CN105013810A - Chromium-contaminated soil remediation medicament and remediation method - Google Patents
Chromium-contaminated soil remediation medicament and remediation method Download PDFInfo
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Abstract
The invention provides a chromium-contaminated soil remediation medicament and a remediation method. The remediation medicament comprises the following ingredients, by weight, 10-70 parts of a reducing agent, 10-40 parts of a curing agent and 1-20 parts of a heavy metal precipitating agent, wherein the curing agent is sodium silicate and the heavy metal precipitating agent is one or two components selected from TMT-15 and dimethyl carbamodithioic acid. The remediation medicament is formed by compounding multiple ingredients, has a reasonable formula, has strong applicability, and can be used to highly efficiently remediate chromium-contaminated soil, especially carry out in-situ remediation treatment on chromium-contaminated soil. The remediation method adopts the remediation medicament for in-situ remediation or ex-situ remediation. The method is simple and easy to implement, is low-cost, has short remediation time of chromium-contaminated soil and has good remediation effects.
Description
Technical field
The invention belongs to environmental technology field, be specifically related to a kind of reparation medicament for chromium-polluted soil and restorative procedure.
Background technology
Along with the industrial expansions such as intermetallic composite coating, ferrochrome smelting, plating, process hides, pigment, refractory material and chemical industry and the continuous application containing chromium chemical substance, pollution of chromium is remained in soil in a large number by processes such as exploiting, process, use, be discarded, thus in worldwide, cause the problems such as soil Cr pollution.Chromium in soil is trivalent chromium and Cr VI mainly, chromic toxicity is far longer than trivalent chromium, it is listed in one of eight kinds of maximum chemical substances of harm, one of internationally recognized three kinds of carcinogenic metal objects, also be simultaneously one of U.S. EPA 129 kinds of priority pollutants of generally acknowledging, the improvement of chromium-polluted soil and repair and be therefore subject to most attention.
At present, the governance way of chromium-polluted soil mainly contains two kinds: one is removed from contaminated soil by chromium; Two is change the existing forms of chromium in soil, is trivalent chromium by hexavalent chrome reduction, reduces its transfer ability in the environment and bioavailability.Wherein, immobilization restorative procedure is paid close attention to widely because obtaining at cost and the requirement that can meet heavy-metal contaminated soil reparation the time better.
The immobilization restorative procedure of chromium-polluted soil specifically can be divided into physics immobilization reparation, chemical immobilization reparation, microbial immobilized reparation etc.Wherein, the immobilized principle of physics utilizes physical method fixed by pollutant or be encapsulated in closely knit inert material, and make a kind of process of its stabilisation, common fixative comprises zeolite, bentonite etc.; And microbial immobilized be transformed by microorganism, passivation and enriching heavy metal, thus improve the biodegradability of soil, fixed-contamination thing, improvement soil.
Chemistry immobilization reparation is the character according to pollutant and soil, suitable fixative is selected to join in contaminated soil, thus make pollutant and fixative that certain chemical reaction occur, to make pollutant change difficult migration, low activity material or remove from soil, usually can be realized by the pH value and/or Eh value regulating soil.Such as, the pH value that can regulate soil by alkaline matter as calcareous material, MgO etc., makes soil be alkalescence, thus reduces the solubility of chromium, impel it to form chromium hydroxide precipitation; In addition also can add the materials such as barium chloride makes chromium form barium chromate precipitation etc.And,, strong toxicity large for chromic solubility, transfer ability are in the environment higher than features such as trivalent chromiums, and can be regulated the Eh value of soil by reducing agent, be trivalent chromium by hexavalent chrome reduction, thus reducing its toxicity in envelope and transfer ability, conventional reducing agent comprises H
2s, FeSO
4, simple substance Fe etc.
Domestic and international at present dystopy immobilization repair process is adopted mostly to chromium-polluted soil, namely chromium-polluted soil excavated, sieve and stir with reparation medicament, mix afterwards, carry out backfill maintenance again, its quantities is large, engineering time is long, rehabilitation cost is high, and its reason may be that current great majority both domestic and external are repaired medicament and needed mix with contaminated soil and stir the good repairing effect of competence exertion.
Fixation in situ repair process is without the need to excavating chromium-polluted soil, reparation medicament is directly injected in contaminated soil by it, thus can repair contaminated soil in original place, therefore operation is easier to, cost is relatively more cheap, and can not spoiled soil structure, obtain at present and paid close attention to widely.But the method only has certain applicability to light intermediate pollution soil, and very limited for the repair process ability of serious pollution soil, and it may be relevant with the drug effect of current reparation medicament.Therefore, if can develop a kind of efficient and the fixation in situization that can be applicable to chromium-polluted soil, particularly chromium serious pollution soil repairs medicament, recovery project cost will greatly be reduced.
Summary of the invention
The invention provides a kind of reparation medicament for chromium-polluted soil, this reparation medicament forms composite for various ingredients, its composition is simple, scientific formulation is reasonable, applicability is strong, particularly can be used in repairing efficiently severe chromium-polluted soil, make the heavy metal chromium complete stability in chromium-polluted soil thus lose biological effectiveness.
The present invention also provides a kind of restorative procedure for chromium-polluted soil, and it adopts described reparation medicament to carry out original position or showering to chromium-polluted soil, not only simple, with low cost, and short to the repair time of chromium-polluted soil, repairing effect good.
Reparation medicament for chromium-polluted soil provided by the invention, its composition comprises: reducing agent 10 ~ 70 mass parts, curing agent 10 ~ 40 mass parts and heavy metal precipitator 1 ~ 20 mass parts, wherein said curing agent is sodium metasilicate, described heavy metal precipitator be selected from TMT-15 and Sodium Dimethyldithiocarbamate one or both.
Reparation medicament for chromium-polluted soil of the present invention, uses collaborative to reducing agent, described curing agent and described heavy metal precipitator; Wherein, reducing agent mainly plays reduction, for being trivalent chromium by hexavalent chrome reduction; Described heavy metal precipitator is mainly used in trapping and is reduced agent and reduces the trivalent chromic ion generated, and makes it generate chelate not soluble in water; The trivalent chromium that described curing agent is mainly used in chelate and the described reducing agent reduction generation described heavy metal precipitator effect generated is cured and wraps up, thus prevents trivalent chromium to be again oxidized to Cr VI; Mutual synergy between various ingredients is good, and it can make the heavy metal chromium complete stability in chromium-polluted soil thus lose biological effectiveness, and repairing effect is good.
TMT-15 of the present invention consists of trithiocyanuric acid trisodium salt, and molecular formula is C
3n
3na
3s
3, it can react rapidly with the chromium in soil at normal temperatures, generates water insoluble and that chemical stability is good chelate, thus reaches the object catching removal heavy metal chromium, can by common commercially available acquisition.Sodium Dimethyldithiocarbamate of the present invention consist of SDD, molecular formula is: (CH
3)
2n CS
2na, can by common commercially available acquisition.
Further, the composition of reparation medicament of the present invention can comprise reducing agent 30 ~ 70 mass parts, curing agent 20 ~ 40 mass parts and heavy metal precipitator 5 ~ 15 mass parts.In concrete scheme of the present invention, the composition of described reparation medicament can comprise reducing agent 50 ~ 70 mass parts, curing agent 25 ~ 35 mass parts and heavy metal precipitator 5 ~ 15 mass parts.
Reducing agent of the present invention is for can become chromic material by hexavalent chrome reduction, such as described reducing agent can be selected from one or more in sodium polysulfide, hydrazine hydrate, ferrous sulfate, frerrous chloride, sodium hydrogensulfite, sodium pyrosulfite, sodium thiosulfate, sodium sulfite and sodium dithionite.
In concrete scheme of the present invention, described reducing agent at least comprises sodium polysulfide, can also comprise hydrazine hydrate further.The molecular formula of sodium polysulfide of the present invention is Na
2s
x, wherein x is the integer of 2 ~ 5.
Further, in reparation medicament of the present invention, described reducing agent can be sodium polysulfide and hydrazine hydrate, and described curing agent is sodium metasilicate, and described heavy metal precipitator is TMT-15.Further, the composition of described reparation medicament can be: sodium polysulfide 40 ~ 60 mass parts, hydrazine hydrate 5 ~ 20 mass parts, sodium metasilicate 20 ~ 40 mass parts and TMT-155 ~ 15 mass parts.In concrete scheme of the present invention, the composition of described reparation medicament can be: sodium polysulfide 40 ~ 50 mass parts, hydrazine hydrate 5 ~ 215 mass parts, sodium metasilicate 25 ~ 35 mass parts and TMT-155 ~ 15 mass parts.
Further, in reparation medicament of the present invention, described heavy metal precipitator can comprise TMT-15 and Sodium Dimethyldithiocarbamate, and the quality proportioning of described TMT-15 and Sodium Dimethyldithiocarbamate can be 1 ~ 3:1, such as 2:1.Particularly, the composition of described reparation medicament can be: sodium polysulfide 40 ~ 50 mass parts, hydrazine hydrate 1 ~ 10 mass parts, sodium metasilicate 30 ~ 40 mass parts, TMT-155 ~ 15 mass parts and Sodium Dimethyldithiocarbamate 1 ~ 10 mass parts.
The present invention also provides a kind of restorative procedure for chromium-polluted soil, comprises the steps:
1) above-mentioned arbitrary described reparation medicament and water are stirred and evenly mixed according to quality proportioning 2 ~ 25:100, make liquid and repair medicament;
2) adopt described liquid to repair medicament and in-situ immobilization process or showering process are carried out to chromium-polluted soil to be repaired, chromium content to described chromium-polluted soil is up to standard, and the use amount that wherein said liquid repairs medicament is 5 ~ 20% of described chromium-polluted soil gross mass.
Particularly, the liquid can preparing different ratio according to the chromium content in chromium-polluted soil to be repaired repairs medicament, and when chromium content is larger, liquid repairs drug concentration higher (content of the reparation medicament namely in liquid reparation medicament is larger).In addition, the addition can also repairing medicament by liquid regulates, and when the chromium content namely in chromium-polluted soil is larger, the addition that described liquid repairs medicament is larger.
Further, described in-situ immobilization process specifically comprises the steps:
211) injection orifice is set on chromium-polluted soil to be repaired and detects well;
212) described liquid being repaired medicament is injected in chromium-polluted soil by described injection orifice, and repair process is carried out in the whole region making described liquid reparation medicament fully infiltrate into chromium-polluted soil;
213) by described detection well sampling, detect the chromium content in the chromium-polluted soil of described repair process, described repair process is proceeded to chromium content up to standard.
Particularly, after analyzing according to the technical indicator such as soil types, physicochemical property, penetrating power, level of ground water of this area Conventional wisdom to chromium-polluted soil to be repaired, spacing between the position of reasonable design injection orifice, injection orifice and detect the position etc. of well, the setting position of described injection orifice should enable the liquid injected through injection orifice repair the whole region that medicament fully infiltrates into chromium-polluted soil.
Further, described that described repair process is proceeded to chromium content is up to standard, specifically can be undertaken by continuing to inject described liquid and repair medicament and/or extend the repair process time.
In-situ immobilization process of the present invention, make liquid repair medicament to repair under the condition mixed and stir with chromium-polluted soil without the need to excavating out by chromium-polluted soil to be repaired, it can effectively by the heavy metal chromium complete stability in chromium-polluted soil under the prerequisite of not spoiled soil structure, thus make it lose biological effectiveness, the Leaching of the chromium in the soil of repair process is low, and repairing effect is good.
Restorative procedure for chromium-polluted soil of the present invention also may be used for carrying out showering process to chromium-polluted soil, and described showering process specifically comprises the steps:
221) excavate chromium-polluted soil to be repaired and be delivered to treatment region;
222) chromium-polluted soil being delivered to treatment region being crushed to the quality that particle diameter is not more than the chromium-polluted soil within the scope of 30mm is more than 80% of gross mass;
223) described liquid is repaired medicament to add to carry out repair process in the chromium-polluted soil of fragmentation;
224) detect the chromium content in the chromium-polluted soil of described repair process, described repair process is proceeded to chromium content up to standard.
Wherein, described that described repair process is proceeded to chromium content is up to standard, can by continuing adding liquid and repair medicament or extend the repair process time to carry out in the chromium-polluted soil through fragmentation.
Further, it is more thin better to be crushed to by described chromium-polluted soil, thus is conducive to chromium-polluted soil and repairs fully mixing of medicament with liquid, and liquid reparation medicament is played a role better.Restorative procedure for chromium-polluted soil of the present invention, can process the chromium-polluted soil that total chrome content is about 20000mg/kg, and the leaching concentration of the Chromium in Soil through repairing is well below " integrated wastewater discharge standard " requirement, and repairing effect is good.
Enforcement of the present invention, at least has following effect:
1, the reparation medicament for chromium-polluted soil of the present invention, composition is simple, rationally, it may be used for carrying out original position or dystopy immobilization reparation to chromium-polluted soil formula, and can repair the soil of various pollution of chromium degree, particularly severe chromium-polluted soil.
2, the reparation medicament for chromium-polluted soil of the present invention is without the need to mixing with chromium-polluted soil and can playing effect efficiently under the condition stirred, and is therefore specially adapted to carry out fixation in situ reparation to chromium-polluted soil.
3, the reparation medicament for chromium-polluted soil of the present invention can adjust its composition and content according to the pollution level of soil to be repaired and/or soil characteristic, and applicability is strong, applying flexible.
4, the restorative procedure for chromium-polluted soil of the present invention, utilize above-mentioned reparation medicament to carry out original position or dystopy immobilization reparation to chromium-polluted soil, the method is simple, with low cost, short to the repair time of chromium-polluted soil, repairing effect good.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with drawings and Examples of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
1. prepare liquid and repair medicament
The hydrazine hydrate of the sodium metasilicate of the sodium disulfide of 50 mass parts, 30 mass parts, the TMT-15 of 10 mass parts and 10 mass parts is mixed and stirs, makes reparation medicament;
Described reparation medicament is mixed according to quality proportioning 12:100 with water, and stirs, make liquid and repair medicament.
2. in-situ immobilization process
The chromium-polluted soil to be repaired of the present embodiment is positioned near the chromium salt factory of Jiangxi, adopt the heavy metal detection method of regulation in " standard of soil environment quality " (GB15618-1995) to measure the content of heavy metal in soil, testing result shows that in this chromium-polluted soil, total chrome content is 18245mg/kg.
After the technical indicator such as soil types, physicochemical property, penetrating power, level of ground water of this chromium-polluted soil is analyzed, estimate the amount of chromium-polluted soil to be repaired, and the position of reasonable design injection orifice, spacing between injection orifice and detect the position of well, chromium-polluted soil to be repaired arranges injection orifice and detects well; Aforesaid liquid being repaired medicament is injected in chromium-polluted soil by injection orifice, and repair process is carried out in the whole region making liquid reparation medicament fully infiltrate into chromium-polluted soil, and the use amount that liquid repairs medicament is 20% of chromium-polluted soil gross mass.
The chemical reaction occurred in repair process comprises:
1) sodium disulfide is to reduction reaction chromic in contaminated soil
Cr
2O
7 2-+3S
2-+7H
2O=2Cr
3++3S+14OH-
2) hydrazine hydrate is also to reduction reaction chromic in contaminated soil
2Cr
2O
7 2-+3N
2H
4·H
2O+=4Cr
3++3N
2+14OH-
3) TMT-15 with react the chromic chelatropic reaction that generates
4) chromic precipitation reaction
Cr
3++3OH-=Cr(OH)
3
Repair process is being carried out after 3 days to chromium-polluted soil, sample by detecting well, the content of heavy metal in chromium-polluted soil leachate after adopting the lixiviate mode of regulation in " solid waste Leaching leaching method sulfonitric method " (HJ/T299-2007) to detect reparation, result is as shown in table 1, table 1 result shows: process after 3 days, chromium content in the chromium-polluted soil of repair process is up to standard and be far smaller than " integrated wastewater discharge standard " and require (total Cr1.5mg/L, Cr VI 0.5mg/L).
Embodiment 2
Adopt the liquid of embodiment 1 to repair the to be repaired chromium-polluted soil of medicament to embodiment 1 and carry out showering process, be specially:
Excavate chromium-polluted soil to be repaired and be delivered to treatment region, chromium-polluted soil being crushed at treatment region the quality that particle diameter is not more than the chromium-polluted soil within the scope of 30mm is more than 90% of gross mass; The liquid of embodiment 1 reparation medicament is added in the chromium-polluted soil of fragmentation, carries out repair process, the use amount that liquid repairs medicament is 15% of chromium-polluted soil gross mass, repair process is being carried out after 3 days to chromium-polluted soil, sampling detects, and the chromium content results in the chromium-polluted soil after reparation is as shown in table 1.
Embodiment 3
The hydrazine hydrate of the sodium metasilicate of the sodium tetrasulfide of 40 mass parts, 30 mass parts, the Sodium Dimethyldithiocarbamate of 15 mass parts and 15 mass parts is mixed and stirs, make after repairing medicament, described reparation medicament is mixed according to quality proportioning 20:100 with water, and stirs, make liquid and repair medicament.
The chromium-polluted soil to be repaired of the present embodiment is positioned near the chromium salt factory of Hunan, and in this chromium-polluted soil, total chrome content is 12341mg/kg.The in-situ remediation method of embodiment 1 is adopted to carry out repair process to this chromium-polluted soil, wherein liquid repairs the use amount of medicament is 15% of chromium-polluted soil gross mass, repair process is being carried out after 3 days to chromium-polluted soil, sampling detects, and the chromium content results in the chromium-polluted soil after reparation is as shown in table 1.
Embodiment 4
Adopt the Ex-situ remediation method of embodiment 2 to utilize the liquid of embodiment 3 to repair the to be repaired chromium-polluted soil of medicament to embodiment 3 and carry out showering, wherein liquid repairs the use amount of medicament is 10% of chromium-polluted soil gross mass, repair process is being carried out after 3 days to chromium-polluted soil, sampling detects, and the chromium content results in the chromium-polluted soil after reparation is as shown in table 1.
Embodiment 5
The hydrazine hydrate of the TMT-15 of the sodium metasilicate of the sodium disulfide of 45 mass parts, 35 mass parts, 10 mass parts, the TMT-15 of 5 mass parts and 5 mass parts is mixed and stirs, make after repairing medicament, this reparation medicament is mixed according to quality proportioning 5:100 with water, and stir, make liquid and repair medicament.
The chromium-polluted soil to be repaired of the present embodiment is positioned near the chromium salt factory of Hebei, and in this chromium-polluted soil, total chrome content is 4960mg/kg.The Ex-situ remediation method of embodiment 2 is adopted to carry out repair process to this chromium-polluted soil, wherein liquid repairs the use amount of medicament is 12% of chromium-polluted soil gross mass, repair process is being carried out after 3 days to chromium-polluted soil, sampling detects, and the chromium content results in the chromium-polluted soil after reparation is as shown in table 1.
Embodiment 6
The hydrazine hydrate of the sodium metasilicate of the sodium pyrosulfite of the trisulfides sodium of 50 mass parts, 10 mass parts, 25 mass parts, the TMT-15 of 5 mass parts and 10 mass parts is mixed and stirs, make after repairing medicament, this reparation medicament is mixed according to quality proportioning 5:100 with water, and stir, make liquid and repair medicament.
The in-situ remediation method of embodiment 1 is adopted to carry out repair process to the chromium-polluted soil of embodiment 5, wherein liquid repairs the use amount of medicament is 20% of chromium-polluted soil gross mass, repair process is being carried out after 3 days to chromium-polluted soil, sampling detects, and the chromium content results in the chromium-polluted soil after reparation is as shown in table 1.
Reference examples
The barium chloride of the sodium pyrosulfite of 60 mass parts, 10 mass parts, the sodium metasilicate of 30 mass parts mixed and stir, makes after repairing medicament, described reparation medicament is mixed according to quality proportioning 12:100 with water, and stirs, making liquid and repair medicament.
Adopt the restorative procedure of embodiment 1 and embodiment 2 to utilize aforesaid liquid to repair medicament and respectively original position and showering process are carried out to the chromium-polluted soil to be repaired of embodiment 1, respectively as reference examples 1 and reference examples 2, repair process is being carried out after 3 days to chromium-polluted soil, sampling detects, and the chromium content results in the chromium-polluted soil after repair process is as shown in table 1.
In repair process after 7 days, chromium content in the chromium-polluted soil of repair process is still not up to standard, the aforesaid liquid reparation medicament continuing to add identical amount carries out above-mentioned original position and showering process, and the chromium content in the chromium-polluted soil of repair process still cannot be made up to standard.
Chromium content in table 1 chromium-polluted soil
As seen from the results in Table 1:
The reparation medicament adopting conventional heavy metal precipitator (as barium chloride) and reducing agent and curing agent to make to the original position of the higher soil of pollution of chromium degree and showering effect all limited, the chromium content in the soil after reparation cannot reach " integrated wastewater discharge standard " requirement; And the soil of reparation medicament to various pollution of chromium degree adopting the present invention to have specific heavy metal precipitator carries out repair process, all can reach good repairing effect, the chromium content after repairing in soil is far smaller than " integrated wastewater discharge standard " requirement.
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (8)
1. the reparation medicament for chromium-polluted soil, its composition comprises: reducing agent 10 ~ 70 mass parts, curing agent 10 ~ 40 mass parts and heavy metal precipitator 1 ~ 20 mass parts, wherein said curing agent is sodium metasilicate, described heavy metal precipitator be selected from TMT-15 and Sodium Dimethyldithiocarbamate one or both.
2. reparation medicament according to claim 1, it is characterized in that, described reducing agent be selected from sodium polysulfide, hydrazine hydrate, ferrous sulfate, frerrous chloride, sodium hydrogensulfite, sodium pyrosulfite, sodium thiosulfate, sodium sulfite and sodium dithionite one or more.
3. reparation medicament according to claim 1 and 2, is characterized in that, described reducing agent comprises sodium polysulfide and hydrazine hydrate.
4. reparation medicament according to claim 1, is characterized in that, described reducing agent is sodium polysulfide and hydrazine hydrate, and described curing agent is sodium metasilicate, and described heavy metal precipitator is TMT-15.
5. reparation medicament according to claim 4, it is characterized in that, it consists of: sodium polysulfide 40 ~ 60 mass parts, hydrazine hydrate 5 ~ 20 mass parts, sodium metasilicate 20 ~ 40 mass parts and TMT-155 ~ 15 mass parts.
6. for a restorative procedure for chromium-polluted soil, it is characterized in that, comprise the steps:
1) arbitrary for Claims 1 to 5 described reparation medicament and water are stirred and evenly mixed according to quality proportioning 2 ~ 25:100, make liquid and repair medicament;
2) adopt described liquid to repair medicament and in-situ immobilization process or showering process are carried out to chromium-polluted soil to be repaired, chromium content to described chromium-polluted soil is up to standard, and the use amount that wherein said liquid repairs medicament is 5 ~ 20% of described chromium-polluted soil gross mass.
7. restorative procedure according to claim 6, is characterized in that, described in-situ immobilization process specifically comprises the steps:
211) injection orifice is set on chromium-polluted soil to be repaired and detects well;
212) described liquid being repaired medicament is injected in chromium-polluted soil by described injection orifice, and repair process is carried out in the whole region making described liquid reparation medicament fully infiltrate into chromium-polluted soil;
213) by described detection well sampling, detect the chromium content in the chromium-polluted soil of described repair process, described repair process is proceeded to chromium content up to standard.
8. restorative procedure according to claim 6, is characterized in that, described showering process specifically comprises the steps:
221) excavate chromium-polluted soil to be repaired and be delivered to treatment region;
222) chromium-polluted soil being delivered to treatment region being crushed to the quality that particle diameter is not more than the chromium-polluted soil within the scope of 30mm is more than 80% of gross mass;
223) described liquid is repaired medicament to add to carry out repair process in the chromium-polluted soil of fragmentation;
224) detect the chromium content in the chromium-polluted soil of described repair process, described repair process is proceeded to chromium content up to standard.
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| CN105694894A (en) * | 2016-03-18 | 2016-06-22 | 济南大学 | Preparation method and application of hexavalent chromium contaminated soil conditioner |
| CN105598146B (en) * | 2016-03-28 | 2018-05-01 | 四川大学 | Curing agent and restorative procedure for chromium-polluted soil reparation |
| CN105598146A (en) * | 2016-03-28 | 2016-05-25 | 四川大学 | Curing agent for restoring soil polluted by chromium and restoration method |
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| CN109365506A (en) * | 2018-08-24 | 2019-02-22 | 湖南永清环保研究院有限责任公司 | A kind of heavy metal deactivator and its application suitable for neutral and alkali cadmium pollution soil |
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| CN110343528A (en) * | 2019-07-12 | 2019-10-18 | 河南省明创环境科技有限公司 | The method repaired the medicament of chromium-polluted soil using Filling Principle and repair chromium-polluted soil using Filling Principle |
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