Embodiment 14 | 44.8 |
Soil with organic matter content after table 6 is repaired
| Organic matter 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 the present invention is made to retouch in detail with general explanation, embodiment and experiment
State, but on the basis of the present invention, some modifications can be made to it or are improved, this is aobvious and easy to those skilled in the art
See.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, are belonged to claimed
Scope.
Claims (2)
1. a kind of restorative procedure for chromium-polluted soil, it is characterised in that including step：
（1）It will be crushed and screened after sugar cane crushing as the bagasse of 10 ~ 100 mesh sizes, wherein will be air-dried after sugar cane crushing to aqueous
Rate is crushed and screened after being 1 ~ 10%；
（2）The bagasse is well mixed with chromium-polluted soil, it is 30% ~ 40% to control its moisture content, obtains chromium-polluted soil and mixes
Compound；
（3）Reparation culture is carried out at a temperature of the chromium-polluted soil mixture is placed on into 20 ~ 45 DEG C；
When hexavalent chromium concentration is less than 1000mg/kg in chromium-polluted soil, addition accounts for the bagasse reparation training of soil dry weight 1 ~ 3%
Support 15 ~ 28 days；Or addition accounts for the bagasse reparation culture 3 ~ 15 days of soil dry weight 3 ~ 10%；
When hexavalent chromium concentration is in 1000 ~ 3000mg/kg in chromium-polluted soil, the bagasse that addition accounts for soil dry weight 3 ~ 10% is repaiied
Cultivate 25 ~ 30 days again；Or addition accounts for the bagasse reparation culture 10 ~ 25 days of soil dry weight 10 ~ 15%；
When hexavalent chromium concentration is more than 3000mg/kg in chromium-polluted soil, addition accounts for the bagasse reparation training of soil dry weight 5 ~ 20%
Support 28 days ~ 0.5 year；Or addition accounts for the bagasse reparation culture 15 days ~ 28 days of soil dry weight 20 ~ 100%.
2. restorative procedure according to claim 1, it is characterised in that the step（3）In, repair cultivation temperature be 20 ~
30℃。
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| CN110531056A (en) * | 2019-10-16 | 2019-12-03 | 北京市环境保护科学研究院 | The Manual Suture test method of Cr VI respiratory pathways in a kind of soil |
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| CN103272832B (en) * | 2013-04-26 | 2015-09-02 | 浙江工商大学 | A kind of method of fortification of plants restoration of soil polluted by heavy metal |
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